PROCEEDINGS OF THE CHEMICAL SOCIETY APRIL 1962 ARTHUR AIKIN (1773-1854) AND OTHER PRESIDENTS* By ANDREW KENT ARTHUR AKIN caught my attention because following our Thomas Graham he was the second President of the Chemical Society because exceptionally he was not a Fellow of the Royal Society and because the Indices of the Journal showed that his death in the day of succulent obituaries seemed not to have evoked a single spagyric sob. I suspected a Scot. The necessary enquiries were brief as in fact Arthur and his relations had far outsoared the J.C.S. to state their case for immortality in the more effective and be it said more objective pages of the Dictionary of National Biography which enshrines Arthur Aikin his grandfather his father his aunt his two brothers and his sister in a memorable Unitarian heptameride.l Arthur was no Scot.His great-grandfather however had come from Scotland-where “Aikin” is a variant of “Aitken”-to settle as a tradesman in London whence his son John re- turned as an undergraduate to Aberdeen Univer- sity achieving a doctorate of Divinity before he became a tutor at the celebrated Warrington Academy and consequently a colleague and friend of that Doyen of Dissent the Reverend Joseph Priestley. John Aikin’s daughter Anna Letitia flourished in this environment and became a well known 44blue-stocking” com- mented on with favour by Dr. Samuel Johnson she married one Rochemont Barbauld of French Huguenot descent-but converted to Arianism at Warrington-with whom she set up a school.Her brother John Aikin secundus was educated at the formidable Academy and proceeded to graduate in medicine (M.D. Leyden 1770) following the ministrations of Cullen Black and William Hunter.2 As Dr. Black’s pupil in Edinburgh he was inevitably attracted to chem- istry. While in practice at Warrington he de- livered a course on chemistry at the Academy for which he translated Baumk’s “Manuel de Chymie.” This John Aikin who eventually established a practice in London had three sons Arthur Charles Rochemont and Edmund and a daughter Lucy who made her name as a historian and biographer. The sons were educated at the Barbauld school ;indeed the second-her husband’s name- sake-was adopted by Mrs.Barba~ld.~ Edmund became an architect of some consequence. Charles qualified in medicine succeeding to his * Reprinted by permission from The Alchemist Glasgow 1962 32 51. John Aikin John secundus and A. L. Aikin (Mrs. Barbauld) Lucy,Arthur Charles Rochement and Edmund Aikin. John secundus Mrs. Barbauld and Lucy still frequent the encyclopedias (e.g. Everyman’s 1958). Cf. also Moore and Philip “The Chemical Society,” London 1947 p. 14. * Lucy Aikin “Memoir of John Aikin M.D.,” London 1823 pp. 1 3 7. Ref. 2 p. 43. 133 father’s practice. Arthur was at first intended for the Unitarian ministry. He had already reached a college of Theology in Hackney when assailed by doubts he re-verted to his father’s other interests in science and was guided by Joseph Priestley to the study of chemistry and mineralogy.He was sometimes described as F.L.S. F.G.S.4 His Linnean fellow- ship instances his interest in botany he was a founder member of the Geological Society (1 807) and was its secretary from 18 1 1 until his appoint- ment as secretary of the influential Society of Arts in 1817. In 1840 he was chairman of this Society’s Chemistry committee and became a founder member and treasurer of the new Chem- ical Society in 1841. In 1843 he succeeded Graham who was curiously enough appointed to succeed him as President for a second term.5 Among other interests Aikin edited a literary “Annual Review’’ to which the entire family offered contributions ! His chief chemical pro- duction was a two-volume Chemical Dictionary in which he was assisted by his brother C.Rochemont.6 The dedication is to Charles Hatchett the emphasis is on chemical manu- factures and the influence of Joseph Black and “caloric” is evident in many pages. Thomas Graham trained by Thomas Thom- son at Glasgow represented the new type of professional scientist which Scotland had pro- duced a specialist and an expert. Arthur Aikin exemplified by his wide interests the older form of natural philosopher so well represented by Joseph Priestley and other English savants. When Graham completed his second spell he Proc. Chem. SOC., 1843 53. Proc. Chem. SOC..1843. 1. 2. 48. PROCEEDINGS was followed by William Thomas Brande’ who as Davy’s successor and Faraday’s colleague stood for the more modern approach which was emphasised by the new Royal Institution.This Hanoverian gentleman preceded Richard Philips,* iatro-chemist and druggist before the first evidence of Oxbridge at this level appeared with the election of C. G. B. Da~bney.~ Here characteristically was a Latin prizeman and a qualified physician who sustained a private ob- session with vulcanism by the tenure of two Cantabrigian chairs chemistry and botany. This by 1851 was almost too much; yet unless on religious topics he and Arthur Aikin would have signalled mutual appreciation. If Arthur Aikin although a man of other distinctions was only the great-grandson of a Scot1* the northern nation is well to the fore in the Presidency.At one time Sir J. J. Dobbie (Glasgow and Edinburgh) appointed in 19 19 was immediately followed by Sir James Walker (St. Andrews and Edinburgh). Graham’s suc-cessors also included Sir William Ramsay (1 907) and Professor G. G. Henderson (1931) while the present incumbent is another Glasgow graduate Sir Alexander Todd. Now the Council has nominated Professor J. Monteath Robertson to succeed him.ll This would provide a second occasion when the head of Glasgow’s department became the head of his profession and the first opportunity for one “Gilmorehill man’’ to transmit the honour to another. Another milestone in a long and eventful history. A. and C. R. Ail& “A Dictionary of Chemistry and Mineralogy,” London Vol.I 1807; Vol. 11 1814. ’Proc. Chem. SOC.,1866 509. Quart. J. Chem. SOC.,1853 155. * Proc. Chem. Soc. 1868 p. xviii. lo E. T. Williams (Ed. “Dictionary of National Biography”) personal communication 18.1.62 writes that on this point the “Concise Dictionary of National Biography” is in error. l1 Proc. Chem. SOC.,1961,477. There is a list of Past-Presidents to 1935 in “List of Fellows of The Chemical Society,” 1936 p. 5 and also one to 1941 given by Moore and Philip (ref. 1 219). APRIL1962 135 GETTING INTO PRINT* When now I want to publish I decide Just where my startling facts will best be seen Nobody looks for X-ray work inside The Oil and Colour Chemists’ Magazine. Things would be so much better I profess If everything were found in J.C.S.In nine weeks flat I made an intermediate The method in Dansk Tidsskr. Farm. was given. The synthesis was finished in a fortnight Translation occupied the other seven. Things would be so much better I profess If everything were found in J.C.S. My Thesis was just ready for the binding When someone pointed out that Popatzar Reported ten years back my basic finding In Doklady Akad. Nauk S.S.R. Things would be so much better I profess If everything were found in J.C.S. With years of work my lab. has come quite crowded Computer cards they lie around in stacks But they’ve a bit to go before they take up As much room as my Chemical Abstracts Short stories are the ones I like the best And there Chem.Abstracts scores on J.C.S. Some journals take six months to print a paper One that I know doesn’t even take half as much. It’s Konin. Ned. Springsto ffenfabrieken. One trouble though it has to be in Dutch! Things would be so much better I profess If they turned out a weekly J.C.S. In current work dear reader you can save me From going o’er already-covered ground If you know where Bull. Acad. polon. Sci. Ser. Sci. chim. geol. geog. is to be found. Chemistry was better I profess When everything was found in J.C.S. When now I get results a first announcement In Tetrahedron Letters comes out fast. A further note in Chem. and Ind. will follow The in J* Org* come last. I’d only get one paper I confess If everything were found in J.C.S.PERCY CUTE * Reprinted by permission from The Alchemist Glasgow 1962 32 54. CORDAY-MORGAN MEDAL AND PRIZE THEfollowing notice which has also been printed in “The Times,” is published at the request of the Charity Commissioners for England and Wales. CHARITY COMMISSION The Corday-Morgan Medal and Prize Fund administered by the Chemical Society. Scheme for the amendment of the terms of the Will. The Charity Commissioners propose to establish a Scheme for this and other purposes. Copies of the proposed Scheme will be supplied on written request to the Charity Commission 14 Ryder Street, London S.W.1 (quoting ref. No. JEH-129779-A), and may also be seen at that address. Objections and suggestions may be sent to the Commissioners within one month from to-day.This notice refers to changes in the conditions for the award of the Corday-Morgan Medal and Prize which have been proposed by the Charity Com- missioners at the request of the Council of the Society. The Corday-Morgan Medal and Prize was established by means of a bequest from the estate of the late Sir Gilbert Morgan a past President of the Society who died in 1940. The terms of the Will have required the Council to make an award in considera- tion of work published in scientific journals during a single calendar year. However since scientific re- search is a continuing process the results of which are normally published over a period of years it has been apparent for some time that the respective merits of two or more individuals cannot always be assessed with justice in this way.Moreover as re- search papers are now frequently published jointly by a number of authors it becomes increasingly hard to evaluate the contribution of one member of a team on the basis of a single year’s work. The Council has therefore requested authority to con- sider before making an award not only the work published in the year of the award but also that which appeared in the five immediately preceding years. This change which has now been embodied in the proposed scheme will it is believed enable a much sounder assessment of the merits of candidates to be made. The Council has also requested that when there PROCEEDINGS appear to be two or more candidates of equal merit To give effect to these changes the Council has it should have authority to divide the prize equally approved new regulations which will subject to con- between them and to award a medal to each.Its firmation of the proposed scheme apply to the next powers in this respect were ambiguous but the award of the Medal and Prize. The new regulations scheme of the Commissioners will confirm the will be published when the scheme has been Council’s authority. established. COMMUNICATIONS The Electron ..=agnet Resonance Spectrum of 2-t-But~~emiquinone and 2-t-C~-13C]&ltylsemiqiquinone A Model for Carbon-Carbon Hyperconjugation By LEONM. STOCKand JOSEPH SUZUKI OF CHEMISTRY OF CHICAGO 37 ILLINOIS) (DEPARTMENT UNIVERSXTY CHICAGO ELECTRON release from unconjugated bonds by the constants (0.4-1.7 gauss) found for other positions mechanism of hyperconjugation was first formalised of semiquinones.2 in 1941.l That presentation did not restrict the treat- ment to carbon-hydrogen bonds but also pointed out the probable importance of carbon-carbon hyperconjugation Meanwhile the emphasis on electron release from C-H bonds has overshadowed the possible significance of release from C-C bonds.As a model for this mode of hyperconjugation we have examined the electron magnetic resonance spectra of 2-t-butylsemiquinone (I) and the labelled semiquinone (11). Typical spectra are illustrated. Spectrum A The eight-line spectrum (A) derived from the three non-equivalent ring protons of 2-t-butylsemiquinone is fully resolved.The coupling constants calculated from the spectrum are aHl 2.85 aH22.10,and aH3 1*65 gauss. These values are similar to those for other semiquinones. -6.60 gauss -+i The observed coupling constant 074 gauss indicates the existence of an important interaction between spin density in the n-system of the semi- Spectrum B Superposition of the spectrum of quinone and the methyl groups of the t-butyl 2-t-butylsemiquinone (52 %) and its [13C]-derivative substituent. This result is predicted and satisfactorily (II) (48%) yields a more complex picture (B). The identified with electron release from carbon-carbon unlabelled semiquinone (I) exhibits the same spec- bonds by the hyperconjugative mechanism. trum as in A and provides a convenient internal reference.In addition there are two lines of one-half intensity flanking each resonance line of the un- We acknowledge the contribution of the U.S. labelled material. These hyperfine splitting are par- Public Health Service toward the purchase of the ticularly evident in the fully resolved outer lines. spectrometer by the University of Chicago. We are These satellite lines arise from a splitting of each of also indebted to the Block Fund of the University of Chicago and to the National Science Foundation for the eight energy levels by the nuclear spin (I= 4) of support. lSC. The coupling constant is calculated to be aC 0.74 gauss. This value is comparable with the (Received February 12tk 1962.) 1 Mulliken Rieke and Brown,J.Amer. Chern. SOC.,1941,63,41. Strauss and Fraenkel,J. Chern.Phys. 1961,35 1738. APRIL1962 137 A New Criterion for MagnetioDipole-Allowed Electronic Transitions in Polyatomic Molecules By S. F. MASON (CHEMISTRYDEPARTMENT, UNIVERSITY OF EXEITR) MAGNETIC-DIPOLE-ALLOWED electronic transitions which have oscillator strengths only of the order of 1V are difficult to identify in polyatomic mole- cules since the non-totally-symmetric vibrations of the molecule confer an oscillator strength of at least this order on an electric-dipole-forbidden transition. Hitherto magnetic-dipole transitions in polyatomic molecules have been authenticated only in com-pounds of rare-earth ions;lS2 the methods used (first polarised absorption by the crystal’ and secondly the wide-angle interference pattern of the emission2) require that the rare-earth ion has an environment of high symmetry in order to avoid a loss of the identifying features of the “pure” excitations through a mixing of transitions.The electronic transitions of dissymmetric molecules are generally mixed and the optical rotatory power of such molecules provides the basis for another method of characterising mag- metic-dipole transitions. The circular dichroism of an optically active molecule namely the differential absorption of left- and right-handed circularly polarised light is due to an electronic excitation with parallel component electric- and magnetic-dipole transition moment^.^ The ratio of the area of a circular dichrosim band to that of the associated absorption band for un-polarised light measures the ratio of the rotational strength to the dipole strength of the transition responsible for the dichroism and the ab~orption.~ The rotational strength of a transition is given by the scalar product of the electric (p) and the magnetic (p) transition moments whilst the dipole strength may be equated to the square of the electric m~ment.