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Proceedings of the Chemical Society. December 1959 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue December,
1959,
Page 377-414
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY DECEMBER 1959 THE CHEMISTRY OF THE UPPER ATMOSPHERE By H. S.W. MASSEY (DEPARTMENT OF PHYSICS UNIVERSITY COLLEGE LONDON) THE upper atmosphere offers a vast photochem- ical laboratory free from solid surfaces so all reactions take place in the gas phase. At 30 km. altitude the pressure has fallen to about one-hundredth of that at ground level and we shall rather arbitrarily regard the upper atmosphere as beginning at that height. A little below 100 km. the pressure has fallen to lC3mm. Hg and is decreasing by a power of ten for every 15 km. increase in altitude. Essentially we are concerned then with the photochemistry of a nitrogen-oxy- gen mixture under low-pressure conditions in which photo-ionisation as well as photodissocia- tion plays an important part.Account must also be taken of the presence of rare constituents such as water vapour and its decomposition products including particularly hydroxyl oxides of carbon methane and strangely enough sodium. The Equilibrium between Ozone and Diatomic and Monatomic Oxygen.-The simplest photo- chemical probIem concerns the variation with height of the relative proportions of oxygen in the monatomic the diatomic and the triatomic form account being taken of photodissociation by sunlight. We can consider this problem with- out allowance for the presence of nitrogen be- cause the production of atomic nitrogen by photodissociation is very slow and its concentra- tion is never high enough to influence the oxygen reactions.The reactions which determine the equilibrium with the corresponding reaction rates are as follows The first of these is produced through the Schumann-Runge continuum the threshold wavelength being 1760 A while the second begins at 2420 A. The absorption coefficient is much higher for the first but the radiation from the 377 Sun in this short-wavelength region is absorbed quite high in the atmosphere and does not penetrate much below 100 km. On the other hand the radiation beyond 2420 8 penetrates almost to ground level (the wavelength cut-off at ground is at 2900 A). Because of these opposing factors the rate of photodissociation of mole- cular oxygen has two maxima one near 100 km.and the other near 30 km. altitude. From a knowledge of the absorption coefficient and of the incoming intensity of solar radiation in each wavelength region it is possible to determine the coefficients J2 and J2’ above as functions of height. It is only in recent years from observa- tions made with vertical sounding rockets that information about the incident intensity of solar radiation has been forthcoming and even now not over-much is known for the short-wavelength band. Rough estimates indicate that the rate of production of atomic oxygen by the process (1) is about lo7 C.C. sec.-l at its maximum near 100 km. and about five times greater for (2) near its maximum at 30 km. Of these processes the first which takes place through the Hartley continuum near 2550 A is much the stronger.Rearrangement 0 4-0 -+ 202 kl,n(03)n(0) . . . (6) Apart from the radiative recombination 0$-0-+02+hv . . . . . . (7) which we can ignore as being too slow to affect the equilibrium except at very high altitudes these are all the effective reactions. PROCEEDINGS We now have the equations for the concentra- tions of the separate allotropes At high altitudes we can ignore the ozone in considering the concentration of 0% and 0 and we find that for equilibrium This shows clearly that under these conditions as the height increases the proportion of oxygen in the monatomic form increases rapidly be- cause both n(M) and 40,) fall off rapidly with height. The calculation of the altitude at which n(0) becomes equal to 40,)depends upon a know-ledge of the magnitude of the rate coefficient kll.This is not available from direct observation but from data given for the recombination of halogeq2 of hydrogen, and of nitrogen4 atoms it appears likely that at ordinary temperatures k, is approximately cm.6 sec.-l. Using this value one finds that the altitude at which the oxygen changes from being primarily diatomic to primarily monatomic is not far from 100 km. At the transition altitude the two-body radia- tive association reaction (7) is certainly unim- portant although at sufficiently great heights it must become more important than (4). This does not affect the general argument as it is only necessary to replace kl,n(M)n(02) in (11) by [k,,n(M) + A]n(O,) where A is the rate co-efficient for (7).If photochemical equilibrium prevails then according to (1 l) the concentration of O2would fall to less than one-hundredth of that of 0 in Bates and Witherspoon Monthly Notices Roy. Astronom. SOC.,1952 112 101. a Christie Norrish and Porter Proc. Roy. SOC.,1952 A 216 152; Rabinowitch and Lehmann Trans. Faraday SOC. 1935,31,689; Rabinowitch and Wood ibid. 1936,32,907; J. Chem. Phys. 1936,4,497. Amdur and Robinson J. Amer. Chem. SOC.,1933 55 1395; Steiner Trans. Faraday SOC.,1955 31 623. Rabinowitch Trans. Faraday SOC.,1937 33 283. DECEMBER 1959 going from 100 to 110 km. and would be quite negligible at 150 km. In fact observations5 of the variation with height of the intensity of solar radiation in the wavelength region 1445-1500 A (which is absorbed exclusively by O,) showed that even at 150 km.n(03is not much less than O.ln(0). The reason for this becomes clear when account is taken of the possibilities of diffusion and mixing. At 150 km. the mean lifetime of a molecule in day-time is as long as 15 days where- as the characteristic diffusion time is less than one day.6 This shows quite definitely that at such an altitude diffusive rather than photochemical equilibrium prevails and this would account for the relatively slow decrease of diatomic concen- tration above the transition altitude. Account must also be taken of mixing due to atmospheric motion the characteristic times for which are difficult to estimate.There is great scope here for further rocket observations. A direct demonstration of the presence of atomic oxygen in considerable concentration in the high atmosphere was provided’ by a night- time rocket flight from White Sands New Mexico during which 18 lb. of nitric oxide were released into the atmosphere at a height of 105 km. This produced a pale green glow in which the peak luminous power was no less than 45 kilowatts. There seems little doubt that the light was emitted through the reactions NO+O+M +N02+M NO+O -+NOz+hV NO2+O +NO+O,’ 02’302 + hv in which the nitric oxide catalyses the recom- bination of oxygen. Turning now to the situation in the region below 100 km. in which ozone must be con- sidered we see from (10) that in equilibrium At altitudes below 70 km.we may neglect the term involving kI3 in the denominator. On substituting in (9) for n(03) we then obtain J2 being negligible in comparison with Jz’. Below about 60 km. the term kl1J3 may be neglected in comparison with k1&12n(O2) and under these circumstances This shows that we would expect the term n(03) to pass through a maximum value at some alti- tude in this range the increase of n(M)n(02)in a downward direction being overcompensated by the rapid increase of J2’,as absorption of the effective radiation becomes strong. The existence of an ozone layer centred around an altitude of 30 km. is well established; but any comparison between the distribution as given by (14) and observed results must allow for the importance of mixing.Nicolet8 has estimated that the time to attain photochemical equilibrium between 0 and 0 + 0 is about a month at 30 km. and several years at 20 km. Under such conditions there will be no appreci- able variation in ozone content between day and night. Further estimates suggest that in the alti- tude range between 40 and about 70 km. photo- chemical equilibrium can be maintained. The first measurementss of ozone concentration up to 70 km. made with rocket-borne instruments provide some support for this view. Nitrogen and the Nitrogen Oxides.-The essential difference between nitrogen and oxygen from the viewpoint of atmospheric photochemistry is the very small cross-section of the nitrogen mole- cule towards dissociation by ultraviolet radia- tion.Only one such process is known which in- volves radiation in the wavelength region from 1200to 1250 A. This is the weak predissociation Friedman Lichtman and Byram Phys. Rev. 1951 83 1025. Nicolet and Mange J. Geophys. Res. 1954 59 15. ’Marmo Pressman Aschenbrand Jursa and Zelikoff J. Chem. Phys. 1956 25 187. Nicolet “The Earth as a Planet,” ed. Kuiper Univ. of Chicago Press Chicago 1954. Johnson Purcell and Tonsey “Rocket Exploration of the Upper Atmosphere,” ed. Boyd and Seaton Pergamon Press London 1954. which was pointed out by Herzberg and Herz- berg.1° There are other processes which lead to dissociation but these involve rare constituents such as positive ions.For example we have the dissociative recombination N2++e+N' +N" . . . (16) and the reaction N2++O+NO+ +N. . . (17) which is of considerableinterest as rocket observa- tions with mass spectrographs showll that NO+ is the main positive ion in the ionosphere up to 150 km. Both of these reactions are unlikely to provide atomic nitrogen at a rate which can off' set the effect of diffusion and mixing. We are not therefore in a position to estimate the concen- tration of atomic nitrogen at any altitude. As far as observation goes it is clear from the presence of strong nitrogen bands in auroral spectra that molecular nitrogen is quite abundant at altitudes up to several hundred kilometres. Again there is no indication of any lines from atomic nitrogen in the night airglow whereas forbidden lines from atomic oxygen are prominent.It is true that N lines do occur in auroral spectra but this does not mean that atomic nitrogen is normally present. The additional exciting agents (fast electrons and protons) which produce the aurora could also produce strong molecular dissociation. Of the nitrogen oxides particular interest attaches to nitric oxide and for two reasons. One has already been mentioned. The second is that it is supposed that ionisation in the D region of the ionosphere located below 80 km. arises initially from photo-ionisation of nitric oxide.la One is forced to this conclusion by the fact that radiation capable of ionising all the major at- mospheric constituents has been completely ab- sorbed before penetrating to the 80 km.level. Nitric oxide has an ionisation potential less than t3at of any of the other important atoms and molecules and the Lyman a radiation from the sun which is short enough to ionise it could penetrate far enough. It is difficult to place definite limits on the concentration required but PROCEEDINGS it is about lo8 molecules per C.C. We are now in the interesting position that recent rocket ob- servation~~~ have shown that in the altitude range 63-87 km. the concentration cannot ex- ceed this value. The technique employed was that of absorption spectroscopy in the wavelength region 1000-3000 A. Absorption spectrograms were taken in the laboratory with NO before and after the flight (recovery of the instrument was completely successful) and used for comparison.If further work reduces the limiting concentration many more problems will be raised about the identification of the source of the D-layer ionisa- tion. It is very difficult to make any theoretical estimate of the concentration of NO the problem being at least as complicated as for atomic nitrogen. Great difficulty was experienced at first in obtaining reliable information about the com- position of the positive ions in the ionosphere using rocket-borne mass spectrographs partly because of the charging-up of the rocket during its flight and partly because of contamina- tion from rocket motor gases.During the International Geophysical Year however much progress has been made in surmounting these difficulties and similar results have been ob-tainedin both the U.S.A. and the U.S.S.R. As mentioned above it appears that NO+ ions are dominant particularly at night-time up to 150 km. at least. At first sight this seems to indicate that an appreciable concentration of NO exists at these altitudes but the fact that the reaction (17) is exothermic renders this conclusion unnecessary. The reaction N + O2+NO+ +NO . . (18) is also exothermic and may contribute appreci- ably to the production of NO+. Unfortunately we have no information about the rates of reactions (17) or (18). It is very difficult to make laboratory measurements because it is necessary to deal with ions with thermal velocities; even rough estimation by theoretical methods is out of the question at present.Little has been done in developing a theoretical approach to such problems and in any case the systems are quite loG. Herzberg and L. Herzberg Nature 1948 161 283. l1 Townsend,Johnson,Holmes and Meadows IGY Rocket Report Series Nat. Acad. of Sci. U.S.A. Vol. I p. 131. Nicolet J. Geophys. Res. 1949 54 373. l3 Jursa Tanaka and LeBlanc Planer. Space Sci.,1959 1 161. DECEMBER 1959 complex. There is opportunity here for much further laboratory and theoretical work. Photochemistry of the Night Airglow.l4-1n addi-tion to moonlight and the integrated light from the stars there is always present a weak glow from the upper atmosphere about as intense as the light from a candle 300 feet away.It is quite distinct from the very much brighter glow characteristic of aurora= in that it is regular ex- hibits relatively little dependence on latitude and involves relatively low excited states of atoms and molecules. A great deal of attention has been devoted to the study of the airglow spectrum which includes many rather remarkable features. The most intense radiation from the night sky falls in the infrared region near 10,400 A. It has been identified quite recently as arising from certain bands of the hydroxyl molecule spectrum. In the visible region the next most prominent features are the green (lS-+ “p> and red (lD -f IS) forbidden lines of atomic oxygen the yellow D lines of sodium and certain molecular oxygen bands the whole comprising a very unusual spectrum.The energy radiated in the airglow is almost certainly stored during the day as a result of dissociation and to a much smaller extent ionisation. The presence in strength of the for- bidden lines of atomic oxygen shows that some at least of the radiation must come from alti- tudes so high that collision deactivation of the upper metastable states involved is not serious. Many attempts were made to determine the height of the emitting layers from ground obser- vations of various kinds but with indifferent success. Some results have been obtained in the last few years by the use of rocket-borne detectors which indicate that the oxygen green line is emitted most strongly from a layer about 30 km.thick centred round a height of 100 km. --close to the transition level between atomic and molecular oxygen. The sodium lines were found to be emitted at a slightly lower level at 85 km. The red oxygen line exhibits a very different behaviour to the green as far as daily and seasonal variations are concerned and there is evidence that it is emitted mainly at a much greater altitude. The nature of the reactions which give rise to atoms and molecules in excited states has been the subject of much speculation. Chapmanls suggested that the source of the excitation energy for the upper state of the green line is the energy of recombination of oxygen atoms in the three-body reaction 0 + 0 + 0 + 02 + O(1S) Even if the chance of excitation at each three- body collision is quite small this seems to be a likely source of sufficient excited atoms.We know however very little about the reaction rate although the reaction is certainly exother- mic. One difficulty is that one would have ex- pected a similar reaction to supply excited O(lD) atoms and hence the red-line emission but the difference between the behaviour of the red and the green line suggests very strongly that they arise from quite different reactions. To explain the strongest airglow emission Herzberglg and Bates and Nicolet17 independent- ly suggested that atomic hydrogen plays a catalytic role through the reactions OH(X~W+ 0(3~)-+ W2S)+ 02(X3C-,) H(2S) + O3-+OH(X217,vS9) + Oz(XsZ-,) Although rare constituents are involved it is possible that the reactions are so fast that the rate of production of excited hydroxyl is great enough.One point in favour of this explanation is that there is insufficient energy available to raise the hydroxyl to a vibrational level with the vibrational quantum number v > 9 and it is a conspicuous feature of the bands in the airglow that none arises from states with v > 9. Apart from this there is little evidence with which to check these suggestions. The presence of the sodium D lines is remark- able in itself apart from any question of the re- actions which are responsible for them. We do not know what is the origin of atmospheric sodium-there is about one ton in the whole atmosphere-but it seems to be concentrated l4 Bates “The Earth as a Planet,” ed.Kuiper Univ. ofChicago Press Chicago 1954. l6 Chapman Proc. Roy. Soc. 1931 A 132 353. l6 G. Herzberg. Pasadena Symposium on Upper Atmospheric Research 1950. l7 Bates and Nicolet J. Geoghys. Res. 1950,55 301. PROCEEDINGS around an altitude of 70-80 km. Chapman1* has suggested that the reaction which leads to excitation involves NaO NaO(X2M) + O(3P)-+ 02(X3C-,) + Na(2P) There is doubt however whether this reaction is exothermic. The dissociation energy of NaO would need to be less than 3.0e.v. and the esti- mate by Bawn and Evanslg gives 3.1 e.v. Bates and Nicolet" have suggested that one should consider NaH rather than NaO allowance being made for the fact that there is atomic hydrogen present through the decomposition of water vapour.The reaction would then become NaH(XIC) + OCP) + Na(2P) + OH(X2D) This would certainly be exothermic but it is difficult to decide whether it is rapid enough there being'no way of determining the concentra- tion of NaH in the atmosphere. There is less difficulty in discussing the source of the molecular oxygen bands. They almost certainly arise from the three-body recombina- tion of normal oxygen atoms. Such recombina- tion need not produce O2 molecules in the ground 3C-,state exclusively but it can also form molecules in the ald, blC+ and A3C+ states all of which dissociate into normal atoms along attractive potential energy curves.These are the upper states of the infrared atmospheric the Kaplan-Meinel atmospheric and the Herz- berg bands of 02,so that these systems would be expected to appear in the airglow. The last two certainly do but the infrared bands fall in a wavelength region not yet studied. On the other hand estimates of the intensities suggest that the proposed source could provide far more intense bands than are naturally observed. These esti- mates are based on the assumption that the chances of forming molecules in the ground state or any one of the three excited states are com- parable. Some inhibiting factor as yet unknown may cause the ground state to be strongly favoured and so reduce the band intensities.Rare Constituents.