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Proceedings of the Chemical Society. May 1963 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue May,
1963,
Page 125-156
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY MAY 1963 THE STRANGE HISTORY OF INTENSIVE DRYING By W. V. FARRAR (Tm UNIVERSITY, MANCHESTER) It is not often that the placid history of chemistry is troubled by a search for the Abominable Snowman. Yet on reading the flurry of papers appearing during the nineteen-twenties on the subject of Intensive Drying one is often re- minded of that elusive creature. The experi- mental results were vouched for by Professor H. B. Baker a man of unquestioned integrity and immense manipulative skill. They have been rather uneasily ascribed to human error and trivial causes; but the whole matter has been allowed to bury itself deep in the archives of chemistry and is now seldom referred to. Herbert Brereton Baker was born near Black- burn in 1862 the son of a clergyman.He was educated at Manchester Grammar School and at Oxford. After graduation he worked under H. B. Dixon then left to teach chemistry at Dulwich College employing his leisure in re- search and publishing a number of papers. He was made a Fellow of the Royal Society in 1902 (the days when this could happen to a school- master already seem as remote as the Crusades). From 1903 to 1912 he was Dr. Lee's Reader in Chemistry at Oxford; he then went to Imperial College as Professor and Director of the Chem- istry Department where he remained until his retirement in 1932. He died in 1935. His first published work dealt with the in- fluence of traces of water on chemical reactivity a theme to which he returned in many later papers.In 1912 however he published jointly with his wife an astonishing claim to have raised the boiling points of dinitrogen pioxide and tetroxide by 44"and 47" respectively. 'In con- sequence of a private communication from Pro- fessor A. Smith with regard to the volatility of dried calomel a search was made through old laboratory notebooks . . .among the determina- tions of the vapour pressure of nitrogen trioxide two instances had been noticed in which this substance carefully dried had failed to boil at 15" the ordinary boiling point being -2O." This observation was further studied and the boiling point of an old dried sample redetermined using an ingenious apparatus to prevent contamina- tion by water.The compound boiled at 43". The authors sketched an explanation according to which dinitrogen trioxide was an associated liquid; absence of water hindered dissociation to simple molecules and allowed the complex molecules to boil as such. Shortly afterwards the first World War diverted Baker's energies into the problems of gas-masks and it was not until 1922 that he returned to the subject in print. The delays caused by the War had extended the drying of the samples to a far longer period than usually allowed for experiments of this sort. Ten liquids of different chemical types were dried over phosphorus pentoxide some (where no reaction was to be feared) actually in contact with the pentoxide. The following remarkable I25 boiling points were observed (normal boiling points in brackets) :bromine 1 18* (63");mercury 42-25" (358"); hexane 82" (68.4"); benzene 106"(80'); carbon disulphide 80" (49-5 "); carbon tetrachloride > 112" (78"); diethyl ether 83" (35"); methanol > 120" (66"); ethanol 138" (78.5"); and n-propanol 134"(95").Baker com- mented "The boiling . . .proceeded quite quietly ; no sign of the violent ebullition which accom- panies the breaking down of a superheated con- dition was observed. There was nothing in the behaviour of the liquids except the reading on the thermometer which suggested anything ab- normal in their boiling. In some cases two thermometers were enclosed in the bulbs one dipping in the liquid and the other about 3 cm.above its surface. The temperatures read on the latter were at most 2" above the normal boiling point of the liquid and yet when the condensed liquid from the distillation was again heated it did not enter into a state of ebullition until the abnormal high temperature had been reached." Most of the liquids especially ether and the alcohols rapidly regained their normal boiling points on exposure to moist air. The benzene however still boiled at 105" after exposure for one day. It was then shaken with water; and "the water could be boiled through the layer of benzene only slow evaporation taking place." (This experiment seems to have been repeated before an audience at a meeting of the Chemical Society.) Some preliminary work was also reported on other properties of the dried liquids.No changes in density were observed; the vapour pressure of the ether was 374 mm. at 20" instead of the expected 442 mm. ; and "definite alterations" were found in the surface tensions. In his next paper (1923) Baker reported that when his dry benzene was distilled the vapour temperature rose during the distillation from 81 " to 87" indicating that fractionation was taking place. The vapour densities of dried ether and methanol were found to be 81.7 and 45 respec-tively instead of the expected 37 and 16. These results were interpreted in terms of the then fashionable theory of allotropy due to Andreas Smits (some of the experiments were performed with the personal collaboration of Smits).Baker's next two communications (1 927,1928) took the unusual form of Presidential Addresses to the Chemical Society. This unfortunately PROCEEDINGS prevented him from going into the detail which the subject so imperatively demands. Apart from a few more instances of aberrant physical pro- perties (vapour densities and latent heats) neither paper was strictly about intensive drying. The first dealt with the effect of "catalysts" on the physical properties of liquids. Acetic acid in con- tact with charcoal platinum black or thoria was found to have a vapour pressure greater than normal by 1-42 mm.; the difference was in-creased by heating and diminished by cooling. The vapour pressure of benzene in contact with finely-divided nickel was increased by 3 mm.and that of ether in contact with charcoal by as much as 60 mm. Surface tension measurements also showed anomalies which were interpreted as increases in molecular weight. It was implied that the effect of water (or its absence) on physical properties was merely a special case of a general effect caused by a whole class of "catalytic" substances. In his second Presidential Address Baker had apparently abandoned this view. He now ex- plained the abnormal properties of intensively dried liquids by supposing that in "ordinary dry" liquids there were minute drops of water (not molecules) which electrostatically destabilised the large "associated" molecules present in the intensively dried liquid.This he tried to confirm by boiling "ordinary dry" benzene between two platinum plates; the boiling point was 79.6". "By connecting the platinum plates with a 400-volt battery for some hours the boiling point of the benzene was raised to 91 '. . . . This effect was not destroyed when the apparatus stood for a few days with the plates disconnected from the battery; the boiling point was 88"and the boiling was steady not violent. While the boiling was proceeding the voltage was again applied and in two minutes the evolution of the bubbles stopped. Measurement of the surface tension of the liquid indicated a molecular weight of between two and three times that corresponding to the formula C,H,." It must be said at once that no one has ever been able to repeat this remarkable experiment.Baker's last long paper (1929) was a detailed account of the techniques which he had found to be necessary to obtain his results. He was particularly insistent on the great affinity of glass for water vapour not only on the surface but in the body of the glass as well. There are many MAY1963 shrewd though unexpected observations; “mod- ern glass contains a large number of bubbles which when drawn out into tubing lead to the formation of capillaries inside or outside the tube. These fill with water . . . and since their walls are very thin the water may accidentally be liberated in the dried apparatus.” Whatever Baker’s other shortcomings everyone who reads this paper will be convinced that his benzene was indeed very dry.Experiments on intensive drying are kery time-consuming and it was several years before attempts to repeat them were made public. Some confirmation of Baker’s results came from Roberts and Bury (1923) and Mali (1925) but their accounts are too vague to have much evidential value. An objection by Balarew (1927) that the use of phosphorus pentoxide for drying causes slow chemical reaction with the substrate was answered by Baker (1927) who indicated that Balarew had probably been using impure pentoxide containing the volatile lower oxide. Serious criticism first came from Lenher and Daniels (1928) working in the du Pont labora- tories. (Dr. Lenher is now a Vice-president of du Pont).They dried benzene and carbon tetra- chloride over phosphorus pentoxide for four and a half years but could find no change in boiling point; this was determined by heating with an immersed platinum wire through which a current flowed. Lenher again (1929) reported normal vapour pressures for carbon tetrachloride dried for five years. (The careful reader will note how- ever that the first determination of vapour density after the tube was opened gave a mole- cular weight of 160.1 instead of 153-8). But Lenher’s really damaging point was to show (1929) that ordinary benzene when heated by means of a bath in an apparatus such as Baker used gave spurious boiling points often quiet as much as 30” above the normal temperature. He confidently ascribed most of Baker’s results to simple superheating.Negative results were also reported by Tim- mermans (1 929) ; Briscoe Peel and Robinson (1929);and Cohen and Cohen de Meester (193 1). The work of Greer (1930) is as difficult to understand as Baker’s own which it is intended to explain. She confined her experiments to measurements of vapour pressure which can be made with great accuracy. Benzene carbon tetra- chloride and carbon disulphide dried over silica gel (but not when dried over phosphorus pent- oxide) showed decreases in vapour pressure comparable with those recorded by other workers. This she ascribed rather to the presence of traces of water in the “normal” liquid than to any catalytic effect resulting from drying; it was not made clear how this could be reconciled with Raoult’s Law which the observations con- travened by a factor of 405.Manley (1929) was equally unorthodox. He observed some remarkable variations in the re- fractivity of benzene during the process of dry- ing which he supposed were due to the slow decomposition of stable benzene hydrates. To explain all his results however he had to postu- late that under some conditions benzene could re-hydrate itself at the expense of slightly moist phosphorus pentoxide. Among Baker’s other critics must be men- tioned Menzies and his colleagues (1929 1930) who showed that when the sample was pure the previous thermal history of a liquid had no effect on its boiling point. Such effects had been observed not only by Baker but as they admit by a large number of other physical chemists.Baker’s final answer to all his critics (193 1) was to point to his 1929 paper and to claim that they had not observed all the stringent precautions set out in it. This (though true) was of course irrelevant to Lenher’s finding that abnormal boiling points can be obtained with undried benzene using Baker’s apparatus. At this point (1931) an ingenious experiment was published by J. W. Smith. He recorded at regular intervals the time taken to distil (in a closed apparatus) a certain fraction of a sample of ethyl bromide while the sample was being dried. Three curves resulted corresponding to kettle temperatures of lo” 15” and 20”; the receiver was always kept in melting ice.In the most striking experiment the time taken in- creased steadily to a maximum at 20 weeks then suddenly returned to its original value; after this it slowly increased again. Smith ascribed this to the sudden bursting of one of the capillaries filled with water which Baker had mentioned. However towards the end of the paper in what looks like an afterthought Smith is prepared to ascribe the whole of the results to superheating. The same loss of confidence can be seen in Baker’s old friend Smits. His early enthusiasm (1924) had so waned by 1928 that he was restrict- ing the effects of drying to what he called “velocity Phenomena” (dynamic effects). BY 1934 in his last paperonthesubject,heseemed to have come Sadly to the conclusion that the whole thing was a mare’s nest.And so it may well have been. Thirty years of experience with liquids dried and undrjed by a body of chemists ten times larger than in Baker’s day has not resulted in even a mythology or underground tradition of the strange behaviour PROCEEDINGS of intensively dried liquids. Yet on re-reading the old papers it is difficult to believe that these able men all fooled themselves so thoroughly. The last word is still with ~nshelwood9s lapidary sentence (193 1) “Experimentally the situation is not unlike that prevailing in psychical research where we are told m~~t ofthe evidence can be ruled out but a small obstinate residuum has to be contended with.’’ “PURE AND APPLIED CHEMISTRY” THE appearance of any new journal these days is apt to be greeted with a mixture of resignation and protest.However when the new venture appears under the eminently respectable aegis of the Inter- national Union of Pure and Applied Chemistry a closer look is warranted before dismissing it as yet another brain-child of a profiteering publisher battening on a captive audience. This project Pure and Applied Chemistry has been designed to centralise in one convenient source the main lectures of selected I.U.P.A.C. Symposia and such internation- al recommendations as nomenclature calibration tables physical data and reports of commis-sions on standardisation. Hitherto such information has been randomly scattered in a highly inconvenient and expensive manner.The new arrangement which is financially as well as scientifically advantageous to I.U.P.A.C. has been made possible by the praise- worthy altruism of the publishers who are producing at their financial risk all that I.U.P.A.C. choose to send them. Each volume of the journal consists of four parts which in the early days appeared at irregular intervals; five volumes have been produced so far and a sixth is due to be completed shortly. The publication rate is now two volumes annually. The usual European languages are used although English has predominated so far. From the point of view of organic chemistry the bulk of material appearing is not readily available elsewhere and frequently has considerable pedagogic as well as scientific utility.The issue containing the special lectures at the Australian Symposium on Natural Products can be taken as a good example (Volume 2). This contains many good things among which may be cited a general appraisal of the present position of natural product chemistry (Lord Todd) authoritative review lectures (e.g. Brockmann on the actinomycins sorm on medium-sized ring ter- penes Barton on lactonic bitter principles and Cornforth on polyisoprenoid biosynthesis) and a dramatic exposition of the solution of a spectacular single problem (Woodward on the synthesis of chlorophyll). There is no insistence on the uniform procrustean prose of many journals and the in- dividual styles of the contributors present interesting contrasts ranging from the magisterial periods of Lord Todd through the mellifluous urbanities of Woodward (which induce a rich feeling akin to gargling with whipped cream) the dead-pan Bartonian inevitability the staccato phrase-pumping of Djerassi to the modest genial intellectuality of Cornforth.However no mere printed words can do justice to the felicity and wit of Lederer’s exposition. Such presentation gives a keen feeling of the excite- ment of the chase and the sheer enjoyment of the subject and these aspects are brought out particu- larly well in Woodward’s contribution. We look forward to Volume 6 which promises a further feast from the recent Prague Symposium on Natural Pro-ducts and a most interesting series of lectures from the Florence Symposium on Pharmaceutical Chem- istry which contains much fundamental work.Physical chemistry is a more closely-knit affair than organic chemistry and the value of symposia is perhaps rather less. The symposium on thermo-dynamics in Volume 2 for example is unexciting, and many of the