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Proceedings of the Chemical Society. November 1957 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue November,
1957,
Page 301-328
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY NOVEMBER 1957 ISOCYANATES* By A. C. FARTHING (IMPERIAL INDUSTRIES RESEARCH CHEMICAL LIMITED LABORATORIES HEXAGON 9) HOUSE,MANCHESTER U~ World War I1 isocyanates were not of Many occur readily on mixing of the reactants L technological interest but during that war in- and catalyst. In general dustrial applications were found independently R-NCO + HX =R.NH*COX in this country and in Germany. Since the war R-NCO + R'OH -+ R*NH*CO,R' they have been the subject of intensive research R-NCO + R'C02H -+ R-NHCO*OCOR' and development in Europe and America and + R~NH-COR'-+ co, many isocyanates are now in regular production R*NCO + H20 +-R-NHCO,H and use. Little work has been done in academic -+ R-NH + Con centres during this period.In all these applica- R-NH + R-NCO -+ RNHCO*NHR tions only polyisocyanates are of value as will be The HX adducts of isocyanates vary widely in seen later and mainly aromatic polyisocyanates. stability. Alkyl urethanes are stable; the adducts Only one method of preparation is of industrial with phenol dissociate to their original com-use at the present time. Phosgene (carbonyl ponents when heated and are therefore used as chloride) converts aromatic and aliphatic amines isocyanate generators or "masked isocyanates" ; into isocyanates smoothly and in high yield. carbamic acids are highly unstable. The adducts with carboxylic acids are unstable and lose car-R-NH + COCl,+ R-NHCOCl + HCl bon dioxide to give carboxylic amides. The addi- R-NHCOC1 -+R*NCO + HC1 tion of HX is subject to a general acid-base The reactions of isocyanates are at first sight catalysis; the polymerisation to cyclic dimers and simple and few but on closer examination pre- trimers occurs in the presence of bases although sent great diversity and complexity.Most reac- at elevated temperatures trimerisation may occur tions occur very readily and comprise addition to without addition of catalyst. the N=C bond either of a molecule containing The reactivity of isocyanates is qualitatively a reactive hydrogen atom or of other isocyanates. simple. The stronger the parent amine the less * This is the first of a series of articles illustrating the scientific background of recent industrial developments 301 reactive is the isocyanate towards HX; aliphatic isocyanates are as a class much less reactive than aromatic.In the aromatic series electron-attract- ing groups increase reactivity and electron- repelling groups decrease it. Thus reactivity may be controlled at will by adjusting the carbon skeleton and the substituent groups. The kinetics and mechanisms of isocyanate re- actions are extremely complicated. The work of Baker in this field is now being taken further in many industrial centres. The irreversible and ap- parently straightforward reaction with alcohol is the most understood. R-NCO + R’OH = Complex Complex + R’OH -+ R.NHCO,R’ + R‘OH In the presence of tertiary amine catalysts we have R-NCO + Base =i Complex Complex + R’OH -+ R-NHCO2R’+ Base The action of other basic catalysts and of acidic catalysts is not fully understood.The urethane product is itself basic and exhibits an extra catalysis particularly in the case of the aliphatic isocyanates. At the moment it is not possible to measure all the rate constants in the above mechanisms. The kinetics are further complicated because most of the HX reactants are capable of associa- tion through hydrogen bonds either with them- selves or with the solvents. Most of them are acidic or basic and are general catalysts; specific catalysts remain to be discovered. Most of the products are feeble bases. In the case of water and carboxylic acids there are several known intermediate products. Much work remains to be done.isocyanates are of great industrial value because the reactions are simply those of ready addition or if anything is eliminated it is carbon dioxide. A molecule containing two or more iso- cyanate groups will thus join two or more mole- cules which contain isocyanate-reacting groups with great ease. The products formed in that way resemble in their essential properties the products which would be expected if they had been built up through other polymer linking molecules but isocyanates are unique in the facility with which links are formed and in the essential irreversibility of the link formation under practical operating PROCEEDINGS conditions. In addition isocyanates confer specific characteristics by secondary reactions for example cross-linking in solid rubbers and gas evolution in foam formation.It is therefore in polymeric products that iso-cyanates find the greatest use. The simplest example is perhaps the preparation of poly-urethanes from simple diols and diisocyanates manufactured in Germany during the war. 1-R-O-CO-NH-R’-NH-CO-O-jn Thus Perlon U was manufactured from butane-1 :4-diol and 1 :6-diisocyanatohexane. When the diol is itself a polymer extremely useful products are formed. Thus polyesters may be prepared by heating together glycols and di- carboxylic acids. The structure of the polyester may be varied at will by choice of reactant it may be (partially) crystalline or amorphous of melting point from below room temperature upwards linear or (by addition of e.g.glycerol or penta- erythritol) branched. The end groups of the poly- ester may be OH or COzH or both depending on the molar ratio of the reactants. Polyesters are the best known and most easily controlled blocks which may be joined by di- or tri-isocyan- ates but polyalkylene glycol ethers e.g. poly-propylene glycol or polytetrahydrofuran with hydroxyl ends are being used increasingly. The first commercial development was of a British rubber. A polyesteramide was made by interaction of ethylene glycol monoethanol-amine and adipic acid. This polymer at about molecular weight 5000 was heated with about an equimolar quantity of 1 :6-diisocyanatohexane to yield a thermoplastic rubber roughly re-sembling natural rubber in its physical character- istics.This rubber developed in Britain during the war as Vulcaprene A can be vulcanised by a formaldehyde-generating resin (probably by formation of methylenebis-amide cross-links) or by cold vulcanisation with an aromatic polyiso- cyanate for example a diisocyanatodiphenyl-methane yielding cold-curing adhesives and flexible lacquers. In Germany two significant applications were made-a rubber known as Vulkollan and a variety of light-weight foams. Otto Bayer investi- gated the reaction of polyethylene adipate a low- melting crystalline polyester with a large variety of isocyanates. Whilst 1:6-diisocyanatohexane NOVEMBER 1957 gave crystalline products bulky isocyanates in particular 1:5-diisocyanatonaphthalene could be used to give a rubbery product.The ester was treated with an excess of 1 :5-diisocyanatonaph-thalene and then with water. This rubber did not crystallise readily on storage. The rubber was slightly cross-linked and these cross-links along with the flexibility and crystallisability of the polyester segments which were held apart by the bulky isocyanate residue produced excellent properties. The cross-links were produced prob- ably from the water which generated urea links in the chain-lengthening stage and these urea groups in turn reacted with isocyanate ends to produce branches and ultimately cross-links. The rubber so produced had remarkable pro- perties in particular tensile strength and tear strength higher than those of any other rubber md a resistance to abrasion some 5-10 times better than that of the best of other rubbers.It became possible to contemplate tyres that might outlast cars. Intensive work goes on in Europe and in the U.S.A. in order to accommodate the process on the factory scale and in orthodox rubber-processing equipment. When branched polyesters are used instead of the linear polyethylene adipate the processing is much simpler but the properties of the rubber are different. By this means there are already being manufactured soft solvent-resistant rollers for use in printing. The other major advance in Germany during the war was that of light-weight foams. The di- isocyanate is mixed with a linear or slightly branched polyester and with water.The reaction with hydroxyl and with carboxyl ends and with water gives chain-lengthening ;the last two reac- tions simultaneously produce carbon dioxide. The gas evolved forms a froth in the rapidly polymerising mixture which finally sets. By suit- able adjustment of the nature and proportion of the reactants and of the conditions of mixing and reaction and by addition of basic catalysts and surface-active agents an extremely light elastic sponge may be formed in a few minutes. The most commonly used ingredients are diiso-cyanatotoluene and a branched liquid polyester based on diethylene glycol and adipic acid. Sponges made in this way have a number of advantages over those made by the more conven- tional process of aerating rubber latex.They have about one-third the density-approximately 2 lb. per cu. ft.-and are much more resistant to oxidation and have such good mechanical strength that they can be stitched etc. Products such as mattresses upholstery materials carpet underlays and toilet sponges are already being made on a large scale. If the polyester is highly branched then the number of cross-links in the final product are that much greater and the resultant foam is rigid. Such light rigid foams are used to fill cavities by simply pouring in the mixture and leaving it to blow and set spontaneously for example thermal insulation in buildings and ships strengthening of empty cavities in aircraft wings. These are the principal applications of iso-cyanates as seen at the moment.The power of polyisocyanates to join together other molecules has also been used in lacquers and wire enamels with branched polyesters ;in powerful bonding agents in resin-curing agents and in casting or spreading films to give waterproof fabric. As pro-duction increases no doubt other uses will be found. Qualitatively most of the reactions of iso-cyanates were known before the war. The in- dustrial applications were founded on these and stimulated by wartime needs. In the formation of rubbers and foams it is the proportion of iso-cyanate which reacts in each particular way and the rate at which each particular reaction pro- ceeds which have a critical effect on the properties of the product.It is the quantitative organic chemistry of isocyanates the kinetics and thermodynamics which now requires detailed investigation and it presents a fascinating field of study. PROCEEDINGS CENTENARY LECTURE* Photodynamically Active Plant Pigments By H. BROCKMA” (GOTTWGEN) IT has been known for a long time that sheep cows and horses that have eaten certain plants belonging to the genus Hypericum become sensitive to light. If subjected to sunlight they become restless and in- dicate by scratching that their skin is irritated. After longer exposure to light oedema and a marked reddening of the skin set in accompanied by an initial rise and subsequent sharp fall of body tenipera- ture. If exposure to light is interrupted in time the animals recover but they still suffer for varying lengths of time from inflammation of the skin.This is especially marked in those parts of the body which are devoid of hair or only sparsely covered such as the nose ears feet and eyelids. Animals with white or pale hair are especially subject to photogenic injury dark hair protecting the body from the light. The same photogenic injuries have been observed in sheep cows and horses that have been fed 011 fresh buckwheat plants. The photogenic injuries re- sulting from the eating of plants of the genus Hypericum have been called “hypericism” and those caused by feeding animals on buckwheat have been given the name “fagopyrism” since the Latin for buckwheat is fagopyrum.Buckwheat is no longer used as- fodder for animals. Consequently cases of fagopyrism no longer occur. Hypericism on the other hand has been observed recently in various parts of the world for example in one or two States in North America and very recently to a greater extent among flocks of sheep in Australia. It remained for a long time an enigma why animals that have eaten Hypericum plants or buck- wheat become sensitive to light. This was only solved when at the beginning of our century von Tappeiner observed that not only micro-organisms but also higher animals could be made sensitive to light by means of fluorescent colouring matters. If for example eosin is fed to animals such as white rats or rabbits which are then subjected to light the animals become excited their skin reddens and oedema sets in.Later after illumination has been stopped infiammation of the skin develops. von Tappeinerl called this sensitization to light by means of fluorescent colouring matters the “photodynamic effect”. It is still unknown what chemical reactions are behind the “photodynamic effect”. Perhaps they are photo-oxidations of proteins catalysed by the fluorescent compounds. The symptoms of the “photodynamic effect” are exactly the same as have been observed in horses sheep and cows that have eaten Hypericum or Fagopyrum plants. This coincidence as well as the observation that Hypericum plants and buckwheat contain red pigments which have a red fluorescence had led already at the beginning of this century to the assumption that those injuries which went under the names “hypericism” and “fagopyrism” were nothing but a “photodynamic effect” arising from red-coloured and red-fluorescent Hypericrrm and buckwheat pigments .Since nothing was known about the chemical nature of these red pigments we started experi- ments shortly before the war attempting to isolate the pigments and determine their constitutioii. The following is an account of some results of our investigation beginning with the pigments of Hypericum. Two widespread varieties of Hypericuni are H. perforatirm (St. John’s wort) and H. hirsutum. If the yellow flowers of these two varieties are extracted by means of methanol red extracts with a red fluorescence and characteristic absorption bands are obtained.From these extracts we were able to isolate the pigment hypericin responsible for the red colour the red fluorescence and the absorption spectr~rn.