~ The band-area ratio is given approximately by the extinction-coefficient ratio (g) termed the dissym- metry factor by K~hn,~ and g-factors rather than band-area ratios are the more generally available.If €1 Ey and E are the extinction coefficients for left- and right-circularly polarised and for unpolarised I ight respectively then3 g = ( ~EI-Er I)/€ = 4 pp cos O/p2 l Sayre Sancier and Freed J.Chem. Phys. 1955,23 2060. Freed and Weissman Phys. Rev. 1941 60,440. Condon Rev. Mod. Phys. 1937,9,432. * Kuhn Trans. Faraday SOC.,1930 46 293. Moffitt J. Chem. Phys. 1956,25 1189. Mathieu J. Chim. Phys. 1936,33 78. ’Kuhn Ann. Rev. Phys. Chem. 1958,9,417. * Mitchell and Simpson J. 1940 784. Mitchell and Gordon J. 1936 853. lo Kuhn and Rometsch Hefv. Chim. Ada 1944,-27 1080 1346. where 6’ is the angle between the directions of the electric- and the magnetic-dipole transition moment. Allowed electric- and magnetic-dipole transition moments have values of the order of the Debye (4-8 x c.g.s.) and the Bohr magnetron (9.3 x c.g.s.) respectively.Thus the g-factor of a formally allowed electric-dipole transition could not exceed the value of about 0.01 even in the improb- able case that the dissymmetric perturbations induce a parallel magnetic moment of a Bohr magneton. A similar upper limit for the g-factor may be set for transitions which are intrinsically both electric- and magnetic-dipole-forbidden but formally allowed magnetiedipole transitions should have g-factors larger than 0.01 if the induced electric moment has a substantial component parallel to the direction of the magnetic moment. Such a condition should obtain generally in optically active molecules belong- ing to the dihedral point groups D, in which trans- lations along and rotations about a given axis have a common symmetry representation.Ligand-field bands of transition-metal complexes have been assigned mainly upon theoretical energy- level schemes but the rotatory powers of the dihedral and the other dissymmetric complexes may now be seen to afford experimental criteria as Moffitt6 envisaged. Theoretically all of the lowest-energy spin-allowed d + d transitions of octahedral transition-metal complexes are magnetic-dipole allowed whilst most of the higher-energy transitions are magnetic-dipole-forbidden. For the complexes d-[M(oxalate),]K, where M = Cr Co Rh or Ir the g-factors are6 0-010-0~045for the lower-energy and 0-00l-OG09 for the higher-energy ligand-field bands. In organic molecules It +n*,but not 7r +P* transitions should theoretically be magnetic-dipole- allowed.For the n + n* bands of the carbonyl,’ nitrite,’ azide,’ nitroso-,8 and nitro-groupg the g-factors are 0-010-0-100, but the highest known g-value for a 7+n* band islo 0.002. (Received February 20th 1962.) PROCEEDINGS Aromatic Hydroxylation :the Electrophilic Character of the Hydroxyl Radical and its Significance in Biological Hydroxylation By R. 0.C. NORMAN and G. K. RADDA (DYSON THE UNIVERSITY PERRINSLABORATORY OXFORD) MOST monosubstituted benzenoid compounds are more reactive than benzene towards the free phenyl radical regardless of the polar characteristics of the substituent.’ Substitution of a polar group into the radical imparts to it some electrophilic or nucleo- philic character,l and we have now found that the hydroxyl radical behaves as a strongly electrophilic radical in aromatic substitution.Hydroxyl radicals were generated from ferrous ion and hydrogen peroxide (Fenton’s reagent2) in aqueous acetone under nitrogen in the presence of EDTA a phosphate buffer and ascorbic acide3 Yields of hydroxylated product were kept low (14%) by using a large excess of the aromatic compound and no dihydroxylation was detected. Isomer distributions (see Table) for the hydroxylation of four benzenoid compounds were determined by gas-liquid chromatography and infrared spectro- photometry (Table) and overall reactivities of three Aromatic compound Anisole Isomer distributions (%) 0-m-p-84 -16 Chlorobenzene 42 29 29 Fluorobenzene 37 18 45 Nitrobenzene 24 30 46 of these compounds relative to benzene (obtained by the competitive method using gas-liquid chromato- graphy for analysis of the products of the competi- tion) were PhOMe:PhH:PhCl:PhNO = 6.35:1 0.55 :0.14.Isomer distributions for chlorobenzene and nitrobenzene are in agreement with those previously rep~rted.~ The observed order of reactivities which is quite different from that for phenylation but is the same as that in an electrophilic reaction such as nitration illustrates the electrophilic nature of the hydroxyl radical and this is supported by the isomer distribu- tions. Isomer distributions for the hydroxylation of anisole were essentially unchanged when reaction was carried out (i) under heterogeneous conditions with water as solvent (ii) without ascorbic acid or EDTA and (iii) with cuprous instead of ferrous ion.Hydroxyl radicals were also generated by ultraviolet irradiation of hydrogen peroxide and in these con- ditions anisole and fluorobenzene gave the same isomer distributions as with Fenton’s reagent. Benzenoid compounds foreign to the animal body are frequently metabolised to mixtures of the 0-,m- and p-hydroxy- derivative^.^ Two simple chemical systems have been proposed as models for the bio- logical process Fenton’s reaction; and a system containing ferrous ion oxygen and ascorbic acid.6 The latter system has sometimes been thought to act through hydrogen peroxide formed by reduction of oxygen by ascorbic acid.3 We have found that the two systems behave differently.Anisole and chloro- benzene when treated with aqueous ferrous ion EDTA ascorbic acid and oxygen gave 0-,rn- and p-hydroxy-derivatives in the proportions 61 :9 :30 and 62 :16:22 respectively. Further hydroxylation took place to the same extent in the presence of catalase and the isomer distributions were un-affected. Evidently this system. hydroxylates by a different mechanism from Fenton’s and in particular does not involve hydrogen peroxide as an inter- mediate or hydroxyl radical as the attacking species. The comparatively unselective nature of the reagent and the high proportion of ortho-substitution are consistent with a radical reaction while the relative reactivities of anisole and chlorobenzene (7 1) show this radical to be electrophilic.(We shall subsequently discuss evidence that the perhydroxyl radical HO,. is involved). Biological aromatic hydroxylation by liver micro- somes is known to result in the incorporation of atmospheric oxygen into the phenol.’ Our results indicate therefore that Fenton’s system being different from the oxygen system is an unsuitable model for such a process. The pattern of hydroxylated metabolites has usually been interpreted as evidence that a free-radical source of oxygen is involved but certain results (for example the exclusive hydroxyla- tion of acetanilide in ortho-and guru-positions) have led to the suggestion that the hydroxyl cation is involved.*Our present results show that these incon- sistent interpretations are compatible since the free- radical source of oxygen should like the systems we have studied have electrophilic character.(Received February 6th 1962.) G. H. Williams “Homolytic Aromatic Substitution,” Pergarnon Press London 1960. Merz and Waters J. 1949 S 15; Weiss Discuss. Furuda-v Soc. 1947 2 188. Breslow and Lukens J. Biol. Chem. 1960 235,292. 4 Loebl Stein and Weiss J. 1949 2074; Johnson Steirr and Weiss J. 1950 3275. R. T. Williams “Detoxication Mechanisms,” Chapman and Hall Ltd. London 1959. Udenfriend Clark Axelrod and Brodie J. Biol. Chem. 1954 208 731. .’ Hayaishi Rothberg and Mehler 130th Amer. Chem. SOC. Meeting 1956 p. 53c. * For a detailed discussion see Mason. in “Advances in Enzymology,” ed.F. F. Nord interscience Pub]. Inc. Vol. XIX 1957. Negative and Positive Ions of 1,tSDiphenylhexatriene By E. DE BOERand P. H. VAN DER MEU (KONINKLUKE/SHELL-LABORATORIUM ; AMSTERDAM INTERNATIONALE MAATSCHAPPIJ SHE~L RESEARCH N.V.) HOIJTINK et a1.l recently emphasised that in the spectra of most negative ions of polynuclear aro- matics compounds absorption bands occur which are due to proton adducts. They may be formed according to the reaction scheme M+e +M-M-+e +M” M2-+ H+-+MH-where M denotes the neutral molecule. Studying the spectra of the ions of normal 1-diphenylp~lyenes~ we indeed found in all cases absorption bands arising from a species other than the ions. For a typical representative of the series 1,6-diphenylhexatriene the absorption spectra of the mononegative and dinegative ions are given in Fig.a and b respectively; the broken line marks the posi- tion of the absorption band of the unknown species. The nature of this substance has been elucidated by the following experiment. 30- 20- 10-a 401 b \ w 7 0 I n w 0 40 30 20 JO 40 30 20 10 Spectra ufi (a) M- + MH- Na+; (b) M2-+ MH-; (c) MH- (a- in tetrahydrufuran);(d) MH+ in 96% H,SO,; (e) M2+ + MH+ in 100% H2S0,. To the solution of mainly dinegative ions (see Fig. b) an equimolar concentration of butanol was added. Rapid reaction was indicated by a colour change from blue to orange. The spectrum taken after addition of butanol (Fig. c) revealed that the band of the unidentified species had gained con- siderably in intensity at the expense of the bands of the dinegative ion.From this result and the fact that the only likely reaction is M2-+ ROH+ MH-+ RO-it may be inferred that the band in question is due to the hydride complex of 1,&diphenylh :xatriene. If the absorption band near 2 x lo4 cm.-l is assigned to MH- the spectra of the ions can be explained satisfactorily by the LCAO-MO theory. In the Table calculated data are compared with the experimental values. The spectrum of M-is charac- terised by a weak and a strong band. This can only be adequately accounted for when configuration in- teraction between the two lowest nearly degenerate singly excited states is considered.The Table shows that the calculation gives too large a configuration- interaction element for these two states. For M2-and MH- the calculations predict only one strong band which is in close agreement with experimental results. Substance Observed Observed Calc. Calc. frequency dipole frequency dipole (X lo3 strength (lo3 strength cm.-l> (A2) cm.-l) (A21 M-11.2 0.75 5.1 0.2 15.9 4.11 17-3 13-4 M2-15-7 5.84 17-5 14.7 M2+ 17.0 -17.5 14-7 MH-19-9 4.23 22.8 7.2 MH+ 21.0 -22.8 7.2 The calculated charge distribution of the dinega- tive ion leads to the conclusion that the added proton in MH-will be accommodated at a carbon atom adjacent to a phenyl group. The pairing properties of the moIecular orbitals of a diphenylp~lyene~ predict an exact resemblance between the electronic spectra of M+ M2t and MH+ and those of the corresponding negative ions discussed above.Fig. d shows the spectrum of 1,Qdiphenylhexa-triene in 96% sulphuric acid. The solution is un- stable and extinction coefficients cannot be given. Hoijtink Velthorst and Zandstra Mol. Phys. 1960 3 533. Hoijtink and van der Meij 2.phys. Chem. (Frankfurt),1959 20 1. McLachlan Mol. Phys. 1959 2. 271. The similarity between the spectra in Figs. c and d suggests that the one in Fig. d is that of MH+ with the proton attached to the carbon atom nearest to the phenyl group. This assignment can be made plausible by calculations on the localisation energies of the three possible MH+ ions.These show that 1,6diphenylhexatriene has a great proton affinity comparable with that of 3,4-benzopyrene,4 and that initially mainly that proton complex will be formed which has the added proton bonded to the same carbon atom as the proton in MH-. By measuring directly after dissolution of M in PROCEEDINGS 100%sulphuric acid we obtained the spectrum given in Fig. e. A new band appeared at a lower frequency pointing to the presence of a species other than MH+. The absence of a small band at still lower frequency suggests that the new species is M2+. Besides M2+ and MH+ the solution contained other compounds giving bands at higher frequencies. Examination of successive spectra of this solution showed that the band due to M2+quickly weakened while the intensity of the band of MH+ increased correspondingly.(Received February 7th 1962.) Mackor Hofstra. and van der Waals Trans. Faraday SOC.,1958 54 66. Evidence for the Unit Negative Charge on the "Hydrogen Atom" formed by the Action of Ionising Radiation on Aqueous Systems By E. COLLINSON D. R. SMITH,and S. TAZUKB F. S. DAINTON (DEPARTMENT 2) OF PHYSICAL CHEMISTRY THE UNIVERSITY LEEDS THE primary oxidising and reducing species pro- duced by the action of ionising radiation on water or dilute aqueous solutions are generally considered to be a hydroxyl radical and a hydrogen atom respec- tively. Recent investigations in several laboratories' have shown that the hydrogen atom can exist in at least two forms designated Ha and Hb that possibly a third form Hc may be produced and that the relation between these forms is expressed in equa- tions (1) and (2) Ha + H+ -+ Hb .. . . . (1) Hb + H+ -% Hc . . . . . (2) If three forms exist then they can only be Ha = e-aq Hb = H and Hc = H2+. Photochemical studies indicate that k = 2.6 x lo31. mole-l sec.-l and there is strong presumptive evidence that k = lO**l 1. mole-l sec.-l. Direct evidence as to the sign and magnitude of the charges on each of these entities can be obtained by studies of the primary salt effect on their reactions with charged solutes. On this basis Czapski and Schwarz2 have concluded that the "H atoms" first formed in irradiated water (i.e. in our terminology Ha) are solvated electrons. We have studied the effect of ionic strength on the ratio of the rate constants for reactions (3) and (4).The results for pH 4 are shown in the Figure from which Ha + Ag+ +Ago ..... (3) Ha + CHs=CHCO*NH + CH3.CHCO-NH2 . . . . . (4) it is seen that d(log, k3/k4)/dJp = -1.1 f0.15 at 25". Since k increases very slightly with ionic strength and since the activity of the argentous ion approximates to the limiting-law expression for p < 0.6 we conclude that at pH 4 Ha has unit negative charge. This is understandable if Ha is a solvated electron (e-w or H20-) and if reaction (1) I I I l l 1 ,,I V.2 0-4 0-6 )J '(2 The variation of loglo (ks/kk) (at 25") with ionic strength at pH 4. Equation of line is log, (k3/k4) (at 25") = 2.92 -1.09 Jp.cannot compete successfully with reactions (3) and (4) at pH 4. Experiments at pH 2 show that the apparent log, k3/k is here independent of ionic strength. Evidently at this pH reaction (1) is faster than the sum of the rates of reactions (3) and (4) the solvated electrons (= Ha) are largely converted into 1 See for example Hayon and Weiss J. 1960 5091; Ban and Allen J. Phys. Chew. 1959 63 928; Dainton and Petersoh Nature 1960 186 878; Proc. Roy. SOC.,1962 A in the press; Riesz and Burr Radiation Res. in the press. Personal communication from Drs. G. Czapski and H. Schwarz. APRIL1962 141 Hb(= H) and then react with Ag+ and acrylamide The observation that the Bransted-Bjerrum rela- according to equations (5) and (6). The fact that at tion applies to reactions of a Ha implies that a sol-p = 0 and 25" k3/k4 e 8k,/k is perhaps some vated electron survives as a distinct entity for at limited additional support for the view that Ha is least as long as may be necessary to build up its negatively charged.ionic atmosphere and raises interesting questions as to the nature of e-aq. These and related matters will H + Ag+ -+ H+ + Ago be discussed elsewhere. H + CH,=CH.CO*NH -+ ..... (5) CH,*CH*CO-NH . . . . (6) (Received February 28th 1962.) Chlorine Atom Abstraction by Methyl Radicals from Methyl Chloroformate By J. C. J. THYNNE GRAY and PETER (SCHOOL UNIVERSITY OF CHEMISTRY OF LEEDS) METHYL radicals have been shown to abstract hydrogen atoms from the acetone (and not from the chlorine atoms from t-butyl hypochlorite in the gas alkyl group of the chloroformate).phase1 and to induce similar reactions2 in the liquid At 109" carbon dioxide and methyl chloride are phase. A potentially suitable substrate to demon- produced in equal amounts in accord with reactions strate halogen atom abstraction by methyl radicals (1) and (2). At loo" the rate of abstraction of a is methyl chloroformate. Abstraction of the chlorine chlorine atom from methyl chloroformate is about atom (reaction 1) would yield methyl chloride and seven times that of abstraction of a hydrogen atom the methoxycarbonyl radical Me0,C-which is from methyl formate. This is consistent with a weaker known to be unstable3 and to decompose exo- bond between halogen and carbon than between thermally4 to carbon dioxide and methyl hydrogen and carbon in the formate esters and this Me.+ CI-CO,Me -+ MeCl + Me0,C-. . . . (1) is reasonable. The kinetics of chlorine atorn abstrac- Me0,C-+CO + Me-. . . . . (2) tion can be expressed by the relation log k (mole-l ~m.~ sec.