papers could have-and some nearly have-appeared in the normal literature where most people could find them if they wanted to. The same is partly true for the 5th European Conference on Molecular Spectroscopy in Volume 4 although here there is a charmingly personal introductory paper by Bright Wilson. There are also useful short surveys of the position in n.m.r. and e.s.r. by Richards and Whiffen respectively-but when are these fields not being surveyed? On the other hand Volumes 4 and 5 both contain papers of outstanding interest to physical chemists.Volume 4 contains special lectures given to the International Symposium on Macromolecular Chem- istry held in Montreal in 1961. Those by Natta on progress in stereospecific polymerisation and by MAY1963 Furukawa and Saegusa on the high polymerisation of aldehydes alkylene oxides and diketen in par- ticular are valuable summaries of the work of the groups associated with these authors and there are many others of similar merit. Equally outstanding but of much wider interest are the plenary lectures given to the 17th I.U.P.A.C. Congress. These are by Dainton Daudel Semenov (on solids now), Schwarzenbach and Wilhelm (on the a priori design of chemical reactors).Dainton’s lecture “New horizons in physical chemistry,” should be required reading for every undergraduate. Two of the other lectures in this symposium emphasize the trend in physical chemistry to study electrochemistry of gases Talrose on ion-molecule reactions and Fells on ionized gases for magnetohydrodynamic power generat ion. Since the renascence of inorganic chemistry no series on general chemistry could possibly be con- sidered complete without a discussion of inorganic complexes. Here in Volume 6 are the papers of the 7th International Congress on Co-ordination Chem- istry. Inorganic chemistry is also served by a com- prehensive table of solubility products in the same volume and by the most important report of the Commission on Atomic Weights in Volume 5.This contains the first table of atomic weights based on the standard 12C = 12 exactly and sumarises the position of all the values given. On the more “applied” side the Wood Chemistry Symposium contains a useful summary of present views on the structure and biogenesis of lignin (Freudenberg) and the wood carbohydrates (J. K. N. Jones; Hirst) and the application of such funda- mental knowledge to the processes involved in wood technology. As an example of a most useful com- pilation of physical-organic data may be cited the bilingual (German and English) compendium of dis- sociation constants of organic acids in aqueous solu- tion (Volume 1) preceded by a critical appraisal of methods (the name and formula of compound 154 p.289 are misquoted). The printing and presentation are of high standard and the clarity of the formula are particularly wel- come. Misprints are very rare although an amusing transposition crops up in Volume 3 (p. 169) where the phrase “conditionnelles du rat” becomes trans- formed into “conditionne Dulles rat” (subconscious Gallic anti-Americanism ?). One criticism involves the rather 19th century aspect of the cover which in combination with the antediluvian appearance of the symbol lends a depressingly drab air to the publica- tion. A little imaginative modernity in the cover- layout would not have come amiss. All in all at a price of ;f6per volume the journal is a good buy and should be available in every science library.A welcome feature is that individual items may be obtained separately at a very reasonable cost. T.L.C. R.A.R. COMMUNICATIONS Reactions of the Intermediate from Reduction of Bis-a-bromobenzyl Ketone By R. C. COOKSON and M. J. NYE (THEUNIVERSITY, SOUTHAMPTON) THEsuggestion has been made from time to time1-* that the Favorskii rearrangement5 of a-halogeno- ketones proceeds at least in some cases through a delocalised intermediate in which the four atoms comprising the carbonyl group and the two a-carbon atoms are in a plane their parallel p-orbitals being occupied by four electrons. In an ingenious experi- ment based on this idea Fort4 has recently reduced bis- a-bromobenzyl ketone (I) with sodium iodide in methanol to benzyl a-rnethoxybenzyl ketone also formed by reaction of benzyl a-chlorobenzyl ketone with 2,6-lutidine in methanol.Since the results did not seem to us to distinguish clearly between a planar delocalised intermediate* (11) and a cyclopropanone (111) (or the interconvertible pair) we have studied the reduction of the dibromide (I) in the presence of olefins and of dienes. Reduction6 with zinc dust in boiling acetonitrile gave the diketone (IV) in 60% yield identical with a sample made by condensation of dibenzyl ketone and * For conciseness we have written the intermediate as an allylic carbonium ion bearing an oxide on the middle carbon atom (cf. ref. 2). Aston and Newkirk J.Amer. Chem. Soc. 1951,73,3900. Burr and Dewar J. Chem. Soc. 1954 1201. House and Gilmore J. Amer. Chem. Soc. 1961 83 3972. Fort J. Amer. Chem. Sac. 1962,84,2620. Kende Org. Reactions 1960 11 261. Gustavson J. prakt. Chem. 1887 36 300. bemy1 a-bromobenzyl ketone.’ The same product was still formed though in lower yield when acrylo- nitrile was used as solvent. Small quantities of the cyclopentenone (V) were also produced. Alkali cyclised the diketone (IV) to (V) and its tautomer (VI). (Satisfactory analyses and molecular weights have been obtained for these and the other new compounds mentioned .) Reduction of the dibromide (I)with sodium iodide in acetone containing tetracyanoethylene led to a ketone m.p. 164-1655” (decomp.) (36 % yield) formulated as (VII) (vmax.1747 cm.-l; Amax. 325 mp E 8,900; in acetone only one singlet apart from aromatic protons at 4.88~)~ which on heating under reduced pressure gave a purple product pre- sumably (VIII). The dibromide (I) with sodium iodide in the presence of cyclopentadiene gave an adduct m.p. 149*5-151*5” (IX; Z = CH.J (Vmax. 1703 cm.-l; Amax 259 mp E 430 and 286 mp E 33; in chloroform above 37 there were a singlet from HA at 3.827 a multiplet from HBat 7.037 a doublet at 6.287 with J = 3 c./sec. from H, and a multiplet from Hzat 7.817). In the presence of furan an analogous adduct m.p. 134-135” (IX; Z = 0),was formed in 65% yield? (vmax. 1702 cm.-l; Amax. 259 mp E 570 and 286 mp E 34; in CCI above 37- a singlet from HAat 3.677 a doublet from H at 5.157 and a doublet also with J = 5 c./sec.from Hc at 6.077). The same adduct (IX; Z = 0)has just been obtained by Fort himselfs by treatment of benzyl a-chlorobenzyl ketone with 2,6-lutidine and furan in dimethylformamide (1 8 % yield). Although other mechanisms can be invented to explain these results the most economical and attractive is to in- voke (11) as an intermediate:** in the case of tetra- cyanoethylene the initial adduct then losing hydrogen cyanide. The simplicity of the proton magnetic resonance spectra of the two adducts (IX) indicates a plane of symmetry through the carbonyl group and the very weak n -+7r* absorption shows that the two phenyl groups must both be eq~atorial.~ A decision between the boat conformation of the six-membered ring with the benzylic hydrogen atoms (H,) trans to those on the bridge-head (H,) and the alternative chair with them cis (X) can be based on the coupling constantro between them.In the former configuration the di- hedral angle is about go” and the expected J = 0 c./sec. in the latter (X) the angle is about 60° PROCEEDINGS giving J = 2 c./sec. The configuration (X) that follows from the measured coupling constant (3-5 c./sec.) is the one that would arise from “endo” addition of the extended conformation (11) of the hypothetical intermediate in analogy with Alder’s rulesr1 Ph (IV) The reasonable assumption4 that iodide ion reduces the dibromide (I) directly to the intermediate (11) (or to the cyclopropanone) is not justified.One minute after treatment of the dibromide with sodium iodide in acetonitrile 87% of two moles of sodium bromide had separated from solution and the CO stretching frequencing had fallen to 1714 cm.-l. Free iodine was then slowly liberated so the products seem to be formed by loss of iodine from the ad-di- iodo-ketone. Although a strong band then developed at 1753 cm.-l there was no absorption in the region 1800-2000 cm,-l so that no detectable concentra- tion of the cyclopropanone (111) can have been pro- duced. More evidence is needed to distinguish between the various possible mechanisms for this reaction. M.J.N. acknowledges with gratitude a Union Carbide Research Studentship (1960-1963).(Received March 12th 1963.) :’)Reduction with zinc dust in acetonitrile containing furan gave the adduct (IX) in lower yield (29 t again by the diketone (IV) (49 %). accompanied Smith and Wilson J. Chem. Soc. 1956 1342. Fort J. Amer. Chent. Soc. 1962 84 4979. Cookson and Wariyar J. Chem. Soc. 1956 2302; Cookson and Hudec J. Chent. SOC.,1962 429. lo Karplus J. Chem. Phys. 1959,30 11; Karplus and Anderson p. 6; Conroy “Advances in Organic Chemistry,” Interscience New York Vol. 2 1960 p. 31 1. l1 Cf. Woodward and Katz Tetrahedron 1959 5 70; Berson and Remanick J. Amer. Chem. SOC.,1961 83 4947 and refs. there. MAY1963 131 A Stereospecific Synthesis of Desosamine Hydrochloride By A. C. RICHARDSON (DEPARTMENT OF ORGANIC CHEMISTRY THEUNIVERSITY BRISTOL) DESOSAMINE, a constituent of a large number of macrolide antibiotics is a 3,4,6-trideoxy-3-dimethyl-aminohexosel to which the D-xylo-configuration has been assigned on the basis of proton magnetic resonance spectroscopy2 and degradation experi- ment~.~ A synthesis is now reported which unequi- vocally corroborates these conclusions.Methyl 3-acetamido-2- O-acetyl-4,6-O-benzyI- idene-3-deoxy-a-~-glucopyranoside* was hydrolysed with 50% aqueous acetic acid to remove the O-benzylidene residue affording the diacetyl derivative (I) in 95 % yield which in turn was converted into the 4,6-di-O-methanesulphonylester (11) by reaction with methanesulphonyl chloride in pyridine. Re- placement of sulphonyloxy-groups by iodide accord- ing to the Oldham-Rutherford rule generally occurs only when the ester groups are at terminal positions.Helferich and Gnuchte16 have however observed that 1,2,3,6-tetra-O-acetyl-4-O-met hanesulphonyl-~-glucose is an exception and undergoes replacement with sodium iodide to give a monoiodo-derivative. In the light of modern concepts it is probable that replacement of this secondary sulphonyloxy-group must be facilitated by participation of the neighbour- ing trans-acetoxy-group (cf. Winstein et aL7) to give either a 4-or a 3-iodo-derivative. When the disul- phonate (11) was treated with sodium iodide in an- hydrous ethyl methyl ketone it was rapidly converted into the 6-iodo-derivative which reacted more slowly with iodide to give the desired 4,6-di-iodo-derivative (111) in 40% yield.Such a compound must have arisen by elimination of the 4-methanesulphonyloxy- group by participation of the neighbouring trans-3-acetamido-group giving an intermediary oxazolin- ium cation which subsequently underwent nucleo- philic attack by iodide at the 4-position of the pyranoside ring (cf. ref. 7). Consequently the di-iodo- derivative is assigned the gluco-configuration. When ly only the primary and the 4-sulphonyloxy-groups were displaced under the conditions used. R pJ ;f-J Hae OW NMc H Hs~,HC~ H OAc HOH HOH (I R=OH (V)R=H (VIO R=O-SO,.Me (VI)R=Me Ul R=I (lV1 R = H The di-iodo-glucoside (111) was reductively dehalogenated with hydrogen and Raney nickel giving the diacetyldideoxy-derivative (IV) which underwent both N-acetyl and O-acetyl fission with hot sodium hydroxide solution.N-Methylation of the resulting amine (V) with formic acid-formalde- hyde8 afforded the di-N-methyl analogue (VI) as a viscous liquid the only non-crystalline intermediate in the synthesis. Hydrolysis with G~-hydrochloric acid then afforded after purification via the free base a 23 %yield of 3,4,6-trideoxy-3-dimethylamino-D-xylo-hexose hydrochloride (VII) m.p. 182" [alD + 48O identical with desosamine hydrochloride (m.p. mixed m.p. infrared spectra and [a]]and converted into a di-O-acetate identical with deso- samine di-O-acetate hydrochloride. This work constitutes the first stereospecific synthesis of desosamine although two non-stereo- specific syntheses of DL-desosamine have been described previously.The author thanks Dr. L. Hough for his advice and encouragement Dr. H. Grisebach for specimens of desosamine hydrochloride and its di-O-acetyl derivative and Dr. K. Gerzon of Eli Lilly & Co. for a gift of desosamine hydrochloride and erythro- methyl 3-acetamido-3-deoxy-2,4,6-tri-O-methane-mycin. sulphonyl- a-D-mannopyranoside was treated similar- (Received March 22nd 1963.) Flynn Sigal,Wiley and Gerzon J. Anier Chem. SOC.,1954,76,3121; Foster and Horton Adv. Carbohydrute Chem. 1959 14,228. Hofheinz and Grisebach Tetrahydroti Letters 1962 377; Woo Dion Durham and Mosher ihid. p. 735. Bolton Foster Stacey and Webber J. 1961,4831; Cheni. and Ind. 1962 1945.Guthrie and Johnson J. 1961 4166. Oldham and Rutherford J. Amer. Chem. SOC.,1932,54 366; Tipson Adv. Carbohydrate Chem. 1953,8 192. Helferich and GnuchteI Ber. 1938 71 712. Winstein Goodman and Boschan J. Amer. Chem. SOC.,1950,72,2311; McCasland Carter and Clark ibid. 1949 71 637. Richardson J. 1962,2758. * Korte Bilow and Heinz Tetrahedroll 1962 18 657; Newman Chem. and Ind. 1963 372. PROCEEDINGS Biogenesis of the Amaryllidaceae Alkaloids. PartIII.l Phenylahine and Protocatechuic Aldehyde as C,C Precursorsof Haemanthamine and Lycorine By R. J. SUHADOLNIK and J. ZULALIAN A. G. FISCHER DEPARTMENT THE ALBERT (&SEARCH LABORATORIES OF BIOCHEMISTRY EINSTEIN MEDICAL PHILADELPHIA, CENTER PENNSYLVANIA) THE direct incorporation of [3-14C]phenylalanine into the Amaryllidaceae alkaloids as a c6<1 unit has been reported for lycorine and belIadine.2~~ Since the suggestion had been made that the c6<1 unit of the 5,lOb-ethanophenanthridinealkaloids may arise by a pathway different than that of lycorine it became necessary to elucidate the biogenetic origin of this unit.* We now report that phenylalanine can serve as the c6+ unit for haemanthamine (I; heavy bonds) and that protocatechuic aldehyde is incor- porated directly into lycorine.The administration of the radioactive compounds and the isolation of the alkaloids have been de~cribed.~.~ c Radioactive haemanthamins (I) was oxidised to oxohaernanthamine (11). The oxidised compound (II) was converted into the methiodide (111) which was cleaved to form the glycine salt6 (IV).Hydro- genolysis of the glycine salt afforded 2-methyl-4,S- methylenedioxybiphenyl (V) which was identical with authentic compound prepared by the Wolff- Kishner reduction of 6-phenylpiperonal. The activi- ties of the products are listed in the Table. The rela- tive activity of the biphenyl (V) was 0.93 of that of haemanthamine. Compound Haemanthamine (I) Oxohaemanthamine (11) Oxohaemanthamine Specific Relative Activity Activity (m pc/mmole) 16.3 1.00 16.6 1*02 16.5 1.01 methiodide (111) SodiumN-Me t h yl-N-(6-phenyl-piperony1)glycine salt (IV) 17.8 1.09 2-Met hyl-4,5-methylene- dioxybiphenyl (V) 15.2 0.93 FHILycorine 2.08 1*oo FH] Hydrast ic anhydride 1.90 0*91* * Corrected for exchange of tritium.We had reported earlier that tritium-labelled pro- tocatechuic aldehyde was incorporated into lycorine and may well serve as the c6.-c1unit for the Amaryl- lidaceae alkaloids? The data in the Table show that the hydrastic anhydride isolated from the degrada- tion of the tritium-labelled lycorine retains 91 % of the radioactivity. These results show that proto- catechuic aldehyde is incorporated directly as the C6<1 unit into lycorine. The condensation of proto- catechuic aldehyde and tyramine to form the SchB base adduct by cell-free extracts by N. incomparabilis is being studied. Intermediates between phenylalanine and proto- catechuic aldehyde that are incorporated into the Amaryllidaceae alkaloids have been reported.' Cin- namic acid p-hydroxycinnamic acid and caffeic acid were incorporated into haemanthamine.In con- trast to earlier work in which whole plants were used these recent experiments have also employed floral primordial tissue that was grown on sterile nutrient agar to produce the radioactive haeman- thamine.l One of us (R.J.S. Career Development Awardee) thanks the National Science Foundation and the United States Public Health Service for support of this work. (Received March 18th 1963.) Part IT Suhadolnik Fischer and Zulalian Biochem. Biophys. Res. Comm. 1963 submitted for publication. Suhadolnik Fischer and Zulalian J. Amer. Chem. SOC.,1962 84 4348. Wildman Battersby and Breuer J.Amer. Chem. Soc. 1962 $4 4599. Wildman Fales and Battersby J. Amer. Chem. SOC.,1962 84 681. Fales Guiffrida and Wildman J. Amer. Chem. Soc. 1956,78,4145. Fales and Wildman J. Amer. Chem. SOC.,1960 82 197. Zulalian Fixher and Suhadolnik Abs. Meeting Amer. Chem. SOC. Los Angeles Calif. 