~?~ It crystallises in dark red needles; 0.5 mg. of it suEces to produce the typical symptoms of a photo- dynamic effect in a white rat. Hypericin was found4 to have the composition C30H16-1808. It contains two C-methyl groups. Benzoylation and reductive benzoylation have shown that of the eight oxygen atoms six are present as hydroxy-groups and two as quinone-oxygen atoms. We found keten to be a good reagent for dis- tinguishing between chelated and non-chelatcd hydroxy-groups it acetylates only non-chelated hydroxy-groups. Then since only two hydroxy-groups of hypericin were acetylated by keten the * Delivered before the Chemical Society on April loth 1957 during the Anniversary Meeting at Cambridge.von Tappeiner Ergebn. Physioi. 1909 8 698. Brockmann Haschad Maier and Pohl Annaien 1942 553 1. Brockmann and Sanne Chern. Ber. 1957,90 in the press. * Brockmann von Falkenhausen Neeff Dorlars and Budde Chern. Ber. 1951 84 865. NOVEMBER 1957 305 remaining four must be chelated i.e. in an a-position to the two quinone-oxygen atoms. Valuable information as to the basic structure of the skeleton of hypericin was provided by distillation with zinc dust; this yielded very small amounts of a red hydrocarbon which was found to be anthro- dianthrene (I). This observation alone would suggest that hypericin is a hexahydroxyanthrodianthrone.Two findings however discount this first this structure requires less hydrogen than is present in hypericin; and secondly there are two methyl groups in the pigment. A satisfactory explanation for all observations however was found in the assumption that hypericin is a quinone derivative whose carbon skeleton is transformed into the carbon skeleton of anthro- dianthrene during zinc dust distillation with ring closure between the two methyl groups. We found there are only two types of quinones which fulfil this condition namely 2 :2’-dimethylhelianthrone (11) and 2 :2’-dimethylnaphthodianthrone (111). From these two compounds we obtained anthrodianthrene by zinc dust distillation in the same small yields as from hypericin.From all these results hypericin must either be a hexahydroxy-derivative (IV) of the 2 :2’-dimethyl-naphthodianthrone or that (V) of 2 :2‘-dirnethylheli-anthrone. Analytically it was not possible to decide definitely between the two possibilities. On the other hand it was possible to do so by a spectro- scopic method developed in our lab~ratory,~ by which the basic structure of polycyclic aromatic bydrouyquinones can be elucidated. This procedure is based on two facts that reduc- tive acetylation of aromatic hydroxy-guinones gives Brockmann and Budde. Chem. Ber... 1953. 86.432. acetoxy-derivatives of the basic hydrocarbons and that these acetoxy-derivatives have absorption spectra very similar to those of the basic hydro- carbons in question.This method will be explained by two examples which were of interest for the proof of structure of hypericin. One example is the tetrahydroxyhelianthrone(VT). The basic aromatic hydrocarbon of this compound is helianthrene (VIII) a red hydrocarbon which was synthesized independently by ClaF in Glasgow and by us7in Gottingen. It is chatacterised by the fact that in light it fades very rapidly forming a yellow QJ&g \ OAc OAc (VII) (VII) A,,,. 574,530mp (in C,H,). (VIII) Amax.% 523 mp (in C,H,). Both are red and fade rapidly in light. peroxide. Reductive acetylation of tetrahydroxy-helianthrone (VI) yielded tetra-acetoxyhelianthrene (VII),S whereby the two quinone-oxygen atoms were split off by reduction.Like helianthrene tetra- acetoxyhelianthrene is red and fades very rapidly in light forming a yellow peroxide. Its absorption curve is very similar to that of helianthrene but the absorption peaks lie at somewhat longer wave-lengths.8 The other example is tetrahydroxynaphthodian-throne8 (IX). The parent naphthodianthrene (XI) is a blue compound which does not fade in light. Reductive acetylation of the tetrahydroxynaphthodi- Clar “Aromatische Kohlenwasserstoffe,”’Sp&ger Verlag Berlip 1952 p. 296. Brockmann and Kluge; F. Kluge Diplomarbeit Gottingen 1950. Brockmann Lindemann Ritter and Depke Chem. Ber. 1950 83 583. anthrone (IX) gave tetra-acetoxynaphthodianthrene (X),which is blue and stable to light and has an absorption curve very similar to that of the parent naphthodianthrene.Here too the absorption peaks of the acetoxy-derivative are at somewhat the longer wavelengths. These and many other experiments established the following principle. If it is desired to establish whether a compound is a hydroxyhelianthrone or a hydroxynaphthodianthrone the compound must be reductively acetylated. If the reduction product is red and sensitive to light and has an absorption h UlI> ‘\’’\Me (x)A,,,. 671,611 mp (in C6H6). (XI) Amax. 660,605 mp (in C6H6). Both are blue and do not fade. (XII) Amax. 543,503 mp (in C6H6); red fading. (XIII) A,,,. 627,578 mp (in C6H6); blue not fading. spectrum like that of helianthrene the compound is a hydroxyhelianthrone if it is blue and has a spectrum like that of naphthodianthrene the com- pound is a hydroxynaphthodianthrone.To apply this spectroscopic procedure to hypericin the then unknown hydrocarbons (XII) and (XIII) had to be prepared. This was accomplished by reduc- tion of the two quinones (11) and (111) with zinc dust in pyridine-aceticacid followed by dehydrogena- tion with chloranil. After this preliminary work hypericin was acetylated reductively :a blue crystalline compound with six* acetoxy-groups was ~btained,~ which almost had the same absorption spectrum as 2 2’-dimethyl- naphthodianthrene (XIII). Therefore the blue reduc- tion product must be a derivative of 2:2’-dimethyl- PROCEEDINGS naphthodianthrene.Since as has already been pointed out four of the six hydroxy-groups of hypericin are in an a-position this establishes formula (XIV) for the blue reduction product from hypericin and hypericin must have formula (XV) in which only the position of the two non-chelated hydroxy-groups remained to be proved. This also was done spectroscopically. The blue reduction product (XIV) of hypericin has two absorption peaks in almost the same position as for 2:2’-dimethylnaphthodianthrene(XIII). This was striking for according to our previous experiments (XIV) Amax. 625 578 mp (in C6H6). (XVI) Amax. 663,609 mp (in C6H6). (XVII) h,,,. 671,611 mp (in C6H6). (XVIII) A,,,. 634 583 mp (in CgHg). with models a bathochromic effect was to be ex- pected from the acetoxy-groups of the hypericin reduction product; i.e.the absorption peaks of the blue hypericin reduction product were expected to be at longer wavelengths than those of 2:2’-di-methylnaphthodianthrene. The following observa- tion~~ explain why this was not so for our reduction product. 3:3’-Dimethylnaphthodianthrene(XVI) has two absorption peaks at wavelengths 2-3 mp longer than for naphthodianthrene (XI). This is normal for methyl groups in aromatic hydrocarbons are in general weakly bathochromic. In contrast to the 3:3’-dimethyl compound 2 :2’-dimethylnaphtho-dianthrene (XIII) has two absorption peaks at wave- lengths about 25 mp shorter than for naphthodian- * Under milder conditions we obtained a hepta-acetoxy-derivative.* Brockmann and Randebrock ibid.,1951 84 533. NOVEMBER 1957 307 threne (XI). This surprisingly large hypsochromic effect of the 2 :2’-methyl groups has doubtless steric reasons:the 2 :2’-methyl groups displace one another from their normal positions as a result of overcrowd- ing causing distortion of the rings ;since the molecule is then no longer completely coplanar the energy of activation is greater and the absorption at lower wavelengths than for naphthodianthrene (XI). From results it was to be expected that acetoxy-groups in naphthodianthrene which in general have a bathochromic effect (as for X),would be hypsochromic if they are sterically hindered that is to say if they are in positions 2 and 2‘ or 7 and 7’.As we were able to show this is indeed the case. Wavelengths of maximum absorption for 2 2’-di- acetoxynaphthodianthrene (XVIII) are shorter than those for naphthodianthrene (XI). It follows that although the blue reduction product of hypericin has six acetoxy-groups its absorption AcO AcO (x 1XI OAc (XIX)X)Amax. 625 578 mp (in C,H,). peaks are in nearly the same position as those of 2 :2’-dimethylnaphthodianthrene(XIII) because the bathochromic effect of the 4:5 :4’:5’-acetox~-groups is compensated by hypsochromic acetoxy-groups. But acetoxy-groups in 2 :2’-dimethylnaphthodian-threne can be hypsochromic only if they are attached in positions 7 and 7’ and consequently sterically hindered. Therefore the blue reduction product has the constitution (XIX).This then establishes for hypericin the positions of the two hydroxy-groups that can be acetylated with keten; hypericin has formula (XX). Synthesis of Hyperkin.-The starting material for synthesislo was the trimethyl ether (XXI) of 1-bromo-emodin which was already known as an inter-mediate in a synthesis of emodin by Adams and Jacobsen.ll When heated in naphthalene with copper powder 1-bromoemodin trimethyl ether gave the di- anthraquinonyl derivative (XXII) in very good yield. We converted this compound (XXII) in an almost quantitative yield into the helianthrone derivative into the naphthodianthrone derivative (XXIV) by means of air in the presence of light. Demethylation of this compound (XXIV) by potassium iodide in phosphoric acid gave the hexa- hydroxynaphthodianthrone (XXV) which crystal- lised in dark red needles and agreed in all its properties with hypericin from Hypericum hirsutum.In our early experiments for this synthesis there was difficulty in obtaining the bromotrimethoxy- emodin (XXI) used as starting material when we (XX I> Me0 Me0 \ Me0 HowMe HO OH (XXV) synthesized this compound according to the direc- tions given in literature the yield was very bad. This synthesis starts from 3 :5-dimethoxyphthalic an- hydride (XXVI) which is condensed (Friedel-Crafts) with m-cresol (XXVII). At first this reaction gave very low yields. In 126 experiments under different experimental conditions we established that the best yields (ca.65%) of the acid (XXVIII) were obtained when not more than 5 g. of the anhydride (XXVI) were used and when condensation was carried out in benzene with two mols. of aluminium chloride. At first also we obtained very small yields in the conversion of the brominated benzoyl benzoic acid (XXIII) by treatment with copper powder in a mix- (XXIX) into the anthraquinone (XXX) the litera- ture of acetic acid and hydrochloric acid (1 5 :1). This turell prescribes that the acid should be heated for was dehydrogenated like its parent helianthrone 3 hours with sulphuric acid containing 7 % of sulphur lo Brockmann and Kluge Naturwiss. 1951 38 141; Brockmann and Muxfeldt ibid. 1953 40,411; Brockmann Kluge and Muxfeldt Chew. Ber.1957 90 in the press. l1 Adams and Jacobsen J. Amer. Chem. SOC.,1924 46,1312. trioxide and 10% of boric acid but in this reaction our yields never exceeded 10%. Wetherefore investigated the use of other reagents such as hydrofluoric acid stannic chloride and chlorosulphonic acid but without success. Coma quently we returned to oleum and boric acid varying the reaction conditions with regard to time and temperature. Surprisingly it was found that ring formation is concluded at 90"in 15 minutes bromo- emodin dimethyl ether 0being thereby pro- duced in an almost quantitative yield. Longer heating clearly destroys this product. Methylation of the phenol (XXX) by dimethyl sulphate then gave the required starting material (XXI). pseudoHypericin.