-The photochemistry of rare but known atmospheric constituents such as l8 Chapman Astrophys. J. 1939 90 309. Bawn and Evans Trans. Faraday SOC.,1937 33 1571. H,O COz,CO CH4 and N20 has been studied by Bates and Witherspoon,l and many interest- ing conclusions have been drawn. As with other aspects of atmospheric photochemistry the work is hindered by very inadequate information on the reaction rates involved. There is an immense field here for further research of all kinds. Atmospheric Photochemical Experiments.-We have already mentioned one example of an ex- periment actually carried out in the high atmos- phere by ejection of a suitable substance in this case nitric oxide from a rocket into the ambient atmosphere.There is clearly great scope for future experiments which may lead not only to new information about the atmosphere but also about the rate of various chemical and ionic reactions in the gaseous phase. A great deal can be done by ground observation of the intensities and wavelengths of the light emitted. Any electron concentrations produced may be studied by radar reflection from a reacting cloud. Already experiments have been carried out20 in which sodium potassium and czsium vapours have been ejected at altitudes between 70 and 120 km. some in day-time during which photo- ionisation is of predominant interest some at night during which photochemical and thermal effects occur and some at twilight so that fluorescence in the light of the setting sun can be observed.These early experiments show that the technique offers much promise. A very desirable experiment would be one in which an ejected substance reacts specifically in some way with atomic nitrogen so that evidence can be obtained about the concentration of this form of nitrogen at different altitudes. Early attempts to do this have been indecisive and it is clear that rocket experiments must be coupled with laboratory investigations so that there is no confusion about the nature of the reactions involved. Concluding Remarks.-The photochemistry of the upper atmosphere is a fascinating but com- plex subject. With the expanded use of rockets as vehicles to convey instruments to high alti- tudes and to carry out experiments as explained 2o Marmo Aschenbrand and Pressman,Planet.Space Sci. 1959 1 227. DECEM~ER 1959 383 above there will be a rapid accumulation of reliable quantitative information on the rates of data which will help to clarify many issues. reactions which are unusual as far as the chemist There will always be the need however for is concerned and occur strictly in the gas phase. LETTER TO THE EDITOR Dear Sir Your new “Presentation of Papers to the Chemical Society” is excellent as far as it goes but I was disap- pointed to find no mention of one aspect of authormanship. I refer to those well-worn phrases to which we have become so conditioned that their true meanings have been submerged.In Glasgow we have issued a glossary of these expressions to our research workers and I append a few examples classified in the time-honoured tradition of the Journal. Introduction “It has long been known that . . .” I haven’t bothered to look ap the original reference. “While it has not been possible to evaluate conclusively . . .” The experiments didn’t work out but I figured I could at least get a publication out of it. Experimental “Three of the compounds were chosen for detailed kinetic study.” The results on the rest didn’t make sense and were ignored. “Microcrystalline.” Amorphous. “The reaction was carried out in the usual manner.” You just try and repeat this. Results “Typical results are shown.” The best results are shown.“Presumably at longer times . . .” I didn’t take time to find out. “These results will be reported at a later date.” I might possibly get around to this sometime. Discussion “It might be argued that . . .” I have such a good answer to this objection that I shall now raise it. “Correct to within an order of magnitude.” Wrong. “It is to be hoped that this paper will stimulate further work in the field.” This paper isn’t very good but neither are any of the others on this miserable subject. Acknowledgements “Thanks are due to James Smith for assistance with the experiments and to John Brown for valuable discussions.” Smith did the work and Brown explained what it meant. Most of these examples are taken from a compilation in the house journal of an engineering concern Messrs.Richardson Westgarth Ltd. a nice demonstration of the universal brotherhood of science. Yours faithfully Chemistry Department R. A. RAPHAEL. The University November loth 1959. Glasgow. [Professor Raphael is a braver man than I am. Nevertheless I can at least say that I shall edit future papers from Glasgow with a new confidence. He and I are both sure that readers could supply additions to the glossary.-EDITOR.] PROCEEDINGS COMMUNICATIONS The Role of Hydroperoxides in the Oxidation of Ethane and Propane at 320"~ By A. D. KIRKand J. H. KNOX (UMVERSITY OF EDINBURGH) HYDROPEROXIDES have often been postulatedl as the degenerate branching intermediates in hydrocarbon oxidation up to 400'c but in spite of extensive efforts to identify them in oxidation products it is only recently that this has been convincingly achieved by Cartlidge and Tipper2 who isolated heptyl hydro- peroxide amongst others from the products of oxidation of heptane at 270'.There is therefore still some doubt as to whether hydroperoxides are of importance above 300"~. The importance of any particular substance as a branching intermediate in an oxidation may be the hydroxyl radicals reacted with the benzene and they gave a quantitative yield of biphenyl. Thus the extent of the homogeneous reaction could be measured independently of the considerable hetero- geneous reaction which also occurred (between 30 and 90% of the total reaction). The Arrhenius parameters derived for the decom- positions of the three peroxides are given in the Table.Their lifetimes at 318" and 270" and the life- times of the branching intermediates in the oxida- tions of ethane and propane are also given. It is clear that the lifetimes of the peroxides are an order of Rate constants for RO-OH = ROO+ *OH at 280-380" lifetimes of peroxides and oxidation intermediates. Hydro-peroxide Log, A (sec.-l) E (kcal. mole-l) Et 13.4 37.7 Pri 14.5 40-7 But 13.7 37.8 critically assessed by comparing its lifetime in the proposed branching reaction with the lifetime of the real branching agent as deduced from the oxidation kinetics. It has long been thought that the slow auto- catalytic acceleration of the oxidation of the lower paraffins requires an intermediate with a lifetime of the order of a minute? This has recently been con- firmed by a more detailed analysis of the kinetics of the oxidations of ethane and propane4 which led to values of 110 and 65 sec.respectively for the lifetimes of the intermediates therein. With these values in mind we have now measured the rates of homo- geneous gas-phase decomposition of the hydroper- oxides EtO-OH PriO.OH and Bu tO.OH between 270" and 380" ROaOH +RO.+ .OH. The rates of the reactions were obtained by using a benzene carrier technique very similar to the Szwarc toluene method? A mixture of -2% of the hydroperoxidein benzene at a total pressure of about 15 mm. Hg was passed through a heated tube. Only Lifetime Lifetime (sec.) (sec.) of oxidn.of RO-OH intermeds. 318" 270" at 318" 3.6 58 Ethane 110 3.8 71 Propane 65 2.0 32 Isobutane ? magnitude smaller than the lifetimes of the branching intermediates in the oxidations. The major conclusion from the results is that ethyl and isopropyl hydroperoxides are unimportant as branching agents in the oxidations of ethane and pro- pane at 3 18". In fact the evidence must be interpreted as showing that these peroxides are never formed at this temperature. Lf they were formed the rate of branching would be much higher and the dependence of the net branching factor on hydrocarbon con- centration much steeper than is observed. One would expect that with peroxide branching the transition from negligible reaction to rapid cool-flame reaction would be very sharp with only a narrow intermediate zone of slow isothermal reaction.With ethane and propane this region of slow reaction at 320" is quite extensive and covers pressures differing by a factor of at least two? (Received October 13th 1959.) Ubbelohde Proc. Roy. SOC.,1935 A 152 354; Walsh Trans. Furaduy SOC.,1946 42 269; Hinshelwood Discuss. Furaday SOC.,1947 2 117. * Cartlidge and Tipper Proc. Chern. SOC.,1959 190. Semenov,"Chemical Kinetics and Chain Reactions," Oxford Univ. Press 1935 p. 68; Norrish Discuss. Fmduy SOC.,1951 10 269. Knox Trans.Faruday SOC.,1959,55 1362. Szwarc Proc. Roy. SOC.,1949 A 198 285. DECMEBER 1959 385 ~~ The Interaction of Cydde Ion and Cobalt(@ Complexes By H.S. NAGARAJAIAH and D. B. WAKEFIELD A. G. SHARPE (UN-IVERSJTY CAMBRIDGE) CHEMICAL LABORATORY ALTHOUGH the hexacyanoco baltate ion Co(CN),S- is usually regarded as a very stable complex ion the only recent work on the action of cyanide ion on co balt(m) complexes is Adamson’s isolation of halo- genopentacyanocobaltates from the reactions be- tween halogenopen tamminecobaltic salts and potassium cyanide.l The interaction of the ions CO(NH,),~,Co(NHd5H2O3+,and Co(NH3)$l2f (present as chlorides or nitrates) and excess of cyanidein aqueous solution has now been examined and three interesting points have emerged. Uptake of cyanide may be followed by titration of residual free cyanide by silver nitrate in the presence of ammonia and iodide (a procedure closely related to that used in the cyanide method for the determina- tion of nickel).In each case only five cyanide ions are taken up per cobalt atom even after many hours; displacement of ammonia from all three ions is com- plete however as has been shown by partition of the liberated ammonia between chloroform and the aqueous layer and potentiometric titration of por- tions of the former against standard acid. The species formed is presumably Co(CN),H,02- and further substitution in this appears to be extremely slow. The rates of the reaction with cyanide differ widely the aquopentammine and the chloropentam- mine ion react almost completely in five minutes but Adamson J.Amer. Chem. SOC.,1956,78,4260. the hexammine is not affected during a few days. In the presence of charcoal as catalyst however the reaction with the hexammine complex reaches a stage corresponding to the uptake of five cyanide ions after a few hours. In such substitutions cyanide ion is competing as an attacking entity with water and hydroxide ion and the latter has previously been believed to be the most powerfd nucleophilic reagent for attack on cobalt(@ complexes in aqueous s~lution.~?~ Cobaltic hydroxide even if freshly formed by heating solu- tions of the ammine complexes is insoluble in potas- sium cyanide solution a fact which suggests that the cyanide complexes are thermodynamically unstable towards alkali but that the reactions (like the ex- change of the hexacyano-complex with labelled cyanide4) are extremely slow.However even when the three complexes referred to are treated with a solution which is 0.05~with respect to both potas- sium cyanide and potassium hydroxide no forma- tion of cobaltic hydroxide takes place and the pentacyano-complex is produced as usual; the rate of the reaction is however considerably diminished. These experiments therefore seem to indicate that at least in certain circumstances cyanide ion may be a better nucleophilic reagent than hydroxide ion for substitutions in cobalt(@ complexes. (Received October 19th 1959.) Brown Nyholm and Ingold J. 1953,2674. Basolo and Pearson “Mechanisms of Inorganic Reactions,” Wiley New York 1958 p.124. Adamson Welker and Volpe J. Amer. Chem. SOC.,1950,72 4030. The Photolysis of Di-t-butyl Peroxide By H. M. FREY (CHEMISTRY UNIVERSITY DEPARTMENT OF SOUTHAMPTON) DURING an investigation of the addition of methyl radicals to acetylene where photolysis of di-t-butyl peroxide was used as the source of methyl radicals,lP2 appreciable quantities of neopentane were found. This led to a reinvestigation of the photolysis of the pure peroxide and the preliminary results are not in agreement with the published work. Photolyses by means of a medium-pressure mercury arc were carried out in both quartz and Pyrex vessels. In most runs 12 mm. of the peroxide were used and the temperature was in the range 20-60”~.To avoid decomposition of the acetone formed in the primary reaction photolysis was restricted in most cases to 4-2 %.Gaseous products were analysed by vapour-phase chromatography. The gaseous products found when the quartz vessel was used were methane ethane isobutane isobutene neopentane and carbon dioxide. With the Pyrex vessel ethane and a small quantity of methane were the only gaseous products. The analytical pro-cedure did not distinguish between methane and carbon monoxide though a few experiments where the gas was passed over moist cuprous chloride showed that carbon monoxide can only be a minor Dorfman and Sakburg J. Amer. Chem. SOC.,1951,73 255. a Volman and Graven J. Amer. Chem. SOC.,1953,75 3 11 1. product. Hydrocarbons containing more than six carbon atoms were not determined.To account for the yields of the various hydro- carbons in the quartz vessel it is necessary to postulate that 11% of the peroxide undergoing photolysis does so according to the equation hv (Me,C.O) -+ 2Me3C-+ 0 *...(1 1 For this reaction dH = 95 kcal. mole-l so that light of wavelength shorter than 3000 A is required. This is consistent with the formation of only ethane and methane when a Pyrex vessel is used. The following reactions can then occur Me,C. -+-Me-+ CMe kz 2Me,C. -+ CHMe + Me,C:CH k3 2Me3C-+ Me,CCMe k Me. + Me -+ C,H k Me,C-+ Me. -+ CH + Me,C:CH k The last reaction accounts for the initial formation of more isobutene than isobutane. At higher percentage decompositions this excess is reduced by the addi- tion of methyl radicals to the isobutene which is confirmed by the presence of 2,2-dimethylbutane in the products.Kinetic theory predicts that k2/k4*k,t = 2 and in PROCEEDINGS a number of similar cases this has been confirmed e~perimentally.~?~ tetramethylbutane was not As determined k4 was calculated from the yield of iso- butane on the assumption5 that k3/k4 = 4-59. A series of experiments at temperatures from 20”to 60” yielded a value for k,/k,tk,+ of 1.57 f0-03. This value seemed improbably low. It appeared that either k,/k > 4.59 or that hydrogen abstraction by the t-butyl radicals occurred to form isobutane. The latter explanation was rejected because of the known properties of t-b~tyl,~ and because the yield of iso-butane was constant throughout the temperature range.k,/k > 4-59 would be expected for vibrationally excited t-butyl radicals. Accordingly the peroxide was photolysed in the presence of carbon dioxide as an inert gas. With 12 mm. of the peroxide and 80 125 190 and 340 mm. of carbon dioxide the values of k2/k44k,# found were 1-86 1.95 1.99 and 1-98 respectively. This suggests that the t-butyl radicals are vibrationally excited and hence we calculate that k3/k4 = 7.4 for these radicals when the peroxide alone is photolysed. Further the radicals undergo between lo4 and lo5 collisions with carbon dioxide before becoming thermally equilibrated. The analyses yield an approximate value for k6/kz of 0.85 f0.1.Work is under way to enable a complete analysis of all the products to be made. It should then be possible to obtain more accurate values for the various rate constants. (Received October 19th 1959.) Knox and Trotman-Dickenson Chem. and Ind. 1959 125. Knox and Trotman-Dickenson Trans. Faruduy SOC.,1959 55 921. Kraus and Calvert J. Amer. Chem. SOC.,1957 79 5921. The Ionisation and Dissociation of Triphenyimethyl Chloride in Liquid Sulphur Dioxide By Y. POCKER OF CHEMISTRY COLLEGE, (DEPARTMENT UNIVERSITY LONDON) CONDUCTIVITY measurements of triphenylmethyl compounds in liquid sulphur dioxide indicate that the perchlorates are almost completely ionised while the corresponding chlorides are only partly s0.l Conductance in this solvent measures only free ions the concentration of triple ions being negligible2 for a uni-univalent electrolyte in a medium of dielectric constant 16.Ion-pairing however is expected to take place and while it does not contribute to the observed conductance it leads to a constant Kcond which is composed of an ionisation constant to ion- pairs K, and a dissociation constant of the ion- pairs to free ions K, as indicated below. Ph,CCl 5 Ph,C+CI-5 Ph,C+ + C1-[Ph,C+] [C1-] -KIK2 _____~ Kcond = { [Ph,CCl] 4 [Ph,C+Cl-I} 1+ K This communication presents a direct proof for the validity of this ionisation scheme by confirming Ziegler and Woolschnitt Annalen 1930 479 90;Ziegler and Mathes ibid. p. 111 ;Lichtin and Bartlett J. Arner. Chem. SOC.,1951 73 5530; Lichtin and Glazer ibid.p. 5537. Harned and Owen “Physical Chemistry of Electrolytic Solutions,” Reinhold Publ. Corp.,New York,1950. DECEMBER 1959 the concurrent existence of triphenylmethyl chloride ion pairs along with triphenylmethyl ions in one and the same solution of triphenylmethyl chloride in liquid sulphur dioxide. This is achieved by employing the spectrophotometric technique in conjunction with the common-ion mass-law repre~sion.