1963 p. 30-L. MAY1963 133 Determination of the Configuration of Branched-chainSugars W. G. OVEREND H. M WALL, By R. J. FERRIER Mrs. G. A. RAFFERTY and N. R. WILLIAMS (CHEMISTRY DEPARTMENT COLLEGE LONDON,W.C.1) BIRKBECK MALETSTREET THE synthesis in our laboratory of a series of branched-chain sugars with general formula 0;R = branching group) was described recent1y.l The con- figuration at position 2 of these compounds was assigned by relating them to methyl 2-C-formyl-p-~- arabinoside (I; R = CHO) which rearranges to the hemiacetal (1I);la this change can occur only if the formyl derivative (I; R = CHO) has the arabo- configuration.Two more direct and conbenient methods of ascertaining configuration have now been examined. Our interest in phenylboronic acid as a reagent in carbohydrate chemistrya led us to note that in chromatographic solvents this acid has a pronounced and specific activity in increasing the mobility of pyranoid derivatives which possess a cis-cis- 1,2,3- trio1 system and can readily assume a conformation having 1,3-diaxial hydroxyl groups. The oxygen atom in the intermediate equatorial position how- ever may be replaced effectively by the oxygen atom in the ring.Work at Royal Holloway College has led to essentially similar finding^.^ Thus we find that the chromatographic mobilities of methyl p-ribopyrano- side and methyl 2-C-methyl-~-ribopyranosidein butan-1-01 ethanol water (4 1 :5 upper phase) are increased by 60% and 30% respectively when 5% of phenylboronic acid is added to the solvent where- as those of methyl p-arabinopyranoside and its 2-C-methyl derivative are not altered. This specificity is similar thereforz to that found in the electro- phoresis of carbohydrates in molybdate buffer.* Infrared spectral studies of compounds in carbon tetrachloride solution at concentrations less than 0-005~ have yielded information about the nature of intramolecular hydrogen bonding5 and hence pro- vided a means of assigning conformation and con- figuration to simple substances related to carbo- hydrates.6 The conformations of some bicyclic carbo- hydrate derivatives have been studied in this way7 and we have now used the method for configurational analysis.During the study of many partially substi- tuted carbohydrate derivatives we have noted that hydroxyl groups which are axial and are bonded to another axially disposed oxygen atom (thereby form- ing a six-membered ring) have characteristically low 0-H stretching frequencies. This is in accord with results obtained with cyclohexane diols5" in which the bonded 0-H absorptions occur as follows 1,2-cis- 3587 cm.-l; 1,2-trans- 3602 cm.-l; 1,3-cis- (diaxia1)- 3544 cm.-l. The other types of bonding which can mr within a pyranoid ring (those in- volving the ring-oxygen atom) give rise to absorp- tionss in the region 3580-3605 cm.-l.We have assigned the band at 3512 cm.-l in the spectrum of methyl 2-C-methyl-/3-~-ribopyranosideto the 2,4-(OH) interaction and have used absorptions at or very near this frequency in the spectra of other branched-chain glycosides as diagnostic of 1,3-di- axial hydroxyl groups. The assignment is based upon the observation that this absorption occurs at a frequency more than 50 cm.-l lower than any other in the spectra examined. Spedding has noted similar absorptions for 1,3-diaxially bonded systems and we find that in the spectrum of methyl 3,6-anhydro- a-D-ghcopyranoside which is constrained in the 1C conformation with the two hydroxyl groups particu- larly close the corresponding 0-H stretching frequency is at 3500 cm.-l.The branched-chain methyl glycopyranosides prepared by our method from,l for example methyl 2,3-0-isopropylidene-4-oxo-~-L-erythro-pentoside (derived from methyl om-lyxoside) and methyl 6-deoxy-2,3 -0-isopropylidene-4 -0x0 -a -L -Zyxu-hexoside (from methyl a-L-rhamnoside) have given positive results in both of the above tests indicating that they have the L-ribo- and the 6-deoxy-L-tulo- configuration respectively and that the carbonyl groups have been attacked from the side unprotected by the ketal rings. We thank members of this Department for samples Dr. H. Weigel (Royal Holloway College) for allowing us to see his results before their publica- tion and the British Empire Cancer Campaign for financial support.(Received March 19th 1963 .) Burton Overend and Williams (a) Chem. and Ind. 1961 175; (b)P~oc.Chem. SOL 1962 181. a Femer J. 1961,2325. a Bourne Lees and Weigel J. Chromatog. in the press. Bourne Hutson and Weigel J. 1960,4252. Kuhn J. Arner. Chem. Soc. (a) 1952,74,2492; (b) 1954,76,4323; (c) 1958,80 5950. * Dobinson and Foster J. 1961 2338 and previous papers in that senes. Spedding,J. 1961 3617. Barker Brimacornbe Foster Whiffen and Zweifel Tetrahedron 1959,7 10. 134 hWEEDINGa Concentration Effects in Proton Magpetic Resow Spectra of Porphyrins By R. J. ABRAHAM A. H. JACKSON,and G. W. KENNER P. A. BURBDDGE ROBINSON UNIWRSITY (THE ROBERT LABORATORIES OF LIVERPOOL) PROTONmagnetic resonance spectra of porphyrins dissolved in chloroform or deuterochloroform are very dependent on the concentration of the solution.The effects are exceptionally large and we draw attention to them now both on account of their theoretical importance and because data which are only partially significant are being pub1ished.l Con-centrations of chloroform solutions should be recorded when ?..values are given or the data should be extrapolated to infinite dilution. MP 1--1 a i G Proton magnetic resonance spectra (60 Mc./sec.) of coproporphyrin IV tetramethyl ester (A) in deutero-chloroform solution (a) 0*2M (6) O-O~M,with tetra- methylsilane. Twospectra (Figure) of coproporphyrin IV tetra- methyl ester (A) illustrate the general phenomena of fine structure in the spectrum of a concentrated solu- tion and on dilution of the fine structure disap- pearing with accompanying shifts of all the reson- ances to low field by varying amounts.In the upper spectrum (0*2~-solution) a triplet (70.18,0.34,0.51) corresponds to the meso-protons and doublets to the methoxyl (T 6-36?6.40) and @-methyl (T 6.56 6-80)protons. In concentrated solutions the type 111 isomer exhibits a doublet for the rneso-protons and triplets for the methoxyl and @-methyl protons while the type I and 11isomers both show singlets for all three classes of proton. On the other hand the spectra of all four isomers become identical when they are extrapolated to infinite dilution; the singlets for the rneso- methoxyl @-methyl and N-H protons are at r -0.20,f6.28 +6.28 +13-72,respectively.We attribute these effects to parallel aggregation of the large planar rings. In such an aggregate the magnetic effect of the ring current in one macro- cycle2 will shift the resonances of its neighbour to high field and this shift will be greatest for the N-H protons and least for the peripheral methoxyl pro- tons as observed. Interactions of the side-chains of adjacent macrocycles could control aggregation and thus cause differences between type isomers. Attrac- tion between the macrocycles is apparently a funda-mental property because similar spectral shifts have been found with variously substituted porphyrins and chlorins.Notable exceptions are N-methyl-aetioporphyrinI3and I13s4 and N-ethylztioporphyrin 11 the spectra of which show only trivial dependence on concentration; in these instances aggregation is probably inhibited by buckling of the macrocycles. Dications of porphyrins (i-e.,their conjugate di-acids) would not be expected to aggregate and in fact spectra of solutions in trifluoroacetic acid do not vary with concentration. Nevertheless type isomers frequently differ and the coproporphyrin I 11 In and IV methyl esters show the expected singlet doublet triplet and triplet resonance respec- tively for the meso-protons. Comparison of these spectra of solutions in trifluoroacetic acid with those of concentrated solutions in chloroform provides unambiguous distinction between the four isomers.Becker Bradley and Watson J. Amr. Chern. Soc. 1961,83 3743; Woodward and Skarie ibid. p. 4676; Katz, Thomas and Strain aid. 1962 84 3587; Caughey and Koski Biochem. 1962 1 923; Mathewson Richards and Rapoport J. Amer. Chem. SOC.,1963,85,364. * Abraham Md.Phys. 1961,4,145. * Abraham Jackson Kenner and Warburton unpublished results. Caughey and Iber J. Org. Chern. 1963,28,269. Abraham Jackson and Kenner J. 1961 3468. MAY 1963 In this way the coproporphyrin ester prepared by acid-catalysed polymerisation of a simple pyrrole6 is Seen to be a mixture.' Bullock Johnson Markham and Shaw J. 1958,1430. 'Cf. Kay Proc. Nut. Acud. Sci. U.S.A. 1962,48 901.We thank Dr. S. F. MacDonald for samples of coproporphyrins I11 and IV tetramethyl esters and the Nuffield Foundation for support. (Received March 19th 1962.) A StereoselectiveSynthesis of (rf)-Dehydrodeisopropylabietic Acid By C. T. MATHEW and P. C. DUTTA (DEPARTMENT CHEMISTRY FOR THE CULTIVATION OF ORGANIC INDIANASSOCLS~ON OF SCIENCE CALCUTTA-32, INDIA) THEunsaturated ester1 (I) on partial hydrolysis and cyclisation with polyphosphoric acid afforded the keto-ester (II) (-50%) which was hydrogenated over 10 % palladium-charcoal in acetic acid stereo- specifically to produce the saturated keto-ester (111) m.p. 67",in 85-90 % yield hydrogen being attached to the double bond from the side of the ethoxy- carbonyl group.2 Angular methylation of this product (110 was carried out with potassium t-butoxide and methyl iodide in t-butyl alcohol after blocking of the a-methylene it led to an acid m.p.141 " (IV) in -30% yield. Methylation was stereoselectively producing only the trans-product apparently not in keeping with the generalisations of Johnson and his co-workers," and evidently controlled by steric factors arising from the substituents at position 1. The structure of this compound was proved by WOW-Kishner reduction to a known acid5 (VI) m.p. 132" which has now been found to be poly-morphous with the acid of m.p. 121 o.6 Confirmation of the structure of our acid (IV) has been obtained by nuclear magnetic resonance studies through the courtesy of Professor Jackman and Dr.Ghatak. Conclusive evidence comes from conversion into dehydrodeisopropylabietic acid (IX). The ester (V) was converted into the Mannich base with paraformaldehyde and diethylamine hydro- chloride8 and then condensed with ethyl aceto- acetate giving the tricyclic ester (VII) m.p. 101" in moderate yield. Treatment with sodium borohydride in methanol produced the corresponding alcohol which when heated with 10% palladium-charcoal at 235-240" for 1 hr. and then hydrolysed with 10% 0 aqueous-butanolic potassium hydroxide gave the acid (IX) m.p. 174" alone or mixed with authentic dehydrodeisopropylabietic acid.' One of us (C.T.M.) thanks the Government of India for a Senior Manpower Scholarship. We also acknowledge the help of Mr.G. Banerjee. (Received March 22nd 1%3.) l Bachmann and Dreiding J. Org. Chem. 1948 13 317. House Paragamian and Wluka J. Amer. Chem. Soc. 1960,82,2561. lreland and Marshall J. Org. Chem. 1962,27,1615; J. Amer. Chem. Soc. 1959,81,6336. Johnson and Allen (Jr.)> J. Amer. Chem. Soc. 1957,79,1261; Johnson Allen (Jr.) Hindersinn Sawn and Pappo ibid. 1962,84,2181. * Sen Gupta unpublished work. Ghatak Saha and Dutta J. Amer. Chem. Soc. 1957,79,4487. Ghatak Dutta? and Ray J. Amer. Chem.SOC.,1960,82,1728. * Cook and Robinson J, 1941 391. PROCEEDINGS Alkylation with BenzyloxymethylChloride. Factors influencing Stereoselectivity in Alkylation By C. L. GRAHAM, F. J. MCQUILLIN,and P. L. SIMPSON (~G’s NEWCASTLE COLLEGE UPON TYNE) -+ ALKYLATION[(I)(II)] with benzyloxymethyl chloride has been examined as a route to the syn-thesis of substances containing the structural unit (111) which in various forms (R = H or OH,R’ = C02H CHO or CH,*OH) is represented amongst terpenoid substances.Successful use of benzyloxymethyl chloride in this way depends on suitable choice of solvent; the alkylation of phenols with reactive halides offers a useful precedent.l We have found dioxan generally satisfactory and using the sodio-enolate of the ketone in this solvent we have examined the follow- ing examples. 2-Met h ycycf ohexanone with benzylox yme t h yl chloride gave a derivative the structure of which was established as (IV) since sodium borohydride reduc- tion and catalytic debenzylation gave the same crystalline diol as could be obtained from 2-ethoxy- carbonyl-2-methylcyclohexanoneby lithium alumin- ium hydride reduction.The octalone (I; R = Me) gave a benzyloxy-methyl ketone (11) consisting largely of one isomer m.p. 69” which for the following reasons we regard R’a HH6 i a (v) CHim (VI) isomeric alcohols respectively (V; R = CH,Ph R = /%OH) and (V; R = CH,Ph R = a-OH) in a ratio of 40:1. Ponndorf reduction gave the same products but in closely equal amounts. The pure alcohols obtained from chromatography of their 3,5-dinitrobenzoates and hydrolysis were de-benzylated by sodium in liquid ammonia to the corresponding diols (V; R = H R = p-OH) and (V; R = H R’ = a-OH). By treatment with acetone and anhydrous copper sulphate both of these diols gave an isopropylidene derivative readily and in high yield.This result appeared to exclude a p-orienta- tion* for the hydroxymethyl group since a diol of structure (VI) may form an isopropylidene derivative only if the diol-containing ring takes up a boat con- formation. Although there is evidence* of some de- formation of the 4,4-disubstituted ring of 4,4-di-methyl-3-0x0-steroids this appears3 to fall much short of chair -boat inversion. Also the rearrange- ment reactions of 4,4-dimethyl steroid 3cu-and 3p-toluene-p-~ulphonates~ become difficult to interpret if the ring carrying these substituents has the boat conformation. A 3a-OH,4p-CH2.0H diol consti-tuted as (VI) which was derived from p-boswellic acid failed to form an isopropylidene deri~ative.~ Hydrolysis of esters of the type 011; R = H R = a-C0,Me) is known6 to be relatively faster when the ester group has the a-rather than the alternative p-orientation (111; R = H R‘ = P-CO,Me).The ketone (V; R = CH,Ph R = 0) by successive Wolff-Kishner reduction hydrogenation and chro- mic acid oxidation gave an acid product the methyl ester of which was found to be hydrolysed by alkali at a rate similar to methyl abietate and much fasrer than methyl U-methylpodocarpate. There is prece- dent‘ for regarding the principal acid product m.p. 103” as belonging to the trans-decalin series i.e. as (111). It proved to be different from the acid m.p. 0& oa 120” of Ghatak Saha and Dutta? to which how- (wi> * (vlil) ever there are groundsg for assigning a cis-decalin as the a-henzyloxymethyl* derivative (V; R = structure.CH,Ph R’ = 0). Reduction of the substance of Benzyloxymethylation of the ethoxycarbonyl-m.p. 69” with sodium borohydride gave a pair of octalin (I; R -C0,Et) also gave a product consist- * Relative orientation of groups is indicated following the steroid convention. Claisen Kremers Roth and Tietze Annalen 1925,442 210; Ciaisen and Tietze Annalen 1926 449 81. a Djerassi “Optical Rotarory Dispersion,” McGraw Hill Co. New York 1960 pp. 76 90 94. * Allinger and DaRooge Tetrahedrun Letters 1961 No. 19,676; Lehn Levisalles and Ourisson ibid. p. 682. * Shoppee and Johnston J. 1961,3261; 1962,2684; Bancroft Haddad and Summers J.1961,3295. Beton Halsall and Jones J. 1956 2904. Campbell and Todd J. Amer. Chem. Soc. 1942,64,928; King Godson and King J. 1955 1117. Sondheimer and Elad J. Amer. Chem. Sue. 1957,79 5542; 1958,80 1967; Gaspert Halsall and Willis J. 1958, 624; Kalvoda and Loffel Helv. Chim. Acta 1957 40; 2340. * Ghatak Saha and Dutta J. Amer. Chem. Soc. 1957,79,4487. * Sondheimer and Rosenthal J. Amer. Chem. Sue. 1958,80 3995. MAY1963 137 ing predominantly of one isomer m.p. 61O. In con- trast with (I; R = Me) however this product proved to have the structure (VII; R = Et) in which the alkyl substituent has been introduced in the p-orientation. The corresponding acid (VII; R = H) on catalytic debenzylation gave a lactone as sole product which must clearly have the structure (VIII).These examples draw attention to the polar nature of a substituent as well as of its bulk as influences which in different cases may determine stereo- selectivity of a reaction. An ethoxycarbonyl group by proximity may facilitate solvolysis of the alkylat- ing agent and so determine the optimum transition state for reaction particularly in a medium of low polarity. (Received March 4th 1963.) Reactions of Sulphur Carbanions By THOMAS HARVEY POBINER, J. WALLACE JOHNE. HOFMA",and ALANScmmsmm -0 RESEARCH COMPANY PROCESS RESEARCH AND ENGINEERING DIVISION EXPLORATORY