-After the structure of hypericin had been proved we concentrated on the question whether hypericin is the only photodynamically active colouring matter in Hypericum plants or whether different varieties contain other similar pig- ments.We had first to investigate in what varieties of Hypericum red-coloured and red-fluorescent pig- ment was present and then whether this pigment was in all cases identical with hypericin. Altogether we examined 22 species of Hyperi~um.~ Fifteen contained red-coloured and red-fluorescent pigment with the characteristic absorption spectrum of hypericin. From all these we isolated the pigments and subjected them to a detailed investigation in- cluding the absorption spectrum in concentrated sulphuric acid in which hypericin gives a green solu- tion with a red fluorescence.To our surprise we found that in almost all the preparations the absorp- tion peaks of the sulphuric acid solution were shifted towards the blue end of the spectrum by about 15 mp if the solutions were exposed to light only with hypericin preparations from H. hirsutum and synthetic hypericin was this shift of the absorption peaks not observed. A more detailed investigation12 then showed that all the colouring preparations the absorption peaks of which were shifted in concentrated sulphuric acid contain in addition to hypericin a second red colour- ing matter very similar to hypericin and responsible Brockmann and Sannt Naturwiss. 1953 40,461. I* Brockmann and Patt ibid.p. 221. Brockmann and Pampus ibid. 1954 41 86. PROCEEDINGS for the shift of the absorption peaks. We called this new pigment pseudohypericin. We were able to separate it from hypericin in the ring paper chromato- gram by the solvent system butyl acetate-forma- mide (1 :3)/phosphate buffer (pH 8-2) pseudu-hypericin moves more slowly than hyperich. The next task was to obtain pseudohypericin in its pure form. As starting material we used flowers of H.perforaturn (St. John's wort) which in addition to hypericin also contained considerable amounts of pseudohypericin. Since St. John's wort is the most widespread variety of Hypericum its flowers are the easiest to collect in large quantities. To start with we tried to separate the pigment mixture obtained from St.John's wort by partition chromatography on cellulose columns using the same solvent system as for the ring paper chromato- graphy. However in spite of many experiments partition in the column remained incomplete. After these failures we decided to carry out the preparative partition also on the ring paper chroma- togram. This involved considerable labour for on one sheet of paper it is impossible to separate more than about 1 mg. of hypericin-pseudohypericin mix-ture. To obtain sufficient quantities of pseudo-hypericin we needed 4,000sheets of paper. So the chromatography was carried out simultaneously on 60 sheets laid one on another to form a pile the mobile phase being brought to this pack by means of an apparatus13 shown in the Figure.Thus we obtained pure pseudohypericin,14 which crystallised in dark red needles 0.5-1 mg. of the new colouring matter was sufficient to produce all the symptoms of photo- dynamic effect in a white rat. We found C32H20010 for the empirical formula of pseudohypericin. pseudoHypericin contains eight hydroxy-groups and two methyl groups. It has the same absorption spectrum as hypericin. Like hypericin it gives a blue naphthodianthrene deriva- tive when reductively acetylated and this has the same absorption spectrum as the blue reduction pro- duct of hypericin. Accordingly pseudohypericin is also a derivative of naphthodianthrone. As already mentioned pseudohypericin is dis-tinguished from hypericin by its photochemicsrl NOVEMBER 1957 behaviour in concentrated sulphuric acid in sul- phuric acid solution its absorption peaks undergo a blue shift by light of about 15 mp whilst the absorp- tion peaks of hypericin remain unchanged.We SUG ceded in isolating the photo-product from pseudo- hypericin in crystalline form. It contains six hydroxy- groups i.e. two less than in pseuduhypericin. Like pseudohypericin the photo-product contains two methyl groups. Valuable information with regard to the structure of the photo-product was given by its reductive acetylation. Thereby a red acetyl compound was formed with a characteristic absorption spectrum similar to that of anthrodianthrene (XI) which as previously mentioned results in small quantities during zinc dust distillation ofhypericin.The photo- product is accordingly a derivative of anthrodian- throne. This and a few other observations not men- tioned here showed that formula (XXXII) can be given to the photo-product. On these grounds as 309 hypericin pseudohyperich and cyclopseudohyperi- cin there is in H. perfuraturn a further red pigment having the structure (XXXIII). It could be designated demethylcyclupseudohypericin. We have not yet succeeded in obtaining it pure. As already mentioned most varieties of Hypericum -insofar as they contain red colouring matter at all-contain hypericin and pseudohyperich side by side. But there are varieties which only contain one or the other of these colouring matters.Thus in four varieties3 we found only pseudohypericin but up to now we have found hypericin as sole colouring matter in only one variety namely H. hirsuturn. Formation of Hypericin in the Plant.-We were of course surprised at first to fmd plant pigments OH OH + H. HO OH OH (XXXIV) (XXXV) 1 n (xxxvr 0-.1 (XX xv0 ovH2*oH Ho 0 OH (XXXIII) well as on the basis of the analyses and chemical properties pseuduhypericin must be given the formula (XXXI). Subjecting pseudohypericin in concentrated sul-phuric acid to light accordingly induces cyclisation with elimination of two molecules of water. In the process the naphthodianthrone skeleton of pseudu-hypericin is changed into the skeleton of anthrodian- throne. On account of this cyclisation we called the illumination product of pseudohypericin cyclupseudo- hyperich.It should be mentioned also that we were able to separate cyclupseuduhypericin from several hypericin preparations which had been obtained from H. per-foratum with exclusion of light. So cyciopseudo-hypericin can be regarded as a new red Hypericum colouring matter with a red fluorescence. Various observations indicate that in addition to 0 (XXXVI II) (XXXIN which contain eight condensed benzene nuclei. But when we then considered that naphthodianthrone can easily be built up from anthranol in the laboratory it seemed to us very probable that in an analogous way hypericin is formed in the plant from emodin- anthranol (XXXIV) as set out in the annexed scheme.Emodin-anthranol (XXXIV) is a reduction pro- duct of emodin. The existence of emodin as well as of emodin-anthranol has been proved in different plants. If it is assumed that the cell can link two molecules of emodin-anthranol (XXXIV) oxyda-tively to diemodin-anthrone (XXXV) further steps in the biological synthesis of hypericin would simply consist of the following reactions :(1) Enolisation of diemodin-anthrone (XXXV) to diemodin-anthranol (XXXVI). (2) Dehydrogenation to the dehydro-derivative (XXXVII). (3) Photochemical dehydro- genation whereby first the helianthrone derivative (XXXVIII) and then hypericin (XXXIX) would result. All these steps are analogous to the well- known oxidation of phenol to 4 :4’-dihydroxydi-phenyl which can occur with air in alkaline solution even at room temperature.In other words no step in this hypericin synthesis would require uncon-ditional recourse to an enzyme. To prove that biosynthesis of hypericin takes place in the way just indicated it seemed helpful to prove first that it is possible to synthesise hypericin by that route We were successful in doing this when we oxidised a solution of emodinanthranol (XXXIV) in a pyridine-piperidine mixture with air. A dark red crystalline compound C,,H,,O could be separated chromatographically from the product. On reductive acetylation it gave a red helianthrene derivative which quickly faded in light and when exposed to light it was converted into hypericin. In this way it was shown that it is possible to synthesise hypericin from emodin-anthranol (XXXIV) and a second synthesis of hypericin has been found.15 To begin with the choice lay between two formulae (XXXVIII) and (XL) for the helianthrone derivative formed by the oxidation of emodin-anthranol (XXXIV).The compound corresponding to the formula (XL) was already known. We had obtained it during the synthesis of hypericin from bromoemodin as intermediate product. It was not identical with our oxidation product from emodin- anthranol for which formula (XXXVIII) is thus proved. After hypericin had been thus synthesised in the laboratory from emodin-anthranol (XXXIV) it had to be shown that hypericin is produced in the same way in the plant. For this purpose the attempt had to be made to separate from the plant the hypericin l5 Brockmann and Eggers Angew.Chem. 1955 67 706. l6 Brockmann and Sanne Nuturwiss. 1953 40 509. PROCEEDINGS precursors demanded by the hypothesis. We first carried out work in this direction16 with H. hirsutum because this species forms only hypericin and separation of hypericin precursors would probably be simpler than from varieties containing also pseudohypericin and its precursors. To obtain the precursors we produced crude pig- ment preparations from flowers of this H. hirsutum with exclusion of light and adsorbed them chromato- graphically from dioxan on columns of calcium sul- phate. Three red zones were formed. The uppermost contained hypericin; the other two contained two red accompanying colouring matters.The colouring matter of the second zone was obtained crystalline. Since it was converted by light into hypericin and was identical with the helianthrone derivative ob- tained by oxidation of emodin-anthranol it had formula (XXXVIII). As this compound is the direct precursor of hypericin we called it protohypericin. Up to the present we have obtained the colouring matter from the third zone only in an amorphous form. It was converted by light first into proto- hypericin then into hypericin. On reduction with zinc dust in acetic acid it was degraded to emodin- anthrone. From these reactions the structure (XXXVII) results. According to our hypothesis this compound is formed by oxidative combination of two molecules of emodin-anthranol.We were able also to separate emodin-anthranol (XXX1V)-in our opinion the mother substance of hypericin-from the methanol extract of H. hirsutum flowers. On the other hand we were unsuccessful in establishing the existence in the Hypericum plant of the precursor of the dehydro-derivative (XXXVII). This precursor is the compound (XXXV) which is to be expected as the primary product of ernodin-anthranol (XXXIv). But since three compounds (XXXIV) (XXXVXI) and (XXXVIII) have been isolated which according to our hypothesis are intermediates in the biological synthesis of hypericin we are convinced that this hypothesis is correct. In our opinion pseudohypericin is formed in the plant in the same way as hypericin.For from H. monranurn which only contains pseudohypericin we were able to separate two pigments,16 which have structures analogous to (XXXVII) and (XXXVIII). If emodin-anthrone or emodin-anthranol (XXXIV) is the mother-substance of hypericin in the plant it does not seem impossible that in the living cell two molecules of emodin-anthranol can also be com-bined oxidatively in the positions 8 and 8’,as shown by (XXXIV) -+ (XXXV). However we could not prove that such a compound was to be found in NOVEMBER 1957 Hypericum species. On the other hand this compound is the penicilliopsin isolated by Oxford and Rais- trick17 from the mycelium of the mould fungus Penicilliopsis clavariaeformis. It was shown to have structure (XLI) t-+ (XLIV).Oxford and Raistrick had discovered that penicilliopsin is oxidised by air to a compound which they called “oxy-penicilli- opsin”. By subjecting “oxy-penicilliopsin” to light they obtained a product which was very similar to hypericin especially in its absorption spectrum but this was not isolated in a pure form. Since in connection with our hypericin synthesis the question interested us as to whether hypericin can be obtained from penicilliopsin we repeated Oxford and Raistrick’s experiments. We did not carry out the aerial oxidation of penicilliopsin in piperidine-pyridine as Oxford and Raistrick did but in a weakly alkaline methanol solution. From the oxy-penicilliopsin thereby obtained we succeeded HO OH OH - HO OH OH (XLI I) (XLI) (XL III) in obtaining chromatographically a crystalline mm- pound identical with protohypericin (XLIII).On subjection to light this compound was transformed into hypericin in an almost quantitative yield.15 Instead of first isolating protohypericin and then converting it photochemically into hypericin it is possible also to subject the reaction mixture to light immediately after aerial oxidation thus obtain- ing 50% of the penicilliopsin used as crystalline hypericin in one operation. Aerial oxidation of penicilliopsin doubtless takes place by way of the enol form (XLI) since oxidation is carried out in an alkaline solution. Thereby the compound (XLII) might be formed. Its enolisation and consequent dehydrogenation then supplies protohypericin.31 1 The partial synthesis of hypericin from penicilli-opsin is noteworthy because the metabolic product of a micro-organism is used to build up the metabolic product of a higher plant. Probably in the future further metabolic products of micro-organisms will be discovered which can be used as valuable inter- mediates for the synthesis of more complicated and perhaps medically interesting organic compounds. Fagopyrin.