~ When triphenylmethyl chloride is dissolved in dry sulphur dioxide the characteristic yellow colour of the carbonium ion appears to be produced instan- taneously. Spectrophotometry in contrast to con- ductance measures the free ions plus ion-aggregates rather than free ions alone.Such measurements show that at 0" a 0-1~-solution of triphenylmethyl chloride in dry liquid sulphur dioxide is ionised to about 3.2% a 0-Oh-solution to about 7.4% and a 0-001wsolution to about 21%. The addition of chloride ions in sufficient amount should suppress entirely the concentration of free triphenylmethyl ions by a mass-law effect. The concentration of tri- phenylmethyl chloride ion-pairs should on the other hand be practically unchanged except for a general salt effect on Kl. When tetra-alkylammonium chlorides are added in increasing amounts to a solu- tion of triphenylmethyl chloride in liquid sulphur dioxide there is a partial discharge of colour which reaches a limiting value. This maximum colour dis- charge depends on the concentration of triphenyl- methyl chloride and on the temperature.It provides a direct measure of the concentration of free car- bonium ions while the amount of colour left provides Pocker. J.. 1958. 240. a measure of the concentration of triphenylmethyl chloride ion-pairs. The limiting amount of colour discharge that can be achieved in a O-l~-solution of triphenylmethyl chloride at 0" is only three-fifths of the original colour so that out of a total of 0.0032 mol. of "ionised triphenylmethyl chloride" 0.00192 mol. is in the form of free ions while 0.00128 mol. is in the form of ion-pairs. Such measurements when carried out in sufficiently dilute solutions and in the absence of hydrogen chloride which is a strong electrophilic catalyst enable one to evaluate separate- ly the ionisation constant to ion-pairs Kl = 1.3 x at 0-O",and the dissociation constant of the ion- pairs to free ions K2 = 3.0 x at 0.0".Using these values one calculates the composite con-ductance constant 1@Kcond = 3.9 moles l.-l in good agreement with 4-03 the experimentally recorded value of Lichtin and Bart1ett.l Further the ion-pair dissociation constant K accords with that calculated by Lichtin and Leftin* on the basis of an assumed Bjerrum-type model and also with that quoted by them as due to Bartlett and We~ton.~ Liquid sulphur dioxide in spite of its low dielectric constant (1 5.4at O") promotes ionisation because of its high capacity for ion (particularly anion) solva- tion. Carbonium ions are not "solvolysed" by it and triphenylmethyl chloride can be recovered after removal of the solvent.(Received September 25th 1959.) * Lichtinand Leftin J. Phys. Chem. 1956 60 164. Bartlett and Weston quoted by Lichtin and Leftin ref. 4 as ONR Technical Report No. 6 under Project No. NR-056-095, Contract No. N 5 ori-76 Task XX April 10 1952. Chemical Studies of the Biosynthesis of Riboflavin By R. M. CRESSWELL and H. C. S. WOOD (THEROYALCOLLEGE AND TECHNOLOGY, OF SCIENCE GLASGOW) 6,7-DIMETHYL-8-RIBITYL-LUMAZINE(I) has been iso- lated together with riboflavin (11) from cultures of Eremothecium ashbyiil and Ashbya gossypii.2 Bio-chemical experiments support the hypothesisl~~ that the lumazine derivative is an intermediate in the bio- synthesis of riboflavin but the observation3 that only 6 % of the radioactivity of 6,7-dimethyl-8-ribityl- [2-14C]lumazine (I) added to extracts of A.gussypii is recovered in riboflavin whereas a 38% recovery of labelled carbon is possible when using the primary purine precursor adenine,2 indicates that an alterna- tive route may also operate. Birch and Moye4 sug- Masuda Pharm. Bull. (Japan) 1956,4 71 375. Maley and Plaut J. Biol. Chem. 1959 234 641. Maley and Plaut J. Amer. Chem. Soc. 1959 81 2025. Birch and Moye J. 1957,412; 1958 2622. gested that this could involve condensation of 5-amino-4-~-ribitylaminouracil (111; R = NH,) and the aldol (IV) derived from two molecules of diacetyl. Further the specific activity of the lumazine deriva- tive (I) isolated from cultures of A.gossypii after the addition of various radioactive precursors is approxi- mately the same as that of riboflavin isolated in the same experiment.2 If then 6,7-dimethyl-8-ribityl- lumazine (I) is excluded as a possible precursor in riboflavin biosynthesis these two compounds may be formed from a common intermediate. The experiments outlined below confirm Birch and Moye's suggestion. We have also shown that con- densation of the uracil (III; R = NH,) with a new trimeric aldol of diacetyl gives both 6,7-dimethyl-8- ribityl-lumazine(I) and riboflavin 0, and we suggest that this reaction could reasonably explain the results of the biochemical studies outlined above. OH MeeCO Me CN\VN Nitration of 4-chlorouracil gave its 5-nitro-derivative which was allowed to react at room temperature with a solution of D-ribitylamhe pre- pared by catalytic hydrogenation of D-ribose oxhe.Chromatography on an anion-exchange resin gave 5-nitro-4-~-ribitylao~~il (III;R =NO&which was reduced and condensed with diacetyl to give 6,7-dimethyl-8-~-ribityl-lumazhe (I) hmX. 258 275 infl. 411 mp at pH 1. A similar condensation with PROCEEDINGS the aldol (IV) gave a pteridine (V) Amax. 254 274 id. 412 mp at pH 1 (or the isomer with the substi- tuents at positions 6 and 7 interchanged). Treatment of this compound with 0-IN-sodium hydroxide gave riboflavin (II) (identified by paper chromatography and ultraviolet spectra). Diacetyl when kept for 4-5 days at room temperature in contact with an anion-exchange resin (Amberlite CG-400 OH form) underwent self-con- densation to give a crystalline aldol.* This aldol which is a trimer of diacetyl and differs from that previously described shows strong bands in the infrared spectrum (CCl solution) at 3436 (OH) and 1706 cm.-l (C=O); the structure of this aldol will be discussed in a separate paper.In aqueous solution it reacts with 4,5-diamhopyrimidine derivatives as a mixture of diacetyl and the aldol (IV) (or the related open-chain hexanetrione). Thus it condensed readily with 4,5-diaminouracil to give a mixture of 6,7-di-methyl-lumazine and 2,4-dihydroxy-7-(2-hydroxy-Z-me thyl-3 -0x0buty 1) -6-me t h ylp t eridine m.p .230-232" (lit.,4 230-232"). The latter product in 0.1~-sodium hydroxide gave lumichrome. A similar condensation with 5-amino-4-~-ribitylamhouracil (111; R = NH& at room temperature gave a mixture of 6,7-dhethyl-8-~-ribityl-lumazine (I) and the pteridine 0,which in O-1N-sodium hydroxide solu-tion gave riboflavin (II)together with unchanged (I). These compounds were readily separated by chroma- tography and identified by comparison with authentic materials. The authors thank the D.S.I.R. for the award of a Research Studentship (to R.M.C.). (Received October 12th 1959.) Diels and Jost Ber. 1902 35,3290. * This aldol also separates from some bottles of diacetyl which have been stored for long periods. The Relative Configuration of Catechin and Epicatechin 1,2-Rearrangement in the Reduction of tbe Diastereoisomers to the Same Enantiomorph of a Propan-1-01 By J.W. CLARK-LEWIS (DEPARTMENT CHEMISTRY OF ADELAIDE, OF ORGANIC UNIVERSITY SOUTHAUSTRALIA) THE single laevorotatory propanol obtained by reductive ring opening of both (+)-catechin and (-))-epicatechin tetramethyl ether with lithium aluminium hydride and aluminium chloride in tetra- hydrofuran,l followed by methylation of the pro- ducts has been found to be 2-(3,4-dimethoxyphenyl)-3-(2,4,6-trimethoxyphenyl)propan-l-olinstead of the isomeric 1,3-diarylpropan-2-01 as was rep0rted.l The racemic propan-1-01 m.p. 108" was prepared Brown and Somerfield Proc. Chern. Soc. 1958,236. Birch Clark-Lewis and Robertson J. 1957 3586. from a-(3,4-dimethoxyphenyl)-/3-(2,4,6-trimethoxy-pheny1)propionic acid by reduction with lithium aluminium hydride and the infrared spectra of the (-)-and the (f)-propan-1-01 (in CClJ were iden- tical but were distinguishable from the closely similar spectra of the isomeric 1,3-diarylpropan-2-01~.~ These 1,Zrearrangements leading to the propan-l- 01 are interesting for two reasons.First they invalidate an objection1 to current views on the DECEMBER 1959 389 stereochemistry of the catechins and secondly re- probably depends upon formation of the 3-carbon- arrangement occurs with both catechin (trans) and ium ion and subsequent 1,Zshift with retention of epicatechin (cis). The relative configuration of the configuration at the migration terminus.The catechins was established by reductive ring opening (2R)-configuration in the diastereoisomeric catechins with sodium in liquid and is supported by thus determines the configuration (2s) of the propan- independent determinations of the absolute con- l-ol formed from (+)-catechh and (-)-epicatechin figuration of (+)-catechin3 and of (-)-epicatechinY2 tetramethyl ether in l0-12% yield by reduction which assign to both diastereoisomers the (2R)-with lithium aluminium hydride and aluminium c~nfiguration.~ Formation of the propan- l-ol from chloride. the trans-compound (catechin) is unexceptional and probably occurs by concerted formation of the I thank Mr. A. G. Moritz for recording and 3-carbonium ion and 1,Zshift of the 2-aryl group commenting on the infrared spectra.with inversion at the migration terminus. Rearrange- (Received October 19tlt 1959.) ment of the cis-compound (epicatechin) however Hardegger Gempeler and Ziist Helv. Chim.Acfa 1957,40 1819. Cahn Ingold and Prelog Experientia 1956 12 81. The Crystal Spectra of Vibrationally Induced Transitions The Naphthalene 3200 A System at 4°K By D. P. CRAIG,L. E. LYONS,S. H. WALMSLEY, and J. R. WALSH OF CHEMISTRY COLLEGE, (DEPARTMENT UNIVERSITY LONDON and DEPARTMENT CHEMISTRY OF SYDNEY) OF PHYSICAL UNIVERSITY MCCLURE'S assignment of the naphthalene 3200 A of a very weak electronically allowed spectrum (f-bands to a B, tA, long-axis polarised transition 0.0002)accompanied by a stronger vibration-induced N is firmly based on the polarised absorption spectrum spectrumCf 0.002).In the crystal the electronically of naphthalene in durene.ll2 The interpretation of the allowed 0-0 band is split into oppositely polarised show that spectrum of pure crystalline naphthalene3** in har- components?~*The measurements at 4'~ mony with this or with any other assignment has the component polarised in the ac crystal plane is at however proved difficult.31,475 m.-l and that normal to the plane at The polarised spectrum of the pure crystal has 31,626 cm.-l. The latter is intensified so much that been measured at 4'~ in a Hilger large quartz spectro- it becomes the strongest of the system. Bandswhich graph E492 Previous work at 20"~has been con-in the vapour spectrum7 are built on the 0-0 with finned and extended.A number of new bands have totally symmetrical intervals show in many cases a been recorded and others resolved into components splittingin the same sense but much reduced in size at the lower temperature. By an extension of the roughly in proportion to their intensities until in the theory5 of intermolecular resonance effects to deal weakest of them no splitting is detectable. The vibra- with the special properties of transitions induced by tion-induced bands beginning with the intense 0-1 vibrational perturbation it has been shown that the at 31,960cm.-l are not signiscantly split; nor are principal structural features of the crystal absorption any that are built on them with totally symmetrical spectrum are compatible with the long-axis assign- vibrations.Their polarisation ratio* of about 4.5 1 ment and with that only. Thus the assignment in favour of the b-axis is close to the calculated B, f-A can be independently sustained from the short-axis value of 7.3 1. McClure and Schnepp spectrum of the pure crystal alone. noted the weakness of intermolecular effects in these The dominant feature of the absorption spectrum bands and suggested a general argument to account of the vapour in this spectral region6s7 is the presence for it. Mcclure J. Chem.Phys. 1954 22 1668. McClure J. Chem.Phys. 1956 24 1. Prikhotjko J.Phys. U.S.S.R. 1944 8 257. McClure and Schnepp J. Chem. Phys. 1955,23 1575. 'For references see Craig and Walsh J. 1958 1613. Herd and de Laszlo Proc. Roy. Soc. 1924 A 105,662.'Craig Hollas Redies and Wait Proc. Chem. Soc. 1959 361. * Craig and Lyons J. Chem. Phys.. 1952,20 1499. We have shown that the splitting and intensity increase in the electronically allowed spectrum can be calculated in the usual the01-y.~ The magnitudes of these quantities indicate that the transition has an octupole transition moment given by the two follow- ing components expressed in spherical harmonics the angle 4being measured in the molecular plane from the longer molecular axis. The splitting is given by the octupole-octupole terms in a manner generally similar to that discussed for benzene by Fox and Schneppg and the intensity by octupole-dipole inter- action mainly with the adjacent 2750 A system. The splitting in members of totally symmetrical progres- sions follows conventionally.1° The fact that the vibration-induced short-axis components although stronger show almost no splitting (less than 1 cm.-l) and a polarisation ratio close to that expected in the oriented gas model can be accounted for in the ordinary rigid-lattice theory of intermolecular resonance.An electronic state with one quantum of a non-totally symmetrical vibration (T has a wave function that can be written to a certain approximation as where c1 c2 c$~and 4s are electronic wave Fox and Schnepp J. Chem.Phys. 1955,23,767. loCraig J. 1955 2302. PROCEEDING s functions for the equilibrium nuclear positions and stands for the one-quantum vibration in the r-th electronic state.$s has the same symmetry as the vibronic product c$~D~(~). The contribution by the large first term representing the perturbed electronic state vanishes in all orders of the intermolecular resonance effects corresponding to the fact that the transition moment to it is rigorously zero. The small second term representing the contribution of the perturbing state alone takes part and its effect which is small in proportion to c12,can be calculated. We conclude that in a vibrationally induced system only the mixed-in electronic state contributes to the intermolecular exciton resonance. This consideration enables the structure of the relatively intense bands in the spectrum of the crystal to be analysed satis- factorily. We believe that the annihilation of the main intermolecular resonance effects in bands in- duced by non-totally symmetrical vibrations occurs widely and is the explanation of a type of "localised excitation" which has been widely invoked to account for lack of splitting and other anomalies in certain bands observed in crystal absorption spectra.This form of localised excitation occurs even in a rigid lattice; localisation may also follow lattice distor- tions. Our results and conclusions will later be published in detail. (Received October 16rh 1959.) Stereochemistry of the Bisbutadiene-Benzoquinone Adduct By RICHARD K. HILLand JAMESG. MARTIN LABORATORY UNIVERSITY N.J.) (FRICKCHEMICAL PRINCETON PRINCETON OF the five theoretically possible perhydroanthr- acenes three have been reported :l the cis-syn-cis- m.p.61" the cis-trans- m.p. 39" and the trans-syn- trans-isomer (I) m.p. 90". Of the two remaining the trans-anti-trans-isomer (IT) requires the central ring to be fixed in the boat conformation and might be expected to be the least stable of a1L2 (1) 0.IX) cco (m> *W) It appeared to us that a representative of the unknown (fifth) ring system (III) the cis-anti-cis- form might be present in the bisbutadiene-benzo- quinone adduct (IV) reported by Alder and Stein.3 These workers demonstrated that only cis-ring junctions were present in the adduct but although they believed it probable that the compound was the cis-syn-cis-isomer they produced no experimental evidence.It might be argued that the alternative cis- anti-cis-configuration would be more likely in view of the preference of dienes for adding to the less hindered side of the dienophile in cases where over- lap of unsaturation is not a fa~tor.~ That this is the case has been verified in the following manner. The adduct (IV) was converted into the bis- (ethylene thioketal) m.p. 297-300" by treatment Cook McGinnis and Mitchell J. 1944 286 and references therein. Johnson Experientia 1951 8 315. Alder and Stein Annalen 1933 501 247. Alder and Stein Angew. Chem. 1937 50 510; Stork van Tamelen Friedman and Burgstahler J. Amer. Chern SOC.,1953 75 384; Vaughan and Yoshimine J. Org. Chem. 1957 22 7. DECEMBER 1959 with ethanedithiol and the boron trifluoride-ether complex at room temperature for 15 minutes.The thioketal was simultaneously desulphurised and hydrogenated to the hydrocarbon (111) m.p. 123-124" (Found C 87-2; H 12.4. C14HF re- quires C 87.4; H 12.6 %) by Raney nickel in boiling ethanol. Isomerisation at the ring junction during formation of the thioketa15 appears unlikely for the following reasons (a) The similar conversion of the trans-syn-trans- diketone obtained by treatment of the adduct (IV) with alkali3 proceeds with retention of configuration to yield the hydrocarbon (I) identical with an authentic sample obtained from Dr. J. W. Cook. (b) The adduct (IV) with 2-mercaptoethanol and the boron trifluoride-ether complex forms a bis-hemithioketal which on hydrolytic desulphurisation with Raney nickel in boiling ethanol,6 gives the same saturated diketone as is obtained from the adduct (IV) by catalytic hydr~genation.~ (c) At room temperature for two hours the adduct is unaffected by the boron trifl uoride-ether complex although at 45" it is isomerised to the cis-trans-diket~ne.