SECTION, RESEARCH LINDEN,NEWJERSEY,U.S.A.) BENZYL ethers benzylamines and quaternary benzyl- ammonium compounds undergo carbanion re-arrangement andlor elimination in the presence of strong base.l Similar studies on benzyl-type sulphur compounds have been limited.We report here some preliminary results on carbanions formed from benzyl sulphide disulphide and sulphoxide. When 0.05 mole of benzyl sulphide was brought into reaction with 0.15 mole of potassium t-butoxide in dimethylformamide at 80" -& 0-5"for 20 hours in a nitrogen atmosphere stilbene (45.4 %) and hydro- gen sulphide were the only products observed. Under similar reaction conditions benzyl disulphide yielded stilbene (17.2 %) and hydrogen sulphide (10%) (and a minor unidentified product); and benzyl sulph- oxide yielded only stilbene (45.6 %). The relatively high yield of olefinic product in the presence of a weak base such as potassium t-butoxide may partially be due to the ability of the dipolar solvent to accelerate carbanion reactions.2 Fluorenyl sul- phide (kindly supplied by P.M. G. Bavin) was found to be unreactive in this medium. Thus it appears that the stability of the initially formed car- banion and steric factors are also important in carbanion reactions of this general type? The formation of stilbene from the above car- banions is a new reaction. Hence these preliminary studies have also been concerned with the mode of formation of the olefin. Several pertinent results in this regard have been obtained. Neither benzyl phenyl sulphide nor the corresponding sulphoxide yields stilbene in the presence of potassium t-butoxide in dimethyl formamide.Gas-liquid chromatography indicated that toluene-a-thiol was not formed from benzyl sulphide. When an equimolar mixture of benzyl sulphide and di-( wmethylbenzyl) sulphide was decomposed in dimethylformamide ultraviolet infrared and mass spectrography indicated that stil- bene and 2,3-diphenylbut-2-ene were formed in 4 l ratio but no a-methylstilbene. Failure to observe the last compound indicates an intramolecular car- banion rearrangement-efimination sequence rather than formation of a carbene. Finally the above reactions were repeated with a 1:l ratio of cyclo- hexene to sulphur compound. Mass spectrography confirmed the presence of stilbene but no parent ion corresponding to 7-phenylnorcarane or its isomer phenylcycloheptene was observed.Thus experi- mental evidence to date suggests that the major reaction path involves rearrangement of the initially formed carbanion to a 172-diphenylethyl sulphide or sulphenate ion which in the presence of an excess of base forms an unstable dianion that rapidly elimin- ates the sulphur portion as shown. The second step -H+ Ph*FH*CYPh+ RO-[~"HPh] X--Ph-CHCHPh + X-where X = -S; -S2-,or -SO-apparently proceeds more readily with sulphides than with ethem5 Further studies on various sulphur oxygen and nitrogen derivatives and activated cyclopropyl compounds are in progress. We thank Professor W. von E. Doering for helpful discussion and Mr. J. M. Kelliher for the mass-spectrographic analyses.(Received February 20th 1963.) Gould "Mechanism and Structure in Organic Chemistry," Henry Holt and Co. New York 1959 Chapter 15; Kobrich Angew. Chem. Internat. Edn. 1962 1 382. Parker Quart. Rev. 1962 16 163. Bavin (Canad. J. Chem. 1962,40,220) has obtained the same result in ethereal solvents. Jones J. Amer. Chem. SOC.,1943,65 1817. Lansbury and Pattison J. Org. Chem. 1962,27 1933. PROCEEDINGS Complexes containingRhodium-Mercury Bonds By R. S. NYHOLM and K VRIEZE (UNIVERSITY LONDON,W.C.l) COLLEGE RECENTLY~ it was shown that tris(diphenylmethy1- these new compounds are given in the following arsine)trichlororhodium(m) is reduced by hypo- Table. All compounds are diamagnetic. phosphorous acid to the monohydrido-complex These compounds may also be prepared by treat- (Ph2AsMe)3RhC12H0 we now find that this b'dride ing the rhodium monohydride with mercurous halide reacts with mercury(@ dihalide or diacetate to yield compounds containing rhodium-mercury bonds.The mercury compound dissolved in warm alcohol is shaken with the rhodium hydride for a short time and the solution is filtered and cooled. The Rh-Hg complex crystallises. We have been able to replace ph the hydrogen atom in (Ph,AsMe),Cl,RhH with p%ws HgF HgC1 Her HgI and HgOAc but in all cases yields are low (10-30%). The very characteristic m-~ frequency at 2077 cm.-i of the or acetate; the byproducts of the reaction are original hydride is absent in the Rh-Hg complexes. mercury and the hydrogen halide (or acetic acid).The complexes (see Table) are stable to air and Irradiation of all Rh-Hg complexes except the Properties of complexes with rhodium-mercury bonds (L = PhAsMe) Complexa LBRHCl Colour Orange M.p. 208 M* (Mean) 953 Concn. (103~) -l*oe L3C12RhH Yellow 1 72-1 75 980(942) -l.oe L3Cl,Rh-H@' Pale green 195 1126(903 4' L~C12Rh-HgClb L,C12Rh-HgBrC Yellow Orange 26)s 165 1144(1 125) (1142) 1203 -22' -25' L3Cl,Rh-HgIc L3C12Rh-HgOAcd Orangeyellow Yellow 155 172 1248(1186) (1 233) (1165) 1150 -25' 5.2' * The calculated value is given in parenthesis. a Analyses for C H Halogen Rh,As and Hg available in nearly every case e.g. (Ph,AsMe,)CI,Rh-HgOAc requires C 42.4; H 3-6; C1 6.1; Rh,8-9; Hg 17.2; As 19-3. Found C 42.3; H 3.9; C1 6.2; Rh,9-0;Hg 17.2; As 18.6%.In all cases molecular conductivity at 0*001~ in PhN08was -1.0 ohm-' cm.2. b c Isomorphous (X-ray powder photograph). d Infrared bands at characteristic of COO structure at 1550 and 1333 cm.-l. e In CH8ClB; isopiestic. f Vapour-pressure osmometer. moisture; they dissolve in nitrobenzene and nitro- black powder presumably mercury. This darkening methane in which they are virtually nonelectrolytes. also occurs with mercurous fluoride and iodide. The The compounds are also slightly soluble in acetone complexes react smoothly with one mole of bromine. and alcohol but are insoluble in water. They are These complexes appear to be the first examples monomeric in benzene solution; other properties of of a metal-metal bond between rhodium(a) and a iodide with ultraviolet light causes decomposition dl0s1 atom.Metal-metal bonds usually arise with with the formation on the surface of the crystals of a metals in low oxidation states;2 the formal configura- Lewis,Nyholm and Reddy Chem. andlnd. 1960 1386. a Nyholm Proc. Chem. Soc. 1961 273. MAY1963 tion of the rhodium(rr) atom is d7 and hence these complexes are isoelectronic with other dl0s-d7 deri-vatives such as P~,P-+AU-M~(CO)~ RH@;-.Mn(CO), and R,Pb-Mn(CO), reported earlier. A study of the behaviour of these compounds with various reagents is in progress and the general a Coffey Lewis and Nyholm J. in submission. 139 application of the reaction R,MH + XHgR' R,M-HgR' + fIX is being investigated. 4 The authors are indebted to the Konin.klyke/Shell Laboratorium in Amsterdam for leave of absence for one of them (K.V.) and for generous financial support.(Received March 11th 1963.) An Improved Synthesis of (Estrogens By T. Mnu K. HIRAGA, and T. ASAKO (RESEARCH LABORATORIES TAKEDA ~~EMICAL INDUSTRIES LTD.,OSAKA JAPAN) THISis to present a direct route to oestradiol and equilenin. The starting material 6-methoxy-1-vinyl-1-tetra101 (I) was condensed with 2-methylcyclopentane-1,3-dione*l in the presence of Triton B to give 3-methoxy- 8,14-secooestra-l,3,5(10),9-tetraene-l4,17-dione (II), which was converted by phosphorus pentoxide at 120" into the known 17-ketone (lII).2 Cyclisation by heating the diketone alone at 140" or with an excess of phosphorus pentoxide yields isoequilenin3 (IV) and 7-methoxy-3'-methyl-l,2-cyclopentanophenan-threne* or).The ketone (III) was treated with sodium boro- hydridet in methanol at -30" yielding 3-methoxy- oestra- 1,3,5( 10),8,14-pentaen-l7/3-01 (VI). Catalytic hydrogenation of this over Raney nickel was found to be stereospecific yielding 3-methoxyestra-1,3,5(10),8-tetraen-l7/3-01 (VII). This compound was subjected to Birch reduction with potassium in liquid ammonia to give (f)-axtradiol3-methyl ether (VIII),identical in m.p. and infrared and ultraviolet spectra with material of natural origin. The tetraenol (VII) was dehydrogenated with selenium dioxide in acetic acid or t-butyl alcohol to ( f)-dihydroequilenin 3-methyl etheI5 (IX). Chromic acid effects the dehydrogenation more smoothly.Thus with the chromic acid-sulphuric acid reagent in acetone both the alcohol (VII) and (f)-8-dehydroestrone gave ( f)-equilenin 3-methyl ether (x). For resolution of the pentaenol (VI) its menthyl- oxyacetate was used. The crystals which were precipi- tated first from benzene-methanol were lzevorota- tory. Hydrolysis of this ester was carried out at room temperature in methanolic potassium hydroxide since the alcohol was unstable in hot alkaline solu- tion. The (-)-alcohol (VI) [a],-126" (in CHCl$ thus obtained was reduced through the tetraenol (VII) [a],-3" (in CHClJ to (+ )-stradio1 methyl ether (VIII) m.p. 98" [a]D +80" (in CHCI$ identical with material of natural origin. (Received March 26th 1963 .) * 2-Methylcyclohexane-l,3-dionewas used by Ananchenko et al.' in the condensation in their synthesis.f Hughes et aL2hydrogenated the diene grouping before the sodium borohydride reduction. Ananchenko Limanov Leonov Rzheznikov and Torgov Tetrakedron 1962,18,1355. a Hughes and Smith Chem. and Ind. 1960,1022;Crispin and Whitehurst Proc. Chem. Soc. 1962,356. Birch Jaeger and Robinson J. 1945 582; Bachmann Cole and Wilds J. Amer. Chem. Soc.,1940 62 824; Johnson Petersen and Gutsche ibid. 1947 69,2942. Cohen Cook and Hewett J. 1935,445. Ranerjee Chatterjee Pillai and Bhatt .I. Amer. Chem. Soc. 1956 78 3769. PROCEEDINGS The Ionic Product of Deuterium Oxide and its Mixtures with Protium Oxide By V.GOLDand B.M. Low (DEPARTMENT OF CHEMISTRY KING'S COLLEGE STRAND LONDON w.c.2) THEionic product of pure deuterium oxide was determined several time~l-~ soon after the discovery of heavy water but there has been virtually no work on the ionic product in H,O-D,O mixturesI~* (this is the sum of the concentrations of all isotopically different hydrogen ions multiplied by the analogous sum for the hydroxide ions).The problem is of renewed interest in view of current discussions of protolytic processes in H,O-D,O mixturesH and of the related more general question of the formula of the hydrogen ion in aqueous solution.&-8 We have studied these equilibria by a new tech- nique in which the e.m.f. of a cell containing a glass electrode (ELL. Type GHS 33) and a silver-silver chloride electrode without liquid junction is measured by use of a precision potentiometer in con- junction with a vibrating-reed electrometer.The composition of the solution is changed from dilute (cu. 0.01~)hydrochloric acid to a similarly dilute mixture of barium chloride and hydroxide by step- wise addition of a more concentrated solution of barium hydroxide as in a potentiometric titration. Use of a Ferranti Mercury computer (University of London Computer Unit) allowed complete analysis of the titration curve with inclusion of ionic strength terms9 and minimisation of uncertainties in com- position by a least-squares treatment. The computa- tion procedure leads to the ionic product and was developed for ordinary water by comparison of the results with precise values in the literat~re.~ At the present stage of refinement of the technique of twenty-two experiments in water performed at different times and with varying concentrations fourteen give an answer within f0.01 and twenty- one a value within f0.015 of the accepted pK valueS (14.00 at 25").The same method of computation modified only to take account of the changed di- electric constantlo in the Debye-Hiickel correction was then applied to experiments in H,O-D,O mix-tures. The dielectric constant was assumed to depend linearly on n the atom fraction of deuterium (Le. I)= 78.54 -0.29n). The results (Figure circles) calculated on a rnolarity basis and referring to zero ionic strength at Results for H20-D20 mixtures.n (The numbers of the culcuiated curves correspond to those of the equations in the text. Circles represent experimental points.) 25",are thought to be reliable to within ca. rt 0.015 unit. Our value for pure DzO (pK = 14436) is slightly higher than the three previous determinations (14~81,~ 14.71 14.80") and corresponds to KH/Kb = 7.2. The values for H,O-D,O mixtures can be com-pared with theoretical predictions based on the three alternative models that have been discussed so far. These are (i) The hydrogen ion contains three equivalent hydrogen atoms (ie.,it is a hydroxonium ion). There is fractionation of deuterium between water and hydroxonium ions but the disproportionation equi- libria between isotopically different hydrogen ions l Abel Bratu and Redlich Z.phys. Clzem. 1935 A 173 353. Wynne-Jones Trans. Faraday SOC. 1936,32 1397. Kingerley and La Mer J. Amer. Chem. SOC.,1941,63 3256. Schwarzenbach Epprecht and Erlenmeyer Helv. Chim. Acta 1936 19 1292; Schwarzenbach 2.Elektrochem., 1938,44,46,302. Purlee,J. Amer. Chem. SOC.,1959,81 263. Gold Trans. Faraday SOC.,1960,56,255. Halevi Long and Paul J. Amer. Chem. Suc. 1961 83 305. * Swain Bader and Thornton Tetrahedron 1960 10 200; Swain and Thornton J. Amer. Chem. Soc.. 1961 83, 3884 3390. Harned and Geary J. Amer. Chem. SOC.,1937,59 2032. lo Wyman and Ingalls J. Amer. Chem. Soc. 1938,60 1182. MAY 1963 (and between isotopically different water molecules) are determined only by statistical factors (“rule of the geometric mean”).There must likewise be fractionation between hydroxide ions and water but there are no other fractionation or medium effects. The predictions of this model (in previousIy used symbols6) are Kn/KH= (1 -n + nlI3 (1 -n + n14 KD/KH), (1) where I (G is an equilibrium constant for deuterium fractionation between H30+and H,O and KH KD and Kn refer respectively to ordinary water deuterium oxide and a mixed solvent characterised by n. (ii) The hydrogen ion is a non-specifically solvated hydrogen nucleus (Le. one hydrogen atom per ion) but the other assumptions stated under (i) still apply.? Extension of our previous treatmenp to this case gives Kn/KH= (1 -n + nL-li2) (1 -n + nL1i2KD/KH). (2) (iii) There are no fractionation effects and the changing value of the ionic product is caused by a medium effect.? No assumptions concerning the stoicheiometry of the hydrogen ion are required.If the Gibbs free energy of solvation is a linear function of n this hypothesis then leads to7 = (KD/KH)n* (3) The predictions of the three equations are plotted in the Figure. The experimental points are drawn as circles with a radius of 0.015 pK unit. The latitude in the predictions set by uncertainty concerning the correct value of L is fairly expressed by the thickness of the lines drawn which in each case covers the full range of plausible values of L [6 to 19 for equation (1) with the most probable value 11 near the top edge; 2 to 19 for equation (2)].Of the three equations only (1) agrees with experiment within the limits of 141 error.