-In conclusion a brief account will be given of the colouring matters of buckwheat which are responsible for fagopyrism (see p. 304). We found that there are at least two such pigments which we have named protofagopyrin and fagopyrin. Our in-vestigations were rendered more difficult by the fact that both pigments are present only in small quanti- ties in the buckwheat plant and almost exclusively in the flowers.To obtain sufficient starting material we cultivated half an acre with buckwheat which yielded 30 kg. of HO 2 OH dried buckwheat flowers. From these we obtained dark red crystalline fagopyrinlS by chromatography as well as by counter-current distribution. It is im- possible to give here details of this isolation but it should be mentioned that we were able to check the enrichment of the pigment by means of a spectral colorirneter for fagopyrin has the same characteristic absorption spectrum as hypericin. For fagopyrin we found C42H,,01,N2 as a provi- sional empirical formula.ls In spite of the fact that fagopyrin contains two atoms of nitrogen and that its formula is bigger than that of hypericin spectro- scopically and in its colour reactions it is very similar to hypericin.Thus for example in reductive acetylation fagopyrin as well as hypericin gives a blue derivative of naphthodianthrene. The relation of fagopyrin to hypericin became especially clear when fagopyrin was heated with l7 Oxford and Raistrick Biochern. J. 1940 34 790. la Brockmann Weber and Pampus Annalen 1952 575 53. PROCEEDINGS pyridinium chloride for we thereby obtained crystalline hyperich. Fagopyrh can then be degraded hydrolytically to hypericin. This and other findings (which cannot be discussed here) led us to the opinion that fago- pyrin is a hypericin derivative in which probably the two 7:7’-hydroxy-groups of hypericin are combined in ether fashion with two “colourless” groups.18 These two groups have together the formula CI2H2?0,N2.Recent ob~ervations~~ have however made it more probable that the two residues are combined with the naphthodianthrone skeleton as in formula (XLV).Our endeavours to discover some- thing about the structure of two residues have hitherto remained without success. In addition to fagopyrin buckwheat flowers con- tain a second red pigment which is transformed into fagopyrin when its solutions are exposed to light. By reductive acetylation it yields a red helianthrene derivative which is sensitive to light. The pigment is thus a derivative of helianthrone.We have called it protofagopyrin. Its structure can be. represented provisionally by the partial formula (XLVI). It is interesting that the buckwheat flowers with which we carried out our investigations contained more protofagopyrin than fagopyrin. Here then the ratio is the reverse of what it is for hypericin and protohypericin in Hypericum flowers in which we always found only small quantities of proto-hypericin. Our discovery that protofagopyrin and fagopyrin are merely compounds of protohypericin or hyperi- cin with as yet unknown residues containing nitrogen leads to the question whether Hypericum plants also contain combinations of protohypericin and hyperi- cin with colourless residues. Our experiments have shown that this is indeed the case.All the hypericin and protohypericin is linked with colourless residues of unknown constitution in Hypericum plants also. Obviously these residues are combined with the two 7 :7’-hydroxy-groups and in such a manner that they are cleaved by the acid used in isolation of the pigments. If one sums up the results of our work it can be said that all the hitherto known photodynamically active plant .pigments are 4 :5 :7:4’:5’ :7’-hexa-droxy-derivatives of helianthrone or naphthodian- throne. They are synthesised in the plant by de- hydrogenation of correspondingly substituted anthrones or anthranols. They are distinguished first by their 2- and 2’-substituents and secondly by their mode of combination and the chemical nature of the colourless residues.This report should not be concluded without thanking the many collaborators to whose devotion energy and skill the results must be ascribed. l@ Brockmann and Pampus unpublished work. LETTER TO THE EDITOR DEAR SIR In Dr. Brewer’s article on “Chemistry at Oxford” (Proceedings July 1957) and Dr. Ing’s obituarynotice of A. F. Walden in the August number conflicting dates are given for the opening of the laboratory at The Queen’s College Oxford neither of which is correct. As I was assisting Walden during the last few weeks of the Long Vacation in 1902 in getting this laboratory ready for opening in the October term I think I know the circumstances as well as anyone now surviving. The Queen’s Laboratory was constructed in a dis- used stable of considerable antiquity during the year 1902; the only building work was that of a chimney which annoyed the Warden of All Souls by obstruct- ing the view from his study window over the back premises of Queen’s-“The Piraeus”.The laboratory was opened in October 1902 and I did a good deal of demonstrating there mainly in substituting for Cronshaw whose duties as Chaplain of Queen’s ap- parently prevented his attendance there on Saints’ Days which always appeared to coincide with his turn in tht laboratory. Some additions were made to the Queen’s Labora- tory in I think 1904/5 again probably by conversion of existing buildings when Dr. Chattaway came to work there. In 1902 Walden was senior demonstrator in the Balliol and Trinity laboratories where I was junior and we seem generally to have taken charge of the Queen’s laboratory on alternate days.We had two first classes both I think from New College men in the Honour Schools of 1903 among our first pupils at Queen’s. Walden’s great reputation in those days was for getting decent classes for men of only moderate gifts and having coached some of them for Mods. in 1902/3 I can vouch that he had a tough job in some cases. Yours etc. JOHN PHELPS. 4 Cornwall Road Cheam Surrey. September 5th 1957. NOVEMBER 1957 313 THE PLACE OF CHEMISTRY. V.*IN A NEW UNIVERSITY By F. C. LAXTON (UNIVERSITY OF NOTTINGHAM) THEfirst big demand for further education was a direct outcome of the industrial revolution.The consequent formation of large cities with vast numbers of skilled artisans most of whom were illiterate resulted in the foundation of technical institutes of various types which were the embryos from which grew the univer- sity colleges and eventually the provincial universities. Education was necessary for the workers many of whom began to realise that without it they could not hope to gain advancement. At the same time there were some industrialists who feared that it would lead to the development of revolutionary elements. The Churches were among the first to see the need for improving the almost heathen existence of the lower classes and instituted Sunday Schools in which both children and adults were taught not only the elements of the scriptures but also to read and write.The first adult school of this type was opened in Nottingham in 1798. Following the lead of the Churches came the philanthropists and idealists and there was also intense agitation for more education from workers’ clubs and societies. Their case was strengthened by the Reform Bill (1832) and only a year later the Government made its first grant of E20,OOO in aid of the educational societies of the Church. The claim for further education of the workers found a firm supporter in the Prince Consort and this gave the movement an air of respectability and served to allay somewhat the fears of many former opponents. In Nottingham the Mechanics Institute opened in 1837; this and similar institutions in many other towns were formed to teach the artisans the theories underlying the processes in their trade.Their scope was soon widened however to include classes of a general scientific and even of a literary nature. The Nottingham institute contained a hall in which concerts were held and classes covering a wide field were arranged the subjects included painting drawing and French as well as most science subjects. The courses given in the first place consisted mainly of simple lectures unrelated to one another and they were of very little educational value but in 1862 a grant from the Department of Science and Art at South Kensington enabled comprehensive courses of lectures on special subjects related to local industries to be arranged for example the chemistry of dyeing bleaching and lace dressing.It was in 1866 that a young Scot named Stewart newly graduated from Cambridge had the idea of forming a nucleus of lecturers from the old universities to travel round and pass on the knowledge which they had acquired to the less fortunate masses in the large towns and during the next few years he was busy lecturing to classes of working men and women in the industrial towns. His plan for “university extension” as he called it was taken up and a syndicate of lecturers was formed in Cambridge. The scheme was almost universally popular ; the industrialists hoped that it would improve the skill of their workmen it gave the children of the middle classes the chance of qualifying for better posts and the workers were enabled to learn the scientific principles underlying their trade.Three young Cambridge dons moved to Nottingham in 1873 under the “extension” scheme and 1,800 people enrolled for this first course of lectures. Unfortunately many were so lacking in elementary knowledge that the lectures were beyond their understanding and by 1878 the numbers had dropped to about 900 although it remained fairly steady at this level. The capacity and general resources of the Institute were quite inadequate for these num-bers and courses and when this was realised a local man who wished to remain anonymous offered E10,OOO for a new building.After much discussion it was agreed to approach the Corporation with the suggestion that they *Other articles in this series are as follows I Oxford Proceedings 1957 p. 185; 11 Cambridge p.190; 111 A public school p. 273 ;IV A grammar school p. 276. 3 14 should provide a new building to house the new University College a public library and a museum whilst the f10,000 should be used to endow the University extension lectures. It was about this time that Joseph Chamber- lain as Mayor of Birmingham was pressing for the improvement of educational facilities in that city and there were men imbued with the same spirit among the Nottingham civic authorities. Thus with little opposition the sGheme was approved. The site was chosen and the foundation stone of the University College in Shakespeare Street was laid in 1877.At this time apart from Oxford Cambridge London and Durham only five other towns contained colleges giving courses approaching a University standard Owen’s College Manchester (1 85 1) ;The College of Medicine Newcastle (1 852) ; Queens College Birmingham (1 843) for medicine and surgery (the building of Mason’s College in that city began in 1875); The Yorkshire College of Science (1874) which developed into the University of Leeds; and the University College of Bristol (1876). The first suggestion that a college be formed in Liverpool came in 1878. Thus the Nottingham University College was among the first of these institutions. It is of interest that it was the only one built and financed by the City Corporation the remainder including Sheffield which was to develop later owing their existence to one wealthy benefactor or to funds raised by public subscription.The University College of Nottingham was opened by the Duke of Albany in 1881. It began with a staff of four professors and six lecturer- demonstrators together with twelve teachers for the government science classes transferred from the Mechanics Institute. Of the four professors three came from Cambridge and one from London. F. Clowes (London) Professor of Chemistry and Metal- lurgy later became the first Principal of the College. J. A. Fleming who had a most dis- tinguished career and was later knighted was responsible for physics mathematics and mechanics.The Reverend J. E. Symes was put in charge of all the arts departments and the Reverend J. F. Blake was appointed Professor of Natural Sciences. Chemistry was well catered for in the new PROCEEDINGS building. There was a large room for the professor a lecture theatre seating 200 students and a smaller lecture room. The main teaching laboratory a lofty chapel-like structure with coloured Gothic windows had ample room for fifty students and two smaller laboratories later became the professor’s and the staff’s research laboratories. A small basement room adjoining