~ 391 Since the ring junctions are also unaffected during the desulphurisation the adduct must have the same cis-anti-cis-skeleton as the new perhydroanthracene.A similar steric result for the cyclopentadiene-benzo- quinone addition has been demonstrated recently by Winstein and his co-workers.' In spite of the fact that alkali quickly isomerises the adduct (IV), it was possible to isolate from it on Huang-Minlon reduction the corresponding diene m.p.94-96' (Found C 89.0; H 10.7. CI4Ha0 requires C 89.3; H 10.7%) in 15y0 yield accom- panied by an oily mixture of other isomers. Hydro- genation of this diene yielded the hydrocarbon (IIL) and dehydrogenation over palladised charcoal gave anthracene. The four perhydroanthracenes have diagnostically different infrared spectra in carbon tetrachloride solution. A Fellowship to J.G.M. from the Danforth Foundation is gratefully acknowledged as is the kindness of Drs. J. W. Cook and J. D. Loudon in providing us with samples of their three perhydro- anthracenes. (Received November 3rd 1959.) Stevenson and Fieser J. Amer. Chem. SOC.,1956 78 1409; cf. however Sondheimer and Rosenthal ibid.1958 80 3995. Rorno Rosenkranz and Djerassi ibid. 1951 73,4961. 'de Vries Heck Piccolini and Winstein Chem. and Ind. 1959 1416. We are grateful to Professor Winstein for communicating his results to us before their publication. The Stereochemistry of Lumisantonin By D. H. R. BARTON and P. T. GILHAM (IMPERIALCOLLEGE S.W.7) LONDON LUMISANTONIN~~~~~ has the constitution (I).2*3 We now report experiments to show that lumisantonin has the stereochemistry depicted also in (I). Oxidation of dihydrolumisantoninic acid1 with chromic acid gave the diketo-acid (II) m.p. 190-192" [u] -91" (all rotations in CHCI,) Amax. 220 and 292 mp (E 5900 and 190respectively; all ultraviolet spectra in EtOH). By analogy with the ready reduction of the system -COC= C-CO- to -COCHCHCO- we expected that a cyclopropane ring could replace the ethylenic linkage [see (XI); arrows].In the event reduction of the acid (11) with a zinc-copper couple in acetic acid at 100" gave the diketo-acid (111) m.p. 110-113" [a] + 5". Further reduction of this with excess of potassium borohydride furnished an acid which spontaneously lactonised. Oxidation of this lactone then gave the desired keto-lactone (VI) m.p. 130' [u],-53" infrared bands at 1770 (7-lactone) and 1710 (cyclohexanone) cm.-l (all infrared data in CHCI,). The stereochemistry of the ring junction in the product (VI) was established by comparison of the rotatory dispersion curve4 {single Cotton effect negative trough5 near 310 m,u ([MI 2400")) with that6 of friedelin' (IX) to which it is analogous.The dispersion curve also corresponded but with inver- sion of sign to the mirror-image type chromophore6 of a-tetrahydrosantonin (X). The configuration of our product (VI) at C(*) is regarded as u (equatorial) Cocker Crowley Edward McMurry and Stuart J. 1957 3416. Arigoni Bosshard Bruderer Biichi Jeger and Krebaum Helv. Chim. Acta 1957 40 1732. a Barton de Mayo and Shafiq Proc. Chem. Soc. 1957 205; J. 1958 140. Djxassi Bull. SOC.chim. France 1957 741 and references there cited Djerassi and Klyne Proc. Chem. Soc. 1957 55. Djerassi Riniker and Riniker J. Amer. Chem. Soc. 1956 79 6362. Brownlie Spring Stevenson and Strachan J. 1956 2419; Corey and Ursprung J. Amer. Chem. Soc. 1956 78 5041;see also Dutler Jeger and Ruzicka Helv.Chirn. Acta 1955 33 1268; Ourisson and Takahashi Chem. and Id., 1955 1155. because this lactone was not isomerised on treatment with s sodium hydroxide on the steam-bath for 1 hour. If we assume that reduction of the acid (111) with potassium borohydride does not invert the con- figuration at C(al we can also regard this centre as cc in (III). PROCEEDINGS 26" in the same solvent mixture N in sodium hydroxide (d[MI + 166").The comparable figures for (IV) were + 34" and -130" (d[MI -164"). The configuration at position 4 in lumisantonin was determined in the following way As already reported lumisantonin gives the lactones (VTI) on 1 H2-Pd; OH-; CrO,. 2 2n-Cu-AcOH. 3 KBH,; CrO,. 4 MeO-. 5 KBH,; CrO,.6 H-Br; pyridine. Treatment of the diketo-acid (III) with sodium hydroxide on the steam-bath for one hour gave a non-crystalline isomer 0.On reduction with potas- sium borohydride and further processing as in the synthesis of (VI) (see above) this afforded a second crystalline keto-lactone m.p. 166" [a],+ 5" infra-red bands at 1770 (y-lactone) and 1710 (cyclo-hexanone) cm.". This is formulated as (IV) for it also showed rotatory dispersion {single Cotton effect negative trough near 310 mp ([MI3800) comparable with that of 0.The epimerisation of the side chain of the acid (III) by base is an expected process. Thus the stereochemistry of (III) requires that the side chain be axial. The configurations at position 6 in lactones (IV) and (VI) are based on the shift of rotation observed on ring opening in alkalf.8Thus the lactone (VI) had [MI -140" in 1 :1 dioxan-water shifted to [MI + treatment with hydrogen bromide and then pyridine.In (VII) the configuration of lumisantonin at posi- tion 4 is preserved unchanged. The rotatory dis-persion curve of (VIJ) (single Cotton effect negative trough near 330 mp ([MI 5700")) is of enantiomeric type to that (single Cotton effect positive peak near 330 mp ([MI 4800")) of the model steroid@ (VIII) and hence the configurations at C(a already given in formula:(I) and (11) must hold. The 3,4-and 1,s-bonds in lumisantonin must be cis to each other since the dicarboxylic acid (XI) readily forms an anh~dride.~ This then defines completely the configuration at position 5.The 6- 7- and 11-centres are not involved in the lumigenesis of lumisantonin from santonin.10 The stereochemistry of lumisantonin shows that the light-induced bond-crossing process involved in Klyne Chem. andInd. 1954 1198. *St. Andrk MacPhillamy Nelson Shabica and Scholz J. Amer. Chern. SOC.,1952 74 5506; Sondheimer and Burstein Proc. Chem. SOC.,1959 228. lo Barton Pruc. Chem. Suc. 1958 61; Helv. Chinz. Actu in the press. DEC~MBER 1959 its formation causes inversion at position 10. A com-parable result is observed in the formation of photo-dehydroergos tero1.l’ Satisfactory analytical data have been secured for all new compounds. We thank Dr. W. KIyne (Postgraduate MedicaI School) for his kindness in measuring the rotatory dispersion curves and for his helpful comments on their interpretation.We are indebted to Dr. F. SonQheimer (Rehovoth) for the ndel compound (VIII). One of us (P.T.G.) acknowledges with gratitude the award of an I.C.I. Fellowship. (Received October 22nd 1959.) l1 Barton and Kende J. 1958 688; Barton Bernasconi and Klein J. in the press. The Structure of Bassic Acid By T. J. KINGand J. P. YARDLEY (DEPARTMENT UNIVERSITY OF CHEMISTRY OF NOTTINGHAM) BASSICacid a trihydroxy-triterpene acid C30H4605 to be an aldehyde and thus the isopropylidene group was first obtained pure and investigated in detail by Kon and his collaborators1 who assigned to it the structure (I). Recently2 it was suggested that the experimental results on which this structure was based could be re-interpreted and did not exclude a 2,3,23(or 24)-tri- hydroxy-structure and that there were no conclusive reasons for the oleanane skeleton assignment.n -\ H0.H2C We have re-investigated the chemistry of bassic acid and have been able to establish that the struc- ture is 2/l,3~,23-trihydroxyolea-5,12-dien-28-oic acid 01). Contrary to earlier findings methyl bassate re- acts quantitatively with periodate and lead tetra- acetate and the crystalline product is identical with the periodate fission product of methyl anhydro- terminolate3 and can thus be formulated as (111). This result proves the complete structure of bassic acid except the stereochemistry at positions 2 and 3 which has been established as follows.Methyl bassate readily forms an isopropylidene derivative which can be oxidised to an 0x0-derivative. Reduction by a modified Huang-Minlon procedure and removal of the isopropylidene group then give deoxybassic acid. The 0x0 derivative [partial struc- ture (IV)J was shown by proton magnetic resonance must bridge the oxygen functions which must be at positions 2 and 3; this deduction is confirmed by quantitative oxidation of methyl deoxybassate by periodate. Thus the 2- and 3-oxygen functions must have a cis-orientation i.e. the secondary alcoholic groups must be both 01 or both 18. Djerassi has pointed out5 that no steroidal 2a,3a-diols have yet been observed in Nature so the probability is that bassic acid has the 2/3,3/3-structure.This has been confirmed by the reduction of the diketone (partial structure V) obtained by oxidation of the bromo- lactone of deoxybassic acid. The diketone (V) which is yellow and gives a derivative with o-phenylenediamine is reduced by potassium borohydride a reagent known to give predominantly p-alcohols from 2- and 3-0x0-steroids and triterpenes,6 to regenerate deoxybassic bromo- lactone. This observation establishes that this compound and hence bassic acid have the 2/!?,3p-configuration Identities have been established by mixed m.p. and by comparison of infrared spectra. We thank Dr. L. M. Jackman for the proton magnetic resonance measurements. (Received November 11 th 1959.) l Heywood Kon and Ware J.1939 1124; Heywood and Kon J. 1940 713. Simonsen and Ross “The Terpenes,” Cambridge Univ. Press 1957 Vol. V pp. 139-147. King and King J. 1956 4469. Slates and Wendler Chem. and Ind. 1955 167. Djerassi Thomas Livingston and Thompson J. Amer. Chem. Suc. 1957 79,5292. * See for instance King King and White J. 1958 2830; Dauben Blanz JU~. Jiu and Micheli J. Amer. Chem Soc. 1956 78,3752. PROCEEDINGS ~~~~ ~ ~~~~~~ ~ Conformation of DimethyIpiperazine in its Palladous Chloride Compound By 0.HASSEL and BERIT F. PEDERSEN (DEPARTMENT OSLO) OF CHEMISTRY RIE UNIVERSITY AVAILABLE analyses of piperazine and its 1,4-deriva- tivesl clearly indicate the greater stability of the chair than of the boat form of the six-membered ring.If a stable bridge is established however between the nitrogen atoms stabilisation of the boat form is of course possible. Chemical results make it probable that this is the case in the com- pound formed by dimethylpiperazine and palladous chloride. In other compounds formed by piperazine or its derivatives endless chains of alternating amine and metal halide molecules may be expected in which the former exhibits the chair form. X-Ray analysis of the solid PdCl,-dimethyl-piperazine compound shows that the six-membered ring is in the boat configuration The crystals are monoclinic (space group P2Jc) with 4 molecules in the unit cell The parameters are a = 7-61A; b = 11.09 A; c = 12-78A; fl = 111" The co-ordinates of palladium and chlorine could be determined more accurately than those of the lighter atoms but it may be stated with confidence that the two nitrogen atoms are situated in the plane containing the palladium and the two chlorine atoms and that the six-membered ring is in the boat configuration (see Figure).The bond distance Pd-Cl is 2.30 A the Pd-N distance 2-00A. The angle CI-Pd-C1 is 92.3' the angle N-Pd-N 71.8". (Received October 26th 1959.) Andersen and Hassel Acta Chem. Scand. 1949 3 1181 and later (unpublished) electron-diffraction data. Mann and Watson J. 1958 2772. a-Elimination and Carbene Formation from Silicon Compounds By R. N. HASZELDINE and J. C. YOUNG (FACULTY THEUNIVERSITY OF TECHNOLOGY OF MANCHESTER) THE compounds CHFClCF,.SiCl (I) and CFCl,CF,.SiCl (11) are prepared as follows hv Cl,,hv SiHCl + CF,:CFCl -+ (I) +(11) and rigorous proof of structure has been obtained in several ways which will not be discussed here.As part of a general study of the thermal reactions of silicon compounds the halides (I) and (11) were pyrolysed in sealed glass tubes at 250". The major organic product was an olefin formed by rearrange-ment of the fluoroalkyl group Pa CHFC1CF2*SiC13-+CHF:CFCl Pa CFCl,*CF2.SiCI -f CFCl:CFCl The reaction gave only small amounts (< 10% of the total organic product) of the olefins CF,:CHCl and CF, CCl, which would result from elimination of fluorine from the p-position with respect to silicon. The primary step in the pyrolysis is considered to be an internal nucleophilic attack on silicon by a fluorine in the a-position (cf.A) followed (or pos-sibly accompanied) by migration of an atom other I/ -C-SiT 'F' (A) than fluorine from the /%carbon atom. In the limiting case such an a-elimination of fluorine would produce a fluoroalkylcarbene (methylene) e.g. CFCl,CF2*SiC13-+CFCl,.CF + SiFCl The fluoroalkylcarbene reactions CFC12-CF -+ CFCl :CFC1 CHFCI-CF -+ CHF :CFCI are in accord with the rearrangements CF,*CH +-CF, CHF c,F,-CH -f CF :CH-C,F reported e1sewhere.l (Received November 12th 1959.) Fields and Haszeldine Proc. Chem. Soc. 1959 in the press. DECEMBER 1959 395 Vinyl Ethers from the Reaction of Decalia with Friedel-Crafts Acylating Agents By M.S. AHMAD,G. BADDELEY and J. W. RASBURN B. G. HEATON (MANCHESTER COLLEGE OF SCIENCE AND TECHNOLOGY) As far as we know no vinyl ether has previously been reported as oxygenantaining product of the interaction of Friedel-Crafts acylating agents and hydrocarbons. We now find that reaction of decalin with acetyl chloride and aluminium chloride under the mildest conditions compatible with a convenient rate of reaction gives 10-vinyl-trans-decalin 1 ,1'-oxidel 0. co -(i) 10-Acetyl-cis-1-hydroxy-trans-decalin (VIII) m.p. W5",obtained by gentle acid hydrolysis regenerates (VII) when heated. (ii) 1&Acety1-trans-1-br omo- trans-d ecalin (IX) obtained by action of hydrobromic acid on the ether (VII) is more readily solvolysed in 90% aqueous acetone than is t-butyl bromide; the product is the alcohol 0and the reaction which doubtless in-t CH,*COCl CH,CHO t HCI H,C-C 4--@ Without doubt d9-octalin is first formed and we suggest that thereafter addition of acetyl cation gives the cation (I) which is highly strained and so rearranges that the four-membered heterocycle be- comes five-membered; loss of a proton at thisstage provides the vinyl ether (VII).The action of hydro- gen chloride and aluminium chloride on the ether (VII) followed by addition of water gives 10-acetyl-cis-2-hydroxy-trans-decalin (IV); apparently re-arrangement effects the further ring enlargement (I1 -+ III)? Rearrangements analogous to (I -+ I1 -+ III) readily account for the products of reaction of cyclo- hexene with benzoyl chloride and aluminium chloride which include 4-chlorocyclohexyl phenyl ketone or after addition of benzene phenyl4-phenyl- cyclohexyl ketone? Study of the vinyl ether (VII) has provided several remarkable reactions Cf.Baddelev and Wrench. J.. 1959. 1324. / OH (VIII) H (VI I) volves the cation (II)as intermediate and subsequent attack by a water molecule at the carbonyl carbon atom is as far as we know the first example of the displacement of halogen by a ketonic oxygen atom. (iii) Reaction of the ether 0with perbenzoic acid gives the hydroxy-&lactone (VI) and the Corres- ponding keto-lactone (V) ;these 8-lactones together with the expected y-lactone are obtained also by ozonolysis. Reaction of decalin with propionyl and isobutyryl chloride gives respectively the mono- and the di-methyl derivatives of the ether (VII).Benzoyl chloride on the other hand gives 10-benz0y1-d~:~- octalin and other products. We thank the Department of Scientific and In-dustrial Research for a maintenance grant to B.G.H. (Received October 26th 1959.) Cf. Noyce ahd Weingarten J. Am&. Chem. SOC.,1957,79 3098. Stevens and Farkas ibid. 1953,75 3306. PROCEEDINGS The Steric Effect of the Trifluoromethyl Group By D. MURIEL M. HARRIS HALL and MARGARET (BEDFORD LONDON, COLLEGE N.W. 1) 2,2'-BISTRIFLUOROMETHYLBENZIDINE first prepared by Cartwright and Tatlow,l has now been obtained optically active and its racemisation rate determined in ethanolic solution at 39" (k = 1-98 x sec.-l; half life 58.4 min.).The hydrogen tartrate of the (&)-base was prepared in 96 % ethanol and allowed to crystallise while maintained at temperatures of not less than 50"; it underwent asymmetric trans- formation by crystallisation (second-order asym- metric transformation) 96% of it crystallising as a singIe diastereoisomeride with [a]::;; -20.5" in acetone (Found C 42-6; H 3.8; N 4-7. C22H220,2N2F6 requires C 42.6; H 3.6; N 4.5%). This salt treated with aqueous ammonia below lo" gave the (-)-base m.p. 182-184" with ct5461 39.0 -0.84" (C 3-23in EtOH) when first Observed (Found c 52.1; H 3.0; N 8.8; F 35.0. C14H10N2F6 requires C 52.5; H 3.1; N 8.8; F 35.6%). The steric effect of CF is of particular interest Cartwright and Tatlow J.1953 1994. * Theilacker and Hopp Chem. Ber. 1959.92 2293. * Lesslie and Turner J. 1932 2021. since this group is of the structural type AX, and thus resembles CH, SO,Ph NMe3+ CMe, and AsMe,+. In effective size it probably falls between CH and S0,Ph. So far the only 2,2'-dimethylbi- phenyl (unsubstituted in the 6,6'-positions) reported to be optically active is 2,3,2' 3'-tetramethyl benzid- he2 in which the blocking methyl groups are buttressed and thus are not suitable for comparison with the trifluoromethyl groups in the present com- pound. A better comparison may perhaps be made between our compound and Lesslie and Turner's diphenyl benzidine-2,2'-di~ulphonate~ with blocking groups-SO,Ph which retained its full optical activity for 3 days at room temperature but racemised rapidly at 100".Quite small ortho-substituents have a profound steric effect on the ultraviolet absorption spectrum of biphenyl and as expected two ortho-trifluoromethyl groups have been found4 to inhibit almost com- pletely the normal biphenyl absorption. (Received October 20th 1959.) Ross Markarian and Schwarz J. Amer. Chem. SOC.,1953,75,4967. Copper and Silver Ethynyl Go-ordination Complexes By D. BLAKE, G. CALVIN,and G. E. COATES (CHEMISTRY THE UNIVERSITY DEPARTMENT, SOUTHROAD,DURHAM) ALKYL-and ARYL-ETHYNYLCOPPER(1) compounds (RCiCCu) are usually obtained as bright yellow to red precipitates insoluble in all solvents with which they do not react.The colourless silver analogues are also insoluble but dissolve to a small extent in inert solvents when R is butyl or a higher allcyl. We regard etc. B etc. these compounds as co-ordination polymers (I) in which there is substantial back co-ordination from filled metal d orbitals to the anti-bonding orbitals of at least two acetylene groups bound to the metal (resulting in near-neutrality of the metal). This should be possible because the anti-bonding acetylene orbitals present a n-aspect to the metal whether end- on or sideways. Additional bonding between layers is to be expected if polymer chains are so placed that acetylene groups lie above and below copper atoms. We have found that for example propynylcopper is unaffected by pyridine bipyridyl o-phenanthrol- ine triethylamine or various other donor sub- stances but readily dissolves in a toluene solution of triethylphosphine forming a yellow crystalline com- plex Et,PCuC i CMe.Evidently a strong donor with back-co-ordinating properties is required to compete with acetylene groups and thereby break down the co-ordination polymer. Pheny le t h y ny1-copper and -silver afford simi lar complexes Et,PCuC i CPh m.p. 138.5-1 39.5" Et,PAgC i CPh m.p. 77-5-78-5" Et,AsAgC jCPh m.p. 89". Phenylethynylsilver in contrast to MeC iCAg dissolves in various amines and with isopropylamine yields an unstable complex DECEMBER 1959 PriNH,AgC iCPh which quickly loses amine on exposure to air.In contrast to (monomeric) Et,PAuC i CPh in which the gold has the co-ordination number two typical of gold(I) in general the copper and silver phosphine complexes would be co-ordinatively un- saturated if monomeric. The degree of association of this copper compound determined cryoscopically in Ph &< E~,P-A[ Pg-PEt \m Nast and Pfab Chem. Ber. 1956 89 415. nitrobenzene is three and it is between 3.3 and 3.8 in benzene whereas that of the analogous silver complex is two in nitrobenzene and 2.6-2.7 in benzene. A structure (in solution) such as (11) seems likely. An ammine of phenylethynylcopper( I) (PhC i CCuNH,), has been prepared by reactions in liquid ammonia. It reverts to polymeric PhC i CCu in a stream of nitrogen and its molecular complexity is not kn0wn.l We thank the Department of Scientific and Industrial Research for maintenance grants (to D.B.and G.C.). (Received November 5th 1959.) The Polymerisation of Methyl Methacrylate Initiated by Alkylboron Compoumls By C. E. H. BAWN,D. MARGERISON and N. M. RICHARDSON (DEPARTMENT AND PHYSICAL UNIVERSITY OF INORGANIC CHEMISTRY OF LIVERPOOL) SEVERALworkers1 have observed initiation of polymerisation of vinyl monomers by alkylborons in the presence of oxygen. Because of the failure to appreciate the importance of oxygen in the initiation process many of their observations are not strictly definable in terms of the reaction variables. Although results2 showed the presence of traces of oxygen to be essential for initiation no explanation of its function was advanced.We now summarise our rate data for the polymerisation of methyl methacrylate in benzene at 25.0" and 48.2",obtained by using various concentrations of tributylboron together with controlled variations in the oxygen content of the polymerisation mixture. A solution of tributylboron in benzene was pre- pared by a method analogous to that of Johnson Snyder and Van Cam~en.