-l) = 10.2 -6300/2-303RT. Thus production of methyl chloride and carbon The value of 6.3 kcal. mole-l for reaction (1) is dioxide induced by a methyl radical will indicate the markedly less than that (9.0 kcal. mole-l) reported3 occurrence of the abstraction reaction (1). for the corresponding hydrogen abstraction from We have studied the influence of methyl radicals methyl formate. generated photochemically from acetone on methyl Below 100" the ratio methyl chloride :carbon di- chloroformate in the vapour phase with pressures of oxide fell somewhat being 0.83:1 at 34") perhaps ca.50 mm. Hg for both acetone and methyl chloro- owing to a finite lifetime of the acetyl radical at formate in light of A > 3000 A at 34-109" (above these temperatures. If acetyl also abstracted chlorine 109O concurrent thermal decomposition of methyl from methyl chloroformate carbon dioxide would chloroformate was too extensive to be allowed for). be produced in excess of methyl chloride Methane carbon monoxide ethane carbon dioxide Me-CO. + ClC0,Me -f MeCOCI + MeO,C-. and methyl chloride were the gaseous products mass-spectrometric analysis of the methane showed We thank D.S.I.R. for a special research grant. that it was wholly attributable to abstraction of (Received,January 19th 1962.) Phillips Proc.Chern. Soc. 1961 338. Evans and Szwarc Trans. Faraday SOC.,1961,57 1905 (and references quoted there). Thynne Trans. Faraday SOC.,1962 in the press. Gray and Thynne Nature 1961 191 1357. Photochemical Decompositions of Aqueous Solutions of Oxyanions of Chlorine and Chlorine Dioxide By G. V. BUXTON and R. J. WILLIAMS (CHEMISTRY RIE UNIVERS~~Y DEPARTMENT OF EXETER) IRRADIATION of hypochlorous acid over the pH 25" of hypochlorite ion in a phosphate buffer at range 1-13 produces according to Young and pH 10. We find that at low conversions the major Allmand,l only chlorate ion oxygen and chloride product is chlorite ion its concentration rising ion. We have studied the photolysis (A 365 mp)at steadily to a maximum of about one-tenth of that of Young and Allmand Canad.J.Chem. 1949,27 By 318. the residual hypochlorite ion. Thereafter hypo- chlorite ion and chlorite ion disappear in proportion the ratio of their concentrations remaining at about 10:1. After allowance for the chlorate ion produced by thermal reaction of chlorite ion with hypochlorite ion at pH 10 (k4=1.6 x lo4 1. mole-' sec.-1)2 it was found that oxygen and chlorate ion are pro- duced in a constant ratio of 3:2 throughout the irradiation the quantum yields for their formation appearing to increase as the decomposition pro- ceeds. Simultaneously the quantum yield for the disappearance of hypochlorite ion decreases slightly initially being 0.55. The only other product detected is chlorine dioxide (trace).These facts appear to be best explained by the following reactions hU CIO--+CI-+0 kl 0+CIO-+ CI0,-ka 0+CI0,-+CIO,-ka 0+CIO*--f 0,+(CI-+O?) k, CIO-+CIOa--tCI-+CIOS-Buxton and Williams unpublished work. a Bowen and Cheung J. 1932 1200. PROCEEDINGS Step 4 may be complex but leads only to oxygen as the identifiable product. The chlorine dioxide we find comes from photolysis of the chlorite ion. In the hypochlorite system this is a side reaction occurring to only a small extent because even when present in its maximum propor- tion the chlorite ion only absorbs about 1%of the light absorbed by the hypochlorite ion. We find the chlorine dioxide which is produced reacts rapidly with hypochlorite ion to form chlorate ion thereby balancing from the point of view of the overall oxygen :chlorate ion ratio the other major product of chlorite photolysis oxygen.This rapid reaction of hypochlorite ion with chlorine dioxide also prevents the photolysis of the latter from interfering in the overall picture of the system. The products of chlorine dioxide photolysis at pH 10 are we find solely chlorate ion and chloride; the quantum yield for its disappearance is 0.65 as opposed to the value 2 reported for an unbuffered solution in water by Bowen and Cheung3 (this difference is perhaps due to their solutions' rapidly becoming strongly acidic). We acknowledge a grant for equipment from the Royal Society. (Received February 13th 1962.) Nitrogen-forming Reactions in the Decomposition of Hydrazoic Acid Solutions By D.L. TRIMM and R. J. WILLIAMS (DEPARTMENT OF CHEMISTRY UNIVERSITY OF EXETER) HYDRAZOIC ACID in solution decomposes to give large amounts of nitrogen. The nitrogen-forming reaction has been formulated as N,. +Na*3 3N ...........(11 for the radiation-induced decomposition1 and as N,. +FeN,Z+-t Fea++3N1 .......(2) for the photolytic decomposition of a solution con- taining femazide ions.2 For the latter system we have found that in acid solution a further reaction occurs namely N,*+ HNa+ He +3Na ........(3) and that here reaction (1) is of minor importance. The evidence for reaction (3) is threefold. First ammonia in quantity is found among the products after irradiation and only this reaction provides the necessary reducing species.Secondly the ratio of nitrogen produced to ferrous ion produced can under suitable conditions exceed the value of 1-5 predicted by mechanisms involving reaction (1) or (2) only reaction (3) being followed by Ha +HN,-+H,N. +N ........(4) *NH +HN -+NH +*N3 ....... (5) reactions for which there is already clear evidence.' Thirdly in the presence of oxygen and added ferrous ion a proportion of the hydrogen atoms is converted into hydrogen peroxide via the hydroperoxy-radical. This leads to a decrease in the ferrous ion concentra- tion after irradiation has ceased. Reaction (3) appears to be the main nitrogen- producing reaction in our system.Thus the rate of formation of products is almost linearly dependent on incident-light intensity whereas if reaction (1) accounted for the nitrogen production a dependence approaching the second order would be expected. That reaction (2) also occurs to a relatively small extent is apparent from the fact that the ammonia nitrogen ratio approaches the maximum possible 1 KelIy and Smith J. 1961 1479 1487; Dainton personal communication; Coatsworth Ph.D. Thesis Leeds 1957. Bunn,Dainton and Duckworth Trans. Faraday SOC.,1961,57 1131. APRIL1962 value of 1 :4. Significant Occurrence of reaction (2) would lead to a large drop in this ratio. In solutions of pH > 6 the reaction corresponding to reaction (3) is *N,+ Na-,H,O + 3N + H,O-.. . . . . (6) While on a thermodynamic basis this reaction is fea~ible,~ being only slightly less exothermic than reaction (3) the results of the radiolysis of alkaline solution of azide ions appear to have been satis- factorily accounted for1 in terms of mechanisms a Evans Yoffe and Gray Chem. Rev. 1959,59 515. which do not include it. Possible reasons why it has not been observed are that it may be a “forbidden” change or that it has a significant activation energy. It is unfortunate that the present system cannot be adapted to test for its occurrence. we achowled&F a grant for equipment from the Royal Society and a maintenance Pant from the D.S.I.R. to one of US (D.L.T.). (Received February 9th 1962.) The Structure of NN’-Ethylenebis(acetylacetoneiminato)copper(n) By D.HALL,A. D. RAE,and T. N. WATERS UNNeRSrrY OF AUCKLAND, (CHEMISTRYDEPARTMENT NEWZEALAND) THE structure of NN’-ethylenebis(acety1acetone-iminato)copper(n) has been determined by two-dimensional X-ray methods. The crystals are monoclinic with a = 11.02 b = 8-97,c = 13.10 A and 18 = 94”. There are 4 molecules per unit cell and the space group is P2,/c. The copper atoms were located from Patterson projections and the carbon nitrogen and oxygen atoms by the heavy-atom method. The expected co-ordination arrangement about the heavy atom was found and the distinction between the light atoms made on chemical grounds. Data were collected about the three axes and refined independently. The numbers of observations and the reliability factors (for observed reflections only) are Axis Reflections observed R 001 135 0.140 010 186 0.114 100 153 0-142 The disposition of two molecules about the crystallographic centre of symmetry is shown in the Figure.The tetradentate ligand expected to be planar except for the gauche conformation of the ethylene bridge is slightly concave towards the centre. The bond lengths (see Figure) show the acetylacetone ring system to be considerably conjugated. The copper atom of one molecule makes its closest inter- molecular contact with a conjugated ring of the other and the arrangement indicates that there is a weak interaction between them. The molecular unit appears to be dimeric bonding between c‘hal~es” being reminiscent of donor-acceptor polarisation bonds between planar organic molecules.1 The struo- ture is also reminiscent of the stronger dimerisation found in bis(dimethylglyoximato)copper(n)2 and NN’-disalicylidene-ethylenediaminecopper(~~)~ where dimers are formed by unique copper-oxygen bonds which establish square-pyramidal stereochemistry about each copper atom.The non-planarity of the ligand is in accord with an analysis of the crystal spectrum? (Received December 19th 196 1 .) l Wallwork J. 1961,494. * Frasson Bardi and Bezzi Acfa Cryst. 1959 12 201. a Hall and Waters J. 1960 2644. Chakravorty and Basu Nature 1959,184,50 and personal communication. PROCEEDINGS Determination of the ReIative Signs of Proton Spin Coupling Constants from Double-quantum Spectra By K.A. MCLAUCHLAN and D. H. WHIFFEN DIVISION PHYSICAL TEDDINGTON, (BASIC PHYSICS NATIONAL LABORATORY MIDDLESEX) OFTENthe most difficult part of the complete analysis of a high-resolution nuclear magnetic resonance spectrum is the determination of the relative signs of the spin-spin coupling constants. Sign determination by exact analysis is at best time-consuming and often inconclusive or impossible. Sign determination by double irradiatiorA2 promises to be the most general method but it requires special equipment and is not easily applicable to some commercial spectrometers. The present Communication gives an example of sign determination by measurement of the double-quantum spectrum.Double-quantum spectra in nuclear resonance were first observed by Anderson3 and by Kaplan and Meiboom4 who discuss the theory as does Yatsiv5 who discusses the intensity problems. The simplest case of interest is that of three hydrogen nuclei A, Byand C with mutual couplings JAB, JBc,JAc and chemically shifted resonance frequencies v, vB and vc. A typical double-quantum transition is that be- tween the state for which nz = -4 for A and B and m = +&for C and the state in which m = +&for all three nuclei. If second-order terms are omitted the energies of these states are (-vA -vB +vc)/2 + (JAB -JBC -J.4C)/4 and (vA -kVB +vC)/2 + (JAB +JBc+JAC)/4; taking half the energy difference since this is a double-quantum transition gives (vA + vB)/2+ (JBc+ JA,)/4 for the transition fre- quency.If C is in the state rn = -9 throughout the frequency is (vA + vB)/2 -(JEc 3. JAc)/4.Conse-quently the double-quantum spectrum in this region consists of two lines of approximately though not e~actly,~ equal intensity centred on (v + v,)/2 with a separation of I(JAc + JBc)/2I. Interpretation of the regular spectrum readily gives IJAc1 and IJBc1. IfJAC and JBC are of the same sign lJAcI + lJBcI = lJAc + JBc I; but if they are of opposite sign with lJAC I > lJBC 1 then I JAC I -lJBC I == lJAC fjBC 1. ap-Dibromopropionic acid CH,BrCHBrCOOH provides an example which is convenient because two double-quantum spectra can be observed in near-optimum conditions with the same radio-frequency power and because double-irradiation ex- Evans and Maher.Proc. Chem. Soc.. 1961. 208. Freeman and Whiffen Mol. Phys. 1961,4 321. a Anderson Phys. Rev. 1956 104 850. Kaplan and Meiboom Phys. Rev. 1957,106,499. Yatsiv Phys. Rev. 1959 113 1522. periments6 have shown JABto be of opposite sign from JAC and JBC. The Figure shows at the top the 12 II 10 9 8 7.6 5 4321 1 Top Regular 60 Mc./sec. spectrum of c$?-dibrorno-propionic acid in benzene. yH112n N 0.04 c./sec. Below The same region with yH1/2rr -2.1 c./sec. In the lower trace the normal lines are broadened by saturation but sharp double-quantum lines can be seen. normal resonance spectrum and below the spectrum re-run with a radiofrequency power equivalent to a value of yH,/27~ = 2-1 c./sec.where H is the circularly polarised component of the radio frequency field.' It was found important to adjust the spectro- meter carefully to remove spinning sidebands and to reduce the contribution of the dispersion mode. Peaks 13 and 14 are the double-quantum lines at (.A + v~)/2* [(JAC + JBC)/4 1. lJAC I = 4.6 c-/sec., which is to first order the separation of 11 and 12 and I JBcI = 10.9 c./sec. that is the separation 9 to 11. The separation 13 to 14is 7.8 & 0.1 c./sec. so that lJAC $-JBC I = lJAC I + lJBC 1 and JAC and JBC are of the same sign. The spectrum plainly shows the separation 13 to 14 to be one-half of that of 9 to 12 not 10 to 11 as opposite signs would require. In contrast the separation 19 to 20 = 2-8 &-0.1 c./sec.is Freeman McLauchlan Musher and Pachler. Mol. Phys. 1962 in the press. Anderson Phys. Rev. 1956 102 151. APRIL1962 clearly one-half that of 2 to 3 not 1 to 4 showing JABand JActo be of opposite sign. This is confirmed 1 numerically as /JAB = 9-9 c./sec. The remaining lines 15 16 17 and 18 represent the third set of double-quantum transitions which for this parti- cular example are more complicated as Y + vC -2v and the strong radiofrequency field partially decouples nucleus B from the others. The complete set of relative signs are implicit in the observations of 13,14,19 and50 which show that * Dischler and Englert 2. Nuturforsch. 1961 16a 1 180. JABis of opposite sign to JAc and JBC. The im- plications of this result are discussed elsewhere6 and the present communication is restricted to showing a method of considerable generality whereby the relative signs may be determined very conveniently.[Addedin proof.] Dr. K. G. R. Pachler has referred us to a footnote by Dischler and Englert on related work on A,B,X spectra.8 We thank A. D. Cohen for helpful discussions. (Received March 12th 1962.) The Reactions of Hydroxylamine and its 0-Methyl Derivative with Carvone By G. BADDELEY and K. BROCKLEHURST (MANCHESTER OF SCIENCE MANCHESTER, COLLEGE AND TECHNOLOGY 1) WE found the reaction of carvone with hydroxyl- amine in neutral or nearly neutral solution as measured by the accompanying change in optical activity to be many times faster than that with 0-benzylhydroxylaminel and now reported for the first time that with 0-methylhydroxylamine.Jencks2 subsequently found that hydroxylamine and its 0-methyl derivative have similar reactivities in their reactions with several aldehydes and ketones. 3r I 3 5 7 9 II PH Rates of ap-addition of (A) hydroxylamine and (B) 0-tnethylhydroxylamine to carvone. We now report that when carvone condenses with these reagents to provide carvoxime and its 0-methyl derivative the relative rates of reaction and their dependence on the pH of the medium are mainly in accordance with the work of Jencks. Carvone unlike the compounds used by Jencks however is an ap-unsaturated ketone which as an alternative to oxime formation can undergo addition of the re- agent to the conjugated ethylenic group? This addi- tion which for hydroxylamine in approximately neutral media is about thirty times faster than oxime formation is the one which differentiates between hydroxylamine and its 0-methyl or 0-benzyl deriva- tive.The relative rates of ap-addition of hydroxyl- amine and its 0-methyl derivative to carvone and Baddeley and Topping Chem. and Znd. 1958 1693. Jencks J. Amer. Chem. Soc. 1959,81,475. Wallach and Schrader .4nnafen 1894 279 366. their dependence on pH are shown in the Figure. In the range of pH 4-8 the rate of oxime formation is given mainly by d[OximeJ/dt K [Carvone] [+NH,-OH] cc [Carvone][NH,.OH][H,O+] and that of cup-addition by d[ ap-Adduct]/dt a= [Carvone] [NH,.OH].When 0-methylhydroxylamine is the reagent @-addition is not only many times slower than that of hydroxylamine but is essentially of second order in carvone when the pH of the medium is ca. 10. This surprising result compels the view that in this addition the effective reagent is the adduct of 0-methylhydroxylamine and the carbonyl group of carvone i.e. that one molecule of carvone catalyses the addition of 0-methylhydroxylamine to another molecule of carvone. Our interpretation of the ap-addition of hydroxyl- amine to carvone is as in the annexed formulae. The first step appears as the reverse of a cis-elimination by an amine oxide. We intend to investigate the stereochemistry of these a/?