* The agreement supports the adequacy of model (i) and the formula H30+ for the hydrogen ion. There is little object at the moment in examining the question whether a superposition7 of theories based on (ii) and (iii) might by introduction of suitably adjusted parameters also be made to fit the data. We have further investigated what effect other assumptions concerning the stoicheiometry of auto-protolysis would have on the agreement between experiment and a single-parameter equation. It appears that the assumption of hydrogen ions with either 3,4 or more equivalent protons leads to accept-able calculated values but the higher numbers (although they give probably a slight improvement on 3) are chemically not reasonable.Alternatively the assumption that the hydroxide ion contains more than one equivalent hydrogen atom has been briefly examined. It emerges that equation (4) Kn/KH = [I-n d-d]3[1 -n + n(k3 KD/KH)1/4]4 (4) based on the assumption of three equivalent hydro- gen atoms in the hydroxonium ion and four in the hydroxide ion (a hypothetical model extrapolated from structural ideas due to Swain and Baderll) would be mathematically satisfactory (see Figure). Indeed it gives a slight but distinct improvement on equation (1). In our view the results of these cal- culations should not be interpreted too literally. They may imply that the formuh H30+ and OH-although they are the only acceptable covalent formulations of the ions compatible with the ionic products-may nevertheless slightly underestimate the total number of hydrogen atoms that are affected sufficiently by the two ions to contribute slightly to the isotope fractionation.In different language this is a slight indication of a small “medium effect.” (Received March 29th 1963.) * It is mathematically impossible to fit equation (2) to the experimental points by any adjustment of L inasmuch as I(,/pl& at any fixed value of n is not a monotonic function of L(pK,-pKH passes through a maximum value which lies below the corresponding point on the experimental curve). l1 Swain and Bader Tetrahedron 1960 10 182. The Fractionation of Hydrogen Isotopes between Hydrogen Ions and Water By V.GOLD* OF CHEMISTRY NATIONAL UPTON L.I. N.Y. U.S.A.) (DEPARTMENT BROOKHAVEN LABORATORY IT is generally accepted that protium and deuterium are not randomly distributed between water mole- cules and hydrogen ions in aqueous acids containing the two isotopes deuterium is concentrated in the water molecules at the expense of the hydrogen i0ns.l In spite of the importance of the effect to the understanding of protolytic processes1 no direct measurements of the fractionation have so far been * Visiting Senior Chemist summer 1962. Present address King’s College Strand London W.C.2. Research performed under the auspices of the U.S. Atomic Energy Commission. For recent discussions and references to earlier work see (a) Purlee J.Amer. Chem. Soc. 1959 81 263; (b) Gold, Trans. Faraday Soc. 1960,56,255; (c) Swain and Bader Tetrahedron,1960,10,182; (d)Halevi Long and Paul,J. Amer. Chem. Soc. 1961,83,305. reported. It is now shown that information concern- ing this problem can be derived from direct proton magnetic resonance measurements on isotopically mixed acid solutions and therefore without reference to the transfer problem.ld The results now reported relate to systems of low protium content (ca. 5%) but there are no fundamental difficulties about ex- tension of the work to media richer in protium. It seems that the assumptions required in the inter- pretation of the results can be stated explicitly and that our extension of the measurements may in due course reduce the area of uncertainty attributable to them.The position of the proton resonance in water is shifted downfield on addition of a strong mineral acid.2 In a system (such as this) in which there is rapid exchange of protons between all non-equi- valent positions the chemical shift A of the resonance relative to a fixed standard is given by A = h (N.6 I) (1) where 8. is the chemical shift associated with the ith group of equivalent protons the atom fraction of which is Ni. For aqueous acids in the absence of deuterium and if shifts are relative to the frequency in pure water equation (1) becomes A = aiT(v 8,). (2) The acid concentration (a) is expressed as the stoicheiometric atom fraction of hydrogen nuclei introduced by the monobasic acid (k,a = ~x]stoich/( [HXlstoich -k 2[H201)~ when no deuter- ium is present).There arej sets of different positions (each set containing v equivalent members) in which protons are placed as a result of the addition of one molecule of HX to light water. In this Note it is assumed that only a single set of v equivalent positions need be considered in the summation (2) so that A = avS, (3) i.e. protons in solvation shells for example are not distinguished from the other protons of water. This assumption has been made by the previous workers2 who in addition adopted the usual con- vention that v = 3 (i.e. hydrogen ion = H30+). Equation (3) must be an oversimplification but can be partially justified as a first approximation since the chemical shift attributable to the hydrogen ion is particularly large.2cre For a deuterium-containing medium we have (expressing the chemical shift relative to the proton resonance frequency in the H20-D20 mixture) PROCEEDINGS A is the concentration of protons in the v sites of the hydrogen ion expressed as an atom fraction of all hydrogen nuclei in the system and p is the corre- sponding fraction of protons in water molecules.It is here assumed that the secondary isotope effect on 8 is negligible (i.e. the proton shift for a hydrogen ion H,DO+ would be assumed to be the same as that for H30+) by analogy with the comparatively small difference3 between H20 and HOD. The proton atom fractions A and p are related to the analogous fractions x' and p' for deuterium nuclei by the equilibrium constant K = XpfAp' (5) which determines the fractionation effect.With the material-balance relationships X + h' = va A+Af+pi-pt= 1 and A' + p' = n (the atom fraction of deuterium in the system) and with the assumption that (A + x') < (p + p') so that $1~= n/(l -n) equation (4) becomes A = avSJ(1 -n + Kn). Slopes of graphs of A against a relating to ordinary water and a mixed solvent characterised by n respectively should therefore stand in the ratio (1 -n + Kn):1. Results obtained for solutions of perchloric acid (with n -0.95 at 31") (Figure) give 1000 Q Resultsfor perchloric acid. A HzO. ByD,O (ca. 95%). a (a) Gutowsky and Saika J. Chern. Phys. 1953 21 1688; (b) Hood Redfich and Reilly &id 1954 22 2067; (c) Shoolery and Alder ibid.1955,23,805; (d)Hod and Reilly ibid. 1957,2? 1126; (e)Hindman ibid. 1962,36 1OOO. Bergqvist and Eriksson Acta Chem. Scand. 1962 16,2308. MAY1963 143 K = 0.69 f 0.02. Analogous experiments with hydrochloric acid yield K = 0.68 0.02. A some-what smaller fractionation effect-also favouring deuterium enrichment of the water molecules-was found for sodium hydroxide as is also suggested by the effect of alkali on the separation factor for the distillation of H,O-D,O rni~tures.~ All chemical shifts were measured at 60Mc (Varian A60) relative to 1 % dioxan as internal reference. The constant K defined by equation (5) corres-Googin and Smith J. Phys.Chem. 1957,61 345. ponds to L-lI6 in previous formulations of the theorylab if Y = 3 or to L-l12 if Y = 1,It is interesting that the former but not the latter,ld assumption leads from the present measurements to a value (L= 9.3) in fair agreement with other estimates (1 1.Ofa; 8~2~~) but in view of the reservations about some of the assumptions implicit in this analysis a more thorough consideration of this point is deferred until our more detailed measurements are completed. (Received April 2nd 1963.) The Enzymic Coupling of Totarol By SHEILAM. BOCKSand R. C. CAMHE (DYSON LABORATORY, PERRINS OXFORD) THEpreparation of the bisditerpenoid podototarin (11) from totarol (I) in 20% yield by the use of an extracellular oxidase from the fungus Polyporus versicolor was reported recent1y.l This result sug- gested that an enzyme with similar activity was prob- ably present in Podocarpus totara the natural source of totarol and podototarin? Using 2,6-dimethoxyphenol as the test substrate buffered aqueous extracts of the fresh leaves of 41 species of the Podocarpaceae and related families have been examined for the presence of an enzymic system which catalyses the formation of 3,5,3’,5’-tetramethoxydiphenoquinone.In addition to that from P. totara extracts of the following were found to have activity similar to that of the fungal enzyme P. acutifolius P. alpinus P. andinus P. elatus P. macrophyllus P. milanjianus P. montanus P. nagi P. spicatus Dacrydium biforme D. intermedium D.laxifolium D. kirkii Cunninghamiu sinensis and Cryptomeria japonicu. Tests for peroxidase in these extracts were consistently negative. The cell-free enzyme isolated on a large scale from the leaves of a convenient source Cryptomeria japonica has optimum activity around pH 4.0. Like the p-diphenolase3 from Polyporus versicolor4 it is aerobic in action and its activity is inhibited by sodium azide destroyed by boiling the solutions for 5 minutes and unaffected by dialysis against sodium acetate buffer (0*001~; pH 4-0).As distinct from the fungal enzyme the leaf oxidase is much more un- stable and initially is only associated with particu- late fractions of freshly prepared extracts. It was however obtained in soluble form when solutions were kept at 0” for a few days.The activity of fresh preparations is enhanced by the addition of calcium chloride indicating that the enzyme is present in the mitochondria? H ‘.I Incubation of the enzyme with a 10% ethanolic solution of totarol(100 mg.) in sodium acetate buffer (0.01~; pH 4-0)at 30”followed by addition of further enzyme at 48 hr. intervals over 2 weeks resulted in the formation of podototarin (58 % yield) which was isolated by alumina chromatography and identified by comparison with a natural sample. This repre- sents the first example of a single C-C oxidative coupling through the action of an enzyme from a higher plant and lends some support to the hypo- theses of Hathway and his co-workerss on the bio- synthesis of tannins since these as well as bisditer- penoids and biflavonyls could be formed by a similar step.Contrary to these theories however is the absence of any indication that the above coupling proceeds through quinonoid intermediates. (Received March 18th 1963.) Bocks Cambie and Takahashi Tetrahedron,in press. Cambie Simpson and Colebrook Tetrahedron,1963,19,209. “Report of the Commission on Enzymes of the International Union of Biochemistry,” Pergamon Press Oxford 1961. Bocks Brown and Todd Proc. Chem. Soc. 1962 117. Tapley J. Biol. Chem. 1956,222 325. For a general discussion see Hergert in “The Che@stry of Flavonoid Compounds,” ed. Geissman Pergamon PTess Oxford 1962 p. 553; Hathway in “Wood Extractives,” ed. Hillis Academic Press New York 1962 Ch.5. PROCEEDINGS The Absolute Sign of the Spin-Spin Coupling Constant By A. D. BUCKINGHAM and K. A. MCLAUCHLAN CHEMISTRY OXFORD, ONORGANIC LABORATORY and BASICPHYSICSDMSION NATIONAL TEDDINGTON) PHYSICALLABORATORY ALTHOUGH several methods exist for the measure- ment of the relative signs of spin-spin coupling con- stants (J) in polyatomic molecules the absolute signs have remained uncertain. It is an inherent property of a nuclear magnetic resonance spectrum that its appearance whilst depending upon the relative signs of the coupling constants is unaffected by a complete sign reversal. The normal high-resolution spectrum exhibits fine structure due to electron-coupled spin- spin interactions alone the nuclear magnetic dipole-dipole interaction being averaged to zero by molecular tumbling.It has recently been predicted (1) that if the system is subjected to a strong electric field a partial alignment of the electric dipoles of the system occurs and produces a non-zero nuclear mag- netic dipole-dipole interaction which is proportional to the inverse cube of the internuclear distance. This appears in the spectrum as an additional splitting which either adds to or subtracts from that due to the isotropic spin-spin coupling according to the sign of J and to the precise geometry of the experi- mental arrangement and of the molecule in a manner which is fully calculable. We have chosen the geometry of the apparatus so as to produce the maximum effect the electric field being applied parallel to the main magnetic field of the spectrometer.The molecule studied was p-nitro- toluene at about 70c.The spectrum of thering protons of this compound approximates to an AB system and with the line width at present available (ca. 3 C.P.S. at half-height) no additional structure is apparent. The experiments were performed on one half of the AB pattern and as is shown in the Figure the applica- tion of an electric field caused a marked decrease (2.4 C.P.S. at 24 kvfcm.) in the observed splitting. Since the proton-proton direction is parallel to the electric dipole moment in this molecule this implies that the ortho ring coupling is absolutely positive. 10c.ps. M 0Field 24 kv./cm. I Experiments with electric fields varying from 0 to 24 kv/cm.confirmed the theoretical prediction that the magnitude of the splitting depends upon the square of the electric field. The absolute sign reported here is in agreement with that which can be deduced on the assumption that the 13C-H coupling is positive. We thank Dr. D. H. Whiffen for continued advice and encouragement. (Received March 18th 1963.) Buckingham and Lovering Trans.Furaday SOC.,1962,58,2077. Radical-anions containing Sulphur Atoms in a Conjugated System By R. GERDIL and E. A. C. LUCKEN (CYANAMID RESEARCH DE LA CAPITE, EUROPEAN INSTITUTE 91 ROUTE COLOGNY GENEVA, SWITZERLAND) APPLICATION of electron-spin resonance to deter- mination of electron distribution in conjugated sulphur-containing compounds and hence to possible decision about the participation of sulphur 3d- orbitals in bond formation1 has been delayed by the lack of reasonably stable sulphur-containing free- radicals.The only simple radicals studied in this way have been the 1,6dithi-inium radical-cations ;2 the spectrum of the thioxanthone SS-dioxide radical- anion has also recently been disc~ssed.~ The prepara- tion of radicals by the action of alkali-metals on the parent compound in ethereal solvents has not so far been applied to sulphur-containing compounds owing to the consequent cleavage of the carbon- ]. Cilento Chem. Rev. 1960 60. Lucken to be published. An account of this work will be presented at the 1963 I.U.P.A.C. conference in London.Vincow J. Gem.Phys. 1962,37 2484. MAY1963 145 TABLE1. Splitting constants in gauss f0.05 and conditions of preparation of sulphur-containing radical-anions. Parent compound Splitting constants Dibenzothiophen 5-16,4-48 1.46,0.86 Thianthrene a-sulphoxide 246 0-13 m.p. 288.5" Diphenyl sulphone 4.64 (para) 2-41 0-65 sulphur bond.4 We have however observed the electron-spin resonance spectra of the radical-anions shown in Table 1 prepared by the action of potas- sium on the parent compound in dimethoxyethane. We similarly prepared radicals from thianthrene monosulphoxide and diacenaphtho[I ,2-b:1',2'-4-thiophen (RRI 7122) but in the former case we suspect that the radical is derived from a cleavage product. With thianthrene we detected only the radical-anion of dibenzothiophen presumably formed by the elimination of sulphur.Resonance spectra from thianthrene p-disulphoxide diphenyl sulphoxide thiophen or benzothiophen have not so far been observed although at low temperatures these compounds form coloured solutions which at room temperature deposit coloured precipitates (the thiophens) or change colour (the sulphoxides). Table 2 shows the theoretical proton splitting constants of dibenzothiophen taken from published calculations of odd-electron density5 by using the Conditions Prepared and observed at -75". At room temp. the spectrum is not resolved and radical slowly decays. Prepared at room temp. but radical disappears in 1-2 hr. Radical is almost colourless.Prepared and observed at -75". At -40" radical decays in a few min. d-orbital model of the sulphur atom and various values for the ratio /3cs//3cc. The value of the pro- portionality factor Q,was taken as 27.0.Table 1 also shows the probable values for the splitting constants TABLE2. Theoretical proton splitting constants for dibenzoihiophen. Position 1 is adjacent to the sulphur atom. Posn. 0-6 PcSlPcc 0.8 1.0 Oh.for phenanthrene 1 2.54 2.84 3.16 3.84 2 0-135 0.27 0.49 1-02 3 2-28 2.48 2-67 3.02 4 1.49 1.47 1.46 0.91 of phenanthrene PcsfPcc= 1 derived by application of the spin-density calculations of McLachlan to its incompletely resolved spectrum.6 These calculations considerably underestimate the splitting constants of dibenzothiophen.(Received April 9th 1963.) Gerdil and Lucken J. in press. ti Koutecky Zahradnik and Paldus J. Chim.phys. 1959 56,455. McLachlan Mol. Phys. 1960,3 233. Reactions of Methyl Radicals with Primary Amines By J. C. J. THYNNE (l3m UNIVERSITY, LEEDS) MUCHhas been reported1 concerning the abstraction of hydrogen atoms by methyl radicals in the gas phase. In most of the work the hydrogen atoms have been attached to the various carbon atoms of the molecule and Rice and Vanderslice2 have obtained results for the rates of hydrogen-atom abstraction from primary secondary and tertiary carbon atoms. For molecules such as amines or alcohols where the abstractable hydrogen atoms are attached to two different atoms there is still uncertainty concerning the position and rate of abstraction and previous work has been interpreted by an arbitrary choice.Kozak and GesseI" concluded from the similarity of the activation energies for methyl-radical attack on diethylamine and triethylamine that the hydrogen atoms attached to the a-or P-carbon atom were removed. Brinton? however suggested from a study of the reaction of methyl radicals with amines that it is the N-H hydrogen atoms which are active in methane formation. We have studied the reaction of methyl radicals with [2H]methylamine over the temperature range 125-175" the radicals being generated by the selective photolysis of azomethane at > 3000 A where the amine has no absorption. CH, CH,D N, and C2H6 were the products measured and may be accounted for by the following reactions Me-N,.Me -+ 2Me.