~ Oxygen was passed through a portion of this solution with the con- sequent formation of the peroxide dibutyl(buty1- peroxy)boron as reported by Davies and Abraham.4 The concentration of this peroxide was estimated iodometrically after the excess of molecular oxygen had been displaced by oxygen-free nitrogen.Polymerisation mixtures consisted of known amounts of tributylboron the peroxide methyl methacrylate and benzene and rates of polymerisa- tion were measured dilatometrically. In most of the experiments the rate decreased slowly with time the decrease becoming more pronounced at later stages in the polymerisation. By appropriate choice of the initial concentration of tributylboron and the time of oxygenation the influence of the concentra- tions of tributylboron and the peroxide on the initial rate of polymerisation was found. In addition varia- tion of the initial rate with monomer concentration and temperature was investigated. The results are summarised in the experimental rate expression (Rplinitial = (-d [M I/dt)initial = kobs[RSB] [R2B*O*OR]t[ where kobs -3 x lo6 exp (-12,900/RT) M] 1.mole-1 sec.-l M = CH2:CMeC02Me and R = Bun.Accepting the arguments of Fordham and Sturm6 and Ashikari and Nishimora6 that the polymerisa- tion is a chain reaction with free-radical carriers we suggest that the mechanism is as shown in reactions ( 1)-(4). Application of the usual steady-state treatment produced the observed rate expression provided that the concentration of the methyl methacrylate-tri- butylboron complex was equated with the initial con- centration of tributylboron-an assumption which Kolesnikov and Sobokva Khim. Nauk i Prom. 1957 2 663; Izvest. Akad. Nauk S.S.S.R. Otdel khim. Nauk 1958 242; Furukawa Tsuruta and Inoue J. Polymer Sci.,1957 26 234; Kolesnikov and Klimentova Itvest Akad.Nauk S.S.S.R. Otdel. khim. Nauk 1957 652; Ashikari J. Pofymer Sci. 1958 28 250. Furukawa and Tsuruta J. Polymer Sci. 1958 28 227; Kolesnikov and Fedorova Izvest. Akad. Nauk S.S.S.R., Otdel khim. Nauk 1958 906. Johnson Snyder and Van Campen J. Amer. Chem. Sue. 1938 60,115. ' Abraham and Davies Chem. and Ind. 1957 1622 J. 1959,429. Fordham and Sturm J. Polymer Sci. 1958,33 503. Ashikari and Nishimura J. Polymer Sci. 1958 31 249. PROCEEDINGS (1) R3B + M + RSB,M Complex formation (2) R3B,M + R,B*O*OR4 RsB,MRO. + R2B.O. Initiation R,B,MRO-+ M +MI* Propagation (3) R2B.0. MI*+ M +M,. etc. (4) M,* + M,* -+ M& or Mz+ M Termination implies that equilibrium (1) lies well to the right and was rapidly maintained.We suggest the participa- tion of such a complex in our scheme to account for the wide divergence of kinetic behaviour with this particular initiating system between one vinyl mono- mer and another. The most important step in the above scheme is reaction (2) since it is from this bimolecular reaction that the initiating species are produced. Further evidence in favour of such a bimolecular reaction is that neither tributylboron nor the peroxide alone initiates the polymerisation of methyl methacrylate in benzene. In conclusion it seems to us that the role of oxygen in these polymerisations is simply to convert a part of the trialkylboron into a peroxide which then re- acts with unoxidised triallcylboron to produce initiating free radicals.In the absence of a polymeris- able monomer analogous reactions no doubt take place with the production via radical intermediates of compounds such as dibutyl butylboronate and butyl dibutylborinate. (Received November 18th 1959.) The Structure of Altenraric Acid By J. R. BARTELS-KEITH GROVE and JOHN FREDERICK INDUSTRIES LIMITED,AKERSRESEARCH (IMPERIAL CHEMICAL LABORATORIES WELWYN,HERTS) ALTERNARIC an ACID C21HS008,antifungal and phytotoxic metabolite of Alternaria solani Ell. and Mart. Jones and Grout contains two hydroxyl groups one carboxyl group and one p-dicarbonyl function? It gives carbon dioxide on acid hydro- lysis and acetone and acetaldehyde on alkaline hydrolysis and the structure has now been elucidated as (I; R = H).Alkaline hydrogen peroxide oxidises alternaric acid to the dicarboxylic acid (II; R = which ye ?H ?ti FH2 R = Me) is oxidised by potassium permanganate to the ester (III). The acid (LI; R = H)is cleaved by lead tetra-acetate to (+)-a-methylbutyraldehyde, carbon dioxide and 5-methyleneoct-2-enedioicacid (IV) whichis isomerised in hot alkali to the 5-methyl- acid (V). Ozonolysis of the acid (IV)gives formalde- hyde succinicacid and la=vulic acid and hydrogena- tion followed by pyrolysis of the product (as its thorium salt) gives 4methylcycloheptanone. Alternaric acid and its derivatives have ultraviolet Me I EtCH .CH-$-CH :CH*CH2*C.CH,-CH2C0,R (n) HO,C-CH :CH CH :C*CHiCHiCO,H CO,R (V) like alternaric acid readily consumes 1 mol.of absorption maxima near 210 and 270 mp in acidic periodic acid giving (+)-a-methylbutyraldehyde. and near 250 and 270 mp in alkaline media.l This The 00-isopropylidene derivative of the ester (II; behaviour recalls that of 2-formyl-5,5-dimethylcyclo-Grove J. 1952 4056. a Bartels-Keith,J. in the press. DECEMBER 1959 399 hexane-1 ,3-diones (VI) and indicates the presence of succinic acid lavulic acid and p-hydroxybutyric- a tricarbonylmethane system in alternaric acid. The acid. Methyl alternarate (I; R = Me) like the ester infrared spectra of alternaric acid and its derivatives (11; R = Me) gives an 00-isopropylidene derivative all contain a band near 1710 cm.-l indicating that which on permanganate oxidation gives the half- the unbonded carbonyl group of the chromophore is ester (111).These findings are consistent only with present in an ester or lactone group. structure (I; R = H) for alternaric acid. Ozonolysis of alternaric acid gives formaldehyde (Received November 12th 1959. Akehurst and Bartels-Keith J. 1957 4798. Anionic Polymerisation of Styrene By C. STRETCHand G. ALLEN (DEPARTMENT UNIVERSITY OF CHEMISTRY OF MANCHESTER) postulated that the polymerisation of by measuring the total iodide ion produced when SZWARC~ styrene by sodium naphthaIene involves electron excess of methyl iodide was added to the solution. transfer to styrene dimerisation of the radical-ion Polymerisations were carried out in dioxan at room thus produced and growth of the di-ions by addition temperature under conditions similar to those of monomer.It follows that the degree of polymerisa- described by Morantz and Warhurst2 in their study tion should be given by of the reactivities of sodium complexes. The poly- 2 x (Moles of styrene reacted) . . .(1) styryl anions were terminated by the addition of D.P. = Moles of complex water or benzoic acid. Molecular weights were This reIation does not appear to have been determined by the light-scattering technique and by quantitatively verified. viscometry in benzene at 25” (we assumed3 [q] We have found accurate determination of this very = 1.12 x 104M0-73).Measured molecular weights reactive complex to be difficult. Owing to side- were 0.80-0-95 of the values calculated from equa- reactions and an incomplete primary reaction be- tion (I) showing that chain termination and transfer tween the metal and hydrocarbon estimates of con- reactions were absent or unimportant.A typical run centration of complex are wrong if based on the gave the following results total amount of sodium or naphthalene and Complex = 2-87 x 10-5mole benzoic acid does not react stoicheiometrically with Styrene = 1-63 x 1W2 mole the complex. Methyl iodide was finally used to M calc. from equation (1) 1.18 x lo5 standardise the sodium naphthalene solution by M, calc. from viscometry (1-03 005) x lo5 titration Na+ CloH8-+ RX-+Na+ + X-+ R-+ M, calc. from light scattering (1.04 & 0-05) x 105 CloHs,and the validity of the method was confirmed (Received November 16th 1959.) Szwarc Nature 1956,178 1168; Szwarc Levy and Milkovich J.Amer. Chem. SOC.,1956,78 2656. Morantz and Warhurst Trans. Faraday SOC.,1955,51 1375. Green J. Polymer Sci. 1959 34 514. The Application of the Stopped-flow Method to the Study of the Dissociation of Some Nickel Complexes By A. K. SHAMSUDDIN AHMEDand R. G. WILKINS (THEUNIVERSITY, SHEFFIELD) JANNIK BJERRUMand his co-workers1 studied actionsa and the results together with those for the amongst other reactions the rates of dissociation of racernic 2,3-diaminobutane (“butylenediamine”) nickel complexes of ethylenediamine in methanol at complexes are shown in the Table. In view of the low temperatures. The results were extrapolated to preliminary nature and the experimental difliculties 0” and are shown in parenthesis in the Table.We of the methanol work our agreement is as good as have now measured these rates in aqueous solution can be expected. The optical densities (at 520 mp of directly using the stopped-flow method for fast re- the tris- bis- and mono-species and at 570 mp of Bjerrum Poulsen and Poulsen Symposium on Co-ordination Chemistry Danish Chem. SOC. 1954 p. 51. See for example Roughton and Chance in “Investigation of Rates and Mechanisms of Reactions,” ed. Friess and Weissberger Interscience Publ. Inc. New York,Chapter 10. PROCEEDINGS the bis- mono- and nickel ions) and the rates of dis- higher complex to dissociate more rapidly (accounted sociation decrease progressively and sufficiently for for in these cases solely by energy of activation the steps to be easily separated analytically.The dis- differences) has now been observed in several sociation of both mono-complexes is slow at 0" and system^.^ Even when there is a change in the ionic the rates can be obtained by simpler means. A charge during the dissociation this relation persists detailed study of these dissociations shows that the for we have studied the sequences [Ni glycine,]-+ rate in O*2~-acidcan be equated to that of the first [Ni glycine2] + [Ni glycine]+ -+ Ni2+and obtained bond rupture of the bidentate ligand.3 approximate half-lives at 20"of O-OO3,0.033,and 1.30 Kinetic data for first-order dissociation of nickel-diamine complexes in O*2~-acid Dissociating ti (sec.) ti (see.) Eact log PZ species (25 ") (0") (kcal./mole) (sec.-l) [Ni en3I2+ 0.008 & 0.001 0.128 & 0.015 18.0 -+ 1.2 15.2 0.8 (0.087) (20.2) (1 7.0) mi en2]% 0133 & 0015 2.66 -+ 0.25 19.8 & 1.0 15.3 & 0.6 (1.1) (I 9-9) (1 5.7) mi enI2+ 478 & 0.25 109 & 2 20.5 0.6 14.3 0.5 (6-9) (22.3) (16.8) [Ni(rac-bn)$+ 0.084 Zt 0.005 14.6 0.3 11.6 & 0.4 [Ni(rac-bn),]" 2-70 & 0.25 16.1 & 0.3 11.2 -+ 03 [Ni(rac- bn)]w 33.9 5 1.0 18.4 & 02 11.8 & 0.2 The slower rate of the butanediamine complex seconds respectively.We hope to apply this method than of the ethylenediamine analogue is due to to labile complexes of other metals for which a much lower PZ value partly offset by a lower quantitative data are lacking. energy of activation. The effect has been observed with other C-and N-alkylethylenediamine com- We thank Professor Q.H. Gibson for the use of plexes3v4 and can be understood in terms of a rela- his stopped-flow apparatus and considerable assist- tively higher solvation of the transition state for the ance with the experiments and the Pakistan Govern- substituted diamine complexes. The tendency for the ment for a maintenance grant. (Received November 13th 1959.) a Ahmed and Wilkins unpublished observations. Wilkins J. 1957 4521. "Citrylidene-malonic Acid" By C. E. BERKOFF and L. CROMBIE (DEPARTMENT KING'S COLLEGE OF LONDON) W.C.2, OF CHEMISTRY (UNIVERSITY STRAND and OF CHEMISTRY COLLEGE AND TECHNOLOGY S.W.7) DEPARTMENT IMPERIAL OF SCIENCE SOUTHKENSINGTON of citral with malonic acid in the Hydrogen chloride converts the first lactonic CONDENSATION presence of pyridine gives "citrylidene-malonic alcohol (vmax.1712 and 3618 cm.-l) into the acid" which has been variously formulated (1-111; chloride (V; R = ClMe,C) which when dehydro- R = C02H R' = H).14 Structure (TV; R = Me) halogenated with pyridine gives the isopropylidene is now proposed. Controlled hydrolysis of "citryli-derivative (V; R = Me&:). The latter can be dene-malonic acid" gives the &lactonic tertiary ozonised to acetone and the keto-lactone (V; R = alcohol (V; R = HO-Me&) but excess of alkali 0:).On pyrolysis of the chloride in vacuo however leads to the isomer (VI; R = OH). The structures of the isopropenyl derivative (V; R = CH,:CMe) is these are established as follows.obtained which on ozonolysis yields formaldehyde Verley Bull. Soc. chim. France 1899 21 414. Griinhagen Dissertation Heidelberg 1898. Vul'fson and Shemyakin J. Gen. Chem. U.S.S.R. 1943 13 436. Kuhn and Hoffer Ber. 1931,64 1243. DECEMBER 1959 and the acetyl compound (V; R = MeCO). The lactones (V; R = ClMe,C Me,C and CH,:CMe) all give the same saturated lactone (V; R = Me,HC) on catalytic hydrogenation. The isomeric 8-lactonic alcohol WI; R =OH) with vrnax. 1712 and 361 1 cni.-l similarly gives a chloride 40 1 cm.-l) may be due to vibrational coupling or steric influences rather than angle strain. Non-bonded interactions favour the all-chair over the A-boat-B- boat-c -chair structure preferential hydrolysis of the B-lactone is then explicable because the tetrahedrally hybridised intermediate resulting from attack by OH-h cv) (VI) (VI; R = C1) and is dehydrated to a compound (VII).The latter absorbs one mol. of hydrogen and its gummy ozonolysis product yields the expected bis-2,4-dinitrophenylhydrazone.Treatment of either of the two chloro- or the hydroxy-&lactone (V and VI) with hydrogen chloride in methanol4 gives the dichlor-oester (VIII ;R = Cl). By dehydrochlorina- tion hydrogenation monobromination dehydro- bromination and ozonolysis the latter was degraded to menthone this establishes the carbon skeleton but has no stereochemical implication. Unsuspected changes leading to earlier misf~rmulation~ of “citrylidene-malonic acid” and both of its mono- lactonic degradation series have been uncovered.Proton magnetic resonance confirms* the chemical proof of the lactonic attachment at C(l) and Crs). Where attachment is at C(l) the T value5 for the C{,)-Me shifts (9.14 doublet for methylcyclo-hexane) to near 8.6. Where attachment is at Crs) the r value for the gem-dimethyl groups on Cfs) (9.15 doublet for isopropylcyclohexane) shifts again to near 8-6. Where chlorine is attached the r value falls to 8-4.“Citrylidene-malonic acid” has no band of r > 9-62,? The bicydo-c-A system in (IV; R = Me) controls the attachment of ring B and to avoid severe strain the A-B fusion must be cis. That this almost strainless system shows two lactone bands (1750 and 1708 CH2C02Me (VIII) at Crp)possesses an intolerable interaction between the C(5) axial proton and one oxygen atom.Formation of “citrylidene-malonic acid” may be visualised as addition to give the hydroxy-dicar- boxylic acid (IX) which may be dehydrated to the triene (1; R = C02H R’ = H) before decarboxyla- tion.s Lactonisation of the latter gives an inter-mediate (X) shown ready to form ring c probably by an acid-catalysed process. Finally ring B is estab- lished as in (XI).$ In support of this mechanism “citrylidene-malonic acid” is obtained when the di- ester (I; R = CO,Et R’ = Et) is hydrolysed and acidified:2 schemes using the s-lactone from (IX) as the cyclising entity are possible but less attractive. * We thank Dr. L. M. Jackman for these measurements and advice on interpretation.f In the current number of Chem. and Ind. (1959 p. 1446) Hyne Mole and Wailes suggest essentially on the basis of the proton resonance spectrum that lactonic attachment is at Ct8)but the above decisive argument is overlooked. 