-additions and to show whether like oxime formation they involve pre- equilibria.K.B. acknowledges his indebtedness to D.S.I.R. for a research studentship. (Received February 13th 1962.) PROCEEDINGS The Separation of Diastereoisomers by Gas-Liquid Chromatography By EMANUEL GIL-AVand DAVIDNUROK (’I’m DANIEL INSTITUTE INSTITUTE Sm RESEARCH THE WEIZMANN OF SCIENCE REHOVOTH ISRAEL) CASANOVA and Corny’s resolution of (&)-camphor by gas chromatography’ prompts us to report our separation of optical isomers by this method. Bailey and Has$ showed that the fugacities of diastereoisomers can differ sufficiently to permit partial separation by distillation. Gas chromato- graphy seemed to offer a more convenient way for obtaining complete resolution. A number of authors3 have indeed reported pairs of chromatographic peaks which they ascribed to the separation of diastereoisomers present in the mixtures analysed.log Retention times of acetoxypropionates of s-alcohols (b and b2) and of a-alkanoyloxypropion-ates of s-butyl alcohol (cl and c2) on polypropylene glycol. Temp. 120”; flow rate 1.5 ml.lmin. We have studied the analytical separation of a series of lactic acid derivatives on two different capillary columns of length 150’ and internal dia- meter 0-Ol”,coated with polypropylene glycol (A) and squalane (B) respectively. * The compounds examined were (a) lactates of secondary alcohols RCHMe-OH (R = Et Prn Bun n-pentyl and n-hexyl) (b) a-acetoxypropionates of secondary alcohols [as for (a)],(c) a-alkanoyloxypropionates of butan-2-01 RCO.O.CHMe.CO,Bus (R =Me Et PP Bun and n-pentyl).A11 the compounds (a) (b) and (c) were racemic; in addition (b; R=hexyl) was prepared from (+)-lactic acid and (+)-octan-2-01. Each compound of groups (b) and (c) gave two distinct peaks on each column and separation without overlap was achieved on column A at 120” with a flow rate of 1.5 ml./min. The lactates (a),however were resolved only to a slight extent. The peaks of each pair had equal areas for com- pounds synthesised from racemic starting materials each peak corresponding to a racemic mixture of one of the diastereoisomers. On the other hand in the case of D-1-methylheptyl L-a-acetoxypropionate of relatively high optical purity the second peak had an area about twenty times larger than the first.In the Figure the log of the retention time for compounds of groups (b) and (c) is plotted against the total number of carbon atoms. For each group the values fall on two nearly straight lines as would be found in two different homologous series. It is reasonable to assume that each line corresponds to compounds having identical or the related mirror- image configuration. From the retention time for the main peak of the optically active 1-methylheptyl a-acetoxypropionate it can be concluded that curves b and c correspond to compounds derived from either L-lactic acid and D-s-alcohols or D-lactic acid and L-s-alcohols whereas curves b2 and c2 corres-pond to compounds having the alternative con- figurations.These relationships should be particularly useful for the determination of the configuration of optically active secondary alcohols in mixtures; the sign of rotation could be deduced from the known * A Perkin-Elmer “Fractometer” provided with a hydrogen flame-ionisat ion detector was used. Casanova and Corey Chem. and Ind. 1961 1664. 8 Bailey and Hass J. Amer. Chem. Soc. 1941,63 1969. 3 Simmons Richardson and Dvoretzky in “Gas Chromatography 1960,” ed. R. P. W. Scott Butterworths Scientific Publns. London 1960 p. 211; J. F. Smith op. cit. p. 222; Vofsl and Asscher personal communication. APRIL1962 147 correlation* of optical activity and configuration in practically independent of the molecular weight the series.whereas it increases in group (b)from 1.038 for R = The Figure shows that the ratio of the retention Et to 1.084 for R =heXY1. time for pairs of diastereoisomers of group (c) is (Received,January 30th 1962.) Mills and Klyne in “Progress in Stereochemistxy,” Vol. I ed. Klyne Butterworths Scientific Publns. London, 1954 p. 205. Delayed Fluorescence from Solutions of Anthracene and Phenanthrene By C. A. PARKER and C. G. HATCHARD NAVALSCIENTIFIC ADMIRALTY LABORATORY, (ROYAL SERVICE MATERIALS HOLTON HEATH,POOLE,DORSET) DELAYED fluorescence from anthracene vapour was attributed by Williams1 to an excited dimer formed by combination of an excited singlet molecule with an unexcited molecule. Delayed fluorescence from phenanthrene vapour was shown by Stevens Hutton and Porter2 to have the spectral distribution charac- teristic of normal anthracene fluorescence and it was assumed to be produced from traces of anthracene present in the phenanthrene specimen by a process involving energy transfer from a long-lived phenan- threne dimer.In solution the majority of the luminescence from the excited pyrene dimerS has a lifetime much shorter4 than in the vapour phase5 and this suggests that the excited states responsible for the two kinds of emission are not of the same type. We have now investigated the luminescence of anthracene and phenanthrene in solution by means of a spectrophosphorimeter.6 In carefully de-oxygenated ethanol we observed a relatively intense delayed fluorescence from anthracene and a weak delayed fluorescence from pure phenanthrene.If traces of anthracene were present in the phenan- threne a stronger delayed fluorescence was pro-duced having a spectral distribution characteristic of anthracene fluorescence. The results were thus qualitatively similar to those previously observed in the vapour phase. The point of special interest concerns the intensity of the delayed emission. This was found to be pro-portional to the square of the rate of light absorp- tion. (For example in 5 x 1(k5~-anthracenesolu-tion the ratio of the efficiencies of delayed to normal fluorescence was 0.009 at a light absorption rate of 3 x einstein 1.-l sec.-l but was reduced to 0.001 at a light absorption rate of 0.33 x einstein I.-l sec.-l).Williams J. Chem. Phys. 1958 28 577. *Stevens Hutton and Porter Nature 1960 185 917. Forster and Kasper 2.Elektrochem. 1955 59 977. Parker and Hatchard. Nature. 1961. 190. 165. .. Stevens Nature 1961; 192 725. We cannot account for this effect by a mechanism involving the formation of an excited dimer of the type proposed by Wil1iams.l Our results can be quantitatively accounted for by a mechanism in which triplet-triplet quenching produces an excited species carrying the energy from two triplet mole- cules aA +3A +X (+A) ...(1) X+A*(+A) ...(2) A* 4A -+hv. *..(3) The species X could be a dimer of the type proposed by CoIpa,7 or a single molecule in an excited (quin- tuplet?) state. In the above scheme the “A” in parentheses would then appear either in step (2) or in step (1).The species X need not have a long life- time because the lifetime of the delayed fluorescence could be accounted for by the lifetime of the triplet state. The possibility that a single molecular species may carry excitation energy derived from two absorbed quanta might be important in connection with the mechanism of photosynthesis. The fact that delayed fluorescence in solution is proportional to the square of the rate of light absorp- tion could explain our failure4 to observe the delayed emission reported by Stevens and Hutton8 for pyrene solutions. In our experiments with pyrene the rate of light absorption was low. In view of the similarity between some of our results in solution and those previously observed in the vapour phase it is now important to establish whether the square-law dependence on rate of light absorption applies in the vapour phase also.(Received,March 16th 1962.) Parker and Hatchard Trans. Faraday Soc. 1961 57 1894. Colpa paper presented at the Fifth European Congress on Molecular Spectroscopy Amsterdam 1961. *Stevens and Hutton Nature 1960 186 1045. PROCEEDINGS The Structure of Calycanthidine By J. E. SAXTON (DEPARTMENT OF CHEMISTRY THEUNIVERSITY LEEDS) W. G. BARDSLEY, and G. F. SMITH (DEPARTMENT OF CHEMISTRY THEUNIVERSITY MANCHESTER) the minor alkaloid of the seeds of crystalline oxalate has now been isolated in 85% CALYCANTHIDINE Calycanthus floridus was first isolated and charac- yield after similar reduction of chimonanthine) and isolated as terised by Barger et aZ.,' who by analysis of the base 1-methyl-3-2'-methylaminoethylindoline and of a number of its salts deduced the molecular the picrate m.p.154-158" in 35% yield identical formula C,,H16N2; this formula was later accepted with the picrate of the base obtained by reduction of by Robinson and his collaborators who proposed f~licanthine.~ for calycanthidine a structure based on a hexahydro-Calycanthidine thus represents the intermediate /3-carboline skeleton.2 stage in the methylation of chimonanthine to Calycanthidine is now shown to have the formula folicanthine and can be formulated as (I)or (1Q6 C2,H2,N, by elementary analysis of the unsolvated base and of its solvate C2,H2,N4,0~5Me2C0.The Me Me ultraviolet spectrum with maxima at 250 and 308 mp (E 15,200,6050) changed to 243 and 298 mp (E 15,050 5100) in dilute hydrochloric acid corresponds to a PhNCaN chromophore; the electrometric titration curve shows the alkaloid to be a diacidic base (pK 7.37 6-04) and therefore to contain two such chromophores in the molecule (cf. f~licanthine~). These structures are fully supported by the nuclear Calycanthidine is thus a fourth member of the "dimerised tryptamine" group to which caly-magnetic resonance and mass spectra of folicanthine ~anthine,~ and chimonanthine6 belong. chimonanthine and calycanthidine. The mass f~licanthine,~ That calycanthidine belongs to the folicanthine- spectral data are of especial interest for they reveal chimonanthine group is shown (i) by the very closely an extremely easy halving of the molecules and thus similar infrared spectra of these three bases (ii) by favour structures of type (I) for the three alkaloids.the specific rotations -280" (in MeOH),l -317" [Added in proof March 19th.j Structures of type (1) (present work) for calycanthidine -329" (in EtOH) for these three alkaloids have now been established for chimonanthine and -364" (in EtOH) for by X-ray analysis of chimonanthine dihydro-folicanthine (cf. calycanthine +684") (iii) by the bromide. rapid formation of a normal dimethiodideY6 and (iv) by smooth reduction by zinc and hydrochloric acid to a mixture of indolines. This mixture has The authors are indebted to the D.S.I.R.for a yielded 3-2'-methylaminoethylindoline isolated as maintenance grant (to W.G.B.). the oxalate m.p. 164-166" in 46% yield (the same (Received February 6th 1962.) Barger Jacob and Madinaveitia Rec. Trav. chim. 1938 57 548. 2 Levy and Robinson Festschrift P. Karrer Zurich 1948 P. 30; Coker D. Phil. Thesis Oxford 1952; Robinson and Teuber Chem. and Ind. 1954 783. Hodson and Smith J.,1957 1877. 4 Woodward Yang Katz Clark Harley-Mason Ingleby and Sheppard Proc. Chem. Soc. 1960 76; Hamor Robertson Shrivastava and Silverton Proc. Chem. Soc. 1960 78. Hodson Smith and Wrbbel Chem. and Ind. 1958 1551. 6 Hodson Robinson and Smith Proc. Chem. SOC.,1961 465. 7 Grant Hamor Robertson and Sim following communication. The Structure of Chimonanthine T.A. HAMOR ROBERTSON, By I. J. GRANT J. MONTEATH and G. A. SIM DEPARTMENT GLASGOW, (CHEMISTRY THEUNIVERSITY W.2) ROBTNSON, HODSON and SMITHrecently reported' calycanthine (I).2 By considering chemical and the isolation from Chimonanthusfragram of a new spectroscopic evidence they narrowed the structural alkaloid chimonanthine C22H26N4 isomeric with possibilities to two formulae (11; R = R' = H) and 1 Hodson B. Robinson and Smith Proc. Chem. Soc. 1961 465. 2 Sir R.Robinson and Teuber Chem. andlnd. 1954,783; Hamor Robertson Shrivastava and Silverton Proc. Chem. SOC. 1960,78; Woodward Yaw Kab Clark Harley-Mason Ingleby and Sheppard Proc. Chem. SOC.,1960,76. APRIL1962 149 X (111). We have now carried out a detailed X-ray analysis of chimonanthine dihydrobromide which r was kindly supplied by Dr.G. F. Smith and find that the correct structure for this alkaloid is Y+ (11; R = R' = H). Me H (1) " '"'= Two other naturally occurring alkaloids caly- canthidine and folicanthine have now been shown3 to represent successive further stages of methylation of chimonanthine; it follows that calycanthidine must be formulated as (11; R = H R = Me) and folicanthine as (11; R = R' = Me). Crystals of chimonanthine dihydrobromide (from dry ethanol) belong to the tetragonal system with cell dimensions a = b = 13.95 c = 26.67 A. There are eight molecules in the unit cell and the space group isP4,2,2 (or theenantiomorphousP4,2,2). 2083 independent structure amplitudes were evaluated.Fourier methods were used for the structure analysis. The third electron-density synthesis is shown in the Figure by means of superimposed con- tour sections drawn parallel to (001) and covering The third three-dimeGional electron-density distribu- tion for chimonanthine dihydrobromide shown by means of superimposed contour sections drawn parallel to (001). the region of one molecule. It will be seen that in the crystal the molecule adopts the cis-conformation. The average discrepancy between measured and calculated structure amplitudes at the present stage is 21 %. Refinement is continuing. The extensive calculations were carried out on the Glasgow University DEUCE computer with pro- grammes devised by Dr. J. s. Rollett and Dr.J. G. She. We thank the University of Glasgow for an I.C.I. Fellowship (to T.A.H.) and the Department of Scientific and Industrial Research for a main- tenance grant (to I.J.G.). (Received March 7th 2962.) Saxton Bardsley and Smith Proc. Chem. Soc. 1962 preceding communication. The Synthesis of AcetyIenes from En01 Phosphates By J. CYMERMAN CRAIGand M. MOYLE (DEPARTMENT OF PHARMACEUTICAL CHEMISTRY UNIVERSITY OF CALIFORNIA SANFRANCISCO, 22) THEmechanism of the biosynthesis of triple bonds has not yet been elucidated although it appears that acetate units are the precurs0rs.l Dehydration of -€OCH,-to -Ci C-could be expected2s3 to take place in two steps via an en01 ester -C(OX):CH-which eliminates an anionic leaving group with simultaneous loss of a proton from the trans-position of the double bond.The reverse reaction is well known in vitro and also occurs bi~logically.~ Both phosphate3 and recently pyr~phosphate~ anions have been suggested as feasible leaving groups in Nature. We now report the smooth conversion of a series of diethyl vinyl phosphates (11) derived6 from the ketones (I) through the sodium enol derivative or the a-chloro-ketone into the corresponding acetylenes Bu'lock and Gregory Biochem. J. 1959,72 322. Bu'lock Quart. Rev. 1956 10 371. Bohlrnann and Mannhardt,Progr. Chem. Org. Nat. Prod. 1957 14 1. Eimhjellen Actu Chem. Scand. 1956 10 1049. Jones Chern. Eng. News 1961,39 No. 12,46. Lichtenthaler Chern. Rev. 1961 61 607. 150 PROCEEDINGS (HI) in high yield on treatment with sodamide in ng 1.5140) gave phenylpropiolamide (72 %; m.p.liquid ammonia. Thus diethyl 1 -phenylvinyl phos- and mixed m.p. 107-108"). phate6 (IIa) gave phenylacetylene (75 %) identified Fleming and Harley-Masonlo converted the en01 p-bromobenzenesulphonate of diethyl benzoyl-(I) RCOCH2R' (a)R = Ph R' = H malonatt into phenylpropiolic acid by dilute alkali. (11) RC:CHR' (6) R = 4-PhC,H4 R' = H However the only recorded transformation of an 1 en01 phosphate into an acetylene appears to be the O-PO(OEt) (c) €2 = R'= p-Me0.C6H formationll of diethyl propynephosphonate by the (111) RCi C-R' (d) R -Ph R = C02Et action of sodium ethoxide on 1-(diethyl phosphato- as the mercury derivative.' Similarly diethyl 1-(4-bi- isopropenyl) diethyl phosphate.We believe that our reaction strongly supports the phenyly1)vinyt phosphate (IIb) (b.p. 184-1 86"/0~005 proposed biosynthetic pathway involving en01 mm. n2,5 1-5680) afforded 4ethynylbiphenyP (92%; m.p. 86-87'). Diethyl trans-1 ,2-di-(p-rnethoxy- phosphates. pheny1)vinyl phosphate (IIc) (m.p. 86-87 ")furnished di-(p-methoxyphenyl)acetyIeneg (94% ; m.p. 142-This work was supported by a grant from the -phenylvinyI di- National Institutes of Health U.S. Public Health 143") and trans-2-ethoxycarbonyl-1 ethyl phosphate (IId) (b.p. 153-1 55"/O.O05 mm. Service. (Received March hd 1962.) Johnson and McEwen J. Amer. Chem. SOC.,1926,48,469. Jacobs and Dankner J. Org. Chern. 