the boiler house was used as the metallurgical laboratory. Some time later the annexe which had been used as a dye house by textile students was taken over as an organic research laboratory for postgraduate students.The courses taken in the beginning were mainly for the London Matriculation and the Cambridge Higher Local Examinations. In 1882 the College became affiliated to Oxford and Cambridge and this meant that a student who had completed a three-year course at Notting- ham on proceeding to Oxford or Cambridge was excused the first three terms of residence. Elementary education which had become general throughout the country in 1870 finished at the age of thirteen. Thus in the early days students were admitted to the College from the age of fourteen this being raised to sixteen in 1883. Most of the classes held during the first few years were therefore of a very elementary nature and in fact only six first degrees were obtained up to 1890.The first doctorate was awarded in 1894 to E. H. Barton who later became Pro- fessor of Physics. The number of day students enrolled up to the end of the century remained fairly steady at about 400 of whom about three- quarters were women. In the first year 1881 there were 623 evening students and by 1902 this number had risen to over 1,700. There appear to have been very few honours chemistry students for some years after the opening of the College only thirteen having obtained this qualification up to the beginning of the First World War. On the other hand no less than forty-six had passed the examination for the Associateship of the Institute of Chemistry.Up to this time Physics appears to have been more popular as a degree subject than Chemistry. Before the First World War openings for research chemists in industry were few and a graduate chemist normally either became an NOVEMBER 1957 analytical chemist in a work’s or in a public analyst’s laboratory or joined the teaching profession. There were few opportunities for doing postgraduate research as grants were almost non-existent. A teacher in a University College had a very full programme of work often up to 35-40 hours a week including evening classes which were part of his normal duties leaving very little time for private work except in the vacations. Nevertheless most of the research published in this country came from the Universities and the Colleges.Professor Clowes left Nottingham in 1897 and was succeeded by F. S. Kipping whose research covered a wide field of organic chemistry but who is best known for his work in organic com- pounds of silicon. Kipping’s brilliant research work and his outstanding ability as a teacher and administrator did much to enhance the standing of the Department of Chemistry and in fact the reputation of the whole College. By 1914 the staff of the Department had increased to a professor and three lecturers. The staff were responsible not only for the degree classes but also for courses of chemistry given to pharmaceutical engineering mining and textile students at both day and evening classes.During the 1914-18 war the number of day students fell to under 300 most of whom were women. Under the direction of Professor Kipping a research school was established to investigate the preparation of a number of synthetic drugs hitherto not available in this country. In 1919 a scheme for the provision of univer- sity grants to ex-service men came into being and the number of day students in the College rose to almost 1,000. This number included over sixty in the first year of the honours chemistry course as well as 100 pharmacists to whom pharmaceutical chemistry was taught by the staff of the chemistry department. A large room in the museum was converted into a laboratory but even then the accommodation was by no means adequate to deal with this influx.Every laboratory throughout the day and evening was packed with students of all grades indis-criminately mixed. Demonstrators were re-sponsible for supervising classes in all branches of the subject and this practice continued throughout the period between the wars. In 1928 the College moved into its new building at Highfields which was provided by the generosity of Sir Jesse Boot. The accom-modation for chemistry was far better than before but by no means lavish and whilst facilities for research were more extensive than in the old building they rapidly became in- adequate. Between the wars the Honours School settled down to an average of about fifteen per year. The staff was still responsible for the evening classes at the old College and as these included eight lectures a week in pure chemistry as well as special classes in chemistry for miners bakers lithographers and laundry operators it put a great strain on the department.This practice continued until 1945 when the old college was taken over by the city authorities and became the Technical College. After the second war the numbers rose again and more accommodation and staff were needed. The Honours School numbered about 40 and naturally all the other classes increased pro- portionately. Two semi-permanent buildings were erected to serve as third-year and elemen- tary laboratories respectively. In 1948 the University College was granted its Charter and attained full University status.In 1953 a Chair of Physical Chemistry was founded and one semi-permanent building was converted into a physical-chemistry research laboratory. The most outstanding change which has taken place over the past forty years has been in the development of research. It was not until the First World War that it was realised by in- dustrialists in this country that industry could not develop without research and this point was further emphasised during the last war. Now-adays grants for research are obtainable not only from government sources but also from most of the larger chemical firms and research schools in the provinces have grown pro-gressively since 19 19. Physical chemistry has become much more important over the same period both as a subject in the first degree examination and also as a research topic.No practical physical chemistry was done by undergraduates in Nottingham until after 1945. Between the wars verv little accommodation was available for research in physical chemistry and very little apparatus was forthcoming. This was un-doubtedly due in some measure to lack of money since physical apparatus was expensive. In 1936 the total sum available for apparatus and material for the whole of the chemistry department at Nottingham was E450.Physical chemistry is no longer the Cinderella of the family but is treated at least as an equal by her sister branches. PROCEEDINGS Next year a new chemistry building is to be started and this will no doubt mark the beginning of a new era in the history of the chemistry department at Nottingham.In conclusion the writer would like to thank Professor A. C. Wood for the use of his book “University College Nottingham” which has proved a fountain of information on the develop- ment of education in this country during the last century. BRITISH ASSOCIATION FOR THE ADVANCEMENT OF SCIENCE DUBLIN MEETING SEPTEMBER 1957 THE119th Annual Meeting of the British Association for the Advancement of Science was held in Dublin on September kllth 1957. It was attended by some 3,100 members of whom about 1,800 came from outside the country and an encouraging feature was the presence of about 800 students. Professor P.M. S. Blackett’s presidential address dealt with “Technology and World Advancement.” Professor Blackett suggested that the western nations should make an annual contribution of about 1 % of their income to help under-developed countries out- side the Soviet orbit.Britain would pay 150 million pounds a year and this would postpone by less than a year the expected rise in British living standards over the next quarter of a century. On the afternoon of Wednesday September 4th Professor W. Cocker and Professor T. S. Wheeler held a reception for young chemists in University College Dublin. There was an attendance of about 200. The first of the main items on the programme of Section B (Chemistry) was the opening by the President of the Section Dr. J.W. Cook of an ex- hibition in University College of glass models illus- trating the principles of stereochemistry. A collection of documents relating to the history of chemistry in Ireland was also shown. Dr. Cook later delivered his presidential address in Trinity College-the Sectional Meetings were held in the Department of Chemistry there. This address which attracted a large audience comprised a master- ly discussion of “Chemical Approaches to the In- vestigation of Lung Cancer.” Professor Cook con- sidered that the statistical evidence of an association between cigarette smoking and the incidence of lung cancer was overwhelming. However this conclusion he said had been vigorously challenged and indeed a relationship had been claimed between the increas- ing incidence of lung cancer and increasing atmos- pheric pollution.Smoking is probably a major cause of lung cancer but it is not the only cause and it is necessary to examine the influence of atmospheric pollution. Dr. Cook described experiments to identify the carcinogens in tobacco smoke. Tars obtained by the use of cigarette-smoking machines are weakly car- cinogenic. No success has been achieved in attempts to produce carcinoma of the type observed in man in experimental animals with cigarette smoke. Dr. Cook emphasised that the balance of evidence is strongly in favour of the view that carcinogenic chemical agents are primarily concerned in the pro- duction of lung cancer. On Friday morning a session on the “Biogenesis of Natural Products” was introduced felicitously by Dr.Cook who commented on the wisdom of choos- ing Sir Robert Robinson as Chairman. Sir Robert gave a brilliant summary of the organic chemist’s contribution to this field. He recalled the progress made since 1917 when he wrote a paper on alkaloid biogenesis. The use of isotope tracers had experi- mentally validated some at least of the early theories. Outstanding examples of the use of the new methods were provided by the proof that fatty acids originate from acetic acid and by the contributions of Professor Birch and Dr. Popjak. Comparison of the more complex structures gives results of greater importance than examination of simpler molecules. Series homologous and ring- homologous to the pyrrolidine alkaloids are found in the piperidine groups.All can originate from lysine. The simpler isoquinoline alkaloids have their counterparts in certain indole bases tryptophan re- placing the substituted phenylalanine as a funda- mental unit. The tryptophan-phenylalanine group first postulated by Barger in 1934 is of great im- NOVEMBER 1957 portance in the indole series. The coupling of substi- tuted phenylalanine with tryptophan leads to the skeletons of what the lecturer called a-and p-indole alkaloids typified by yohimbine and strychnine res- pectively. In these structures the phenylalanine moiety is barely recognisable. Woodward suggested in relation to the biogenesis of strychnine that it is broken in a particular manner and this suggestion has greatly facilitated the recognition of hidden stm tural patterns in the indole-alkaloid groups.Applica- tion by the lecturer of the Woodward theory to a protoberberine gave a possible biogenesis of emetine ; the fission was assumed exactly as in strychnine. The cinchona group of alkaloids can also be linked in this way with an a-indole-alkaloid structure. Molecules are normally illiterate but they seem to have learned to read Sir Robert’s writings on biogenesis. Professor A. J. Birch (Manchester) discussed the use of 14C-labelled acetic acid methionine and formic acid for testing hypotheses based on structure-analysis. The work was carried out with moulds because of the ease of handling them and because of the wide variety of compounds which they produce.Much of the work followed the pioneer isolation work of Professor Raistrick. A postulated biosynthesis of griseofulvin by the head-to-tail linkage of seven acetic acid units has now been confirmed by degradation of the substance produced biosynthetically from CH,.14C0,H. It was shown that in mycophenolic acid and sclerotiorin C-methylation can occur from methionine or formic acid in the same way as can 0-,S-,or N-methylation. Among substances probably produced in this way and now under investigation are tetracycline deriva- tives and macrolide antibiotics. Extensions to terpene biosynthesis were discussed using the mould products mycelianamide and myco- phenolic acid and it was shown that meralonic acid is an irreversible terpene intermediate in these cases.Professor Birch pointed out that the results obtained could be extrapolated to products from higher plants in particular anthoxanthins and anthocyanins. Professor T. S. Wheeler (Dublin) gave a brief account of modern views on the biogenesis of flavonoids. He recalled that this family had funda- mentally a six-three-six carbon structure all mem- bers belonging to the hierarchy of the