2 Structure (IV; R = Me) and mechanistic rationalisation of the formation and pyrolysis was proposed in 1956 by one of the authors and J. L. Tayler? who carried out preliminary work. Notation of Tiers J. Phys. Chem. 1958 62 1151. * Patai Edlitz-Pfeffermann and Rozner J. Amer. Chem. SOC.,1954 76 3446. Tayler Thesis London 1956. PROCEEDINGS Pyrolysis of “citrylidene-malonic acid” gives 5,9-dimethyldeca-2,4,8-trienoicacid,8 its unsatur- ated &lactone its decarboxylation product 4,s-dimethylnona-l,3,7-triene and the isopropenyl lactone (V; R = CH,:CMe).Both lactone rings seem necessary for the catenation as various mono- lactones (V; R = Me& CH,:CMe Me,CH and Me&-OH) (VI; R = H) and (VII) survive the pyrolysis. This suggests a pathway of the type ~ ~ ~~ indicated by dotted arrows in (XII) or by the full arrows. The latter pathway leads initially to the monocyclic &lactone and better accommodates the stereochemistry of the trienoic acid which is ap- parently cis-2 since it is produced when the mono- cyclic &lactone is treated with sodium methoxide. Farnesal condenses with malonic acid to give a lactone (IV; R = Me& CH.[CH&. (Received November 17th 1959.) Batty Burawoy Heilbron Jones and Lowe J.1937 755. NEWS AND ANNOUNCEMENTS Vacancies on Council 1960.-The following vacant places in the Council fall due to be filled at the Annual General Meeting to be held in Belfast on Thursday April 7th 1960 Office No. of vacancies President .. .. .. .. .. .. .. .. .. ONE Vice-presidents who have filled the Office of President Vice-presidents who have not filled the Office of President. . .. .. .. ONE THRIZE Honorary Secretary .. .. .. .. .. .. .. Elected Ordinary Members of Council Constituency I (South-East England) .. .. .. .. Constituency I1 (Central and South-West England and South Wales) . . .. .. .. .. .. .. .. Constituency 111 (North-West England North Wales and Isle of Man) .. .. .. .. .. .. .. .. Constituency V (Scotland) .. .. .. .. .. .. ONE TWO ONE ONE ONE Names of Members who are to retire Professor H. J. Emelkus Professor W. Baker Professor R. D. Haworth Dr. L. E. Sutton Professor K. W. Sykes Professor R. S. Nyholm Dr. R. E. Richards Professor J. C. Tatlow Professor A. J. Birch Dr. J. D. Loudon With the exception of Professor K. W. Sykes who was appointed under Bye-Law 42,the members who are to retire are not eligible for reelection to the same Office until a lapse of one year. No vacancy arises in Constituencies IV or VI. In accordance with Bye-Law 24 the Council has nominated Sir Alexander Todd to the Office of President and Professor K. W. Sykes to the Office of Honorary Secretary. In accordance with Bye-Law 46 Professor H.J. Emelkus becomes a Vice-president who has filled the Office of President. Nominations by Fellows for the Officesof President Vice-president who has not filled the Office of President and Honorary Secretary should be made in writing and must be signed by at least twenty Fellows. Fellows resident in a constituency may nominate any Fellow resident in that constituency for election to the Council to fill a vacancy among Elected Ordinary Members of Council allotted to that constituency. Every such nomination must be in writing signed by at least fifteen Fellows resident in that constituency. Fellows may obtain forms of nomination from the General Secretary and should state the vacancy for which they are requested. Every nomination must relate to one vacant place only and must be accompanied by a signed declaration by the nominee that he is willing to accept office if elected.Nominations must be received by the Society before Monday February 15th 1960. Hamson Memorial Prize.-The Selection Com- mittee consisting of the Presidents of The Chemical Society The Royal Institute of Chemistry The Society of Chemical Industry and The Pharma- ceutical Society will in 1960 consider making an award of the Harrison Memorial Prize. The Prize which consists of a bronze plaque and a monetary payment of 100guineas will be awarded to the chemist of either sex who being a natural-born British subject and not at the time over thirty years of age shall in the opinion of the Selection Com-mittee during the five years ending December lst DECEMBER 1959 1959 have conducted the most meritorious and promising original investigations in Chemistry and published the results of those investigations in a scientific periodical or periodicals.Applications five copies of which must be sub- mitted should include the full names of the applicant; age (birth certificate to be enclosed); degrees (with name of University); any other qualifications and experience; titles and reprints if available of pub- lished papers (with co-authors’ names) ; where re search was carried out ;testimonials and references and any other relevant particulars. The Selection Committee is prepared to consider applications nominations or information as to candidates who have not attained the age of thirty years at December lst 1959 and are otherwise eligible for the Prize.Any such communication must be received by the President The Chemical Society Burlington House Piccadilly London W. 1 not later than Thursday September lst 1960. Library Photocopying Charges.-It has been found necessary to revise the prices charged for photo- copies supplied by the Library. Photocopies of material in the Library which normally includes all periodicals from which Current Chemical Papers is compiled can usually be supplied for purposes of research or private study at a standard cost of 3s. Od. for each separate order with in addition a charge of 2s. Od. per page or part of a page for positive photo- prints or 4d.per page for negative microfilm. Pay- ment should be made at the time of ordering and a declaration on a form available from the Librarian must be signed in compliance with the Copyright (Libraries) Regulations 1957. The Davy Medal.-The President and Council of The Royal Society have awarded the Davy Medal to Professor R. B. Woodward (Honorary Fellow of The Chemical Society) of the Department of Chemistry Harvard University Cambridge Mass. U.S.A. for his distinguished researches in organic chemistry and particularly for his contributions to the structure and synthesis of natural products. Congress.-The Third International Congress of Surface Activity will be held in Cologne Germany on September 12-17th 1960. Enquiries should be addressed to Generalsekretariat des 111 Inter-nationalen Kongresses fur Grenzflachenaktive Stoffe Bonn a.Rh.Koblenzer Strasse 232 Germany. National Lending Library for Science and Tech- nology.-A consultative Committee has been ap- pointed to advise the Department of Scientific and Industrial Research on the services of the National Lending Library for Science and Technology. Literature is now being collected for the National Lending Library for Science and Technology by the D.S.I.R. Lending Library Unit at 20 Chester Terrace Regents Park London N.W.l. The Library will be located near Boston Spa Yorkshire and its transfer will take place in the first half of 1961. Its collection of scientific literature which will become the largest in the United Kingdom will be available to any organisations through loan and photocopying services.The Chairman of the Committee is Sir Lindor Brown and the members include Professor J. D. Bernal Dr. R. E. Fairbairn (Head of the Library Department Imperial Chemical Industries Limited Dyestuffs Division) Professor G. Gee and Professor W.T. J. Morgan. Physical Society Exhibition.-The Physical Society Exhibition of Scientific Instruments and Apparatus 1960 will be held at the Royal Horticultural Society’s Old and New Halls Westminster London on Monday January 18th to Friday January 22nd. This Exhibition shows new developments in scientific instruments and apparatus and possibilities of their application. Fellows of The Chemical Society may obtain tickets to visit the Exhibition on the Physical Society Members’ morning Monday January 18th when the Exhibition is not so crowded.Application should be made to the General Secretary The Chemical Society Burlington House London W. 1. Forensic Science Society.-A decision to form a Forensic Science Society was taken at a well-attended meeting held at Nottingham University on October 31st 1959. The object of the Society is to advance the study and application of forensic science in all its branches. With this aim in view a series of symposia to be held alternately in London and in the provinces is being arranged. Among the subjects suggested for discussion are Blood Hypoglycaemia Street Accidents and Instrumentation. All persons professionally interested in forensic science are eligible for membership.The president of the Society is Dr. J. B. Firth and the secretary Dr. E. G. C. Clarke of the Royal Veterinary College London N.W. 1 from whom further information can be obtained. Election of New Fellows.-37 Candidates whose names were published in Proceedings for October have been elected to the Fellowship. Deaths.-We regret to announce &he deaths of the following Mr. S. W. Atherley (22.10.59) Director of Dalmas Ltd. Dr. hr.Brandon (14.10.59) Director of Tyne Chemical Co. Ltd. Mr. B. A. Bull (1 5.1 1.59) formerly Production Director Boots Pure Drug Co. Ltd. and Mr. L. Hamache (5.10.59), of Solvay and Co. Brussels. Dr. Walter J. Murphy Editorial Director of the American Chemical Society Applied Publications died on November 26th after a brief illness.Personal.-Dr. H. R. Ambler has been appointed to the newly created post of Scientific Adviser to the U.K. High Commissioner in New Delhi. In addition to advising the High Commissioner on scientific matters he will be responsible for furthering the exchange of information between British and Indian scientists. Dr. K. W. Bagnull in charge of a section of the Radiochemistry Branch of the Chemistry Division at Harwell has been promoted to the post of Senior Principal Scientific Officer under the provisions of the scheme for the promotion of individual research workers in the Scientific Civil Service on the grounds of exceptional merit. Dr.J. W. Barton has been appointed Lecturer in Organic Chemistry in the University of Bristol. Dr. J. K. Brown has been appointed Lecturer in Chemistry in the University of Birmingham. The Council of the University of Leeds has agreed to confer the title of Emeritus Professor upon Professor D. Burton on his retirement from the Chair of Leather Industries. Dr. J. Chatt has been appointed to the position of Distinguished Visiting Professor of Chemistry at the Pennsylvania State University for the period February-May 1960. Professor E. G. Cox Professor of Inorganic and Structural Chemistry in the University of Leeds is to succeed Sir William Slater as Secretary of the Agricultural Research Council on Sir William’s retirement next year. Professor Cox’s appointment will take effect from July lst 1960.Dr. R. J. Cremlyn has been appointed a Lecturer in Organic Chemistry at the Brunel College of Technology London. Dr. C. E. Dalgliesh has been appointed to the Board of Directors of Miles Laboratories Ltd. Professor K. G. Denbigh Professor of Chemical Technology in the University of Edinburgh has been appointed to the University Chair of Chemical Engineering Science tenable at the Imperial College of Science and Technology from October lst 1960. The following members of the Department of Chemistry University College of Rhodesia and Nyasaland are now visiting London and expect to be here until the dates indicated. Communications can be addressed to them in care of Rhodesia House Strand London W.C.2.Professor S. H. Harper (February 2nd) Mr. A. J. Eve (early February) Dr. E. R.Swart (February 20th). Dr. G. G. Haselden has been appointed to the PROCEEDINGS Brotherton Chair of Chemical Engineering in the Houldsworth School of Applied Science University of Leeds with effect from September 1st next. Sir Cyril Hinshelwood President of The Royal Society is one of the 12 members of the Advisory Committee on the selection of low-priced books for oversea recently appointed by the Chancellor of the Duchy of Lancaster. The Ministry of Aviation has announced that Dr. C. M. Johnson has been appointed Director of the Explosives Research and Development Establish- ment at Waltham Abbey. Dr. L. A. Jordan and Professor A.V.Hill have been appointed members of a scientific commission estab- lished by the Pakistan Government to examine the organisation of scientific and technical institutions in the country and to make recommendations for their development and co-ordination. Dr. F. E. King formerly Director of Research in British Celanese has been appointed Scientific Adviser to the Refineries and Technical Department of the British Petroleum Co. Dr. R. N. Lacey has relinquished his position as Deputy Manager of the Hull Development Depart- ment of the Distillers Company Ltd. (Chemical Divi- sion) to take up an appointment at the BP Research Centre Sunbury-on-Thames. Dr. P. B. D. de la Mare Reader in Chemistry at University College has been appointed to the Uni- versity Chair of Chemistry tenable at Bedford College from October lst 1960.Dr. A. R. Mathieson has been appointed Lecturer in the Chemistry of High Polymers in the Department of Textiles Industries University of Leeds. The title of Reader in Chemistry in the University of London has been conferred on Dr. D. J. Millen in respect of his post at University College. Mu. Edward A. Smith has been elected to the Board of Directors of Acheson Colloids Ltd. the principal subsidiary of Acheson Industries (Europe) Ltd. Dr. A. F. Thomas has been appointed Lecturer in the Department of Organic Chemistry in the Uni- versity of Leeds with effect from January 1st next. Dr. G. H. Williams Lecturer at King’s College London has been appointed to the University Readership in Organic Chemistry tenable at Birk- beck College London.Mr. R. L. Wilson has retired as Manager of the Refining and Distribution Department of the Kuwait Oil Co. Ltd. DECEMBER 1959 405 PROGRAMME OF MEETINGS* JANUARY TO JUNE 1960 London Thursday January 14th 1960 at 7.30 p.m. Tilden Lecture “Progress in the Study of Hetero- geneous Catalysis,” by Professor C. Kemball M.A. Ph.D. F.R.I.C. To be given in the Lecture Theatre The Royal Institution Albemarle Street W. 1. Thursday February 11 th at 7.30 p.m. Tilden Lecture “Hydrocarbon-metal Carbonyls,” by Professor P. L. Pauson. To be given in the Lecture Theatre The Royal Institution Albermarle Street w.l. Thursday February 25th at 7.30 p.m.Centenary Lecture “Some Glimpses into the Varia- tions which Nature brings about in Acetylenic Com- pounds,” by Professor N. A. Smensen. To be given in the Large Chemistry Lecture Theatre Imperial College of Science and Technology South Kensing- ton S.W.7. Thursday March loth at 7.30 p.m. Liversidge Lecture “Ionic Crystals and their Melts,” by Professor A. R. J. P. Ubbelohde M.A. D.Sc. F.R.S. To be given in the Large Chemistry Lecture Theatre Imperial College of Science and Technology South Kensington S.W.7. Thursday May 5th at 7.30 p.m. Adolf Windaus Memorial Lecture. To be given by Professor A. Butenandt in the Rooms of the Society Burlington House London W. 1. Thursday June 2nd at 7.30 p.m. Centenary Lecture “Chemical Constitution and Immunological Specificity,” by Professor M.Heidel-berger. To be given in the Rooms of the Society Burlington House London W. 1. Aberdeen (Meetings will be held in the University Union.) Thursday January 21st 1960 at 8 p.m. Lecture “Synthetic Detergent Washing Powders,” by Mr. L. N. Savidge. Joint meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. Friday February 19th at 8 p.m. Centenary Lecture “Some Glimpses into the Varia- tions which Nature brings about in Acetylenic Com- pounds,” by Professor N. A. Smensen. Wednesday March 16th at 8 p.m. Lecture “Complexometric Methods of Analysis Metals and Non-metals,” by Dr. T. S. West. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry.Aberystwyth (Meetings will be held in the Edward Davies Chem- ical Laboratories University College of Wales.) Thursday January 21st 1960 at 5 p.m. Lecture “Chemistry of Pyrazoles,” by Dr. I. L. Finar. Joint Meeting with the Royal Institute of Chemistry. Thursday February 25th at 5 p.m. Lecture “The Molecular Structure of Benzene,” by Dr. D. H. Whiffen. Thursday March 3rd at 5 p.m. Lecture “Death by Poisoning,” by Dr. A. C. Hunt. Joint Meeting with the Cardiganshire Branch of the Pharmaceutical Society of Great Britain. Birmingham (Joint Meetings with the University Chemical Society to be held in the Large Chemistry Lecture Theatre The University.) Friday January 15th 1960 at 4.30 p.m.Official Meeting and Lecture “Alkali-metal Deriva- tives of Organic and Organometallic Compounds,” by Professor G.E. Coates M.A. D.Sc. F.R.I.C. Friday February 5th at 4.30 p.m. Lecture “Big Rings,” by Professor R. A. Raphael Ph.D. A.R.I.C. Friday March 4th at 4.30 p.m. Lecture “Weak Very Weak and Extremely Weak Bonds,” by Dr. L. J. Bellamy. Friday April 29th at 4.30 p.m. Lecture “Halogenation Kinetics of Some Reactive Species,” by Mr. R. P.Bell M.A. F.R.S. Bristol (Meetings will be held in the Department of Chem- istry The University unless otherwise stated.) Friday January 8th 1960 at 6.30 p.m. Lecture “Radiochemical Analysis,” by Dr. J. N. Andrews A.R.I.C. Joint Meeting with the Society for Analytical Chemistry the Royal Institute of Chemistry and the Society of Chemical Industry to be held at the College of Technology Ashley Down Bristol 7.Thursday January 14th at 6.30 p.m. Lecture “The Dyeing of the Newer Synthetic Fibres,” by Mr. J. G. Graham B.Sc. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. * Reprints of this programme can be obtained from the General Secretary The Chemical Society Burlington House, Piccadilly London W. 1. Thursday January 21st at 5.15 p.m. Lecture by Professor D. H. Everett M.B.E. D.Phil. Joint Meeting with the Student Chemical Society. Thursday January 28th at 6.30 p.m. Lecture by Professor A. L. Roberts. Joint Meeting with the Royal Institute of Chemistry the Society of Chemical Industry and the Institute of Fuel.Thursday February 4th at 5.15 p.m. Lecture “Chemisorption on Platinum,” by Professor J. G. Aston. Joint Meeting with the Student Chemical Society. Thursday February 11 th at 6.30 p.m. Liversidge Lecture “Ionic Crystals and their Melts,” by Professor A. R. J. P. Ubbelohde M.A. D.Sc. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. Thursday February 18th at 5.15 p.m. Lecture “Biogenesis of Porphyrins,” by Professor A. W. Johnson Ph.D. Sc.D. A.R.C.S. Joint Meeting with the Student Chemical Society. Thursday February 18th at 7.30 p.m. Lecture “Chemotherapeutic Research,” by Dr. F. L. Rose O.B.E. F.R.I.C. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Technical College Brunswick Road Gloucester.Thursday February 25th at 5.15 p.m. Lecture “Nuclear Magnetic Resonance,” by Dr. R. E. Richards M.A. F.R.S. Joint Meeting with the Student Chemical Society. Thursday March 3rd at 6.30 p.m. Lecture “Some Aspects of the Photographic Repro- duction of Colour,” by Dr. H. Baines F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. Thursday March 17th at 6.30 p.m. Lecture “X-Ray Fluorescence Analysis,” by Mr. J. R. Stansfield. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. Cambridge (Meetings will be held in the University Chemical Laboratory,Lens field Road.) Monday January 18th 1960 at 5 p.m.Lecture “Chelatometry,” by Dr. T. S. West. Tuesday January 19th at 11.30 a.m. Lecture “The Analysis of Microgram Amounts of Organic Compounds,” by Dr. T. S. West. Friday January 29th at 8.30 p.m. Lecture “The Structure of Myoglobin,” by Dr. J. C. Kendrew M.A. Joint Meeting with the University Chemical Society. PROCEEDINGS Friday February 5th at 8.30 p.m. Lecture “Some Antibiotics Derived from Actino- mycetes,” by Professor A. W. Johnson Ph.D. Sc.D. A.R.C.S. Joint Meeting with the University Chem- ical Society. Friday February 19th at 8.30 p.m. Lecture “Electron Resonance Studies of Unstable Radicals,” by Dr. D. J. E. Ingram. Joint Meeting with the University Chemical Society.Friday February 26th at 8.30 p.m. Lecture “Alkali-metal Derivatives of Organic and Organometallic Compounds,” by Professor G. E. Coates M.A. D.Sc. F.R.I.C. Joint Meeting with the University Chemical Society. Monday February 29th at 5 p.m. Lecture “Rotational Isomerism (and Energy Bar- riers) in Organic Nitrites,” by Dr. Peter Gray B.A. Monday March 7th at 5 p.m. Lecture “Steric Effects of Hyaluronic Acid on the Distribution of Other Solutes,” by Dr. A. G.Ogston. Monday April 25th at 5 p.m. Lecture “Some Applications of Mass Spectrometry in Organic Chemistry,” by Dr. J. H. Beynon. Monday May 2nd at 5 p.m. Lecture “Acylation and Phosphorylation Mechan- isms,” by Dr. R. F. Hudson A.R.C.S. A.R.I.C. Friday May 27th at 5 p.m.Centenary Lecture “Chemical Constitution and Im- munological Specificity,” by Professor M. Heidel- berger. Cadiff (Meetings will be held in the Chemistry Department University College Cathays Park.) Monday January 25th 1960 at 5.30 p.m. Lecture “Some Models of Physical Adsorption,” by Professor D. H. Everett M.B.E. D.Phi1. Monday March 7th at 5.30 p.m. Lecture “Developments in the Chemistry of Bacterial Walk,” by Professor J. Baddiley Ph.D. D.Sc. Monday May 2nd at 7 p.m. Meeting for the reading of original papers. Durham (Meetings will be held in the Science Laboratories South Road.) Monday January 25th 1960 at 5 p.m. Lecture “Reactions in Liquid Dinitrogen Tetroxide,” by Dr. C. C. Addison F.Inst.P. F.R.I.C. Joint Meeting with the Durham Colleges Chemical Society.Monday February 8th at 5 p.m. Lecture “The Anti-knock Action of Tetraethyl- lead,” by Professor A. D. Walsh M.A. Ph.D. Joint DECEMBER 1959 407 Meeting with the Durham Colleges Chemical Society. Monday February 22nd at 5 p.m. Tilden Lecture “Hydrocarbon-metal Carbonyb,” by Professor P. L. Pauson. Monday March 7th at 5 p.m. Lecture “The Organic Chemistry of Metal Car- bonyls,” by Dr. M. C. Whiting. Joint Meeting with the Durham Colleges Chemical Society. Monday May 9th at 5 p.m. Lecture “Electrode Processes Involving Transition Ions,” by Mr. N. S. Hush M.Sc. Joint Meeting with the Durham Colleges Chemical Society. Edinburgh (Meetings will be held in the North British Station Hotel unless otherwise stated.) Friday January Sth 1960 at 7.30 p.m.Lecture “Chemistry applied to Criminal Investiga- tion,” by Detective Chief Inspector J. K. McLellan. Joint Meeting with Royal Institute of Chemistry and the Society of Chemical Industry. Tuesday February 2nd at 7.30 p.m. Lecture “Reaction Mechanisms,” by Professor E. D. Hughes Ph.D. D.Sc. F.R.I.C. F.R.S. Joint Meet- ing with the Royal Institute of Chemistry and the Society of Chemical Industry and Edinburgh Uni- versity Chemical Society. To be held in the Biochem- istry Lecture Theatre The University Teviot Place. Thursday February 18th at 7.30 p.m. Lecture by Professor J. Hawthorn. Joint Meeting with Local Sections of the Royal Institute of Chem- istry and the Society of Chemical Industry and the Food Group of the Society of Chemical Industry.Thursday March 17th at 7.30 p.m. Three short papers provided by Scottish Agricultural Industries Ltd. Cerebos Ltd. and the Department of Chemistry The University. Exeter (Meetings will be held in the Washington Singer Laboratories Prince of Wales Road.) Friday February Sth 1960 at 5 p.m. Lecture “The %Ray Analysis of Molecular Structure,” by Mrs. D. M. Crowfoot-Hodgkin Ph.D. F.R.S. Friday May 6th at 5 p.m. Lecture “Insulin,” by Dr. F. Sanger F.R.S. Glasgow (Meetings will be held in the Chemistry Department The University unless otherwise stated.) Friday January 22nd 1960 at 4 p.m. Lecture “Energy Transfer in Gases,” by Professor T.L. Cottrell. Joint Meeting with Alchemist’s Club. Wednesday February 17th at 4 p.m. Centenary Lecture “Some Glimpses into the Varia- tions which Nature brings about in Acetylenic Com- pounds,” by Professor N. A. Sarensen. This meeting will be followed by the Annual General Meeting of Fellows in the area. Friday March 18th at 7.15 p.m. Meeting for the reading of original papers to be held in the Royal College of Science and Technology. Hull (Meetings will be held in the Organic Lecture Theatre Chemistry Department The University unless otherwise stated.) Thursday February 4th 1960 at 5 p.m. Lecture “Atomic Reactions,” by Dr. J. W. Linnett F.R.S. Thursday February 25th at 5 p.m. Lecture “Anthraquinone Chemistry,” by Dr. S. Coffey F.R.I.C.Joint Meeting with the University Student Chemical Society. Wednesday May 25th at 5.30 p.m. Official Meeting and Centenary Lecture “Chemical Constitution and Immunological Specificity,” by Professor M. Heidelberger. To be given in the Physics Lecture Theatre The University. Irish Republic (Meetings will be held in the University Chemical Laboratory Trinity College Dublin unless other- wise stated.) Wednesday January 6th 1960 at 5.30 p.m. Lecture “Aescigenin,” by Dr. J. B. Thomson. To be given in The Chemistry Department University College Dublin. Wednesday February 3rd at 5.30 p.m. Lecture “Some Aspects of the Chemistry of Quaternary Ammonium Compounds,’y by Dr. J. McKenna M.Sc. F.R.I.C. To be given in the Department of Chemistry University College Dublin.Thursday February 4th at 7.45 p.m. Lecture “Some Recent Advances in the Synthesis of Fatty Acids and Phospholipids,” by Dr. R. E. Bowman. Joint Meeting with the Werner Society. Friday March llth at 7.45 p.m. Lecture by Professor R. C. Cookson M.A. Ph.D. Joint Meeting with the Werner Society. April 27th April 29th and May 2nd. Lecture “Some Recent Developments in Explo-sives,” by Dr. J. Craik M.A. Joint Meetings with the Institute of Chemistry of Ireland Royal Institute of Chemistry and the Society of Chemical Industry to be held as follows Wednesday April 27th in the Department of Chemistry University College Dublin. Friday April 29th in the University College Cork. Monday May 2nd in the Chemistry Department University College Galway.Tuesday May 17th. Centenary Lecture “Chemical Constitution and Immunological Specificity,” by Professor M. Heidel- berger. Leeds (Meetings will be held in the Chemistry Lecture Theatre The University unless otherwise stated.) Monday January 11 th 1960 at 6.30 p.m. Lecture “Some Observations on Analytical Chem- istry,” by Dr. J. Haslam M.Sc. F.R.I.C. Joint Meeting with the Society of Chemical Industry to be held in the Houldsworth School of Applied Science The University. Monday January 18th at 6.30 p.m. Lecture “Aromatic Fluorocarbons,” by Professor M. Stacey Ph.D. D.Sc. F.R.I.C. F.R.S. Joint Meeting with the Royal Institute of Chemistry. Monday February 15th at 6.30 p.m.Lecture “Some Aspects of the Structural Chemistry of Platinum,” by Professor E. G. Cox T.D. D.Sc. F.R.I.C. F.R.S. Joint Meeting with the Royal Institute of Chemistry. Thursday February 25th at 6.30 p.m. Lecture “Developments in the Study of Electro- philic Substitution,” by Sir Christopher Ingold D.Sc. F.R.I.C. F.R.S. Joint Meeting with the University Union Chemical Society. Leicester (Meetings will be held at the University.) Monday February 8th 1960 at 4.30 p.m. Lecture “Alkali-metal Derivatives of Organic and Organometallic Compounds,” by Professor G. E. Coates M.A. D.Sc. F.R.I.C. Joint Meeting with the University Chemical Society. Liverpool (Meetings will be held in the Department of In- organic and Physical Chemistry The University.) Thursday January 28th 1960 at 5 p.m.Tilden Lecture “Progress in the Study of Hetero- geneous Catalysis,” by Professor C. Kemball M.A. Ph.D. F.R.I.C. Joint Meeting with the University Chemical Society. Thursday February 25th at 5 p.m. Lecture “Chemotherapy,” by Dr. F. L. Rose O.B.E. F.R.I.C. F.R.S. Joint Meeting with the University Chemical Society. PROCEEDINGS Manchester Monday February lst 1960 at 6.30 p.m. Lecture “Structure and Reactions of the Gallium Halides,” by Dr. N. N. Greenwood. Joint Meeting with the Chemistry Department Manchester College of Science and Technology to be held in the College of Science and Technology. Tuesday February 9th at 4 p.m. Lecture “Looking for New Drugs,” by Dr. F. L.Rose O.B.E. F.R.I.C. F R.S. Joint Meeting with the Students’ Chemical Society University of Manchester to be held in the Large Lecture Theatre Chemistry Department The University. Monday February 15th at 6 30 p.m. Lecture “Rotational Isomerism in Organic Nitrites,’’ by Dr. Peter Gray. Joint Meeting with The Chem- istry Department Manchester College of Science and Technology to be held in the College of Science and Technology. Tuesday February 23rd at 6.30 p.m. Official Meeting and Centenary Lecture “Some Glimpses into the Variations which Nature brings about in Acetylenic Compounds,” by Professor N. A. Smensen. To be given in the Large Lecture Theatre Chemistry Department The University. Thursday March 3rd at 5 p.m. Lecture “Recent Developments in the Chemistry of Some Less Common Elements,” by Professor R.S. Nyholm F.R.I.C. F.R.S. Joint Meeting with the Students’ Chemical Society Royal Technical College Salford to be held in Room C6 Royal Technical College Salford. Thursday March loth at 4 p.m. Lecture “The Structure of Yeast,” by Professor A. A. Eddy. Joint Meeting with the Students’ Chemical Society University of Manchester to be held in the Large Lecture Theatre Chemistry Department The University. Thursday May 19th at 6.30 p.m. Centenary Lecture “Chemical Constitution and Immunological Specificity,” by Professor M. Heidel-berger. To be given in the Large Lecture Theatre Chemistry Department The University. Newcastle upon Tyne (Meetings will be held in the Chemistry Department King’s College.) Friday January 29th 1960 at 5.30 p.m.Bedson Club Lecture “Activation of Carbon-Carbon Double Bonds by Cationic Catalysts,’* by Professor A. G. Evans Ph.D. D.Sc. Wednesday February 17th at 6 p.m. Lecture “Why Polymerisation Occurs,” by Professor F. S. Dainton Ph.D. F.R.S. Joint Meeting with the Royal Institute of Chemistry. DECEMBER 1959 409 Friday February 26th at 5.30 p.m. Bedson Club Lecture “Complexometric Titrations,” by Dr. H. M. N. H. Irving M.A. F.R.I.C. Friday March 4th at 6 p.m. Lecture “The Biogenesis of Porphyrins,” by Profes- sor A. Neuberger Ph.D. F.R.S. Joint Meeting with the Royal Institute of Chemistry. Wednesday March 16th at 5.30 p.m. Tilden Lecture “Progress in the Study of Hetero-geneous Catalysis,” by Professor C.Kemball M.A. Ph.D. F.R.I.C. Monday May 23rd at 5.30 p.m. Centenary Lecture “Chemical Constitution and Immunological Specificity,” by Professor M. Heidel-berger. North Wales (Meetings will be held in the Department of Chem-istry University College of North Wales Bangor.) Thursday January 28th 1960 at 5.45 p.m. Lecture “Synthesis and Dissolution of Starch in Plants,” by Professor Helen K. Porter D.Sc. F.R.S. Joint Meeting with the University College of North Wales Chemical Society. Thursday April 28th at 5.45 p.m. Lecture “Aromatic Fluorocarbon Derivatives,” by Professor J. C.Tatlow D.Sc. F.R.I.C. Joint Meeting with the University College of North Wales Chemical Society.Northern Ireland (Meetings will be held in the Department of Chem- istry Queens University Belfast.) Tuesday January 26th 1960 at 7.45 p.m. Lecture “Electron Resonance of Free Radicals,” by Dr. D. H. Whiffen M.A. Joint meeting with the Royal Institute of Chemistry and the Society of Chemical Industry. Tuesday April 5th to Friday April 8th. Joint Annual Meetings of the Chemical Society and the Royal Institute of Chemistry. Full details are being circulated to all Fellows. Nottingham (Meetings will be held in the Chemistry Department The University.) Tuesday January 26th 1960 at 8 p.m. Official Meeting and Tilden Lecture “Hydrocarbon- metal Carbonyls,” by Professor P. L. Pauson. Tuesday February 2nd at 5 p.m. Lecture “The Behaviour of Ionic Solutions in Hydrogen Peroxide,” by Professor W.F. K. Wynne-Jones D.Sc. Joint Meeting with The University Chemical Society. Tuesday February 23rd at 8 p.m. Lecture “Developments in the Study of Electrophilic Substitution,” by Sir Christopher Ingold D.Sc. F.R.I.C. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the University Chemical Society. Oxford (Meetings will be held in the Inorganic Chemistry Laboratory Oxford.) Monday February Sth 1960 at 8.15 p.m. Lecture “The Behaviour of Electrons in Molecules,” by Dr. J. W. Linnett M.A. F.R.S. Joint Meeting with the Alembic Club. Monday February 29th at 8.15 p.m. Lecture ‘‘Chemical Engineering Aspects of Atomic Energy,” by Professor P. V. Danckwerts G.C.M.B.E. Joint Meeting with the Alembic Club. St. Andrews and Dundee Tuesday January 12th 1960 at 5 p.m. Lecture “The Chemical Contribution to Cancer Research,” by Professor A. Haddow F.R.S. To be given in the Chemistry Department Queens College Dundee. Friday January 15th at 5.15 p.m. Lecture “Some Effects of Remotely Placed Groups upon Reactions of Organic Molecules,” by Professor H. B. Henbest Ph.D. A.R.C.S. A.R.I.C. Joint Meeting with the University Chemical Society to be held at the Chemistry Department St. Salvators College St. Andrews. Monday February 8th at 5 p.m. Lecture by Professor C. A. Coulson F.R.S. To be given in the Chemistry Department Queens College Dundee. Friday February 12th at 5.15 p.m. Lecture “Vitamin BI2,” by Professor A.W. Johnson Ph.D. Sc.D. Joint Meeting with the Uni- versity Chemical Society to be held in the Chemistry Department St. Salvators College St. Andrews. Friday February 26th at 5.15 p.m. Lecture “The Chemistry of Poisoning,” by Dr. A. S. Curry. Joint Meeting with the University Chemical Society and the Royal Institute of Chemistry to be given in the Chemistry Department St. Salvators College Dundee. Friday April 8th at 5.15 p.m. Lecture “Nuclear Resonance,” by Dr. R. E. Richards M.A. F.R.S. Joint Meeting with the University Chemical Society to be held in the Chem- istry Department St. Salvators College St. Andrews. Friday April 22nd at 5.15 p.m. Lecture “Are Scientists Literate ?” by Mr. John Maddox.Joint Meeting with the University Chem- ical Society to be held in the Chemistry Department St. Salvators College St. Andrews. SheBeld (Meetings will be held in the Chemistry Department The University.) Thursday January 21st 1960 at 4.30 p.m. Lecture “Some Recent Studies with Natural Products,” by Professor E. R. H. Jones Ph.D. D.Sc. F.R.I.C. F.R.S. Joint Meeting with the Royal Institute of Chemistry and the University Chemical Society. Tuesday February 2nd at 8 p.m. Liversidge Lecture “Ionic Crystals and Their Melts,” by Professor A. R. J. P. Ubbelohde M.A. D.Sc. F.R.S. Thursday February 18th at 4.30 p.m. Lecture “Some Reactions of Bicycloheptadiene,” by Professor R. C. Cookson M.A. Ph.D. Joint Meet- ing with the Royal Institute of Chemistry and the University Chemical Society.Southampton (Meetings will be held in the Chemistry Department The University unless otherwise stated.) Friday January 29th 1960 at 5 p.m. Lecture “Homogeneous Catalytic Activation of Molecular Hydrogen,” by Professor J. Halpern Ph.D. Joint Meeting with the University Chemical Society. Friday February 12th at 5 p.m. TiIden Lecture “Hydrocarbon-metal Carbonyls,” by Professor P. L. Pauson. To be given in the Lecture Theatre Engineering Department The University. PROCEEDINGS Friday March 11 th at 5 p.m. Lecture “Some Problems in Phosphonitrilic Chem- istry,” by Dr. N. Paddock. Joint Meeting with the Royal Institute of Chemistry and the University Chemical Society. Swansea (Meetings will be held in the Department of Chem- istry University College.) Monday February 29th 1960 at 5.15 p.m.Lecture “Design in High Polymers,” by Professor C. E. H. Bawn C.B.E. Ph.D. F.R.S. Joint Meeting with the University College Chemical Society. Tuesday March Sth at 5.15 p.m. Lecture “Developments in the Chemistry of Bacterial Walls,” by Professor J. Baddiley Ph.D. D.Sc. Joint Meeting with the University College Chemical Society. Monday March 14th at 5.15 p.m. Lecture “Optical Rotatory Dispersion in Structural Organic Chemistry,” by Dr. W. Klyne M.A. Joint Meeting with the University College Chemical Society. Tees-side Wednesday January 20th 1960 at 8 p.m. Lecture “The Development and Uses of the Patent System,” by Mr.R. T. Swarbrick. Joint Meeting with the Royal Institute of Chemistry to be held at the William Newton School Norton-on-Tees. Thursday March 24th at 8 p.m. Lecture “The Organic Chemistry of Ferrocene,” by Professor P. L. Pauson. Joint Meeting with the Royal Institute of Chemistry to be held at Stockton and Billingham Technical College Billingham-on- Tees. APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objections to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedings. Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Ansel Michael. Bostar Hall University College Oxford.Auger Christopher John. 11 Kinlet Road Plumstead S.E.18. Beard James Andrew Threlfall B.A. 56 Cedar Drive Chichester. Beetham Jack Thomas HaIsey B.Sc. 50 Henley Road Southsea Hants. Berninger Carl J. B.A. 732E Waverly Street Tucson Arizona U.S.A. Blandamer Michael Jesse B.Sc. Chemistry Department The University Southampton. Blight Lawrence M.Sc. A.R.I.C. 20 Cold Blow Crescent Bexley Kent. Bowie John Hamilton BSc. 44 Ferndale Road Glen Iris S.E.6 Victoria Australia. Bradley John Newton Ph.D. A.R.I.C. Department of Inorganic and Physical Chemistry The University. Liverpool. Brauman John I. B.S. Department of Chemistry Uni- versity of California Berkeley 4 California U.S.A. Bryant Rhys B.Sc. 43 Graiglwyd Road Sketty Swansea Glam.Bullock Derek John William. 