1957,22 1424. Wiechell Annalen 1894 279 338.lo Fleming and Harley-Mason,Proc. Chem. Soc. 1961 245. l1 Jacobson Griffin Preis and Jensen J. Amer. Chem. Soc. 1957,79,2600. x-Hydroperoxy-esters By MOSHEAVRAMOFF and YAIR SPRINZAK (DANIEL INSTITUTE,WEIZMANN OF SCIENCE ISRAEL) SIEFF RESEARCH INSTITUTE REHOVOTH WEshowed previousIy the pronounced reactivity of R'RZCH.CO~RS -+ HOz+CR1RB.C0,R34 HO*CRIRzCOoR* hydrocarbons of the cyclopentadiene series in (1) (1') (111) pyridine in the presence of benzyltrimethylammon- The esters (I) (0.005 mole) were oxidised in ium hydroxide in particular their autoxidation to pyridine (25 ml.) containing benzyltrimethyl-ketones hydroperoxides and alcoho1s.l We now ammonium hydroxide. The catalyst had to be supple- report the synthesis of a novel type of hydroperoxide mented continuously as it was consumed by acids viz.a-hydroperoxy-esters by extension of the arising from hydrolysis of part of the esters and from Oxidn. Hydroperoxide Alcohol Rf R2 R3 Time(hr.) Temp. Yield (%) M.p. M.p. Ph Ph Me 4 -30" 28 69.5-70'5 " 72-73 CHzPh Ph Me 38 0 26 108-109.5 88-89a p-MeOC,H,.CH Ph Me 6 -18 45 90-91 83.5" Et 6 -18 40 73-5-75 62-64" 9 7 p-C,H,Me p-C,H,Me Et --40-65 -66-67 I p-ClC,H,.CH Ph Me 40-65 -70-72 Redn. by (a)KI-AcOH (6) NaHSO,. autoxidation to esters of diaryl- and (arylalky1)aryl- decomposition of the hydroperoxy-ester into alkyi acetic acids. The formation of these compounds also hydrogen carbonate and ketone. The products were constitutes a new route to the corresponding isolated as described previously1 and recrystallised K-hydroxy-esters as these are obtained quantita- from light petroleum ether.They are listed in the tively by reduction of the hydroperoxy-esters. The Table; the last two hydroperoxides were not ob-hydroxy-esters were also present in the untreated tained pure the yields stated being based on oxidation mixture. titrations. (Received,February 2nd 1962.) Sprinzak J. Amer. Chem. SOC.,1958 80 5449. a Acres Ber. 1904 37 2764. APRIL1962 151 -~ The Absolute Configuration of the Asymmetric Centre at Position 11of Santonin By Mmo NAKAZAKI and Hmo ARAKAWA OF CHEMISTRY KITA-KU OSAKA JAPAN) (DEPARTMENT OSAKACITY UNIVERSITY THE absolute configuration of (-)-santonin hasbeen well established except for position 11 which has been under dispute.lS2 We now report our results which proved the (flconfiguration around this centre.Hyposantonin (IV) prepared from santonin oxime (11) through the dienamine (111) by dienamine benzene rearrangement was refluxed with iodine in acetic acid solution for 3 hours giving santinic acid (V) which after chromatography on silica gel had m.p. 125-127" [a]D + 57.3" (in ethanol). Santinic acid (V) with diazomethane gave the methyl ester (VI) which was converted into the hydrazide (VII). VI :R=C&Me) HO,C ",,Me VII:R=CO-NH Y ,-(IX) m.p. 172-174" [aID -12.7" (in CHCId which was dissolved in chloroform and exhaustively ozonised for 9 hours. 90% Acetic acid was added to the remaining solution and ozonolysis was con-tinued for an additional 12 hours.After oxidation with peracetic acid and concentration the reaction mixture was hydrolysed by hot 20% hydrochloric acid then chloride ion was removed by Amberite IR4B resin giving a solution which showed the presence of alanine on paper chromatography. The alanine was converted into (+)-benzoylalanine (X) which showed after recrystallisation from benzene m.p. 148-151" [N]D + 7.4" (f4") (c 0.597 in N-KOH) (Found C 61.9; H 6.0; N 7-3. Calc. for C,,H,,NO, C 62.2; H 5.74; N 7.25%) with an infrared spectrum (in dioxan) superimposable on that of an authentic sample. These facts show that (+)-santinic acid (V) has the (S)-configuration. Further since from a mechan- istic standpoint epimerisation at position 11 is in- conceivable during the conversion of santonin (I) into the acid (V) (-)-santonin must also have the (S)-configuration at this centre thus confirming the assignment made by Abe et aL2 (x) NHB* We thank Drs.K. Takeda and K. Kuriyama Shionogi Pharm. Co. for measurement of optical The amine (VIII) obtained from this hydrazide rotations on a Rudolph spectropolarimeter model by the Curtius rearrangement (retention of con-200. figuration) was directly benzoylated to the amide (Received January 29th 1962.) Woodward and Yates Chem. andInd. 1954 1391; Cocker and McMurry Tetrahedron 1960,8 181. Abe Miki Sumi and Toga Chem. andhd. 1956,953. The Biosynthesis of Xanthopterin By ALEXANDER and H. C. S. WOOD STUART (THEROYALCOLLEGE AND TECHNOLOGY, OF SCIENCE GLASGOW) WEYGAND et a2.l have shown by using 14C-labelled precursors that guanosine or its 5'-phosphate is the precursor of xanthopterin (V) and leucopterin in the butterfly Pieris brassicae L.They suggest that this transformation involves the following steps (a) ring cleavage of the imidazole ring of guanosine to give a 5-amino-4-ribosylaminopyrimidine(I) (b) Amadori rearrangement of this glycosylamine to the corres- ponding 1 -(substituted amino)-1 -deoxypentuIose (11; R = NHa and (c) cyclisation of this ketose to a polyhydroxyalkylpteridine(III)which serves as the immediate precursor of xanthopterin (V). We now report the synthesis of the 1 -pyrimidinylamino-1- deoxypentulose (II;R = NHa and its conversion in vitro into xanthopterin.Nitration of 2-amino-4-chloro-6-hydroxypyrimi-dine gave its 5-nitro-derivative which was condensed with 1 -amino- 1-deoxy-D-erythro-pentulose,2to give the nitropyrimidine (11; R = NO,) isolated as its crystalline oxime. Catalytic reduction over Raney nickel gave the corresponding 1 -pyrimidinylamino- 1-deoxypentulose (11; R = NHJ Amax. 270 mp at pH 1. Attempted isolation of this pyrimidine resulted in intramolecular ring-closure to a tetra- Weygand Simon Dahms Waldschmidt Schliep and Wacker Angew. Chem. 1961,73,402. Neilson and Wood J. 1962,44. I52 hydropteridine (In),A,,,. 275 mp at pH 1 that was readily oxidised in alkaline solution by air to 7,8-di- hydroxanthopterin (IV) identified by comparison with an authentic ~pecimen.~ Prolonged aerial ?* H-$-OH H-$-OH HO OH CH2*OH HN%‘j& (0H)12cH2*m H2N6N H N (m> Albert and Wood J.Appl. Cltern. 1952 2 591. Goto and Forrest Research Cumm. 1961 6 180. PROCEEDINGS H (IV) (v) oxidation or treatment with cold alkaline potassium permanganate3 gave xanthopterin (V) identical with authentic material. We believe that these results provide experimental support for the biosynthetic pathway suggested by Weygand et aL,l although a definite decision can only be made as a result of experiments in vivo. The recent isolation4 of a phosphorylated pteridine (VI) from E. coli lends further support however to this hypothesis- (Received January 30th 1962.) Carbon-13 Splittings in Proton Magnetic Resonance Spectra of Alkylcyclopropenes By G.L. CLOSS (DEPARTMENT THEUNIVERSITY CHICAGO OF CHEMISTRY OF CHICAGO 37 ILL. U.S.A.) THEobservation that the magnitude of the nuclear 13C-H spin-spin coupling is determined pre-dominantly by the Fermi contact interaction has been well documented.la-C The resulting linear rela- tion of this valuela>b to the hybridisation of the carbon atomic orbitals involved is of great potential use in developing suitable models for the unusual types of bonding encountered in small-ring com- pounds. We have measured the 13C-H coupling constants in the methylcyclopropenes (I) and (11)2 by observing the proton-resonance satellites of hydrogen on carbon-1 3 in natural abundance.The values found for the olefinic C-H coupling constants in these compounds are (I) 220 and (11) 218 i-1 c./sec. CMe2 {I) R = H /\ HC=CR (a) R = Me respectively corresponding to 44 % of s-character of the carbon atomic orbitals used for bonding of hydrogen. These values constitute good evidence for a model for cyclopropenes essentially similar to that developed for cyclopropanes with “bent” ring-skeleton bonds and increased s-character of the exo- cyclic atomic orbitals.* With regard to the vinyl- hydrogen bonds cyclopropenes thus appear to be more closely related to acetylenes than to olefins a conclusion which finds its chemical justification in the recently observed relatively large acidity of these proton^.^ Using Muller and Pritchard’s equation relating C-H coupling constants with bond lengths1“ one finds 1.068 8 for compounds (I) and (11) to be compared with the experimental values of 1.056 and 1.086I$ for the C-H bonds in propyne4 and eth~lene,~ respectively.J (13C-H) for the gem-dimethyl groups in both cyclopropenes are 123 c./sec. the normal value for sp3-hybridised carbon atoms. The allylic-methyl protons in compound (11) are slightly more strongly coupled (128 c./sec.) a situation similar to that in propyne which also shows increased s-character of the methyl C-H bonds (132 c./sec.).lU We thank the National Science Foundation for a grant. (Received March Sth 1962.) * The exocyclic bonds of cyclopropane have been measured by the nuclear magnetic resonance technique to contain 32% of s-character.l* (a) Muller and Pritchard J.Chem. Phys. 1959 31 768 1471 ; (6) Shoolery ibid. p. 1427; (c) Muller ibid. 1962 36 359. Closs and Closs J. Amer. Chem. Sac. 1961 83 2015. Closs and Closs J. Amer. Chem. Suc. 1961 83 1003. Trambarulo and Gordy J. Chem. Phys. 1950,18 1613. Allen and Plyler J. Amer. Chem. SOC.,1958 80 2673. APRIL1962 153 An Unusual Formation of a Boron-Hydrogen Bond* H. S. TURNER, By R. K. BARTLETT R. J. WARNE M. A. YOUNG,and (in part) W. S. MCDONALD (NATIONAL LABORATORY, CHEMICAL D.S.T.R. TEDDINGTON) THE formation of B-trichloroborazoles by dehydro- chlorination of primary amine-boron trichloride adducts is well known? -HCI -HCI We now report that 2,6-dimethylaniline behaves anomalously.Thermal dehydrochlorination of its adduct (I) in solution gives the compound (TI; R = 2,6-Me2C,H,) and not the borazole (111); however with suitable tertiary amines this product reacts further and gives the dichloroborazole (IV; R= 2,6-Me,C,H3). R xfN\yx RN ,NR B (W The formula of this product has been established by elemental analysis and molecular-weight determina- tion and its structure by spectroscopic and chemical studies. The infrared absorption spectrum shows a B-H stretching band at 2524 crn.-I. A nuclear mag- netic resonance study shows “aromatic” and “ali- phatic” protons in the ratio 1:2 but the proton attached to boron could not be detected; however since in N-triphenylborazole the B-H resonance was weak and diffuse the failure to detect it in our pro- duct which has only one B-H link is not surprising.In replacement reactions our product shows two or three reactive centres according to the reagent. With water and similar nucleophiles the chlorine atoms are replaced while the B-H link is unaffected and the products (IV; X = OH OR NR’R” etc.) are hydrolysed by alkali with liberation of hydrogen. Reaction of alkyl- or aryl-lithium with our product or with its derivatives in which the chlorine atoms have been replaced gives B-trisubstituted borazoles which no Ionger absorb in the 2500 cm.-l region and do not liberate hydrogen on hydrolysis. The dihydroxy-compound (IV; X = OH) is remarkably stable and is reconverted into the di- chloride by thionyl chloride containing pyridinium chloride.The mechanism of the overall reaction has not yet been established but the hydrogen atom attached to boron appears to come from the tertiary base. When triethylamine is used acetaldehyde and diethylamine may be isolated from the reaction mixture sug-gesting the loss of a hydride ion from the base:2 -H-+ + CH3*CH,.NEt2-+ [CH,-CH-NEt +-+ CH,*CH:NEt,] -+ CH,-CHO + NHEt Other 2,6-disubstituted anilines have been found to give compounds analogous to (IV). We thank Dr. L. M. Jackman (Imperial College) for the nuclear magnetic resonance spectra and for discussion of the results. (Received March Sth 1962.) * A preliminary account of this work was read at the International Symposium on Inorganic Polymers University of Nottingham July 1961.E.g. Sheldon and Smith Quart. Rev. 1960 14 203. Cf. BuckIey Dunston and Henbest J. 1957,4903. NEWS AND ANNOUNCEMENTS Chemical Society Lectureships.-The Council has made the following appointments for 1962-63 Hugo Muller Lecture- ship .. . . Pedler Lectureship . . Tilden Lectureship .. Centenary Lectureship Professor D. H. R. Barton. Dr. F. Sanger. Dr. A. R. Battersby Dr. R. E. Richards. Professor F. H. Westheinier (Harvard) Professor R. Kuhn (Heidel-berg). Local Representatives.-Council has approved the following changes of Local Representatives Aberystwyth Birmingham Cambridge Glasgow Leicester Newcastle Nottingham .. Dr. A. H. Price in place of Dr.W. J. Orville-Thomas. .. Dr. A. B. Foster in place of Dr. A. S. Jones. .. Dr. E. A. V. Ebsworth in place of Dr. A. R. Katritzky. .. Dr. H. C. S. Wood in place of Dr. G. H. Nancollas. .. Mr. R. W. Bott in place of Dr. E. R. A. Peeling. .. Dr. J. G. Buchanan in place of Dr. F. J. McQuillin. .. Dr. W. E. Addison in place of Dr. T. J. King. Southampton .. Dr. G. W.A. Fowles in place of Dr. I. G. M.Campbell. Swansea.. . . Dr. R. F. Curtis in place of Mr. R. H. Davies. Library.-The Library will close for the Whitsun Holiday from 6 p.m. Friday June Sth until 9.30 a.m. Wednesday June 13th 1962. Library Photocopy Service.-The Library has recently installed a xerographic copying machine which greatly speeds the process of photocopying and also reduces its cost.As from May lst prints the same size as the original will be available on demand at a price of 2/-for the first page and 1/-for each subsequent page. Microfilm will still be available at 2/-for the first page and 6d. for each subsequent page. Election of New Fellows.-227 Candidates whose names were published in Proceedings for February have been elected to the Fellowship. Deaths.-We regret to announce the deaths of the following Dr. H. H. Mann (1.12.61) formerly Assistant Director-in-Charge Woburn Experimental Station ;Mr. E. C. Sayers (1 7.1.62) of Twickenham Middlesex; and Professor H. E. Stapleton (12.2.62) formerly of Presidency College Calcutta. Honours.-A Life Peerage has been recommended for Sir Alexander Todd President of the Society.Royal Society.-The following were included amongst those elected to the Fellowship of the Royal Society on March 15th Dr. LRslie Ewart Orgel Assistant Director of Research in Theoretical Chemistry in the University of Cambridge. Distinguished for his application of molecular-orbital theory to the structure of complex ions and to the nature of the bonding involved. Title Journal of the American Chemical Society .. .. Journal of Physical Chemistry .. . . .. .. Journal of Organic Chemistry .. .. .. .. I Journal of Chemical and Engineering Data . .. Chemical Reviews . . .. .. .. .. Journal of Chemical Documentation .. .. .. Chemical and Engineering News .. .. .. ..Analytical Chemistry .. .. .. .. .. Journal of Agriculture and Food Chemistry .. .. Inorganic Chemistry .. .. .. .. .. Biochemistry .. Journal of Medicinaj ‘and Pharmaceuticai Chem%ry . Industrial and Engineering Chemistry I&EC plus 1 quarterly . . .. .. I&EC plus 1 quarterly (Internitlonalj . .. .. I&EC plus 2 quarterlies .. .. I&EC plus 2 quarterlies (InterdAionaij .. .. I&EC plus 3 quatterlies .. . . I&EC plus 3 quarterlies (Intekitionaij .. .. PROCEEDINGS Professor Ralph Alexander Raphael Regius Pro-fessor of Chemistry in the University of Glasgow. Distinguished for his work on the synthesis of natural substances. Memorial to Dr. J. Kenyon.-To commemorate the long association of the late Dr. J. Kenyon F.R.S.with the Chemistry Department of Battersea College of Technology the Governors in consultation with Mrs. Kenyon have decided to name the Organic Chemistry Research Laboratories of the College “The Joseph Kenyon Research Laboratories,” and to erect a memorial plaque. Anyone wishing to be associated with this memorial is invited to send a contribution towards its cost to the joint organisers Dr. Henry Philips O.B.E. and Dr. J. E. Salmon c/o the Chemistry Department. Cheques etc. should be made payable to “Battersea College of Tech- nology Dr. Kenyon Memorial Fund.” It is proposed that any money received in excess of that required for the plaque shall be treated as a memorial fund to be used for purposes to be decided by the Principal and Governors in consultation with Mrs.Kenyon and the Chemistry Department. The Laboratory of the Government Chemist.-The Council for Scientific and Industrial Research has decided to set up a Steering Committee for the Laboratory of the Government Chemist. The Com- mittee will consist of Dr. B. K. Blount (Chairman) Professor R. Belcher Mr. R. C. Chirnside Dr. D. T. Lewis,and Mr. H. Wooldridge.It will be responsible to the Council for the general programme of work of the Laboratory. American Chemical Society Publications 1962.