propane bridge. They were distinguished one from another by the oxidation level of the bridge. He showed how these compounds might be elaborated from well- known naturally occurring nine-carbon units and indicated how Sir Robert Robinson’s pioneering ideas on the biogenesis of these compounds had been kerified.Professor WheeIer included in his talk a general description of the use of tracers and their application in flavonoid biogenesis. Professor T. R. Seshadri (Delhi) in his address discussed the occurrence of eight-carbon units in plant products. He dealt with depsides and dep- sidones which are present in lichens. Study of these compounds revealed the important modifications which the eight-carbon unit can undergo and led to the conclusion that the earliest stage of this unit should be a hydroxy-aldehyde derived from two molecules of a tetrose. The eight-carbon rule was also applied to mould products under the headings (1) benzene derivatives (one C unit) (2) toluquinone derivatives (one C unit) and (3) anthraquinone derivatives (two C units).Dr. G. J. Popjak (London) who concluded the session spoke on sterols. He discussed the formation of cholesterol in animal cells and described the tracer technique which established the pattern of the acetic acid carbon atoms in the molecule. Earlier work had shown that lanosterol is formed in the plant by cyclisation of squalene and is itself a precursor of cholesterol. Until recently little was known of the early stages of synthesis from acetate. Last year the discovery of mevalonic lactone in distillers’ soluble residues suggested the possibility later confirmed that it might be an intermediate in the formation of squalene and hence of sterols. The morning of Monday September 9th was devoted to a symposium on “Making and Breaking Polymer Molecules.” Professor Charles Kemball (Belfast) was Chairman.The subject was introduced by Dr. L. C. Bateman (Welwyn) who spoke first on the synthesis of polymeric compounds. This involves the technique of combining units efficiently in a con- trolled manner so as to obtain the high degree of geometrical regularity in their structure which is characteristic of Nature’s method and proves to be crucial to their physical properties. Dr. Bateman then stressed the importance of studying the breaking of polymer molecules. When and how this breaking occurs greatly influences the processing of the poly- mer and its durability. A new method of making a wide range of polymers involved the chemical shear- ing of suitable polymers such as rubber.Large free radicals are produced which can be used to polymer- ise added monomers to form co-polymers. Condi- tions required for such reactions were simple and machines suitable for continuous operation had been used successfully. Dr. Bateman demonstrated the process using a macerating machine. Professor H. F. Mark (New York) discussed stereospecific polymerisations. He treated of reac- tions effected by the recently discovered Ziegler catalysts. These catalysts are extremely active and readily induce polymerisat ions previously realised only with difficulty or not at all. They have for the first time given polymers with almost the same struc- tural symmetry as their natural congeners.The poly- thenes thus produced had fewer side-chains and therefore higher melting points than the high-pressure products. Dr. C. H. Bamford (Maidenhead) spoke on syn- thetic polypeptides as models for natural proteins. He discussed the transformation of amino-acid units into polymers (polypeptides) akin to the animal protein fibres wool and silk. These of amino-acids may be regarded as simple protein models and much information relevant to proteins has been obtained by studying them. Dr. C. W. Bunn (Welwyn) outlined the relations between the structure and the properties of polymers. Although the basic molecular requirements for the various classes of polymers have been known for some time the effect of relatively minor but none the less significant structural variations on the physical and technological properties of say a rub-ber or a plastic had remained ill-defined.In fact knowledge of how to make polymers has outstripped knowledge of exactly how they must be made to obtain desired properties. Rational guidance on the production of polymers to meet physical specifica- tions is increasingly necessary and more correlations as they become available will provide the basis for new “tailor-made” materials. A discussion on “Chemistry in the Service of Agriculture” was opened on the Tuesday September loth by Mr. A. W. Marsden (Reading). He pointed out that the available supply of food is not sufficient for a reasonable level of nutrition among the present population.Yet by a greater application of science to agriculture the world could feed 5,000 million people more than twice its present population. The chemist can serve the farmer by providing better fertilisers feeding-stuffs pest-control chemicals and pharmaceutical products. This work is more import- ant than replacing agricultural products by synthetic materials. Mr. J. W. Parkes (Dublin) recounted the history of the fertiliser industry in Ireland. He discussed the position of the industry in 1835 1857 1878 1908 and 1957 the years in which the Association met in Dublin. He mentioned that at the 1857 meeting a paper was read on “Urea as a Direct Source of Nitrogen to Vegetation.” Dr. T. Walsh (Dublin) surveyed the chemical evaluation of soil fertility.Chemical soil tests must be calibrated against crop response through the medium of well-designed field experiments carried out on soil of different types. This allows the estab- lishment of growth and crop-yield curves related not only to the chemical constitution of the soil and the PROCEEDINGS characteristics of each particular crop but also to other environmental factors and varying soil condi- tions. From the use of such growth curves it has been possible to establish the rational use of fertilisers in terms of yield response and also to evaluate yield response on an optimum economic basis against the nutrient status of the soil as revealed by chemical analysis. Dr. P. W. Brian (Welwyn) discussed three kinds of plant hormones ; auxins kinetin and gibberellic acid.The most widespread natural auxin is 3-indolyl- acetic acid. Synthetic auxins of similar structure are now employed to stimulate rooting of stem-cuttings and to improve fruit-set and as selective weed- killers. A recently isolated pure substance kinetin is involved in cell division e.g. if it is added to tobacco- pith cultures at concentrations as low as one hundred-thousandth of a milligram per litre it will enable such cultures to multiply indefinitely. The most striking effects of gibberellic acid are on flower- ing. Some biennial plants such as sugar-beet if treated with this acid flower in their first season; normally this does not occur until their second season of growth. It should eventually be possible by using natural or synthetic hormones to modify the rate of growth habit and flowering time of field crops to suit soil and weather conditions or other cultural requirements.Much attention was attracted by a special session (Monday afternoon September 9th) which was addressed by Mr. H. S. C. McKay and Dr. J. Milsted of Harwell on nobelium (element 102). Mr. McKay described the steps leading to the production from uranium of elements up to fermium eIement 100 by bombardment with light particles e.g. neutrons. Development of the use of heavy ions as missiles made possible a jump of several places at a time; cyclotron bombardment of uranium-92 by nitrogen ions gave einstenium-99. Dr. Milsted dealt with the preparation of element 102.It was obtained by the fusion of carbon-1 3 (from Harwell) and curium-244 which was prepared in the Materials Testing Reactor in Idaho as a product of irridiating plutonium with neutrons. The fusion was effected in the cyclotron in the Nobel Institute in Stockholm. The 17 atoms of nobelium observed were characterised by alpha-activity. The chemical experi- ments in each case used ion-exchange techniques. Outside of Section B there was much to interest the chemist. A joint symposium of Section B and Section K (Botany) discussed the biology of yeast. There were also for example papers on thermo- nuclear fusion on the evolution of stars on the sun’s magnetism on photosynthesis and on archaeological problems. In all there were some 289 addresses.NOVEMBER 1957 The Chemistry Section dinner which was held in the Dining Hall Trinity College had the record attendance of 170. The excursions to factories and to places of scenic interest around Dublin were well patronised. Highlights of the meeting were the recep- tions by the President of the Republic and by the 319 Taoiseach (Prime Minister) Mr. de Valera. Of interest is the fact that Mr. de Valera who was a Vice-president of the Meeting attended the previous (1908) Meeting in Dublin. E. M. PHILBTN T. S. WHEELER I.U.P.A.C.SYMPOSIUM ON MACROMOLECULAR CHEMISTRY AT PRAGUE SEPTEMBER 1957 A SYMPOSIUM Macromolecular Chemistry was on held in Prague between September 9th and 15th 1957 under the auspices of the International Union of Pure and Applied Chemistry and the Czechoslovak Chemical Society.This was one of the series of Symposia on this subject held since the war; the preceding one had been held in Tsrael and the next will be in Nottingham in 1958. The Symposium was inaugurated at a meeting in the Rudolfinum in the centre of Prague. After addresses of welcome from the Chairman of the Czechoslovak Chemical Society Professor Luke3 the Minister of Chemical Industry Ing. PuEik and the Secretary General of <he Czecho- slovak Academy of Science Professor Sorm there was a short piano recital. Then Professor P. Doty of Harvard gave a lecture on biological polymers describing some of the recent work on helix forma- tion in solutions of synthetic polyamino-acids and of polyribonucleotides.The other main Symposium lec- ture was by Professor H. Mark of Brooklyn who spoke of some of the newer types of synthetic materials now being developed in various countries. There were 18 other lectures and about 180 papers were read by authors from about 20 countries. Al- together there were over 900 registered participants. Printed abstracts were distributed before the meeting and for most of the papers pre-prints also were sup- plied. In the lecture rooms simultaneous translations of the talks were communicated by a short-range radio transmitter to individual receivers incorporated in head-sets; the languages used were Czech French German Russian and English. The lectures and papers were divided into two main groups viz.the Physics and Physical Chemistry of Macromolecules and Polyreactions; inside these groups there was further division. All the lectures were very well at- tended and they provoked lively and profitable dis- cussions which were held in smaller rooms some time after the delivery of the actual papers. This unusual arrangement proved extremely successful. Almost all the foreign visitors were accom-modated at the International Hotel. This is a large and well-appointed hotel on the outskirts of the city ; frequent transport between the hotel and the centre of the city was provided throughout the day. It was a great convenience that lectures and discussions were held in rooms in the hotel. The Organising Committee under the chairman- ship of Professor Wichterle obviously had made every effort to ensure the smooth running of the Symposium and they were indeed successful.Very able and helpful interpreters for the main languages were available at the Symposium office. A full social programme had been arranged. It included a memor- able performance of Dvorak’s “Rusalka” at the National Theatre and a performance of national songs and dances. There were several receptions in- cluding one by the Minister of Education and Cul- ture and another by the Mayor of Prague; the latter reception was followed by a tour of the flood-lit city. The Symposium banquet was held in a magnificent mirrored hall of the Wallenstein Palace. There were also many opportunities for organised tours of Prague and its surroundings; after the Symposium visits to certain factories and Research Institutes were arranged.Some of the members of the Symposium were renewing acquaintance with Czechoslovakia but most of course were paying their first visit to this interesting and beautiful country. The main impres- sion gathered from the stay in Prague was that the Czechs are friendly and hospitable and most anxious to establish scientific contacts with the Western nations. There was a very large contingent of Russians including Professor and Mrs. Semenov Professor Kargin and Professor Medvedev. On the last evening of the Symposium the British participants were the guests of the Russian delegation at an informal dinner party.J. C. BEVINGTON A. R. PEACOCKE F. W. PEAKER PROCEEDINGS COMMUNICATIONS Synthesis of ( &)-6p-Hydroxy-2a:5 :5 :9/3-tetramethyl-trans-decal-l-one the Racemate of a Degradation Product of a-Amyrin* By FRANZ and Dov ELAD SONDHEIMER (THEDANIEL INSTITUTE INSTITUTE SIEFFRESEARCH WEIZMANN OF SCIENCE REHOVOTH, ISRAEL) WE report here the ten-step conversion of the recently described ( f)-5fl-benzoyloxy-l 1 lOfl-trimethyl-d*-octal-2-0nel~~ (I) into ( &)-6/?