+ N . . . (1) Me. + Me.N,-Me -f CH + CH,.N,.CH .. . (2) Me. + Me-ND -f CHI + .CH,.ND * . (3) Me-+ MeSND -f MeD + Me.ND. 2Me. -+ C,H * . . (5) Trotman-Dickenson and Steacie J. Chem.Phys. 1951,19,329; Trotman-Dickenson "Gas Kinetics," Butterworths London 1955. a Rice and Vanderslice J. Amer. Chem. Soc. 1958 80 291. Kozak and Gesser J. 1940,448. Brinton Canad.J. Chem. 1960 38 1339. 146 PROCE~EDINGS If the accepted value5 of 13-34for log k (mole-l cm.3 sec.-l) is used OUT results can be expressed by the equations log k3 (mole-l cm.3 sec.-l) = 11.15 -9000/2-303BT’ and log k4 (mole-l cme3 sec.-l) = 9.61 -7000/2.303RT A direct comparison of the C-H and N-H hydrogen abstractions (ie.reactions 3 and 6) Me + Me-NH -f. CX4 + MeSNH. . . . (6) can be made by assuming for k,/k4 that the ratio of the rates corresponds to the maximum deuterium isotope effect at these temperatures? Recent work in this laboratory indicates that this is an accurate assumption. Using these values gives an activation Shepp J. Chem. Phys. 1956,24,939. Wberg Chem Rev. 1955,55,’?13. energy for reaction (6) of 5-7 kcal. mole-l and the rates of hydrogen-atom abstraction (mole-J. ~rn.~ sec.-l) by methyl radicals for reactions (3) (4),and (6) at 150” are lP5,1W0 and 1Vg6, respectively. These results indicate that hydrogen atoms are abstracted from both the alkyl and the amino-group and the similarity of the rate constants for reactions (3) and (6) indicate that within this temperature range they have similar reactivities towards methyl radical attack.I thank Professor Peter Gray for helpful discus- sions D.S.1.R for a research award and the Research Fund of the Chemical Society for a grant. (Received April 8th 1963.) Organogermanium-phosphorus Compounds By F. GLOCKLING and K. A. HOOTON (THEUNIVERSITY, DURHAM) ALTHOUGHcompounds are known in which an organogermane is also bonded to nitrogen) the analogous phosphorus compounds have not PK viously been reported (Et,Sn.PPh is known2). We have obtained diphenyl(triethylgermyl)phosphorus, Et,Ge.PPh2 b.p. 146°/10-3mm. by interaction of bromotriethylgermane and lithium diphenylphos- phide in tetrahydrofuran and have examined some of its reactions.Hydrolysis of the Ge-P bond in our compound by a ten-fold excess of 10% aqueous lY2-dimethoxy- ethane was complete in 5 minutes at room tempera- ture 2Et,Ge.PPh2 + H20 -(Et,Ge),O + 2Ph2PH. Oxidation by oxygen at room temperature cleaved the Ge-P bond giving the monomeric ester Et,Ge-O+P(O)Ph, b.p. 160°/103 mm. [Ge-OP at 956 cm.-l in contrast to Ge-0 stretch at 851 cm.-l in (Et,Ge),O]. Bromination of our compound was rapid in carbon tetrachloride at -20° giving bromo- triethylgermanium (69 %) and bromodiphenyl-phosphine (65Oh whilst with silver iodide it formed the colourless well-crystalline complex (Et,Ge-PPh,,AgI), m.p. 183 O (decomp.). Cleavage of the Ge-P bond by n-butyl-lithium proceeded rapidly at 0” EtBr Et,Ge-PPh + BuLi -3 Et,BuGe + LiPPh -+ Ph,PEt In a similar reaction phenyl-lithium had reacted incompletely (50%) after 2 hours in refluxing ether.Methyl iodide (2 mol.) also cleaved the Ge-P bond giving triethyliodogermane and dimethyldiphenyl- phosphonium iodide Me1 Et,Ge-PPh + Met-Et,Gel + Ph,PMe-+ [Ph,Me,P]+I-Attempts to prepare tetrakis(dipheny1phosphino)-germane (Ph,P),Ge have so far been unsuccessful (amine analogues are known’). Lithium diphenyl- phosphide and germanium(rv) chloride react in tetrahydrofuran to give tetraphenyldiphosphine and an amorphous reddish-brown material approxi-mating to [(Ph,P)GeJ,. This material resembles the phenylgermanium polymer obtained from the re- action of germanium(@ iodide with phenyl-lithiurns We consider that the reaction probably involves reduction of germanium(Iv) to germanium(1x) (the reaction mixture is colourless until 1.8 mol.of Ph2PLi have been added after which it rapidly becomes deep red) GeCI + 2Ph2PLi -4 2LiCI + Ph,P + GeCI followed by normal condensation and “halogen- metal” exchange leading to polymeric products Ph,PLi In marked contrast to diphenyl(triphenylgermy1)-phosphorus the red polymer was not hydrolysed by water but was oxidised in air with the formation of GeO and PO groupings. (Received March 20th 1963.) “Organometallic Compounds,” Vol. 11 ed. M. Dubb Springer Verlag 1962. Kuchen and BuchwaId Chem. Ber. 1959,92,227. Glockliig and Hooton J.1963 1849. MAY1963 147 Spectroscopic Evidence for the Sdphide Ion in Aqueous Soldon By M. J. BLANDAMER,J. M. GROSS and M. C. R. SYMONS (DEPARTMENT nEe UNIVERSITY, OF CHEM~Y LEICESTER) SULPHIDE ion has a negative ionisation potential in the gas-phase and the possibility of its separate existence in aqueous solution has been questioned? Direct spectrophotometric evidence for the forma- tion and stability of sulphide ions in aqueous alkaline solutions is now presented. Aqueous alkaline solutions of sodium sulphide between pH 7 and 14 exhibit an absorption band having Vmax. 43,480 cm.-l which has been attributed to the HS-ion.2 We have found that on increasing the pH to 15 in the absence of oxygen a new band is formed at 27,750 cm.-l at the expense of that attributed to HS-ion.Reduction of the pH to the region of 14 resulted in almost complete loss of this band which was re-formed on further addition of alkali. This sequence of events suggests that the species responsible for the new absorption band is sulphide ion. That a discrete electronic excited state of relatively high energy exists is to be expected by analogy with solvated halide ions whose spectra have been described as involving charge transfer to solvent? A characteristic of such spectra is the linear decrease of Vmax. with increase in temperature? The position of the maximum of the band attributed to sulphide was found to decrease linearly over the range 2 to 73" with dEmgx./dTequal to -8.9 cal.deg.-l. This value is smaller than that for iodide in water -30 cal. deg.-l in accord with the postulate that these shifts are a consequence of an expansion of the solvent shell around the ion.3 Thus a doubly charged ion is expected to have a more tightly bound solvent shell Platzman and Franck 2.Physik 1954 138,411. Ellis and Golding J.,-1959 .. 127.-which will have a smaller temperature coefficient of expansion. The position of the absorption maxima of iso-electronic chloride and sulphide ions in crystalline and aqueous environments can be compared. Chloride ions in watef' have an absorption maximum at 55,200 cm.-l whereas casium chloride crystals,6 having the sodium chloride structure have a maxi- mum at about 58,350 cm.-l at room temperature.At 77"~ barium sulphide which is isoelectronic with csesium chloride has its first maximum at 31,470 cm.-1.6 Although the dependence of this band maxi- mum on temperature is not known it is probably small and since the shifts for alkali halides are com- parable with those for hydrated halide ions we have used the value -8.9 cal. deg,-l to obtain the value 30,820 cm.-l for the first exciton band for barium sulphide at room temperature. The energy differences between the absorption maxima of the two ions chloride and sulphide in aqueous and crystalline environments is thus found to be 3,150 cm.-l and 3,070 cm.-l respectively. The trends are so similar that there can be little doubt that the species at 27,750 cm.-l in aqueous solution is indeed sulphide and that the transition is comparable with that for halide ions in solution.Thanks are offered to the Department of Scientific and Industrial Research for a maintenance grant (to J.M.G.). (Received March 13th 1963.) Griffiths and Symons Trans.Faraday SOC.,1960,56 1125. Scheibe 2.phys. Chem. 1929,5,355. Eby Teagarden and Dutton Phys. Rev. 1959,116 1099. (I Saum and Hensley Phys. Rev. 1959,113 1019. The Chlorination of Z,Z&T~rnethy1pentane By A. E. FULLER and W. 3. HICKINBOTTOM (DEPARTMENT QUEEN LONDON 'J3.1) OF CHEMISTRY MARYCOLLEGE OBSERVATIONS in the literature suggest that 2,2,4- trimethylpentane behaves abnormally in free-radical reactions. It is attacked by t-butoxy-radicals less readily than might be expected from the behaviour of less substituted hydrocarbons.' Similarly chlorina- tion by N,2,4,6-tetrachloroacetanilideis much slower than that of the isomeric trimethylpentanes.2 Wibaut Brook Trans.Faraaky Sac. 1957,53 327. a Boocock and Hickinbottom,J. 1963 1234. and Strang3 report that although monoethylheptanes and dimethylhexanes are autoxidised at 78 O 2,2,4-trimethylpentane is unchanged. Beckwith4 recently reported that the products of reaction of anthracene with free radicals from 2,2,4-trimethylpentane are those derived &om primary radicals. These observations have been explained by a Wibaut and Strang Proc.,k. ned. Akad. Wetenschap. 1953,54,By229. Beckwith J. 1962 2248. 148 PROCEEDMGS assuming that the tertiary hydrogen which should be the most reactive is shielded from attack by t-butoxy- radicals or the oxygen molec~le.~~~ This hypothesis may be tested by examining the behaviour of 2,2,4trimethylpentane towards a range of chlorinating agents of different effective bulk.For this purpose we compare the relative proportion of substitution at the primary secondary and tertiary positions by chlorine activated by a weak source of ultraviolet light with that produced by sulphuryl chloride or N-chlorosulphonamides R.SO,.NClR’ where R = Me Ph or p-tolyl and R’ = But or where R = p-tolyl and R’ = Bun under the in- fluence of 2 moles % of benzoyl peroxide at 85”. All the chlorinations were carried out in an excess of hydrocarbon and the composition of the product was determined by gas-liquid chromatography.A11themonochlorotrimethylpentaneswere formed. A search for dichloro-compounds was inconclusive; if the latter were formed they constituted less than 3% of the total product and therefore did not seriously interfere with the general inferences to be drawn from the distribution of the isomers in the product. The Table summarises the results. With the exception of sulphuryl chloride there is a striking uniformity in the composition of the pro- duct whether it is produced by the light-induced chlorination by chlorine or the peroxide-induced chlorination by an N-alkyl-N-chlorosulphonamide. It may be inferred that the effective bulk of the chlorinating agent has no appreciable influence on the ratio of primary secondary and tertiary replacements.An unusual feature of all these chlorinations is the low reactivity of the tertiary hydrogen. In all the chlorinations of other alkanes previously reported the order of reactivity is tertiary > secondary > primary; there appears to be no other recorded except ion. From models of 2,2,4-trimethylpentane it appears that free rotation about the 3,4-carbon-carbon bond is seriously restricted. On this basis it is possible to explain the chlorination figures given here by assuming that only a fraction of the 2,2,4-trimethyl- pentane molecules have a conformation permitting free access of the chlorinating agent. (Received March 29th 1963.) Chlorinating agent Composition of product (%) Ratio of f n \f A 7 primary secondary tertiary primary secondary tertiary Chlorine .... .. 66 24.4 9.4 1 2-8 2.1 Sulphuryl chloride MeSO,.NClBut .. Ph*S02*NClBut.. .. .. .. 58 65 64 31.5 25 27 10.5 10 9 1 1 1 4.1 2.9 3.2 2-7 2-3 2.1 p-C,H,Me.SO,.NClBut p-C,H4MeS0,*NClBun 62 63 28 28 10 9 1 1 3.4 3.3 2.4 2.1 Some Unusual Reductions by the Hydrated Electron By J. H. BAXENDALEand R. S. DIXON (CHEMISTRYDEPARTMENT,THEUNIVERSITYOF MANCHESTER) ITis known that in acid solution oxidising ions such as Few and Cuzt are effective in reducing the 100 ev yield of hydrogen G(H& from y-irradiated aqueous solutions of alcohols because they compete for hydrogen atoms,’ as follows Y H,O -+ H HO H, H,O H + CH,*OH -+ H + .CH2.0H H + Fe3+-+ H+ + Fez+ We now find that many metal ions which are not normally regarded as oxidising ions and which have IL Baxendale and Hughes 2.phys.Chem. 3958,14 306. * Matheson Ann. Rev. Phys. Chem. 1962,13,77. no effect on G(Ha from acid methanol solutions have a profound effect even at low concentrations when the solutions are neutral. Some of our observa- tions are given in the Table. In view of recent evidence it seems probable that this difference between acid and neutral solutions is due to presence of the reducing species in the latter predominantly as solvated electrons (eaq) and as such they are much more potent reducing agents than the hydrogen atoms into which they are transformed in acid solution esq+ H,O+ 3 H + H20 MAY1963 Thus the reductions in G(Ha are we suggest due to reactions such as Zn2+ + eaq -+ Zn+ which remove the electrons before they form hydrosen atoms esq+ H20-+ H + OH-The unstable valency states which are formed may be oxidised back by the radical HO-or CH,-OH or may be reduced further to the metal by CH,.OH or by dismutation.Detailed product analysis should decide between these possibilities but reduction does occur since we have observed precipitates of the metals in solutions containing Cd2+ Zn2+ or Pbz+. Furthermore when the pulsed radiolysis technique3 is used strong transient absorptions have been observed4 which are probably due to the inter- mediate valency states. It will be seen from the Table that of the transition ions only Mn2+ is unreactive and that neither alkali- metal nor alkaline-earth ions are effective although it is possible that in such cases the reduced forms e.g.Mn+ or Na atoms regenerate hydrogen atoms by reaction with water. The present preliminary survey indicates the following order of reactivity with hydrated electrons Pb2+ > Cd2+> Ni2+ > Co2+> Cr3+ > Zn2+ We have also found that higher concentrations of these ions which do not react with hydrogen atoms seem unable to decrease G(Ha below about 1-0 whereas ions such as Ag+ Cu2+ and Few readily Hart and Boag J. Amer. Chern. Soc. 1962,84,4090. Adams Baxendale and Boag unpublished work. Allan and Scholes Nature 1960,187,218. decrease G(H& to 0-4,the molecular yield (GH).This indicates as suggested previously,5 that in addi- tion to a 100 ev yield of electrons Ge = 2.2 there Efect of various ions on the hydrogen yields from y-irradiated 0.1wrnethanol in neutral and acid solurion Doses from 0.4 to 1.0 x lola ev per C.C. Ion added Concn. as sulphate (104M) None -Zn2+ 1.0 Ni2+ 1.0 co2+ 1.0 Cd2+ 1.0 C13+ 1.0 Pb2+ 1o.ot Mn2+ 10.0 Mg2+ 10.0 ca2+ 100 Ba2+ losot cs+ 1o*ot Na+ 50.0 NH$ 50.0 G(H2) aH2) neutral in acid* 3.10 4.07 2.52 4.07 1-35 4.00 1.70 4.05 1 *22 4-02 1-91 4.03 1 so2 4.02 -3-20 -3.16 -3-06 3.1 1 -3.00 --3-14 3-21 -* These yields are for 0.1N-sdphuric acid containing the ion at 10-3~,except that 0.1N-perchloric acid was used with Pb2+.t Added as chloride. is also a small yield of hydrogen atoms G = 0.6. The latter are not scavenged by CdU- PbU- etc. and together with GH = 0.4 they account for the lower limit G(H& = 1.0. (Received March 1 1 th 1963.) CHEMICAL SOCIETY MEETING London Thursday June 6th 1963 at 6 p.m. Meeting for the Reading of Original Papers “Some Observations on the ‘Rare-gas Rule’,” by D. P. Craig and C. Doggett. “Molecular Orbital Theory of Organometallic Com- pounds. Part IV. Substitution Reactions of Tri- carbonylbenzenechromium,”by David A. Brown. “Structure and Reactivity of the Oxyanions of the Transition Metals. Part XV. Mechanism of Oxida-tion by Chromate and Related Ions,” by M.C. R. Symons. To be held in the Rooms of the Society Burlington House W.l. (British Railways are offering concessionary fares for this meeting and a travel voucher will be sent by the General Secretary on receipt of a stamped and addressed envelope.) PROCEEDINGS NEWS AND ANNOUNCEMENTS Nominations to Honorary Fellowships-The Coun-cil has made the following nominations for election to Honorary Fellowship. Subject to Bye-Law 13 these elections will be confinned in June. Professor Melvin Calvin (California) Nobel Laureate. Distinguished for his researches in con- nection with the application of radioactive traces to the problems of photosynthesis and his work in a new field of exobiology. Professor J. Heyrovsky (Prague) Nobel Laureate.Distinguished for his development of the polaro- graph as a valuable quantitative analytical technique and its use in the investigation of the reduction and oxidation potentials of inorganic and organic substances. Dr. E. Lederer (Gif-sur-Yvette) Director of the Institute of Biological Chemistry. Distinguished for his researches in the field of biological organic chem- istry and for his remarkable contributions inter alia to our knowledge of the constituents of the tubercle bacillus. Research Fund.-The Research Fund of the Chemical Society provides grants for the assistance of research in all branches of Chemistry. Applica- tions for grants will be considered in December 1963 and should be submitted on the appropriate form not later than November 15th 1963.The total amount available for distribution is approximately gl,O00 and applications from Fellows will receive prior consideration. Forms of application together with the regulations governing the award of grants may be obtained from the General Secretary. Election of New Fellows.