-Under a reciprocal agreement Fellows of The Subscription classification Domestic or Foreign .. Domestic or Foreign .. Domestic or Foreign .. Domestic or Foreign .. Domestic or Foreign .. Domestic or Foreign ..Domestic or Canada .. Foreign . . .. Domestic or Canada .. Foreign . . .. .I Dom&tic or Foreign .. Domestic or Foreign .. Domestic or Foreign .. Domestic or Foreign .. Domestic or Canada .. Foreign .. .. .I Domestic or Canada Foreign .. .. Domestic or Canada .. Foreign .. .. .. Subscription rates 1 2 3 year years years 9630.00 -24.00 --25.00 18.00 -20.00 10.00 - 6.00 10.00 14.00 15.00 27.50 40.00 5.00 9.00 12.00 15.00 27.50 40.00 20.00 - 22.00 26.00 20.00 - 3.00 4.50 5.00 13.00 25.50 38.00 5.00 7.00 7.50 15.00 27.50 40.00 7.00 9.50 10.50 17.00 29.50 42.00 Titles of Quarterly Sections are A Process Design and Development; B Product Research and Development; C Fundamental.The discount does not apply to postage which is an additional charge on all subscriptions. APRIL1962 Chemical Society may enter subscriptions to the journals published by the American Chemical Society at a discount of 10% from the non-members’ rates. No discount is available on Chemical Abstracts which is no longer published as a periodical but is authorised and priced as a service. The non-member prices of publications for 1962 are given in the Table. All enquiries should be addressed to The American Chemical Society 1155 Sixteenth Street N.W. Washington 6 D.C. U.S.A. Symposia etc.-A Symposium on “Theory and Structure of Complex Compounds” will be held in Wroclaw Poland on June 15-19th 1962.Further enquiries should be addressed to Prof. Dr. B. J. Trzebiatowska Department of Inorganic Chemistry Wroclaw University Wybrzeze Wyspianskiego 29 Wroclaw Poland. The Third Congress of the European Federation of Chemical Engineering organised jointly by the Institution of Chemical Engineers and the Society of Chemical Industry will be held in London on June 20-29th 1962. Further enquiries and requests for registration forms should be addressed to the Insti- tution of Chemical Engineers 16 Belgrave Square London S.W.l. An International Summer School on Theoretical Chemistry will be held in Konstanz Bodensee Germany from September 10-28th 1962 and will deal with ligand-field theory and its applications.Further enquiries should be addressed to Ferienkurs Institut fur physikalische Chemie 6 Frankfurt am Main 1 Robert Mayer-Strasse 1 1 Germany. A Conference on “Low Energy Nuclear Physics,” sponsored by the Institute of Physics and the Physical Society will be held in London on September 12--14th 1962. Further enquiries should be addressed to The Institute of Physics and The Physical Society 47 Belgrave Square London S.W.1. An “International Symposium on the Condensa- tion and Evaporation of Solids” will be held at the Biltmore Hotel Dayton Ohio U.S.A. on September 12-14th 1962. Further enquiries should be ad- dressed to Office of Aerospace Research attn. Capt. D. Beitsch U.S.A.F. Shell Bldg.47 Canter- steen Brussels Belgium. Personal.-Dr. F. Aylward has been appointed Professor and Head of the new Department of Bio- chemistry Nutrition and Food Science at the Uni- versity of Ghana and is serving also as Scientific Adviser on Foods and Nutrition to the Ministry of Agriculture in Ghana. Dr. C. H. Bamford has been appointed to the Campbell Brown Chair of Industrial Chemistry at the University of Liverpool as from October lst 1962 succeeding Professor T. P. Hilditch who held it from 1926 to 1951. Professor W. F. Barker who retired as Professor and Head of the Department of Chemistry Rhodes University South Africa has had the title of Professor Emeritus conferred on him. Dr. A. R. Battersby has been appointed to a Chair of Organic Chemistry at the University of Liverpool which has been established in addition to that occupied by Professor G.W.Kenner. Dr. R. C. Cambie has been promoted to Senior Lecturer in Chemistry in the University of Auckland. Dr. G. 0. Doak and Dr. P. Wilder,jun. have been appointed to serve on the State Scientific Advisory Committee for North Carolina U.S.A. Dr. J. A. Elvidge has been appointed to the Readership in Organic Chemistry tenable at the Imperial College of Science and Technology. Professor E. 0.Fischer of Munich University is visiting this country under the Foreign University Interchange Scheme sponsored by the British Council. He will lecture on “Recent Results on Metal v-Complexes of Unsaturated Hydrocarbons” in Glasgow Durham Manchester Oxford Abing- don London and Cambridge.Mr. R. S. Forsyth has relinquished his appoint- ment with the U.K.A.E.A. Dounreay Scotland and has taken up a post in AB Atomenergie at the Nuclear Research Centre Studsvik Sweden. Sir Harry Jephcott is Chairman and Dr. B. A. Hems and Dr. T. 10. Macrae have been appointed Directors of the newly created Glaxo Research Limited. Dr. Gurnos Jones Lecturer in Organic Chemistry University of Keele has been appointed Visiting Scientist at the National Institutes of Health Bethesda Maryland for six months from March lst 1962. The title of Reader in Biochemistry has been con- ferred on Dr. A. E. Kellie in respect of his post at the Middlesex Hospital Medical School. The Honorary D.Sc.of Manchester University is to be conferred upon Dame Kathleen Lonsdale. Mr. A. T. Mackie formerly Technical Director East Africa Industries Ltd. Nairobi Kenya is now with Unilever Ltd. London. Dr. R. J. Magee Lecturer in Inorganic Chemistry Queen’s University Belfast has been appointed to a Visiting Professorship at the Case Institute of Tech- nology Cleveland Ohio for a six-months’ period from July next. Dr. J. R. Nunn has been appointed Professor of Organic Chemistry Rhodes University South Africa. Dr. S. C. Nyburg Lecturer in Physical Chemistry University of Keele has been appointed Visiting Professor in Crystallography at the University of Pittsburg for the year commencing August lst 1962. Dr. G. B.Petersen is on leave for two years from the Plant Chemistry Division of D.S.I.R. Palmer- ston North and is working in the Biochemistry Department Oxford University. Dr. M. A. T. Rogers has been appointed Assistant Head of the Research and Development Depart- ment Imperial Chemical Industries Limited Head Office. Dr. M. E. Spaght President of the Shell Oil Company in the United States and a Director of the American Petroleum Institute has been appointed President of the Society of Chemical Industry for the year 1962-63. Dr. Spaght will be installed as President by Lord Fleck during the Annual Meeting of the Society in Newcastle upon Tyne on July 1 1 th 1962. Dr. J. Taylor a Director of Imperial Chemical Industries Limited has been appointed Chairman of the Board of Imperial Metal Industries Ltd.a new holding company formed to take over responsibility for the present Metals Division which is to become a new operating company Imperial Metal Industries (Kynoch) Ltd. Dr. R. E. Thornton formerly Head of the Science Department Guthlaxton Grammar School Wigston PROCEEDINGS Magna Leicester has been appointed a Research Chemist with the National Coal Board Research Establishment Stoke Orchard Cheltenham. The University of Edinburgh is to confer the honorary degree of Doctor of Laws upon Sir Alexander Todd. Mr. T. A. Turney has been awarded the Easterfield Medal of the New Zealand Section of the Royal Institute of Chemistry. Mr. J. H. P. Utley’s N.A.T.O. Fellowship is held at the University of Delft and not at Munich as stated in Proceedings for February 1962.Professor K. Venkataraman Director of the National Chemical Laboratory at Poona India is spending the second semester at Purdue University as Visiting Professor of Chemistry. Dr. R. L. Williams of the Admiralty Materials Laboratory has been appointed Superintendent of Analytical Services at the Explosives Research and Development Establishment Waltham Abbey. Mr. R. 0.Williams,formerly a Research Student at the University of Southampton has been ap- pointed a Research Associate in Chemistry for one year at Johns Hopkins University Baltimore U.S.A. FORTHCOMING SCIENTIFIC MEETINGS London Thursday May loth at 7.30 p.m. Tilden Lecture “Stereoselectivity in the Reactions of Cyclic Compounds,” by Professor H.B. Henbest D.Sc. Ph.D. F.R.I.C. to be held in the Large Chem- istry Lecture Theatre Imperial College of Science and Technology South Kensington S.W.7. Thursday June 7th at 7.30 p.m. Meeting for the reading of original papers. To be held in the Rooms of the Society Burlington House w.l. Birmingham Friday May 11 th at 4.30 p.m. Lecture “Developments in Magnetic Resonance,” by Dr. R. E. Richards M.A. F.R.S. Joint Meeting with the University Chemical Society to be held in the Chemistry Department The University. Cambridge Monday May 7th at 5 p.m. Lecture “Optical Rotary Dispersion as a Tool in Structural Organic Chemistry,” by Professor W. Klyne M.A. Ph.D. D.Sc.to be given in the Uni- versity Chemical Laboratory Lensfield Road. Dublin Friday May 18th at 7.45p.m. Lecture “Recent Developments in Acetylene-Allene Chemistry,’’ by Professor E. R. H. Jones D.Sc. F.R.S. Joint Meeting with the Werner Society to be held in the Department of Chemistry Trinity College. Durham Wednesday May 2nd at 5 p.m. Lecture “Recent Results on Metal n-Complexes of Unsaturated Hydrocarbons,” by Professor E. 0. Fischer Dr.rer.nat. Joint Meeting with the Durham Colleges Chemical Society to be held in the Science Laboratories The University. Edinburgh Tuesday May 8th at 4.30p.m. Lecture “Neutron Activation Analysis,” by Profes- sor H. Irving M.A. D.Phi1. Joint Meeting with the University Chemical Society to be held in the Department of Chemistry The University.Oxford (Joint Meetings with the Alembic Club to be held in the Inorganic Chemistry Laboratory.) APRIL1962 Monday May 7th at 8.30p.m. Lecture “Recent Results on Metal n-Complexes of Unsaturated Hydrocarbons,” by Professor E. 0. Fischer Dr.rer.nat. Monday May Zlst at 8.30p.m. Lecture “The Way Ahead with D.S.I.R.,” by Sir Harry Melville K.C.B. D.Sc. F.R.S.Joint meeting with the Royal Institute of Chemistry. Monday May 28th at 8.30p.m. Lecture “Tetraterpenes,” by Professor B. C. L. Weedon Ph.D. F.R.T.C. Monday June 11 th at 8.30 p.m. Lecture “Ions and Electrons in Flames,” by Dr. T. M. Sugden. Keele Tuesday May lst at 8.30 p.m. Lecture “Science in Art and Archaeology,” by Dr.A. E. A. Werner M.A. A.R.I.C. Joint Meeting with the University College Science Society and the Royal Institute of Chemistry to be held in the Department of Chemistry University of Keele. Reading Tuesday May 15th at 6 p.m. Lecture “Fast Halogenation Reactions,” by Mr. R. P. Bell M.A. F.R.S. Joint Meeting with the University Chemical Society and the Royal Institute of Chemistry to be held in the Large Chemistry Lecture Theatre The University. Southampton Friday May llth at 5 p.m. Tilden Lecture “Stereoselectivity in the Reactions of Cyclic Compounds,” by Professor H. B. Henbest D.Sc. Ph.D. F.R.I.C. To be given in the Institute of Education The University. APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objections to the election of these candidates should communicate with the Honora Secretaries within ten days of the publication of this issue of Proceedings.Such objections will be treated as confidentix The forms of application are available in the Rooms of the Society for inspection by Fellows.) Ablewhite Alan James. “Wyelands,” Naldon Road, Tiptree Colchester Essex. Abraham Carl Joel B.A. M.S. Department of Chem- istry University of North Carolina Chapel Hill North Carolina U.S.A. Accascina Filippo Dr.chem. Via Archirafi 26 Palermo, Italy. Acland Julian Duke M.A. B.M. Department of Pharmacology and Therapeutics The University, Sheffield 10. Adegbola Timothy Siyanbade. Mellanby Hall University College Ibadan Nigeria. Adlard Maxwell Wright B.Sc.I.C.I. Ltd. Akers Research Laboratories The Frythe Welwyn Herts. Alcorn Percival George Ernest B.Sc. 213 Bonney Avenue Clayfield Brisbane Australia. Allinson Iyowon Ishola Olnkayode. Kuti Hall University College Ibadan Nigeria. Amiet Richard Gary B.Sc. 22 Parnell Sheet Elstern- wick Melbourne Victoria Australia. Anderson Roy Scott MSc. Ph.D. 66 Catherine Street Apt. B-3 Bloomingdale New Jersey U.S.A. Anusiem Alphonso Chikwendu Iheanyichukwu. Mellan- by Hall University College Ibadan Nigeria. Ataga David Omuekpen. Mellanby Hall University College Ibadan Nigeria. Atwater Norman W. M.A. Ph.D. 5 W. South Street Arlington Heights Illinois U.S.A. Bafus Donald Allen M.S. 606 W. Ohio Street Urbana Illmois U.S.A. Baker Frederick Stanley.27 Hamlet Court Opal Street Kennington S.E. 1 1. Baldwin Roger A. Ph.D. 11627 Starlight Avenue Whittier Calif. U.S.A. Ball Christopher Roger. “Aberfoyle,” Long Ashton Bristol. Barreras Raymond Joseph B.S. Kedzie Chemical Laboratory Michigan State University East Lansing Michigan U.S.A. Barton Allan Francis Murray B.Sc. 3 Auckland Road St. Heliers Bay Auckland E.1 New Zealand. Beichl George J. Ph.D. 6387 Drexel Road Philadelphia 51 Pa. U.S.A. Bell Kevin Hilton B.Sc. Chemistry Department New- castle University College Tighes Hill 2-N N.S.W., Australia. Benfield Glyn B.A. St. John’s College Oxford. Bentata Albert B.Sc. 120 Caroline Street Flat 3 South Yarra Melbourne Victoria Australia. Beveridge Alexander David B.Sc. 3 1 Fereneze Avenue Clarkston Glasgow .Bicknell Robert Christopher Luke B.Sc. 37 Westfield Road Eastbourne Sussex. Bishop Edward Oliver M.A. B.Sc. D.Phi1. Physical Chemistry Laboratory South Parks Road Oxford. Blackmore David Richard B.A. Corpus Christi College Oxford. Bobbins Francis John. Room B-53 Hirst Research Centre North Wembley Middlesex. Bohannon Byron O’Rear M.S. Department of Chem- istry Florida State University Tallahassee Florida U.S.A. Bowen Timothy. 47 Northbrook Road Nichols Town Southampton Hank Brewis Derek McHardy B.Sc. The University Hull. Bridge Michael Roger B.Sc. 57 Lausanne Road, Hornsey N.8. Bridge Noel James B.A. 3 Stratford Road Ifffey Road Oxford. Broadbent Colin Percival. 6 Grove Mead Maghull Lancashire.Brody Frederick B.S. Ph.D. 505 West 162 Street New York 32 N.Y. U.S.A. Broughton Shelby Moreland B.S. 315 College Avenue Ithaca N.Y. U.S.A. Byme Monica Mary B.Sc. Mount St. Joseph Convent Deane Bolton Lancs. Caine Drury S. B.A. Ph.D. Chemistry Department Columbia University New York 27 N.Y. U.S.A. Cameron Alan Iain. “Mariefield,” Southend Campbel- town Argyll. Campbell-Ferguson Hugh James. Christ’s College, Cambridge. Cantor Stephen Edward B.S. Chemistry Department University of Rochester Rochester New York U.S.A. Cantrell Thomas Samuel M.S. McPherson Chemistry Laboratorv. Ohio State University. Columbus 10. -_ Ohio U.S:A. Cash Derek John B.Sc. A.R.C.S. Chemistry Depart- ment. Duke University Durham North Carolma U.S.A.Charalambous George Ph.D. 391 5 Jamieson Avenue St. Louis 9 Missouri U.S.A. Chauffe Leroy B.S. Department of Chemistry Univer- sity of California Davis California U.S.A. Choi So0 San B.Sc. Phllco Corporation Research Division Blue Bell Pennsylvania U.S.A. Chopard Pierre-A. Ph.D. Cyanamid European Research Institute 91 Rte. de la Capite Cologny Geneva Switzerland. Choulis Nicolas. Chelsea School of Pharmacy Manresa Road London S.W.3. Clague Alfred Derek Hunter B.Sc. Chemistry Depart- ment A. & M. College of Texas College Station Texas U.S.A. Cohen Robert L. B.S. 147-34 70 Road Flushing 67 New York U.S.A. Coller Bruce Arthur William B.Sc. Physical Chemistry Laboratory South Parks Road Oxford. Cowan Duncan Robert.45 High Street East Glossop Derbyshire. Cragg Gordon Mitchell Lyan B.Sc. Dyson Perrins Laboratory South Parks Road Oxford. Craig John Thorburn B.Sc.,Ph.D. A.R.I.C. Chemistry Department Victoria University Wellington New Zealand. Craven Brian Raymond MSc. Physical Chemistry Department School of Chemistry University of New South Wales Kensington N.S.W. Australia. Dedek Jaroslav Vladimir Otto Joseph. Christ Church Oxford. Dewar Jams Hilton A.R I.C. Department of Chemical Technology Bradford Institute of Technology, Bradford 7. Dodd Nicholas John Francis B.A. 22 Breckon Hill Road Middlesbrough Yorks. Dunn Howard Eugene A.B. 808 West Illinois Urbana Illinois U.S.A. Dutton Walter Arthur B.Sc. 65617th Avenue, Lachine Quebec Canada.Eades Joseph Francis Kiernan PhD. Wye College University of London Nr. Ashford Kent. Eaton Gareth Richard. Lowell E-12 Harvard University Cambridge 38 Mass. U.S.A. Eckroth David Raymond B A Frick Chemical Labora- tory Princeton New Jersey U.S.A. Edwards Anthony John Ph.D. A.R.C.S. 281 The Broadway Dudley Worcs Ela Stephen White B.A. Department of Chemistry U C.L A ,Los Angeles 24 Calif. U.S.A. PROCEEDINGS Ellis Stephen Harold A.B. 1102 New Hall Columbia University New York 27 N.Y. U.S.A. Elmes Bryan Claremont B.Sc. 36 Grove Road Adding- ton Christchurch New Zealand. Elwood James K. B.A. Kedzie Chemical Laboratory Michigan State University East Lansing Mich., U.S.A. Emerson George Frederick B.S. Department of Chem- istry University of Texas Austin Texas U.S.A.Fairweather Ronald Morrison B.Sc. 35 Fountainhall Road Edinburgh 9. Fanica Louis. 