-hydroxy-2a 5 5 916-tetramethyl-trans-decal-1-one (X),the racemic form of a degradation product of ~x-amyrin.~ Saponification of the keto-benzoate1*2 (I) yielded the keto14 (11) m.p. 91-93" which was hydrogen- ated in ethanol over palladium-charcoal at 24" to the non-crystalline saturated ketol (III) (all new sub- stances gave correct analytical results and showed infrared spectra compatible with the assigned struc- tures).Conversion into the dihydropyranyl ether (IV) followed by successive lithium aluminium hydride reduction to the alcohol 0,benzoylation to the ester (VI) and treatment with acid produced the hydroxy-benzoate (VII) m.p. 153.5-155" oxidation of which with chromium trioxide in acetic acid led to the keto-benzoate (VIII) m.p. 92-93.5 '. An over-all yield of ca. 60% from the keto-benzoate (I) was achieved despite the seven steps involved and the two new asymmetric centres introduced. Saponi- fication of the benzoate (VIII) and subsequent acetylation furnished the keto-acetate OX) m.p.95-97 ". At this stage Dr. T. G. Halsall informed us that he and his co-workers had prepared the keto-acetate (1% by a different sequence of the steps and had proved the trans-ring f~sion.~ Direct comparison showed the substances (IX) prepared by the two routes to be identical. On the other hand we found our keto-benzoate (VIII) to differ from the com- pound (rn.p. 89-92") to which structure (VIII) had been assigned by King et al.' A difference in the steric configuration of the hydroxyl group or of the ring junction may well be responsible for this non- identity. The keto-benzoate (VIII) was condensed with ethyl oxalate by means of sodium hydride in ben- zene and the resulting ethoxalate was methylated with methyl iodide in boiling acetone containing potassium carbonate.Treatment with sodium eth- oxide in ethanol then produced the tetramethyl- ketol (X),m.p. 114.5-115"; the acetate (XI) had m.p. 99*5-100.5". The new methyl group is assigned the equatorial a-configuration. When asked for a comparison sample of optically active (X) derived from a-amyrin3 for comparison Professor 0. Jeger kindly informed us that Drs. J. Kalvoda and H. Loeffel in his laboratory had also synthesized the racemic compound (X).' Our syn- thetic samples were shown to be identical with each other (direct comparison) and to be the racemate of the optically active degradation product (X) (identity of infrared spectra). We are indebted to Professor 0. Jeger Dr.T. G. Halsall and Dr. C. J. Timmons for interesting discus- sions for information before publication and for supplying samples for comparison. (Received October 14th 1957.) * Syntheses in the Terpene Series. Part IV. For Part 111 see ref. 1. Sondheimer and Elad J. Amer. Chem. Soc. in the press. Elad and Sondheimer Bull. Res. Council Israel 1956 5 A 269. Ruegg Dreiding Jeger and Ruzicka Helv. Chim. Acfa 1950 33 889. Cocker and Halsall Chem. and Ind. 1956 1275 J. 1957 3441. Gaspert Halsall and Willis J. in the press. King Ritchie and Timmons Chem. and Ind. 1956 1230. Kalvoda and Loeffel et al. Helv. Chim. Acta in the press. NOVEMBER 1957 321 The Synthesis of 2'-Deoxyuridine By D. M. BROWN,D. B. PARIHAR and Sir ALEXANDER C.33.REESE TODD (UNIVERSITY LABORATORY, CHEMICAL CAMBRIDGE) ALTHOUGH the structures of the naturally occurring deoxyribonucleosides (e.g. I) derived from deoxy- ribonucleic acids have been fully established,l no synthesis of a member of this series has been re- ported. Earlier work2 indicated that methods suited to ribonucleoside synthesis were not conveniently applicable to the preparation of the deoxy-com- pounds and it was evident that syntheses basedon the readily available ribonucleosides would have many advantages. HO In experiments already briefly reported,3 02: 2'-cyclouridine was converted by sodium ethyl sulphide into an ethylthiodeoxyuridine from which by Raney nickel reduction a deoxynucleoside was obtained. Although the product was so similar to the naturally occurring 2'-deoxyuridine that we were for a time convinced of their identity careful comparison with the natural product has now shown that they are not.Another possible route to deoxyribonucleosides studied by Dr. A. M. Michelson involved the reac- tion of 2'-O-methanesulphonyladenosinewith halide or thiocyanate ions followed by reduction. The dis-placement reaction gave a very low yield and more- over the deoxynucleoside finally obtained was not identical with although it resembled natural deoxy- adenosine. Further work on the nature of these pro- ducts is under way but meanwhile we can report that a route analogous to the second of these applied in the uridine series leads readily to 2'-deoxyuridine.5'-O-Acetyl-2'-O-toluene-p-sulphonyluridine4 is converted almost quantitatively by sodium iodide in acetonylacetone at 100" in 2.75 hr. into the 2'-deoxy- 2'-io&-derivative m.p. 167". Catalytic reduction over palladium-bar ium sulp ha te ,and deace t yla tion then gives in high yield 2'-deoxyuridine (I) m.p. 167" undepressed by a specimen of the natural nucleoside.6 Chromatographic characteristics and infrared spec-tra of the natural and the synthetic substance are identical. Details of these experiments will be published shortly and further work is directed to an assess- ment of the generality of this synthetical route for deoxynucleoside synthesis. Our thanks are due to Dr. T. J. Bardos Armour and Company Chicago for a sample of 2'-deoxy-uridine and to the Ministry of Education Govern- ment of India for an All India Overseas Scholarship (held by D.B.P.).(Received October 2nd 1957.) Brown and Lythgoe J. 1950 1990; Andersen Hayes Michelson and Todd J. 1954 1882; Michelson and Todd, J. 1955 816. Davoll and Lythgoe J. 1949 2526 3Brown Todd and Varadarajan in the Ciba Foundation Symposium on "The Chemistry and Biology of the Purines," J. and A. Churchill Ltd. London 1957 p. 108. Idem. J. 1956 2388. Dekker and Todd Nature 1950 166 557. Ditertiary Arsine-Metal Carbonyl Complexes of Groups Mand VIII By H. L. NIGAMand R. S. NYHOLM (WILLIAM AND RALPHFOSTER RAMSAY LABORATORIES UNIVERSITY GOWER W.C.1) COLLEGE ST. LONDON THE great interest at present in substituted metal carbonyl complexes prompts us to communicate the preparation and properties of some recently isolated ditertiary arsine complexes several of a new type.The preparation of mixed carbonyl complexes of chromium molybdenum and tungsten by direct re- placement of up to three of the six carbonyl groups by various ligands has been reported by Hieber and Hieber and his co-workers 2. anorg. Gem. 1935 221 his co-workers.' With pyridine (Py) complexes of the type M(CO),Py and M(C0)3Py have been isolated where M = Cr Mo and W whilst the chelate group o-phenanthroline (o-phen) yields M(CO),(o-phen). The low solubility of these com-pounds in organic solvents renders a study of their properties rather difficult. Other compounds ob- tained by direct replacement include the isocyanide 337 349; 1955 280 241 252; Chem.Ber. 1956 89 616. PROCEEDINGS derivatives Cr(CO),(RNC) and the cycZopentadieny12 Mo(CO) at 2,014 cm.-l (in tetrachloroethylene) is derivatives M(C0)5(C,H,)2 where M =Mo or W. replaced by three bands for Mo(CO),Diarsine and By indirect methods hexasubstituted compounds of by five bands for Mo(CO),(Diarsine),. Similar be- the type Cr(RNC) have been prepared but in no haviour is observed with the chromium and tungsten case have more than three CO groups been directly compounds The spectra are being further studied by replaced. Mr. Gatehouse. Using Cr(CO), Mo(CO), and W(co)6 with the Substance ditertiary arsine chelate group o-phenylenebisdi-(D =Diarsine) Colour M.p. (in vacuo) methylarsine we have replaced directly two and four Cr(CO),D White 170" of the original CO groups obtaining compounds of Decomp.220" the formulae [M(CO),Diarsine]O and [M(CO),(Di- Cr(CO),D2 Yellow 158" arsine),I0. Their solubility in organic solvents per- Mo(CO),D White Mo(CO),D Golden-yellow Decornp. 180" mits one to investigate many physical properties. The W(CO),D Pale yellow 168" monochelate derivatives are prepared by heating the Decomp. 200' hexacarbonyl with the diarsine in an evacuated tube W(CO),D Yellow Fe(CO),D Golden-yellow 131" for 4-6 hours at 150". Further heating of the mono- FeCOD Dull yellow Decomp. 150" diarsine complex with more diarsine at 200-240" yields the bisdiarsine complex. Replacement of the EarlieI-4 the preparation of Ni(CO),Diarsine and remaining two CO groups appears to be much more its halogen oxidation product cis-Nil,Diarsine was difficult but some evidence for this has been obtained; reported.Carbonyl derivatives of other metals of this should lead to the formation of [M(Diarsine),]O group VIII have been treated similarly with the and this is being further investigated. Our new com- diarsine;Fe(CO) yields [Fe(CO),Diarsine]O and plexes are listed in the Table all are stable in air and [Fe(CO)(Diarsine),]O as crystalline solids. Cobalt soluble in the usual organic solvents especially carbonyl also reacts readily. All of these diarsine benzene in which they are monomeric; they are carbonyls react with halogens to yield a series of diamagnetic and are virtually non-electrolytes in halogeno-diarsine-metal carbonyl complexes such as nitrobenzene (Alooo<1.0 r.0.).Mo(CO),(Diarsine)I, providing a range of oxida-The electric dipole moment of [Mo(CO),(Di-tion states the properties of which are being arsine) Jo (6.5 D) indicates a &-arrangement of the investigated. two CO groups. The single strong infrared band of (Received,October 17th 1957.) a Wilkinson J. Amer. Chem. SOC.,1954 76 209; Fischer Z anorg. Chem. 1956 282 47. Malatesta and his co-workers Cazzetta 1952 82 576 586; Ann. Clzim. (Italy) 1953 43 622. Nyholm J. 1952 2906. The Constitution and Stereochemistry of Drimenol By C. J. W. BROOKS (M.R.C. CLINICAL RESEARCH CHEMOTHERAPEUTIC UNIT WESTERN INFiRMARY GLASGOW) and K. H. OVERTON (CHEMISTRY THE UNIVERSITY DEPARTMENT GLASGOW) was isolated from the bark of Drimys Appel who provided a substantial quantity of DRIMENOL winteri Forst.by Appel and his collaborators,lV2 who drimenol for which we record our warmest thanks also accomplished its degradation to two compounds we have been able to continue these studies and now which have been the keystones in the derivation of present our conclusions. its structure. The results published by these workers Dehydrogenation of drimenol on palladised char- may be summarised as follows. Drimenol was shown coal afforded as the sole identified product 1:2 5-to be a bicyclic singly unsaturated primary alcohol trimethylnaphthalene in about 30 %yield. for which the formula C1,H,,O was favoured. Cata- Drimenol m.p. 93-94" [ct] -18" (in C,H,) ~~~~215,in EtOH vmRX.(in lytic reduction afforded the saturated drimanol ~~14~210 ~~~~250 which on oxidation with Beckmann's mixture gave Nujol) at 814 cm.? (trisubstituted ethylenic linkage the corresponding drimanic acid. Oxidation of band not present in drimanol) and 3280 cm.-' drimenol with the same reagent yielded the ketone (hydroxyl) gave a positive reaction with tetra-drimone C,,H,,O and oxidation of this also with nitromethane (Found C 80.75;H 11.7. C15H2,0 Beckmann's mixture gave the dibasic drimic acid requires C 81.0; H 11.8%) and is assigned the C,,H,,O,. Through the great generosity of Dr. structure (I). Oxidation of drimanol (U) m.p. Appel Gleisner and Sahli Scientia (ChiEe) 1948 15 31. Appel Rotman and Thornton ibid.,1956 23,19.NOVEMBER 1957 110-lll" [a],+ 14" (in C,H6) (Found C 80.4; H 12.65. C1,H,,O requires C 80.3 ; H 12.6%) with chromic anhydride and potassium hydrogen sulphate in acetic acid and further oxidation of the crude aldehyde with silver oxide afforded drimanic acid (111) m.p. 135-136" [a],+ 14" (in CHCI,) (Me ester m.p. 49-50"). The constitution (IV) of drimone? for which we propose the revised name nordrimenone m.p. 83-84' [aID -67" (in C,H,) showing (in EtOH) Amax. 235 mp (E 6500) and vma. (in CCl,) at 1670 cm.