77 Purrett Road Plum- stead S.E.18. Burn John B.Sc. 19 Hilden Gardens Newcastle upon Tyne 7. Bursey Maurice Moyer B.A. Department of Chemistry, The Johns Hopkins University Baltimore 18 Mary-land U.S.A. DECEMBER I959 Carnduff John B.Sc. 16 West Road Irvine Ayrshire Scotland. Carrington Roy. 35 Skirbeck Road Gillshill Road Hull. Cohen Arnold Jeffrey B.Sc. 58 Allerton Road London N.16. ColIman James Paddock M.S. Ph.D. Chemistry Department University of North Carolina Chapel Hill North Carolina U.S.A. Cox Geoffrey Alan. Ferens Hall Hull Yorks. Cragg Richard Henry. 30 Park Lane Workington Cumberland. Cresswell Ronald Morton B.Sc. 122 Barrachnie Road Garrowhill Glasgow.Dainer Russell James. Flat 2 849 Drummond Street N. Carlton Victoria Australia. Davidson Robert Stephen. 3 Montagu View Oakwood Leeds 8 Yorks. De Anil Kumar M.Sc. D.Phi1. Department of Chem- istry Jadavpur University Calcutta 32 India. Dows David A. Ph.D. Department of Chemistry Uni- versity of Southern California Los Angeles 7, California U.S.A. Dutta Jadugopal M.Sc. D.Phi1. Chemistry Department College of Arts and Science Jadavpur University Calcutta 32 India. Eraut Michael Ruarc. Trinity Hall Cambridge. Finch Neville Ph.D. Chemistry Department Stanford University Stanford California U.S.A. Fincham Robert Anthony. Ferens Hall Cottingham Yorks. Furst Andor Dr.Sc. Research Depot F. Hoffman-La Roche and Co.Ltd. Grenzacherstrasse Basle, Switzerland. Giacometti Giovanni Ph.D. Instituto Chimica Fisica Via Loredan 4 Padova Italy. Gittens Gerald James B.Sc. Chemistry Department Chelsea College of Science and Technology Manresa Road London S.W.3. Goldman Norman Lewis Ph.D. Department of Chem- istry Imperial College Imperial Institute Road, London S.W.7. Green Brian Ph.D. Department of Chemistry Univer- sity of Maine Orono Maine U.S.A. Hare Curtis Robert B.S. Department of Chemistry 128 Kedzie Chemical Laboratory Michigan State Univer- sity East Lansing Michigan U.S.A. Heatlie James William Macrae B.Sc. The Chemistry Department Queens College Dundee. Hill Hugh Allen Oliver B.Sc. 31 Cairnburn Crescent Stormont Belfast Northern Ireland. Hofmann Hans Dr.rer.nat.26-28 West Cromwell Road London S.W.5. Horsley John Bryan. 119 Heaton Park Road Newcastle upon Tyne 6. Houlton Dennis John. “Thetis,” Thornton Road, Goxhill Barrow-on-Humber Lincs. Humphries John Frank. 100 Higgins Lane Quinton Birmingham 32. Hunter Geoffrey. 48 Allenby Road Cadishead Man- Chester Lancs. Iley Ralph Ph.D. A.R.I.C. 14 Coast Road North Shields Northumberland. Insole Joan Margaret B.Sc. 9 Kendale Road Bromley Kent. Itzcovitz Stephen. 94 Bermondsey Street Bermondsey S.E.1. Jeffrey Raymond Frederick William. 16 Kenmore Grove Cadishead Manchester. Kelly William Ph.D. clo C.S.I.R.O. Coal Research Station P.O. Box No. 3 Chatswood New South Wales Australia. 41 1 Kennedy James B.Sc. 93 Mountblow Road Dalmuir West Glasgow.Kidd Robert Garth B.Sc. 47 Hornsey Rise Gardens London N.19. Kovalendo Vladimir B.A. 1102 East Limberlost Drive Tucson Arizona U.S.A. Lamson Davis William B.S. Chemistry Department University of Arizona Tucson Arizona U.S.A. Langworthy William Clayton B.S. 1314 Arch Street Berkeley 8 California U.S.A. Linde Horst H. A. Dr.Phi1. 12a Courtfield Gardens London S.W.5. Litt Morton Herbert Ph.D. Chemistry Department College of Forestry Syracuse 10 New York U.S.A. Longworth Wilfred Roy M.Sc. Ph.D. Chemistry De- partment Huddersfield College of Technology, Huddersfield. Luckcock Ronald George B.Sc. A.R.J.C. 110a Alexandra Park Road Muswell Hill N.lO. McGarvey James Edward Brian B.Sc. 7 Malone Avenue Belfast 9.MacLean Ian Ross B.Sc. 72 Wallace Street Greenock Renfrewshire. Mahishi Narain Bindu Rao M.Sc. Department of Organic Chemistry Indian Institute of Science. Bangalore 12 India. Mellor Ann Sylvia B.Sc. 150 Sutton Flats Salford 6 Lancs. Mitchell Francis William Ph.D. 933 Dudley Street Saskatoon Saskatchewan Canada. Monsimer Harold Gene M.S. Ph.D. 341 Hansberry Street Philadelphia 44,Pennsylvania U.S.A. Morrison Anthony. 50 Shaftesbury Avenue Southamp- ton. Moss Gerald Peter B.Sc. A.R.C.S. 30 Culverhay, Ashtead Surrey. Nyburg Stanley Cecil Ph.D. 29 The Cottage Keele Staffs. Ottesen Martin Dr.Phi1. Carlsberg Laboratory 10 GI. Carlsbergvej Copenhagen Valby Denmark. Parfitt Robert Thomas B.Pharm. 48 Arboretum Street Nottingham.Pearce Christopher Arthur Ph.D. 113 Swifts Green Road Stopsley Luton Beds. Pike Dennis Gordon. 30 Mayfield Street Spring Bank Hull. Pike Ronald Marston M.S. Ph.D. Chemistry Depart- ment Lowell Technological Institute 1 Textile Avenue Lowell Mass. U.S.A. Poad Norman Evan John. Needler Hall Cottingham Hull. Pyke David Anthony. 13 Ayr Road Shadsworth, Blackburn Lancs. Reaveley David Andrew. Cobh Main Street Swanland N. Ferriby East Yorks. Rees William Teifian. 4 Ffordd-y-Brain Fforest-fach Swansea. Ridge Mayhew John M.Sc. C.S.T.R.O. Division of Building Research Graham Road Highett Victoria Australia. Ridgewell Brian John. Crewe Hall Clarkehouse Road Sheffield 10. Riding Robert Furniss. 17 Shepley Drive Hazel Grove via Stockport.Riley Philip Neville Keith. 8 Fairfield Road Sandylands Morecambe. Ruegg Rudolf Dr.Sc. Research Department F. Hoffman-La Roche and Co. Ltd. Grenzacherstrasse Basle Switzerland. Sacco Adriano. Via Pietro da Cortona 11 Milan Italy. Sammes Peter George. 122 Woodrow Avenue Hayes Middlesex. Scattergood Allen A.B. Ph.D. Lowell Technological Institute 1 Textile Avenue Lowell Massachusetts U.S.A. Schnider Otto Dr.Plii1. F. Hoffman-La Roche and Co. Ltd. Department VI Grenzacherstrasse Basle, Switzerland. Schofield John Trevor B.Sc. 37 Plymouth Road, Penarth Glam. Scott Michael Delmage B.Sc. 30 Queens Park West Drive Bournemouth. Scuffham James Barrie. 9 Lowfield Avenue Brambles Farm Est. Middlesbrough. Searle David Anthony.Ferens Hall Cottingham Hull. Selman Lawrence H. A.B. 40 Dunstan Road London N.W.ll. Shephard Francis Eli B.Sc. 4 Sydney Terrace St. James Street Londonderry Northern Ireland. Shepherd Robert Gordon P1i.D. University Chemical Laboratory Lensfield Road Cambridge. Sims Robert Fraser B.Sc. “Fairneyknowe,” Rignals Lane Galleywood Chelmsford Essex. Smith Anthony David. Christ Church Oxford. Snelling David Roy B.Sc. 120 Willows Road Cannon Hill Birmingham 12. Somerfield Adrian Edward Ph.D. Derrydown Kilmas- hogue Rathfarnham. PROCEEDINGS Surtees John Richard B.Sc. A.R.C.S. A.R.I.C. The Flat East Mead New Brighton Road Emsworth Hants. Taylor John Robert. Ferens Hall Cottingham East Yorks. Turco Aldo Dr. Chem.Instituto Chimica Generale Via Loredan 6 Padova Italy. Vazakas Aristotle John M.S. Ph.D. 15A Franklin Park Apartments Philadelphia 38 Pennsylvania U.S.A. Vickery Brian. Organic Chemistry Research Laboratory The University Reading. Warburton Dennis BSc. 4 Spring Gardens Little Sutton Wirral Cheshire. Warman John Melvin. 105 Ellesmere Road Newcastle upon Tyne 4. Warren Keith Derek Ph.D. 153 Victoria Road, Southend-on-Sea. Welch Malcolm James B.Sc. 41 Boma Road Trentham Staffs. Welham Robert David. 24 Lancaster Gardens Kingston upon Thames. Wells Robin John M.Sc. 12 Heathcote Street London W.C.1. Yardley John Patrick B.Sc. Organic Chemistry Depart- ment The University Nottingham. Young David Anderson Ph.D. A.R.C.S. Lind House Orchard Lane East Hendred Berks.Young Thomas E. M.S. Ph.D. Chandler Chemistry Laboratory Lehigh University Bethlehem Penn-sylvania U.S.A. ADDITIONS TO THE LIBRARY Chemie Lexikon. H. Rompp. 2 vols. 4th edn. Pp. 5104. Franckh’s Verlagshandlung. Stuttgart. 1958. Lehrbuch der organischen Chemie. P. Karrer. 13th edn. Pp. 1057. Georg Thieme Verlag. Stuttgart. 1959. (Presented by the Publishers.) Beilstein’s Handbuch der organischen Chemie. Edited by F. Richter. Drittes Erganzungswerk die Literatur von 1930-1949 umfassend. Vol. I. Part 3. Pp. 2539-5953. Springer-Verlag. Berlin. 1959. (Presented by the Editor.) Tabellen zur Rontgen-Emissions-und Absorptions- Analyse. K. Sagel. (Anleitungen fur die Chemische Laboratoriumspraxis. Vol. 2.) Pp.135. Springer-Verlag. Berlin. 1959. Tables of constants and numerical data. 10. Selected constants optical rotatory power. 111. Amino-acids. J.-P. Mathieu P. Desnuelle and J. Roche. Publication sub- sidised by the International Commission of Tables of Constants and by the Centre National de la Recherche Scientific. Pp. 61. Pergamon Press. London. 1959. Perfumes cosmetics and soaps with special reference to synthetics. W. A. Poucher. Vol. I being a dictionary of raw materials together with an account of the nomencla- ture of svnthetics. 6th edn. PP. 463. ChaDman and Hall. London.ll959. Chemistry and chemical technology in Ancient MesopotaAa. M. Levey. Pp. 242. Elsevier Publishing Co. Amsterdam. 1959. Pioneers of petrol a centenary history of Carless Capel and Leonard 1859-1959.E. Liveing. Pp. 95. H. F. and G. Witherby Ltd. London. 1959. (Presented by Carless Capel and Leonard Ltd.) An introduction to chemical nomenclature. R. S. Cahn. Pp. 96. Butterworths Scientific Publications. London. 1959. (Presented by the Author.) Physical chemistry. N. K. Adam. 2nd edn. Pp. 658. Clarendon Press. Oxford. 1958. (Presented by the author.) Liquids and liquid mixtures. J. S. Rowlinson. Pp. 360. Butterworths Scientific Publications. London. 1959. Liquid-liquid extraction theory and laboratory practice. L. Alders. 2nd edn. Pp. 205. Elsevier Publishing Co. Amsterdam. 1959. Fluidization. M. Leva. Pp. 327. McGraw-Hill Book Company Inc. New York. 1959. Dendritic crystallisation. D. D.Saratovkin. 2nd edn. Translated from the Russian by J. E. S. Bradley. Pp. 126. Consultants Bureau Inc. New York. 1959. Elektronen-und Ionenprozesse in Ionenkristallen mit Beriicksichtigung photochemischer Prozesse. 0. Stasiw. (Struktur und Eigenschaften der Materie in Einzeldarstel- lungen. Vol. 22.) Pp. 307. Springer-Verlag. Berlin. 1959. Modern aspects of electrochemistry No. 2. Edited by by J. O’M. Bockris. Pp. 416. Buttenvorths Scientific Publications. London. 1959. Electrolytic conductance. R. M. Fuoss and F. Accascina. Pp. 279. English edn. Interscience. London. 1959. Electrolyte solutions the measurement and interpreta- tion of conductance chemical potential and diffusion in solutions of simple electrolytes. R. A. Robinson and R.H. Stokes. 2nd edn. Pp. 539. Butterworths Scientific Publications. London. 1959. Some problems of chemical kinetics and reactivity. N. N. Semenov. Translated by J. E. S. Bradley. Vol. 2. 2nd edn. Pp.168. Pergamon Press. New York. 1959. DECEMBER 1959 A supplement to W.H. Keesom’s “Helium”. E. M. Lifshits and E. L. Andronikashvili. Translated from the Russian. Pp. 167. ConsultantsBureau Inc. New York.1959. Ammonia manufacture and uses. A. J. Harding. Published under the auspices of Imperial Chemical lndustries Ltd. Pp. 41. Oxford University Press. 1959. (Presented by the publishers.) Electrolytic manufacture of chemicals from salt. D. W. F. Hardie. Published under the auspices of Im- perial Chemical Industries Ltd. Pp. 74. Oxford University Press.1959. (Presented by the publishers.) Uranium production technology. Edited by C. D. Harrington and A. E. Ruehle. Pp. 579. D. Van Nostrand. Princeton N.J. 1959. Zinc the science and technology of the metal its alloys and compounds ; prepared with co-operation of the American Zinc Institute. Edited by C. H. Mathewson. (American Chemical Society Monograph No. 142.) Pp. 721. Reinhold Publishing Corporation. New York. 1959. Rubber to metal bonding. S. Buchan. 2nd edn. Pp. 300. Crosby Lockwood and Son. London. 1959. (Presented by the publishers.) Organic chemistry of bivalent sulfur. E. E. Reid. Vol. 1. Pp. 539. Chemical Publishing Co. New York. 1958. Thermodynamic properties of methane. H. E. Tester. Pp. 58. British Petroleum Co.Ltd. Sunbury-on-Thames. 1959. (Presented by the publishers.) Oberflachenaktive Anlagerungsprodukte des Athylen- oxyds ihre Herstellung Eigenschaften und Anwendung. N. Schonfeldt. Pp. 459. Wissenschaftliche Verlagsgesell- schaft M.B.H. Stuttgart. 1959. The physico-chemical constants of binary systems in concentrated solutions. J. Timmermans. Volume I. Two organic compounds (without hydroxyl derivatives). Pp. 1259. Vol. 2. Two organic compounds (with at least one hydroxyl derivative). Pp. 1272. Interscience Publ. Inc. New York. 1959. Polyester handbook. Issued by Scott Bader and Co. Ltd. Polyester Division. 4th edn. Pp. 128. Scott Bader and Co. Ltd. Wollaston Northants. 1959. (Presented by the publishers.) Techniques of polymer characterisation.Edited by P. W. Allen. Pp. 256. Butterworths Scientific Publications. London. 1959. Linear and stereoregular addition polymers poly-merisation with controlled propagation. N. G. Gaylord and H. F. Mark. (Polymer Reviews. Vol. 2.) Pp. 571. Interscience Publishers Inc. New York. 1959. Aromatic substitution ; nitration and halogenation. P. B. D. de la Mare and J. H. Ridd. Pp. 252. Butter- worths Scientific Publications. London. 1959. Organic chemistry. I. L. Finar. Vol. 2. Stereochemistry and the chemistry of natural products. 2nd edn. Pp. 834. Longmans Green and Co. Ltd. London. 1959. (Pre- sented by the author.) Steroids. L. F. Fieser and M. Fieser. Pp. 943. Rein- hold Publishing Corporation. New York. 1959. Mono- and sesquiterpenoids.P. de Mayo. (Chemistry of Natural Products. Vol. 2.) Pp. 320. Interscience Publishers Jnc. New York. 1959. The higher terpenoids. P. de Mayo. (Chemistry of Natural Products. Vol. 3.) Pp. 239. Interscience Pub- lishers Inc. New York. 1959. Principles of biochemistry. A. White P. Handler E. L. Smith and D. Stetten jun. 2nd edn. Pp. 1149. McGraw- Hill Book Company Inc. New York. 1959. Medicinal chemistry. A series of reviews prepared under the auspices of the Division of Medicinal Chem- istry of the American Chemical Society. Edited by F. F. Blicke and R. H. Cox. Vol. IV. Pp. 334. John Wiley and Sons Inc. New York. 1959. The viruses biochemical biological and biophysical properties. Edited by F. M. Burnet and W. M. Stanley.Vol. 2. Plant and bacterial viruses. Pp. 408. Academic Press Inc. New York. 1959. Antibiotics their chemistry and non-medical uses. Edited by H. S. Goldberg. Pp. 608. D. Van Nostrand. Princeton N.J. 1959. Behavior of enzyme systems an analysis of kinetics and mechanism. J. M. Reiner. Pp. 317. Burgess Publishing Co. Minneapolis. 1959. (A)Vitamin D4bioassay of oils and concentrates. Pp. 17. (B) Vitamin A potency of beta-carotene. Pp. 11. (C) Assay of vitamin A oils. Pp. 7. I.U.P.A.C. Appl. Chem. Section Food Divn. Vitamin Assay Subdiv. Butterworths Scientific Publications. London. 1959. Determination of copper content of foodstuffs :photo-metric method. Pp. 4. I.U.P.A.C. Appl. Chem. Section Food Divn. Trace Elements in Food Subdiv. Butter- worths Scientific Publications.London. 1959. Tobacco Manufacturers’ Standing Committee research papers No. 4. Cigarette smoke condensate preparation and routine laboratory estimation. H. R. Bentley and J. G. Burgan. Pp. 9. Tobacco Manufacturers’ Standing Committee. London. 1959. (Presented by the publishers.) Ultracentrifugation in biochemistry. H. K. Schachman. Academic Press Inc. New York. 1959. Researches in geochemistry. Edited by P. H. Abelson. Pp. 51 1. John Wiley and Sons Inc. New York. 1959. The geochemistry of rare and dispersed chemical elements in soils. A. P. Vinogradov. Translated from the Russian. 2nd edn. Pp. 209. Consultants Bureau Inc. New York. 1959. Apparatus and methods of oceanography. Part I Chemical. H. Barnes.PD. 341. George Allen and Unwin -Ltd. London. 1959. River Pollution. Vol. 1. Chemical analysis. L. Klein. Pp. 206. Butterworths Scientific Publicahons. London. 1959. Analysts’ handbook. Issued by the British Transport Commission. British Railways Research Department. Chemical Services. Vol. 3. Pp. 22. British Transport Commission. London. 1959. (Presented by F. Fancutt.) Gas chromatography. A. I. M. Keulemans. Edited by C. G. Verver. 2nd edn. Pp. 231. Reinhold Publishing Corporation. New York. 1959. Source book of industrial solvents. I. Mellan. Vol. 3. Monohydric alcohols. Pp. 276. Reinhold Publishing Corporation. New York. 1959. The design and construction of high pressure chemical plant. H. Tongue. 2nd edn. Pp. 250. Chapman and Hall.London. 1959. International Committee of Electrochemical Thermo- dynamics and Kinetics. 9th Meeting. Paris. 1957. Pp. 489. Butterworths Scientific Publications. London. 1959. Hydrogen bonding papers presented at the Symposium on Hydrogen Bonding held at Ljubljana 1957. Edited by D. Hadzi and H. W. Thompson. Sponsored by the Inter- national Union of Pure and Applied Chemistry and the Union of the Chemical Societies of F.P.R. Yugoslavia. Pp. 571. Pergamon Press. London. 1959. La chimie des hautes tempkratures second colloque national Paris 1957. Organised by the Centre National de la Recherche Scientsque. Pp. 178. Centre National de la Recherche Scientifique. Paris. 1959. (Presented by the French Embassy.) Proceedings of the Second United Nations International Conference on the Peaceful Uses of Atomic Energy held in Geneva 1958.Volume 20. Isotopes in research. Pp. 267. United Nations. Geneva. 1958. Utilization of nitrogen and its compounds by plants. 414 PROCEEDINGS (Symposia of the Society for Experimental Biology No. Khimicheskaya Nauka i Promyohlennost from 1958, 13.) Pp.385.The University Press. Cambridge. 1959. 3 (2). VI Jubileuszowy Zjazd Polskiego Towarzystwa Optics and Spectroscopy (Translation of Russian Chemicznego held in Warsaw 1959. Streszczenia Journal-Optika i Spetroskopiia) from 1959 6. komunikatow. (Chemia Analityczna 1959. Special Radiokhimiya 1959 1. Supplement.) Pp. 477. Panstwowe Wydawnictwo Nauk- West African Journal of Biological Chemistry from owe.Warsaw. 1959. (Presented by C. S.General Secre- 1959 3 (2). tary.) Biochemical Biophysical Research Communications NEW JOURNALS 1959 1. Journal of Nuclear Materials 1959,l. Rubber Chemistry and Technology from 1959 32.
ISSN:0369-8718
DOI:10.1039/PS9590000377
出版商:RSC
年代:1959
数据来源: RSC
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