52 Boulevard de la Villette Paris 19-e France. Firth Richard Andrew. Christ Church Oxford. Foote Christopher S. A.M. Ph.D. Department of Chemistry University of California Los Angeles 24 Calif. U.S.A. Fresco James M. A.B. Ph.D. Chemistry Department University of Arizona Tucson Arizona U.S.A. Fullagar Ronald Hugh B.A. 22 Franklin Road Jacks- dale Nottingham. Galloway Warren John M.Sc. Chemistry Department University of Canterbury P.O. Box 1471 Christchurch New Zealand. Garrigan Owen W. A.B. Ph.D. Seton Hall University South Orange New Jersey U.S.A. Garst Roger Harry B.A. 141 Thayer Street Providence 6 Rhode Island U.S A.George David Rodney. Whiffen & Sons Ltd. Willows Works Derby Road Loughborough. Gilchrist Thomas Lonsdale B.Sc. 2 Gubyon Avenue London S E.24. Goldberg Joseph Louis M.A. Ph.D. Department of Chemistry City College of New York 139th Street and Convent Avenue N.Y.C. 31 New York U.S.A. Grace Alan. 84 Saint Anthony Road Sheffield 10. Grant Ian James B Sc. 1007 Mosspark Drive Glasgow s.w.2. Gray Charles John B.Sc. Chemistry Department The University Edgbaston Birmingham 15. Grigg Ernest Christopher Milner M.Sc. 55 Depper Street St. Lucia Brisbane Australia. Grunewald Helmut Dr.rer.nat. Ziegelhauser Land-strasse 35 Heidelberg Germany. Guertin J.P. B.Sc. Room 502 Chemistry Budding McGill University Montreal 2 P.Q. Canada.Gupta Mahipal M.Sc. 205 Saket Meerut India. Gutteridge Norman James Albert. 34 St. Margaret’s Avenue South Harrow Middlesex. Gwynn Donald Eugene Ph.D. Crellin Laboratory, California Institute of Technology Pasadena Calif. U.S.A. Hakka Leo Ernest. 74 Villa Crescent Ottawa Ontario Canada. Hamilton Rodney Dean B.S. Chemistry Department Indiana University Bloomington Indiana U.S.A. Hammer Robert Nelson Ph.D. Department of Chem-istry Michigan State University East Lansing, Michigan U .S.A. Hanna Samir Botros M Sc. Chemistry Department 4-465 M.I.T. Cambridge 39 Mass. U.S.A. Harle Alfred John M.Sc. School of Chemistry Univer- sity of Sydney Sydney N.S.W. Australia. Harris Glyn Islwyn A R.I.C. 8 Eastbrook Close Dinas Powis Glamorgan South Wales.Harrison Godwin Fayeofori Sokari. Mellanby Hall University College Ibadan Nigeria. Havinga Egbertus Drxhem. Laboratory of Organic Chemistry Hugo de Grootstraat 25 Leiden The Netherlands. APRIL1962 Hawkins Clifford John B.%. Department of Medical Chemistry John Curtin School of Medical Research Australian National University Canberra A.C.T. Australia. Hickman William Stuart B.Sc.275 Green Lane Heaton Norris Stockport Cheshire. Holman Donald John. 2A Anerley Park Anerley, S.E.20. Holmes William Samuel Ph.D. 8 Chequers Avenue Wombourn Wolverhampton Staffs. Huckle David. 97 Askew Road Shepherds Bush W.12. Hussey Clive Wilfred Theodore B.Sc. 3 Cyril Crescent Roath Cardiff Wales. Jackson Robert H. Ph.D. 12 Oxford Street Cambridge 38 Mass.U.S.A. Jenkins Harry Donald Brooke. 171 Ash Road Denton Manches ter . Jones Alan 10 Maureen Avenue Tunstall Stoke-on- Trent Staffs. Jones Edward Ph.D. A.R.C.S.T. A.R.T.C. 9 Queen’s Park Avenue Glasgow 5.2. Jones Harold Lloyd BSc. Department of Chemistry University of Cincinnati Cincinnati 21 Ohio U.S.A. Kakis Frederic J. B.S. Chemistry Department Stanford University Stanford California U.S.A. Katchy Emesi Mofunanya. Kuti Hall University Col- lege Ibadan Nigeria. Kay Joseph B.Sc. 13 Milford Road Harboume, Birmingham 17. Kellerman Dagobert B.Sc. Chemistry Department University College of London Gower Street London W.C. 1. Kemp Anthony Lionel Wickenden B.Sc. 3771 W. 11th Avenue Vancouver 8 B.C. Canada.Kesslin George Ph.D. 100 Blauvelt Street Teaneck New Jersey U.S.A. Kilmuny Lindsay B.Sc. Department of Chemistry, University of Toronto Toronto 5 Ontario Canada. Kinstle Thomas H. B.A. 208 W. John Street Cham- paign Illinois U.S.A. Kjaer Anders M.Sc. D.%. Organic Chemical Labora- tory Royal Veterinary and Agricultural College, Bulowsvej 13 Copenhagen V Denmark. Knapman John Bellamy Ph.D. 150 Grove Park, Knutsford Cheshire. Knaust Raymond Allen B.Sc. A.R.I.C. Derby and District College of Technology Kedleston Road, Derby. Knight Clive Graham B.Sc. 39 Shaldon Drive Morden Suri ey. Kornreich Lawrence David B.A. Department of Chemistry University of Delaware Newark U.S.A. Krishnamurti M. Ph.D. Chemistry Department Uni- versity of Delhi Delhi 6 India.Lamb Donald Charles PkD. 203 Manzanita Palo Alto Calif. U.S.A. Lamoureux Richard T. M.S. 2392 Pilot Knob Drive Santa Clara Calif. U.S.A. Landesberg Joseph S.B. Mallinckrodt Chemical Labora- tory 12 Oxford Street Cambridge 38 Mass. U.S.A. Larkin John Michael B.S. 1201 17 Street Apt. 4, Boulder Colo. U.S.A. Latta Thomas Melville A.B. M.S. Department of Chemistry University of Illinois Urbana Ill. U.S.A. Lee Donald Garry M.A. Chemistry Department, University of British Columbia Vancouver 8 B.C. Canada. Lidgett Ronald Arthur B.Sc. A.R.T.C. Bronant, Berwyn Street Llangollen North Wales. Liebig Danuta Mario. 46 Vesper Gate Crescent Leeds 5. 159 Lindsey David Charles B.Sc. 20 Bernard Shaw Court St. Pancras Way London N.W.1.Livesey Paul. 60 Exchange Street Accrington Lanca- shire. Lloyd-Owen Denis Richard. 111 Ridgeway Avenue Dunstable Bedfordshire. Lobo Angel0 Peter B.Sc. Chemistry Department, Indiana University Bloomington Ind. U.S.A. Lodam Banjamin Dusu. Mellanby Hall University College Ibadan Nigeria. Lohner Donald B.S. 59-21 54 Street Maspeth 78 New York U.S.A. McCann Anthony Pad Ph.D. Department of Chem- istry University of Ghana Legon Accra Ghana. McGillivray Brian B.Sc. 52 Auldlea Road Beith Ayrshire. McGonigal William Edward B.S. 1595 Olympian Way S.W. Atlanta 10 Georgia U.S.A. McGrath Brian Patrick B.Sc. Department of Chemistry Sheffield University Brook Hill Sheffield 10. McGrath David M.Sc. Chemistry Department Univer- sity College Galway Ireland.McKinnon David Graham. 51 Tobermory Road, Cathkin Rutherglen Nr. Glasgow Scotland. Macnamara Thomas Edmund. 1 Lee House Ordnance Road Enfield Middlesex. March Jerry Ph.D. Department of Chemistry Adelphi College Garden City New York U.S.A. Marchand Alan Philip B.S. 1400 East 53rd Street Chicago 15 Illinois U.S.A. Marlow Richard Godfrey. 17 Brooke Avenue Upton Heath Chester. Matthews Colin Edward B.Sc. Junior Leader Company Kings African Rifles B.F.P.O.lO. Melvin Alec Ph.D. Gas Council Research Group, Fulham Works Kings Road Fulham S.W.6. Menahem Jacob M.Pharm. 36 St. Kilda’s Road, London N.16. Mente Peter Gustav. 64 Lansdowne Place Hove Sussex. Midgley John Morton MSc. M.P.S. Department of Pharmaceutical Chemistry The School of Pharmacy, University of London 29-39 Brunswick Square, W.C.1 .Migliorini Maria T. B.A. 3 Walker Street West Somerville 44,Mass. U.S.A. Miller Gerald Ray Ph.D. Physical Chemistry Labora- tory South Parks Road Oxford. Milne Andrew Peter. 10 Chester House Eccleston Place London S.W.1. Moodie Iain MacArthur. c/o Mrs. W. Arlette 19 Athelstane Road Glasgow W.3. Motroni Giuseppe Dr.chem. c/o Clarke 49 Hamilton Street Saltcoats Ayrshire. Newman Barry Charles B.Sc. 136 Gymea Bay Road Gymea N.S.W. Australia. Newton Geoffrey William Alexander A.R.I.C. “Green- oaks,” Moss Lane Leyland Lancashire. Ng Chung Yau B.Sc. Department of Biochemistry, Oklahoma State University Stillwater Oklahoma U.S.A. Nichol Alan William B.Sc.32 View Street Chatswood N.S.W. Australia. Nicholls Derek. 5 Albermarle Street Clitheroe Lancs. Njoku Boniface Onogbo. Mellanby Hall University College Ibadan Nigeria. Noble John Alfred B.A. 5 Moss Bank Road Swinton Manches ter . Norin Torbjorn. Dyson Perrins Laboratory South Parks Road Oxford. Norling Parry McWhnnle AB. Frick Chemlcal Laboratory Princeton University Princeton N.J. US A. Nwankwo Sunday Igweiro B.Sc. Mellanby Hall, University College Ibadan Nigeria. Okogun Joseph Ibomein. Sultan Be110 Hall University College Ibadan Nigeria. Ott Donald George Ph.D 2215 36th Street Los Alamos, New Mexico U.S A. Owyang Raymond B S. Department of Chemistry, Stanford University Stanford Caltf. U.S.A Oyeka Christopher Chike.wllanby Hall University College Ibadan Nigeria. Parkms Rachel Mary. Springwood Ringshall Berkham- sted Herts. Percy Richard Keith. 30 Upland Road Sutton Surrey Perkins Michael John. 7 Cliff Mount Leeds 6. Peyser Pincus A.B. Ph.D. 122 Addington Road, Brookline 46 Mass. U.S.A. Phillips Dorothy Ann B.Sc. 10-A Alma Square St. John’s Wood N.W.8. Phillips David Meredith B.Sc. Chemistry Department University College Singleton Park Swansea South Wales. Phillips John Hartley. Christ’s College Cambridge Pilling Richard Lister B A. B.Sc. Keble College, Oxford. Pocock Francis John. 125 Kidmore Road Caversham Reading Berkshire. Poulter John William 96 Stamford Court London W 6. Rae Douglas Alan. 17 Rosslyn Drive Aspley Notting- ham.Ramsbottom Jeffrey Victor. Balllol College Oxford. Rasmussen Malcolm. 36 Balfour Street Carlton N.S.W , Australia. Rees Norman Howell Ph.D. 15 Woodland Place, Penarth. Glamorgan. South Wales. Reid David Sincliir. .191 Campsie Street Balornock Olasgow N.l. Rhodes Philip Edwin. 71 Hazel Road Bognor Regs Sussex. Rice Francis John. “Wendover,” Derby Road Milford Belper Derby. Richardson Ronald Dawson Ph.D. A.R.I.C. 15 Conifer Crescent Billingham-on-Tees Co. Durham. Rickard Clifton Edward Frank B.Sc. 39 Arney Road Remuera Auckland S.E.2 New Zealand. Rieber Manuel. Manchester College of Science and Technology Manchester 1. Robinson George F.R.I.C. 27 Newlyn Road Sheffield 8. Roelofs Wendell Lee B.A. Department of Chemistry Indiana University Bloommgton lnd.U.S.A. Ross Robert Edward B.S. 218-C Marshall Street, Princeton New Jersey U.S.A. Roth Wolfgang Ph.D. University of Koln Institut fur Organische Chemie Zulpicherstr. 47 Koln West Germany. Rowe Gerald B.Sc. 35 Meadow Croft Hatfield Herts. Saha Jadu Gopal M.Sc. Department of Chemistry University of Saskatchewan Saskatoon Sask ,Canada Saha Maitreyl B.Sc. Department of Chemistry Univer- sity of Saskatchewan Saskatoon Sask. Canada. Sambrook Ralph Harold. 14 Oaks Avenue Hanworth Feltham Middlesex. Sandall John Paul Benet B.Sc. 13 King Street Ash- bourne Derbyshm. Schildknecht Hermann Dr.phil.nat. Ebrardstrasse 13, Erlangen Germany. Schunbor Richard Frank B.S. Room 530 1010 W. Green Street Urbana Illinois U.S.A.PROCEEDINGS Schreiber Jacob Dr.sc.techn. Organ. Chem. Labora-torium E.T.H. Universitaestr. 8 Zurich 6 Switzer-land. Schugar Harvey Jay M.A. Ph.D. 377 S. Harrison Street Apt. 15-D East Orange New Jersey U.S.A. Settepani Joseph Anthony M.S. Department of Chem-istry University of Maine Orono Maine U.S.A. Seyd George Malcolm. 1 Orchardton Terrace Goose- well Plymstock Nr. Plymouth Devon. Sheard Brian. 28 Ravenshouse Road Scout Hill Dewsbury Yorkshire. Sheller Alan. 112 High Street Ponders End Enfield Middlesex Shirley David Allen Ph.D. Department of Chemistry, University of Tennessee Knoxville U.S.A. Shone Robert Larry M.S. 1574-D Spartan Village East Lansing Michigan U.S A. Shono Toshiyuki Ph.D. Department of chemistry The University of Aruona Tucson Aruona U.S.A.Silverthorne Merlin Edward M.S. 1030 El Monte Avenue Apt. 201 Mountam View Calif. U.S.A. Simpson John Ph.D. Department 2824 Bell Telephone Laboratories Murray Hill New Jersey USA. Smith Barry Russell B Sc. Chemistry Department University of Auckland Auckland New Zealand. Smith George Norbury B.Sc. Chemistry Department The University Glasgow W.2. Smith Keith Martin “Westholme,” 4 Newbury Road Fordhouses Wolverhampton Staffs. Smithies Adrian Christopher. 12 Bennett Lane Batley Yorkshire Stainer Philip John. 7 Portman Crescent Southbourne Hants. Steward Omar Waddington B.S. Ph.D. 332 East Park Road Leicester. Strachan William Michael John M.A. Chemistry Department University College Gower Street W.C.1. Suginome Hiroshi. University Chemical Laboratory Lensfield Road Cambridge. Surrey Alexander Robert Ph.D. Sterling-Winthrop Research Institute Rensselaer New York U.S A. Swan Timothy. St. John’s Vicarage Blackburn Lancs. Taylor Malcolm Stuart. 43 Reresby Road Whiston Nr. Rotherham Yorks. Taylor Peter John Meddows Ph.D. Laporte Industries Ltd. Kingsway Luton Beds. The Kwat Ie B.Sc. 25 Sturt Street Kmgsford N.S.W., Australia Thomas Michael John. 40 Low Ash Grove Wrose Shipley Yorkshire. Thompson David Crompton. St. John’s College, Cambridge. Timms Peter Leslie B.A. B.Sc. Merton College Oxford. Tomahn Geoffrey. Clapham House Bodmgton Hall Otley Road Leeds 16. Tomlinson George. 21 Hope Street Hazel Grove, Stockport Cheshire.Towle Jack Lewis Ph.D. Terrace Park Apartments 13800 Terrace Road East Cleveland 12 Ohio U.S.A. Udo Eno Jumbo. Mellanby Hall University College Ibadan Nigeria. Udo-Unwa Israel Thompson. Mellanby Hall University College Ibadan Nigeria. Una Sylvester Joseph B.Sc. Department of Chemistry University College Ibadan Nigeria Ushioda Satoshi M.Pharm. Ph D Department of Chemistry University College Upper Merrion Street Dublin Ireland. Van Sickle Dale Elbert Ph D. Organic Chemistry Section Stanford Research Institute Menlo Park Calif. U.S.A. Vanston Nicholas John. Balliol College Oxford. Venkatasubramanian Nurani Krishnan M.Sc. c/o Dr. C. R. Narayanan National Chemical Laboratory Poona 8 India. Vogt Lester H. Jr. M.S. 2170B Eastern Parkway Schenectady 9 New York U.S.A.Wagar Nelson WilIiam B.S. 546 Glen Street Glens Falls New York U.S.A. Wallis Adrian Fredric Arthur B.Sc. 38 Puriri Street Christchurch 4 New Zealand. Walton Donald James M.A. Ph.D. Medicinal Chem- icals Process Development Department Pfizer Ltd. Sandwich Kent. Ward Barry B.Sc. Chemistry Department The Univer- sity Sheffield 10. Watson Errol James M.Sc. A.R.A.C.I. Department of Physical and Inorganic Chemistry University of New England Armidale N.S.W. Australia. Wenisch Franz Dr.rer.nat. 22 Queensway Manchester 19. Wesley Thomas Alexis Bien B.A. 1 Adam Road Cambridge. Williams Martin Robert. 74 Crowshott Avenue Stan- more Middlesex. Wills-Johnson Graham B.Q. Chemistry Department University of Western Australia Nedlands Western Australia.Wilson John Alan Ph.D. 117 Broadway Chadderton Oldham Lana. Wise Anthony George B.Sc. Department of Physical and Inorganic Chemistry The University Bristol8. Wissman Vincent George B.S. 101 Frick Chemistry Laboratory Princeton University Princeton New Jersey U.S.A. Wolf Mary Ann B.A. 630 South Lahoma Norman Oklahoma U.S.A. Wong Kam Toi B.Sc. Chemistry Department Univer- sity of Alberta at Calgary Calgary Alberta Canada. Woodbury Edgar Christenson B.Sc. 3 1 Perkins Hall Harvard University Cambridge 38 Mass. U.S.A. Wysocki Donald C. B.S. Chemistry Department Uni- versity of Pittsburgh Pittsburgh 13 Pennsylvania, U.S.A. Yule Kerr Carmichael. 18 Mid Street Livingston Station West Lothian Scotland.Zimmerman Gary Alan B.S. Department of chemistry, University of Wisconsin Madison 6 Wisconsm, U.S.A. OBITUARY NOTICES THOMAS MALKIN 1897-1961 THOMAS MALIUN,well-known for his work on long- chain aliphatic compounds carried out in the University of Bristol over a period of thirty-six years was born on December 28th 1897 in Warrington. After leaving school he worked for a time in the laboratories of the soap manufacturers Joseph Crosfield and Sons in Warrington and his contact there with the higher fatty acids was to be an im-portant factor in deciding his future career. He attended the Manchester Municipal College of Tech-nology as a part-time student between 1917 and 19 19 entered the Victoria University of Manchester in 1919 and took the London external degree of B.Sc.in Chemistry in 1920. He then returned to the College of Technology and carried out research in the Dyestuffs section of the Department of Chemistry between 1920 and 1922 and then proceeded to the University of Manchester where for three years 1922-1925 he worked with Sir Robert Robinson on benzyl phenyl diketone and the synthesis of pelargo-nidin and galanginidin chlorides,l being awarded the Ph.D. degree in 1926. In 1925 Malkin accepted the post of Research Assistant to Dr. (now emeritus Professor) S. H. Piper of the Department of Physics at the University of Bristol to undertake with Professor Francis Francis the synthesis of a comprehensive series of Malkin and Robinson J.1925 369 1190. long-chain aliphatic compounds required for physico- chemical and X-ray studies. Malkin was appointed to a Lectureship in Organic Chemistry at Bristol in 1929 was awarded the D.