-77 Candidates were elected to the Fellowship in April 1963. Deaths.-We regret to announce the deaths of Mr. E. R,Bugge (23.3.63) Chairman and Founder of Bugges Insecticides Limited Sittingbourne and Dr. J. B. Whitworth (March 1963) University Chemical Laboratory Cambridge. Oxford Inorganic Discussion.-The second Ox-ford Inorganic Discussion sponsored by the Society will be on “Ultraviolet and Visible Spectra of Metal Complexes” and is to be held in the Inorganic Chem- istry Laboratory Oxford on Friday September 27th 1963.Speakers will include Professor C. J. Ballhausen Dr. T. M. Dunn Dr. S. F. Mason and Dr. R. J. P. Williams. Full details will be circulated later. Beilby Medal and Prize.-The Administrators of the Sir George Beilby Memorial Fund representing the Royal Institute of Chemistry the Society of Chemical Industry and the Institute of Metals have made awards from the Fund each consisting of the recently instituted gold medal with a prize of 100 guineas to the following Professor R. W. K. Honeycombe (University of Sheffield) in recognition of his work in physical metallurgy with special reference to the study of precipitation processes and the modes of plastic deformation of metals and alloys.Dr. R. W. B. Nurse (D.S.I.R. Building Research Station) in recognition of his work on the chemistry and technology of cement with special reference to the study of the fundarnental chemistry of cement and its application to the practical problems en- countered in the setting-up of a cement industry in Uganda. The Administrators are to revert to the practice of awarding the Beilby Medal and Prize annually pro- vided there is a candidate of sufficient merit and the next award will be made in 1964. Meldota Medal.-The Council of the Royal Institute of Chemistry with the concurrence of the Society of Maccabaeans has awarded the Meldola Medal for 1962 to Dr. J. Trotter for his work in the field of chemical crystallography with special reference to the structures of polynuclear aromatic compounds.British Association for the Advancement of Science.-The Annual Meeting of the British Association for the Advancement of Science will be held in Aberdeen from August 28th to September 4th 1963. The Annual Meeting is the largest scientific gathering of its kind in the year and the only one which members of the general public can join on equal terms with scientists. It not only provides a platform on which scientists can discuss their work with their colleagues in their own language and one on which scientists in separate but related fields can consider the “growing points’’ of science but also affords a chance for the layman to learn something of the progress of science from the scientists con- cerned.The Annual Meeting is open to all who are interested in the progress of science and in its impact through its applications on society as a whole. Enquiries should be addressed to the British Associa- tion Office 3 Sanctuary Buildings Great Smith Street London S.W.1. Joint British Committee for Vacuum Science and Technology.-The second Bulletin of the Joint British Committee for Vacuum Science and Tech- nology is available and it is proposed to issue further bulletins at six-monthly intervals. The bulletins can be obtained initially free of charge from the Joint British Committee for Vacuum Science and Tech- nology 47 BeIgrave Square London S.W. 1. MAY1963 Symposia etc.-An International Plastics Exhibi- tion and Convention will be held in London on June 12th-22ndY 1963.Further enquiries should be addressed to British Plastics Dorset House Stam- ford Street London S.E.1. The Sixth Biennial Conference on Carbon will be held in Pittsburgh Pennsylvania on June 17th- 21st 1963. Further enquiries should be addressed to R. A. Friedel U.S. Bureau of Mines 4800 Forbes Avenue Pittsburgh Pennsylvania. A Conference on New Nuclear Materials Tech- nology including Non-metallic Fuel Elements will be held in Vienna on July lst-5th 1963. Further enquiries should be addressed to the International Atomic Energy Agency 11 Karntner Ring Vienna Austria. A Symposium on Microscopy sponsored by the International Microscopy Symposium Association will be held in Brighton on July 22nd-26th 1963.Further enquiries should be addressed to Elisabeth C. Bitoy Secretary McCrone Research Institute 451 E. 31st Street Chicago 16 Illinois. An International Conference on Nucleon Struc- tures will be held in Stanford California from July 24-27th 1963. Further enquiries should be ad- dressed to Professor Robert Hofstadter Department of Physics Stanford University Stanford California. The Sixth International Union of Crystallography General Assembly and International Congress will be held in Rome on September 9-18th 1963. Further enquiries should be addressed to D. W. Smits General Secretary of the Union c/o Mathe- matisch Instituut University of Groningen Reitdiep- skade 4 Groningen.Netherlands. Personal.-Mr. N. W. Alcock has been pre-elected into a W. M. Tapp Fellowship for Research in Chemistry at Gonville and Caius College from October lst 1963. Professor F. A. L. Anet of the University of Ottawa has been appointed Visiting Professor Department of Chemistry. University of California Los Angeles for the Spring Semester 1963. Dr. M. F. Ansell Lecturer at Queen Mary College has been appointed to the Readership in Organic Chemistry tenable at that College. Mr. J. E. G. Rurnett has been appointed to a Lectureship in the Department of Physiology and Biochemistry at the University of Southampton with effect from September 1st. 1963. Professor F. Rergel has been appointed Dean of the Institute of Cancer Research Royal Cancer Hospital London S.W.7.Professor J. D. Rernul. Professor of Physics at Birkbeck College has been appointed to the newly instituted Chair of Crystallography at that College from October 1st 1963. Dv. M. J. Blandamer has been appointed Lecturer in Chemistry at the University of Leicester. The title of Reader is to be conferred on Dr. D. Bryce-Smith Lecturer in Chemistry at the University of Reading from October lst 1963. Dr. A. W. Chapman is to retire from his post as Registrar of the University of Sheffield in September. Dr. J. Clark a Director of Imperial Chemical Industries of Australia and New Zealand Limited and Head of the Australasian Department is to be seconded for two years to Imperial Chemical Industries (Malaya) Limited.Dr. P. L. Coe has been appointed Lecturer in Chemistry at Birmingham University from October lst 1963. Dr. D. S. Duvies has been appointed Head of the Petrochemical and Polymer Laboratory of Imperial Chemical Industries Runcorn Heath Cheshire. Dr. A. J. Edwards has been appointed Lecturer in the Department of Chemistry at Birmingham University from October lst 1963. Mr. R. C. Feather has been elected Chairman of the Governors of Twickenham College of Tech- nology. He has been re-appointed as a Governor of Isleworth Polytechnic and of the Twickenham Secondary Schools. Dr. H. M. Frey has been appointed Senior Lecturer in the Department of Chemistry at Southampton University with effect from October lst 1963.Dr. F. M. Hanzer has been awarded the Royal Photographic Society’s Progress Medal for 1962 and has been elected an Honorary Fellow of that Society. Dr. J. N. Hawthorne has been appointed Senior Lecturer in Medical Biochemistry and Pharmacology at Birmingham University from October lst 1963. Mr. H. Huyhurst has retired from his position with the Research Department of British Railways and has established a consulting practice at “Fouray” Parkfield Road Didsbury Manchester 20 (Telephone Didsbury 3224). specialising in Pest Control and Industrial Weed Control. Mr. E. J. Hemer formerly Assistant Works Manager Nylon Works Imperial Chemical In- dustries Limited Dyestuffs Division Wilton. has been appointed Nylon Works Manager Billingham.Dr. R. D. HiU formerly of Beecham Research Laboratories Limited has been appointed Marketing Manager at the Research and Industrial Instruments Company London. Sir Hurry Jephcutt is to retire on June 30th 1963 from his position as Chairman of the Board of Glaxo Group Limited. Although leaving the Board Sir Harry will become Honorary President of the Glaxo Group. Sir Alan Wilson has been appointed Chairman of the Board. PROCEEDINGS Dr. P. Johnson formerly of Birmingham Medical School has been appointed Visiting Lecturer in the Bio-Chemistry Division University of Illinois U.S.A. Dr. S. E. Livingstone formerly Senior Lecturer in Chemistry has been appointed Associate Professor in Inorganic Chemistry at the University of New South Wales.Mr. J. G. Maltby will be retiring on June 30th 1963 from his post as Senior Analytical Adviser with the Distillers Company Limited Research Department Epsom. Dr. P. C. H. Mitchell formerly of Oriel College Oxford has been appointed Lecturer in Chemistry at the University of Reading from September 30th 1963. Dr. C. T. Mortimer has been appointed Senior Lecturer in the Department of Chemistry at the University of Keele from October lst 1963. Mr. J. Ormston has been appointed Head of the Science Department College of Further Education Darlington. Professor T‘. M. Oza has retired from his post as Principal and Professor of Chemistry Government College Jamnagar. Dr. A. Parker has been elected President of the National Society for Clean Air in succession to Lord Cohen.Dr. T. E. Peacock and Dr. M. J. Perkins have been appointed Lecturers in Chemistry at King’s College London. The Honorary Degree of LL.D. has been con- ferred on Sir Rudolph Peters by the University of Glasgow. Dr. G. 0. Phillips and Dr. E. Whittle have been appointed Senior Lecturers in the Department of Chemistry at the University College of South Wales and Monmouthshire Cardiff from October lst 1963. Dr. F. Popplesdor-has been appointed Research Scientist at Union Carbide Chemicals Company South Charleston Virginia U.S.A. Dr. N. H. Rees has been appointed Lecturer in the Department of Chemistry at the University College of South Wales and Monmouthshire Cardiff from October lst 1963.Dr. R. E. Richardq Demonstrator in Chemistry Oxford University is to visit and lecture at Scientific Institutions in the U.S.S.R. by arrangement between the Royal Society and the Soviet Academy of Sciences for the annual exchange of four highly qualified scientists. Such visits take place under the Anglo-Soviet Cultural Agreement and in consulta- tion with the British Council. Dr. A. C. Richardson,formerly of Bristol has been appointed Lecturer in Chemistry at the University of Reading from September 30th 1963. Mr. R. Robinson retires at the end of April from the position of Chief Chemist of International Paints Limited. Sir Robert Robinson and Lord Fleck have been elected Honorary Fellows of the Institute of Chem- istry of Ireland.Dr. J. H. Skellon has been awarded the degree of D.Sc. of the University of London. Dr. W. A. Srneaton has had the title of Reader in the History and Philosophy of Science conferred on him in respect of his post at University College London. Professor M. Stucey Mason Professor of Chem- istry has been elected to be Dean of the Faculty of Science at Birmingham University for three years from July 15th 1963. Mr. J. L. Sweeten has been elected to the Board of Steels Process Plants Ltd. as Engineering Director. Dr. J. Tinsley has been elected a Fellow of the Royal Society of Edinburgh. Professor R. L. Wain is to receive the Honorary Degree of Doctor of Agricultural Sciences from the Agricultural University of Ghent Belgium.Dr. T. S. West formerly of Birmingham Univer- sity has been appointed to the Readership in Analytical Chemistry tenable at the Imperial College of Science and Technology. Dr. A. M. Beryl Whitaker formerly Senior Lecturer in Chemistry has been appointed Head of the Science Department Reading Technical College. Dr. A. H. Willbourn has been appointed Manager of the Technical Service Department Plastics Division Imperial Chemical Industries Limited. 1963:page 90 col. 2 Formula (VIII) and (IX) should be ERRATA 1963,page 74,right-hand column line 15 in the article on the Chemical Society’s Publications Survey it is stated that the latest supplement to Beilstein covered the literature only to 1939. This should have read 1949 and the typographical error is much regretted.1963 page 115 footnote for structure (11) read structure (I). MAY1963 153 ~~ ~ OBITUARY NOTICES EDWIN PERCIVAL TAYLOR 1913-1963 Fbwm PERCIVAL was born at Southampton TAYLOR on December 27th 1913 and died at Hertford on September 22nd 1962 leaving a widow and two young children. He was educated at Brighton Tech- nical College and graduated B.Pharm. in 1934 and B.Sc. with First Class Honours in Special Chemistry (University of London) in the following year. Four years later he was awarded the degree of Ph.D. of the University of London and became lecturer in chem- istry at Brighton Technical College. In 1940 he entered on an industrial career first with May and Baker Ltd.and then with the Drake Law Labora- tories. This was interrupted by four years’ service in the Royal Air Force after which he joined the staff of the British Drug Houses Ltd. and finally the staff of Alien and Hanburys Ltd. where he was Head of the Chemical Research Department until his fatal illness. In spite of great determination Taylor had some difficulty in obtaining entry into one of the Services and it was not until 1942 that he finally overcame the obstacles in the way of those in a reserved occupation and was granted a commission in the technical branch of the Royal Air Force as an Armament Officer. He had 2Q years active service in the North African and Italian Campaigns and the experiences he underwent at this time were doubtless responsible for the strong sense of loyalty that he both expected from and gave to those with whom he was associated in his work.The administrative experience gained during those years proved invaluable when he became responsible for the organisation of a large research group at Allen and Hanburys. In 1945 on the cessation of hostilities in Europe Taylor was partly responsible for the development of the R.A.F. Educational and Vocational Training School in Naples of which he became Commanding Officer. This no doubt gave him that interest in the welfare and further education of his younger colleagues that characterised his later career; nothing gave him so much pleasure as the academic successes of those of his junior staff who qualified “the hard way,” and for whose successes he could justifiably have taken some of the credit- although he never did.Taylor’s best work was done in the research laboratories of Allen and Hanburys Ltd. at Ware particularly in collaboration with H. 0. J. Collier the then Head of the Pharmacology Department. Between 1949 and 1953 they published a dozen or so papers on the chemistry and neuromuscular blocking activities of a series of heterocyclic decamethylene- bisquaternary ammonium salts. These were com- paratively simple analogues of (+)-tubocurarine with true curare-like activity. The most active of them decamethylene-bis-[1-(3,4-dimethoxybenzyl)-1,2,3,4-tetrahydro-6,7-dimethoxy-2-methylisoquino-linium iodide] “Laudolissin” or Laudexium was tested in human volunteers and found to be nearly as potent as (+)-tubocurarine chloride.Subsequent- ly Taylor prepared compounds with structural features common to both laudexium and suxa-methonium in the hope of obtaining short-acting true curarising agents. In fact many of the com- pounds were antagonised by neostigmine and some of them were short-acting. Some were long-acting however and one of them the dimethiodide of 2-dimethylaminoethyl-w-(N- tetrahydropapaveriny1)-caproate is one of the most active synthetic neuro- muscular blocking agents known being 30 times as potent as (+)-tubocurarine chloride in the cat. Taylor was a recognised authority on neuromuscular blocking agents and the author of several reviews.The most fruitful result of the collaboration between Taylor and Collier from the industrial point of view was the development of a series of bis-quaternary ammonium salts for use as anti-microbial agents. The most important of these was deca-methylene-bis-4-aminoquinaldiniumchloride “De- quadin” or Dequalinium with a very wide anti- microbial spectrum and negligible toxicity when administered by mouth. It is now one of the most widely used synthetic antimicrobial agents. A related compound hexadecamethylene-bis-isoquinolinium methosulphate “Teoquil” or Hedaquinium was a very effective antifungal agent in vitru but enjoyed only a limited