%. degree of London in 1934 and became Reader in Organic Chemistry in 1945. For many years before the war as Professor Francis became increasingly involved in University matters Malkin energetically shouldered the major burden of organic chemistry teaching in the Univer- sity and was very largely responsible for building up a thriving school of teaching and research. He took an active part in many University matters; he served on the Council from 1947 to 1949 was a co-opted member of the Senate from 1951 and took a great interest in students and in student affairs as he did in the general cause of education in the South-West.In addition he found time to take an active part in the local and central activities of the Chemical Society the Society of Chemical Industry and the Royal Institute of Chemistry having at some time served on the Councils of all three bodies. In spite of all these calls upon his time Malkin was always ready to deal promptly and sympathetically with any personal difficulties of the students. In committee his contributions though typically outspoken were always good-natured and tinged with a natural sense of North-Country humour which he retained all his life. During the Second World War Malkin carried out much work in Bristol on nitration processes for the Ministry of Supply.Malkin’s own research interests naturally drew him into close contact with the Oils and Fats Group of the Society of Chemical Industry and indeed this became his major interest in his later years; he was a founder member of the Group in 1951 vice- chairman from 1956-1958 and chairman from 1958-1960 his 1960 chairman’s address “Recent Work in the Phospholipid Field”2 being his last published work. Malkin was well-known on the Continent and in parts of the U.S.A. both personally and for his work on fats and he was honoured by being President-elect of the Sixth Congress of the International Society of Fat Research to be held in London in 1962. Besides his many original papers mainly published in the Journal of the Chemical Society he was joint editor of the six volumes of “Progress in the Chsmistry of Fats and Other Lipids” published by Pergamon Press.For many years Malkin was a keen and almost the only campaigner in pressing the caus’e of research on oils and fats in this country and he continually stressed the need for the establishment of a national research institute to study all aspects of the chemistry physical properties biochemistry and physiology of these essential foodstuffs. He held the view that in spite of the many institutions on the Continent and in the U.S.A. devoted to the study of oils and fats there was urgent need to establish such an institute here. Malkin has not lived to see the founding of this institute but it is hoped that his activities to this end may some day bear fruit.Malkin bore with characteristic courage the developing cardiac trouble of his Iast few years but he was still active in his work till his sudden but peaceful passing just over two years before his normal age of retirement. Our sympathy is extended to his widow a graduate of the Honours School of English at the University of Manchester and his son Hugh Malkin a mining engineer and his daughter Isobel a doctor. In the Departments of chemistry at Bristol where he will long be missed his memory is to be retained in the annual “T. Malkin Prize,” endowed by his friends in the University and in industry. Malkin’s first work on the molecular structure and polymorphism of long-chain fatty acids and their derivatives was published with Dr.S. H. Piper in Malkin Chem. and Ind. 1961 605. PROCEEDINGS 19263 and with Piper and Professor F. Francis in 1930 and he later independently or with his own students published the results of X-ray diffraction and melting-point studies of many higher saturated fatty acids. These showed that the even-numbered acids are polymorphic and can exist in two and sometimes three different modifications. From 193 1 onwards he also published X-ray and thermal (transi- tion and melting-point) data on the ethyl esters and anhydrides of the fatty acids and discussed the structure of the polymorphic forms and the alterna- tion in melting points in even- and odd-numbered fatty acids. His chief contribution in this field was however the accumulation of X-ray and thermal data for a very comprehensive and systematic series of simple and mixed triglycerides together with other seIies of mono- and di-glycerides.The simple saturated triglycerides were investigated by Clarkson and Malkin5 who showed that they can exist under suitable conditions in three poly-morphic forms. After studying mixed triglycerides (containing two saturated acids) these workers re- investigated the simple triglycerides and found that four forms can exist; in order of increasing melting point vitreous (analogous to a glass) a-(vertical and rotating molecules) p’-and p-(tilted chains p-being the stable modification). In the course of the preparation of mixed saturated triglycerides Malkin and co-worker~~?~ prepared both the 1-mono- and the 1,3-di-glycerides.These were found to exist in three forms (K- p’- Is-) with no indication of a vitreous form whilst some 1,2-diglycerides later examined by Howe and Makin* appeared to be anomalous since only a-and /%modifications were observed. In the course of these studies Malkin and his students recorded transition and melting points and long and short X-ray spacings for all the poly- morphic forms of nine simple saturated triglycerides nine 1-monoglycerides five 2-monoglycerides nine 1,3-diglycerides and twenty-four mixed triglycerides with two saturated acids. The study of over fifty homologous saturated glycerides of these various types involved a great amount of difficult synthetical work and of physical observations by means of cooling and heating curves (thermal studies) and of long and short spacings (X-ray diffraction).The results form a mass of systematic data of the highest value in a difficult field of preparative work and physical observations. Piper Malkin and Austin J. 1926 2310. Francis Piper and Malkin Proc. Roy. SOC.,1930 A 128 214. Clarkson and Malkin J. 1934 666. Malkin and Shurbagy J. 1936 1628. ’Malkin Shurbagy and Meara J. 1937 1409. Howe and Malkin J. 1951 2663. APRIL1962 Some details of Malkin’s conclusions have not escaped criticism by workers in the U.S.A. who denied in particular the existence of a vitreous form; Malkin replied to these criticisms in an article in Malkin also studied glycerides containing un-saturated acyl groups commencing (1947) with tri- erucin trielaidin and tribrassidin2O The cis-erucic acid triglyceride gave rise to four forms (vitreous a- /?-,p-) whereas trans-elaidic and brassidic acid had only the polymorphs the p’-form being absent.Later1’ thermal and X-ray data were given for the vitreous a-,p-,and @forms of trihydnocarpin and trichaulmoogrin from the respective natural cyclo- pentenyl fatty acids. The usual four polymorphic forms were also observed12 in 2-oleodimyristin 2-oleodipalmitin and 2-oleodistearin and in 1-mono- and in 1,3-di-olein -elaidin -erucin and -brassidin. For nearly twenty years during which Malkin and his school compiled this exhaustive systematic in-formation on the polymorphism of glycerides they were almost the only workers in the field until Daubert Lutton and others in the U.S.A.began similar studies in about 1944. In the last ten years of his life Malkin became much interested in the synthesis of the phospholipids a group of com-pounds in which research centres in America Germany and this country were prominent and continue to publish important results. Malkin’s con- tributions to the synthesis of phospholipids many in collaboration with Dr. T. H. Bevan from 1951 until his death include those of (racemic) forms of the dilauroyl dimyristoyl dipalmitoyl and distearoyl members of a-and p-cephalin (phosphatidylethanol- amines),13 a series of lyso-cephalins,14 a-and /3-lecithin14 (phosphatidylchohes) and the lyso-1e~ithins.l~ A number of other syntheses included the glycol cephalins,’6 the alkyl analogues of cephalin,15 and phosphatidyl serine.ls Later synthetic work was directed towards improved syntheses of DL-di-oleoylcephalin2 and DL-diOleOyl-kCithin.He also described new syntheses of phosphatidic acids (1 955)” and of dihydrosphingosine (195 1),18 of palmitoyl~ephalin~~ (formerly supposed to be typical of plasmalogens) in 1953 and of a-batyl- and a-chimyl-cepha1inls and also @-batyl-cephalin20 (which are dihydroplasmalogens produced by hydrogena- tion of the natural plasmalogens now known to be a-vinyl ethers of p-acylphosphatidylethanolamine). He propounded (1953) a structure for the inositol phospholipid21 present in groundnuts and shortly before his death (1959) described syntheses of glycerol inositoyl phosphate and of phosphatidyl- inositol.22 W.BAKER. T. P. HILDITCH. “The Polymorphism of Glycerides,” in “Progress in the Chemistry of Fats and Other Lipids,” Pergamon Press London 1954 pp. 20-25. lo Carter and Malkin J. 1947 554. l1 Gupta and Malkin J. 1952 2405. l2 Malkin and Wilson J. 1949 369. l3 Bevan and Malkin J. 1951 2667. l4 “The Synthesis of Phospholipids,” in “Progress in the Chemistry of Fats and Other Lipids,” Pergamon Re% London Vol. IV 1957 pp. 97-139. l5 Baylis Bevan and Malkin J. 1958 2962. l6 Bevan Malkin and Tiplady J.,1957 3086. l7 Baylis Bevan and Malkin Chem. and Ind. 1955 67. l8 Gregory and Malkin J.1951 2453. In Egerton and Malkin J. 1953 2800. 2o Bevan and Malkin J. 1960 350. 21 Malkin and Poole J.,1953 3470. 22 Davies and Malkin Nature 1959 184 789; Davies and Malkin Chem. and Ind. 1959 1155. BRUCE NORMAN FEITELSON 1925-1 960 BRUCENORMAN was born in London on FEITELSON May 13th 1925. He was educated at Christ’s School Finchley and at Ashford Grammar School Kent where he showed promise of his undoubted abilities. He then studied at the University College of the South West (now the University of Exeter) where he obtained a 2nd Class Honours B.Sc. in Chemistry with mathematics as subsidiary subject. During this period he was an active member of the University Training Squadron. In 1946 Feitelson joined the Chemical Research Department of The British Drug Houses Ltd.His early work with Dr. (now Professor) W. Bradley dealt with the preparation of 3-aryloxypropane- 1,2- diols and related compounds. These readily access- ible and simple structures had shown a surprising range of biological properties. Feitelson extended the series in several directions acquiring en passant con- siderable skill in distillation techniques. In 1948 Dr. W. Bradley moved to Leeds to take up the Chair of Colour Chemistry and on the resulting reorganisation of the Department Feitelson was moved to the research team directed by Dr. 0. Stephenson under whose aegis he worked happily and productively At about this time interest had focused on methods for the synthesis of vitamin A.Feitelson’s early experience in distillation techniques proved in- valuable in this field of study in which crystalline products are the exception and not the rule. Col- laborating with Dr. 0. Stephenson he made a detailed study of the Reformatski reaction as applied to p-ionone a study which led to his first publication entitled “The synthesis of 4-hydroxy-6-2’:6’ :6’-trimethylcyclohex- 1 ’-enyl)-$-methylhex -5-en-1-yne” in the Journal of Pharmacy and Pharmacology. There after his collaborative studies covered a range of topics including the preparation of new derivatives of benzimidazole and the structural requirements for antibiotic activity in the chloramphenicol series. Restless and ambitious Feitelson sought yet a further outlet for his energies finding it in evening study for a Ph.D.degree. Ehrlich’s work on the organic arsenicals had fascinated him and he now turned to a study of 9-arsafluoreninic acid hoping thereby to find compounds of biological interest. As the corresponding antimonials eluded all efforts at preparation he extended the work to the formally related derivatives of 2-azafluorene and 2-aza-9- fluorenylideneacetic acid. These mature and capabIe studies led to the coveted Ph.D. degree which he obtained in 1952. In 1951 in order to obtain a wider research experience Feitelson applied for leave of absence in order to take up a post as research chemist at 1’Institut de arotherapie Hemopoietique in Paris He returned to England in 1954 and between the years 1954-1957 worked as a Senior Development chemist at Parke Davis and Company Hounslow.His studies covered a miscellany of chemical develop- ment problems including improvements to the manu- facturing processes for chloroamphenicol diphenyl- hydantoin and Benadryl. With his colleague Dr. D. S. Morris he was co-inventor of a new process for the preparation of N-methylphenylsuccinimide. In 1957 his affection for France took him once more to Paris to become head of chemical research and development at Les Laboratoires Cassene. He threw himself into this new appointment with customary vigour. Shortly before his death he was appointed Director of Chemical Services SociCte Normande d’Extraction et Synthese Eure. Feitelson’s range of intellectual interests was wide and he was a cosmopolitan in the best meaning of the word.A loyal companion and colleague he was equally at home “talking shop” at the bench dis- cussing music indulging in those useless but fascinating discussions on how to remodel the world or weighing up the pros and cons of ? commercial venture. He leaves a widow seven-year-old son and a baby daughter born six months after his death which came tragically when his car crashed near his place of work. V. PETROW. ADDITIONS TO THE LIBRARY Elektronen-Donator-Acceptor-Komplexe. G. Briegleb. Pp. 279. Springer-Verlag. Berlin. 1961. Notes on molecular 01bital calculations. J. D. Roberts. Pp. 156. Benjamin Inc. New York. 1961. Molecular orbital theory for organic chemists.A. Streitwieser. Pp. 489. John Wiley & Sons. New York. 1961. Determination of organic structures by physical methods. Edited by F. C. Nachod and W. D. Phillips. Vol. 2. Pp. 771. Academic Press. New York. 1962. Chemische Transportreaktionen. H. Schiifer. (Mono- graphien zu “Angewandte Chemie” und “Chemie Ingenieur Technik” Nr. 76). Pp. 142. Verlag . Chemie. Weinheim. 1962. Neuartige polarographische Methoden. H. Schmidt and M. von Stackelberg. (Monographien zu “Angewandte Chemie” und “Chemie Ingenieur Technik” Nr. 77). Pp. 97. Verlag Chemie. Weinheim. 1962. Carbohydrates of living tissues. M. Stacey and S. A. Barker. Pp. 215. Van Nostrand. London. 1962. (Presented by the authors.) Contributions to the thermodynamics of surfaces.J. J. Bikerman. Pp. 76. Published by the author. Mass. 1961. (Presented.) Solid surfaces and the gas-solid interface papers presented at the Kendall Award Symposium honoring Stephen Brunauer Division of Colloid and Surface Chemistry 139th Meeting of the A.C.S. St. Louis Mo., 1961. (Advances in Chemistry Series No. 33.) Pp. 381. A.C.S. Washington. 1961. (Presented by the publisher.) Proceedings of the Second International Congress on catalysis held in Paris 1960. 2 Vols. Pp. 2811. Editions Technip. Paris. 1961. Proceedings of the Congress of Analytical Chemistry Budapest 1961 ;held under the auspices of the Society of Hungarian Chemists. 3 Vols. (Acta Chimica Hung. 1961, Vols. 26 27 28.) eademiai Kiado. Budapest.1961. Fungicides in agriculture and horticulture papers read at a symposium organised by the Pesticides Group of the S.C.I. London 1961. (S.C.I. Monograph No. 15.) Pp. 145. Society of Chemical Industry. London. 1961. (Presented by S.C.I.) NEW JOURNALS Industrial Engineering Chemistry. Fundamentals from 1962 1. Industrial Engineering Chemistry. Process Design and Development from 1962 1. International Chemical Engineering from 1962 2. Inorganic Chemistry from 1962 1.