success in the treatment of human dermatophytes. A by-product of this investigation was the preparation of 4-amino-1-(6,4‘-quinaldinyl-aminohexy1)quinaldinium iodide hydriodide first obtained as an impurity in hexamethylene-bis-(4-aminoquinaldinium iodide) and shown to be responsible for the apparent trypanocidal activity of the latter.The impurity when prepared in the pure state by an unequivocal synthesis was found to be very active against T.congdense in mice and field trials in Africa showed it to be an effective thera- peutic agent in cattle but unfortunately its prophy- lactic activity was disappointing. Taylor’s work on bis-quaternary salts was his most important contribution to medicinal chemistry but he also worked in a number of other fields. Thus he and his colleagues prepared a number of deriva- tives of 4-hydroxyisophthalic acid many of which 154 exhibited biological activity some new derivatives of chloramphenicol and a series of new thiobarbituric acids with a very short duration of action.Taylor was elected to the Fellowship of the Royal Institute of Chemistry in 1955 and was Hon. Recorder of the Fine Chemicals Group of the Society of Chemical Industry until his illness. He was also a member of the Scientific Advisory Committee of Hatfield College of Technology. That Taylor became a chemist by way of pharmacy was of importance in determining his ultimate career for it was only natural that when the opportunity came he should have elected to carry out research in medicinal chemistry. His earlier training and back- ground made it easier for him than for most chem- ists to collaborate with his pharmacological bac- teriological and pharmaceutical colleagues.Taylor had strong views about many things but this trait did not prevent him from working amicably with the PROCEEDINGS biologists to form an effective and dedicated team; indeed his critical outlook and forceful comments often led to a speedy resolution of interdepartmental difficulties. It was in fact good team-work that lay behind much of the success of the research effort for which Taylor was responsible. He gained the respect of both his senior and junior colleagues and was always ready to press for improvements in the con- ditions under which his staff worked. He had a special interest in further education encouraging and advising his laboratory technicians to study for what- ever qualification seemed best suited to their require- ments and abilities.Taylor was a keen Churchman and took an active part in supporting many worth- while causes particularly those associated with the resettlement of refugees. It is a great tragedy that an active and useful life such as his should have been cut short prematurely. F. A. ROBINSON. THOMAS SHERLOCK WHEELER 1899-1 WITH the sudden death in Dublin of Thomas Sherlock Wheeler on December 13th 1962 Ireland lost one of her foremost scientists. Born in Dublin on April 30th 1899 the eldest of four brothers he was the son of Martin Redmond Wheeler Account- ant and Head of the Dublin Municipal School of Commerce.He received his early education at O’Connell Schools where he proved to be one of the brightest of their students. At the Annual State Examinations in which he competed he was twice placed first in Ireland in the Science and Mathematics groups. He also won first place in English with a special prize for English Composition. Leaving school in 1916 on examination results he was awarded two scholarships one tenable in University College Dublin and the other-for which he opted- in the Government Royal College of Science for Ireland. Four years later he obtained the Associate- ship of the latter Institute. At the various examina- tions held during his course he performed brilliantly and was awarded in all fourteen prizes. On gradua- tion he took up his first post as a Demonstrator in Chemistry at the Royal Technical College Glasgow where he became interested in research.At the same time he collaborated with two of his colleagues W. M. Cumming and I. V. Hopper in writing the manuscript of “Systematic Organic Chemistry” which was published in 1923. The book has since run into several editions and is still used in many laboratories throughout the world. In 1921 he was awarded a D.S.I.R. grant and transferred to the Royal Naval Cordite Factory Dorset where he worked on the oxidation of hydrocarbons. On the 962 results of this research he obtained the degree of Ph.D. (London) in 1924. His next post was as Research Chemist at Woolwich Arsenal where he worked on high explosives and later on the experi- mental detonator plant.In after years he had many amusing stories of his experiences during this period. In 1926 while still at Woolwich he married his cousin Una Brigid Sherlock. It was an ideal union and throughout his life he regarded marriage as a solution to numerous ills. To many a doleful student his parting words said with a cheery grin were “get married-I did it myself when I was twenty-six and I’ve always regretted the years I wasted up to that.” From 1928 to 1931 he was Senior Research Chemist with Imperial Chemical Industries Limited at Winnington. There he was in charge of a Gas Reaction Group composed of chemists physicists and engineers. This team developed a high-tempera- ture high-space-velocity method for carrying out gas reactions and the research was the subject of several publications including many patents.This early work still attracts attention as instanced by a visit of interested scientists from abroad to University Col- lege Dublin some years ago. During this period he gained a good deal of experience in the design of chemical plant and in chemical engineering generally. This knowledge was of inestimable value to him when in after years in India he prepared plans for a Department of Chemical Technology in the University of Bombay. In 1931 he applied for and obtained the post of Principal and Professor of Organic Chemistry Royal Institute of Science Bombay. The Institute which MAY 1963 was affiliated to the University of Bombay had 60 members of staff and about 600 students.There were professorships in the usual science disciplines. Tom Wheeler took an active part in the work of the University and served on all its authorities; for two years he acted as Dean of the Faculty of Science. His advice and help were at the service of all. At the request of the authorities he drew up a scheme in- volving the establishment of a Department of Textile Chemistry and a Department of Chemical Engineer- ing. His plans were accepted by the University Senate and put into operation and today the flourishing Department of Chemical Technology in that University owes a great deal to his enthusiasm initiative and ability in bringing it into being. He was general adviser on scientific matters to the Government of Bombay and served on all selection committees for scientific posts.He was Examiner in Chemistry for the Indian Civil Service Commission and for most of the Indian Universities. He was proud of the fact that he was a Foundation Fellow (and sometime Vice-president) of the National Institute of Science of India. With an immense capacity for hard work and an ability to do several things well at the same time Tom Wheeler in parallel with his administrative and teaching duties was expanding the research school in the Institute. The work was mainly on the chemistry of flavonoids-a field in which he became an inter- nationally recognised expert. During the years he was in charge about 100 communications were published from the Organic Laboratory.The ideas set out in a paper published with his co-workers in 1938 on the Wessely-Moser rearrangement have stood the test of time and the remethylation technique which he suggested is now standard practice in reactions where such rearrangement may occur. Apart from his Organic Chemistry he was a keen mathematician and had an interest in the application of mathematics to chemical problems. While in Bombay he published a series of papers on the theory of liquids to which reference is still made. His years in India were happy fruitful ones; he made lifelong friends and when he was leaving that country tributes were paid to the great work he had done for the Institute by among others the Governor of Bombay and by heads of various Government Departments.An unnamed student wrote of him in “The Times of India” “He set an example to the students by his great industry and infected them with his own zeal for research . . .the eminent place the Royal Institute of Science occupies today is due solely to his efforts and his premature retirement is a great loss to the progress of scientific teaching of our Presidency.” These words with little change might have been said by one of his last research students. In 1938 he returned to ‘Ireland as State Chemist. His duties involved control and supervision of the State Laboratory where all scientific work in con- nection with Government Departments is under- taken. He also acted as expert adviser to the Govern- ment on industrial and scientific matters.Once back he rapidly became associated with every scientific undertaking in Irish life and some of his dynamic energy seemed to permeate everything he touched. He was appointed a Member of the Board of The Dublin Institute for Advanced Studies. He was a Member of the Chemotherapy Tuberculosis Com- mittee of the Medical Research Council of Ireland; indeed this very successful chemotherapeutic unit was formed at his instigation. During the War he served on the Emergency Scientific Research Bureau a body set up to investigate means of supplying manufacturers with substitutes for materials no longer available from outside. Wheeler’s team of chemists soon got used to seeing his familiar figure arriving on his bicycle at any hour of the day or night.While State Chemist he was precluded from carrying out research in the ordinary way so he became interested in the development of science teaching in Ireland during the nineteenth century. As a result he published accounts of the life and work of Sir Robert Kane and of Dr. W. K. Sullivan who had succeeded Kane as President of Queen’s College Cork. In the early 1940’s his interest was also stimulated by courses of lectures on various aspects of quantum mechanics delivered at the Institute for Advanced Studies by Professors Schrodinger and Heitler both working in Ireland at the time. As a result of this association he published two theoretical papers-one dealing with the energy states of two-electron ions the other outlining a new series solu- tion for the evaluation of some atomic integrals.In 1945 he was appointed to the Chair of Chem- istry in University College Dublin a post which he held until his death. In Ireland there was little tradi- tion in physical or inorganic chemistry and one of the first tasks he set himself was to expand this section of his Deparment. This he achieved by attracting to his side young chemists who had trained outside Ireland. On his staff when he died were chemists from America England Germany India and Japan as well as his Irish colleagues. He had an international outlook and he ensured that members of his department were given every opportunity for study abroad.Throughout his years at University College a steady stream of famous chemists lectured in Dublin and many an American or European scientist who never thought of visiting Ireland found himself “diverted” to Dublin on his way to a meeting in another capital. In the last ten years he organised a number of symposia in his Department. One on the “Chemistry of Pyrones” held in 1955and a later one on “Humic Acids” brought participants from all over the world. He was also primarily responsible for inducing the British Association for the Advancement of Science to hold its annual meeting in Dublin in 1957. He was closely concerned with all College activities and as in India was a member of all the authorities. He must be one of a few people to serve as Dean of a Faculty in two Universities.As a member of the Building Committee his advice and experience were of immense value in planning the Science Block now in course of erection on the new University site on the outskirts of Dublin. The chem- istry building will be ready for occupation at the beginning of the 1964-65 session and it is a matter of deep regret to his colleagues that he will not be here to see and enjoy the culmination of his efforts. In recent years he made tremendous efforts to improve science teaching in Irish schools. He was primarily responsible for the modernised examina- tion syllabuses now coming into operation. To help teachers with the changed courses he organised in his Department several series of lectures on new ideas in chemistry and gave generously of his time to visit schools to advise or lecture as the need arose.He acted on various chemical bodies and was a Member of Council and sometime President of the Irish Chemical Association (later the Institute of Chemistry of Ireland) sometime Member of Council and of the Publication Committee of The Chemical Society a Member of the Editorial Board of Tetra-hedron sometime Vice-president and Member of Council of The Royal Institute of Chemistry. While on the Education Committee of the Council he was one of those responsible for the upgrading of the Associateship Examinations of that Institute. His wide interests were reflected in his membership of the -~~~~ Institution of Chemical Engineers and of the Institute of Physics.Other bodies on which he served were the Council of the Royal Irish Academy the Science Committee of the Royal Dublin Society as well as several Government Boards. He was the representative for Ireland on the O.E.E.C. Committee for Scientific and Technical Personnel. With all this he published while at University College about 100 papers. The work was mainly in the flavonoid field and over the years he contributed many new methods for the syntheses of these com- pounds as well as investigating the mechanism of some of the reactions concerned. In 1952 he dis- covered that certain Il’-alkoxyflavonoids undergo a Wessely-Moser type of rearrangement. This finding had wide implications for chemists investigating products with this substitution pattern.Meanwhile he was co-author of two books; with his colleague Dr. Gowan he published “Name Index of Organic Reactions” and with Professor Partington the “Life and Work of William Higgins.” Tom Wheeler was a born leader a first-class administrator and an outstanding chemist. With his gay spirit his tireless energy and his passion for progress it was impossible to work close to him and not be affected by his enthusiasm. But more im- portant than his competence and ability were his great humility and unfailing kindness. In the years I knew him his help was freely sought and generously given. His untimely death is a tragic loss. He is survived by his wife Una his son Desmond Assistant Professor of Chemistry in the University of Nebraska his daughter Brenda a chemist with the Agricultural Institute in Dublin and his daughter Thomasina who is still at school.E. M. PHILBIN. ADDITIONS TO THE LIBRARY Chlorine its manufacture properties and uses. Edited by J. S. Sconce. (A.C.S. Monograph No. 154.) Pp.901. Reinhold. New York. 1962. Aromatic fluorine compounds. A. E. Pavlath and A. J. Leffler. (A.C.S. Monograph No. 155.) Pp. 820. Reinhold. New York. 1962. Organic chemistry. Vol. 1. The fundamental principles. I. L. Finar. Pp. 853.4th edn. Longmans. London. 1963. (Presented by the publisher.) Gas chromatography. H. Purnell. Pp. 441. J. Wiley and Sons. New York. 1962. Gas chromatography. A. B. Littlewood. Pp.514. Academic Press. New York. 1962. Thin film chromatography. E. Vernon Truter. Pp.205. Cleaver-Hume. London. 1963. Techniques in protein chemistry. J. Leggett Bailey. Pp. 310. Elsevier. Amsterdam. 1962. Advanced materials refractory fibres fibrous metals composites. C. Z. Carroll-Porczynski. Pp. 286. Astex. Guildford. 1962. (Presented by the publisher.) Metal colouring. D. Fishlock. Pp. 393. Robert Draper Ltd. Teddington. 1962. Chemical reaction engineering :an introduction to the design of chemical reactors. 0. Levenspiel. Pp. 501. J. Wiley and Sons. New York. 1962. Gas chromatography 1962. Proceedings of the fourth symposium organised by the Fachgruppe Analytische Chemie of the Gesellschaft Deutscher Chemiker and the Gas Chromatography Discussion Group of the Hydro- carbon Research Group of the Institute of Petroleum, held at the Auditorium Maximum Hamburg 1962. Edited by M. van Swaay. Butterworths Scientific Publications. London. 1962. NEW JOURNALS Radiochimica Acta from 1962 1.
ISSN:0369-8718
DOI:10.1039/PS9630000125
出版商:RSC
年代:1963
数据来源: RSC
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