-l (ap-unsaturated ketone) (Found C 81-35; H 10.55. C1,H,,O requires C 81.5; H 10-75%) receives further support3 from its ozonolysis to drimic acid (V) m.p. 167-168", [!ID -7" (in acetone) (m.p. undepressed when med with a specimen obtained by Appel's method) and acetic acid (identified by the infrared spectrum of the derived sodium acetate and conversion into p-bromophenacyl acetate in 43 % yield).The genesis of nordrimenone from drimenol has precedent? Drimanic acid was identical with the compound having the same physical constants obtainable from oleanolic acid and ambrein,6 and drimic acid with the compound of the same constants from onocerin and abietic acid6 (as shown by the identity of m.p. and mixed m.p. with authentic materials very kindly supplied respectively by Professor E. Lederer Paris and Professor 0. Jeger Zurich). The constitution stereochemistry and absolute configuration of drimenol are thus secured. Drimenol now takes its place with iresin' as the second sesquiterpenoid compound having the di-cyclofarnesol skeleton of type (VI) to be found in Nature.Its simple derivation from farnesol has obvious implications for terpenoid biogenesis. We hope in due course to present a fuller account of this work as well as of a number of further transforma- tions of drimenol including attempts to convert it into a-onocerane . We are indebted to Professor D. H. R. Barton F.R.S. for valuable discussion and one of us (C.J.W.B.) thanks Dr. J. Reid for his encourage- ment. (Received October 7th 1957.) a See inter ul. Barton and Seoane J. 1956 4150. Barton and Brooks J. 1951,257. Ruzicka Gutmann Jeger and Lederer Helv. Chipn. Actu 1948 31,1746. Schaffner Viterbo Arigoni and Jeger ibid.1956 39,174. Djerassi and Rittel J. Amer. Chem. Soc. 1957 79,3528. Ruzicka Experientia 1953 9 357. Barton and Overton J. 1955 2639. The Optical Resolution of Asymmetric Phosphoryl Compounds By M. GREEN and R. F. HUDSON (QUEEN MILEENDROAD,LONDON,E.l) MARYCOLLEGE THEresolution of phosphoryl derivatives is greatly facilitated by anionic' and cationic2 groups in the asymmetric molecule. We have recently used the formation3of molecular complexes with a-(2:4 5 :7-tetranitro-9-fluorenylideneamino-oxy)propionic acid (I) for preparing optically active phosphonates and phosphonothiolates. According to this method the acid (I) is added to an excess of an asymmetric phos- phorus compound containing a condensed aromatic system and from the insoluble complex the ionised form of the acid (I) is removed with sodium hydrogen carbonate solution leaving a partly resolved phos- phorus compound.No complex was formed how- ever between the acid (I) and the a-naphthylphos- Aaron and Miller J. Amr. Chem. SOC.,1956 78 3538. Coyne and Van der Werf? ibid. p. 3061. Newman and Lutz ibid. p. 2469. O=b-SCH,Ph Me-0Me 0 MI-& 6 om phinate (II) although the geometrically similar com- pound a-naphthyltripropylsilane readily formed a complex. This suggests that the absence of complex PROCEEDINGS formation with the phosphinate (II) is due to electro- (IV) m.p. 69" was synthesised. This ester (4.2 g.), static repulsion between the oxygen atoms of the and the acid (T) (5-2 g.) in glacial acetic acid gave a phosphinate (11) and the nitro-groups of the acid (I).yellow complex which was dried and suspended in Since Newman and Lut2 resolved sec.-butyl a-ether. After liberation of acid (I) with sodium naphthyl ether by this method the alkyl alkylphos- hydrogen carbonate and recrystallisation of the phonate (111) was prepared. With the acid (I) it gave residue the phosphinothiolate (2.0 g.) m.p. 67" a red complex (m.p. 111 ") from propionic acid-light [01]420 f 17.0" (c 3.0in benzene) was obtained. petroleum (b.p. 60-80"; 1 :1). The complex when Similar treatment of the acetic acid filtrate gave the treated as described above gave a main fraction phosphinothiolate (1.73 g.) m.p. 69-5" -13.1" b.p. 116-1 18"/10-3 mm. nD201.5813 + 44" (c 2.0 in benzene).(c 1-5 in dioxan). As an ester with only one func- tional group the 3-phenanthrylphosphinothiolate (Received September 27th 1957.1 NEWS AND AI\JNOUNCEMENTS Nobel Prize for Chemistry.-The Swedish Academy sisting of one or more general lectures followed by of Science has announced the award of the Nobel contributed papers. Preprints will be circulated to Prize for Chemistry to Professor Sir Alexander participants before the Conference and a full report Todd in recognition of his work on synthesising will be published later. coenzymes. Sir Alexander Todd has served on Excursions to various laboratories and research Council 1939-42 and 194548 and as Vice-establishnents are being planned. A special pro- President 1948-51 and from 1955 to date.gramme of social events and functions will be Simonsen Lecture.-The Council is pleased to arranged for ladies accompanying participants. announce its acceptance of a gift by Lady Simonsen Further details of the scientific programme to found a Lectureship in memory of her husband registration methods of payment and hotel accom- the late Sir John Simonsen F.R.S. The Simonsen modation will be sent to those who reply to the Lecture which will take its place amongst the other circuIar which will shortly be distributed and which Endowed Lectures of the Society will be given once may be obtained from the Secretary International in every three years and will be published in Conference on Co-ordination Chemistry The Proceedings. It is intended that the Lecturer shall Chemical Society Burlington House London W.1. normally be chosen from amongst the younger chem- Anniversary Meetings 1960.-The Council has ists of any nationality working in the field of natural accepted an invitation to hold its Anniversary Meet- product chemistry. ings jointly with those of The Royal Institute of The first Simonsen Lecture entitled "Some Chemistry in Belfast during the week commencing Aspects of Sesquiterpenoid Chemistry," will be given April loth 1960. by Professor D. H. R. Barton F.R.S. on January Library.-The Library will close for the Christmas 16th 1958. Holiday from 1 p.m. on Monday December 23rd International Conference on Co-ordination Chem- until 10 a.m. on Saturday December 28th 1957. istry.-The next International Conference on Co- The Joint Library Committee regrets that a charge ordination Chemistry will be held in London from of 6d.per parcel will have to be introduced to meet Monday April 6th to Saturday April 11th 1959 the cost of packing materials used in wrapping books under the sponsorship of The Chemical Society. issued on loan from the Library. The Conference will be mainly concerned with Prices for Preprints 1958.-The Council regrets recent developments in that for reasons which have been described by the (1) The Co-ordination Chemistry of Carbon and the Honorary Treasurer (Proceedings 1957 105-106) Use of Carbonyls Organometallic Compounds the Society is unable in future to allow authors any Hydrides etc. as Reagents and Catalysts in free preprints of papers published in the Journal.Organic Chemistry. From January 1958 the following charges will (2) The Theory and Physical Chemistry of Co-apply: ordination Compounds. Number of Price without Price with (3) The Complex Chemistry of the less Common preprints covers covers Ligand Atoms (e.g.,P As Sb S Se Te F'). E s. d. E s. d. (4) Metal Compounds of Topical or Industrial 50 300 500 Interest. 75 3100 5160 Special emphasis will be placed on topic no. (1). The 100 4 0 0 612 0 subjects will be presented in Symposia each con- Per 25 additional 10 0 16 0 NOVEMBER 1957 325 Alchemy and Early Chemistry.-The revival of Arnbix (the only journal devoted exclusively to the history of alchemy chemistry and chemical tech- nology before the time of Dalton) has aroused sufficient interest to warrant regular publication in the future.The Society for the Study of Alchemy and Early Chemistry founded largely through the initia- tive and enthusiasm of the late Dr. Sherwood Taylor published its first issue of Ambix in 1937. After many delays Volume V was completed in October 1956. The first part of Volume VI was produced in August this year and the second part is due to appear in December. The scope of the journal may be indicated by the main articles in the latest issue “The Gnomon” (H. E. Stapleton); “A Licence of Henry V1 to practise Alchemy” (D. Geoghegan);“Tanning Tech- nology in Ancient Mesopotamia” (Martin Levey); “L B. Guyton de Morveau 1737-1816” (W.A. Smeaton). The Council of the Society under its Chairman Dr. E. J. Holmyard is now in a position to invite contributions to Anibix in the hope that it will soon prove possible to issue one volume a year. Articles should be sent to the Hon. Editor D. Geoghegan Esq. Higher Westerland nr. Paignton Devon. Volume subscriptions (&2 2s. Od. to individuals enrolling as members of the Society; &2 12s. 6d. to institutions libraries etc.) should be sent direct to the Hon. Treasurer W. A. Smeaton Ekq. 28 Elm Grove Harrow Middx. General enquiries should be addressed to the Hon. Secretary Dr. F. W. Gibbs c/o 30 Russell Square London W.C.l. Reorganisation in Imperial Chemical Industries Limited.-The Board of Imperial Chemical Industries Limited have decided to separate the interests of Billingham Division in organic chemicals based primarily on petroleum and a new Heavy Organic Chemicals Division will be created with effect from January 1st next.The Chairman of the new Division will be Dr. S. W. Saunders at present Managing Director of the Billingham Division. The Company have also decided to reduce the size of the Metals Division by transferring some of its activities to a new Company to be established jointly with the Yorkshire Copper Works Limited. International Congresses.-An International Con- gress on Metallurgical Research will take place in Likge on June 17-21st 1958. Further details may be obtained from the Centre National de Recherches Metallurgiques Section de Likge Abbaye du Val Benoit Rue du Val Benoit Liege Belgium.The 7th International Cancer Congress will be held in London on July 6-12th 1958 under the auspices of the International Union against Cancer. Further information may be obtained from the Secretary-General 7th International Cancer Con- gress 45 Lincoln’s Inn Fields London W.C.2. An lnternational Conference on Semi-conductors will be held in Rochester New York on August 18-23rd 1958. Enquiries should be addressed to Dr. M. H. Hebb Conference Secretary General Electric Research Laboratory P.O. Box 1088 Schenectady New York. An International Congress of the Jnternational Federation of Electron Microscope Societies will be held in Berlin on September 3-9th 1958. Enquiries should be addressed to Dr.T. F. Anderson The School of Medicine The Eldridge Reeves Johnson Foundation for Medical Physics 612 Maloney Building University of Pennsylvania Philadelphia 4 U.S.A. Deaths.-We regret to announce the death of Mr. R. V. Euton (3.10.57) Superintendent of the Royal Naval Propellant Factory Caerwent; of Dr. R. D. H. Heard (8.9.57) of the Department of Biochemistry McGill University Montreal; and of Mr. A. E. Parkes of Bow London who was elected to the Fellowship in 1901. Personal.-Mr. R. P. Bell has been appointed by the War Office as a member of the Council to advise on major matters of policy connected with the Royal Military College of Science at Shrivenham. Dr. F.P.Bowden has been transferred to a profes- sorial Fellowship of Gonville and Caius College Cam bridge.Dr. f. B. M. Coppock is relinquishing his post as Director of Research of the British Baking Industries Research Association to become Director of Re-search at Spillers Ltd. on January 1st next. Professor E. G. Cox has been made a member of the Agricultural Research Council. Dr. J. D. Dunitz has been appointed to a Chair of Crystallography at the Swiss Federal College of Technology Zurich. Dr. E. B. Evans has received the Eastlake Medal of the Institute of Petroleum. Dr. G. E. Foster has been elected Chairman of the British Pharmaceutical Conference 1957/58. Dr. S. J. Green has been appointed a Director of Fisons Milk Products Ltd. a subsidiary of Genatosan Ltd. Mr. H.J. Hadow Scientific Attach6 at the British Embassy in Washington and Director of the United Kingdom Scientific Mission there since 1954 has taken up his appointment as Secretary of the National Physical Laboratory Teddington. Dr. H. B. Henbest has been appointed to the Chair of Organic Chemistry at the Queen’s University of Belfast. Mr. H. Holness formerly Senior Lecturer in Chemistry at the S.W. Essex Technical College has been appointed as Senior Lecturer in Analytical Chemistry in the Department of Chemical En- gineering Faculty of Technology University of Manchester. Mr. T. W. Howard chairman of Howards of Ilford Ltd. has been elected as new chairman of the British Standards Institution’s Chemical Divisional Council.At the American Society for Metals Congress which was held in Chicago on November 2-8th Dr. W. Hume-Rothery of Oxford University was given an honorary life membership of the Society in honour of his “outstanding contribution to the know- ledge of the nature of the atom and particularly its behaviour in metals and alloys.” Dr. 5’. S. Israelstam has been appointed Associate Professor in the Department of Chemistry and Chemical Engineering of the University of the Witwatersrand. Professor H. D. Kay C.B.E. Director of the National Institute for Research in Dairying was presented with the Gold Medal of the Society of Dairy Technology at the meeting held in the Grand Council Chamber of the Federation of British In- dustries in London on October 21st.Mr. C. Kennedy has been appointed Deputy Area Chief Scientist in the Scientific Department of the West Midlands Division of the National Coal Board. Mr. J. M. Leonard has been appointed a Trustee of The Perkin Centenary Trust. PROCEEDINGS Dr. P.G. Owston has been appointed to represent the Society on Group B of the British Conference on Automation and Computation. Mr. H. M. Powell St. John’s College has been re- elected as Reader in Chemical Crystallography in the University of Oxford for seven years with effect from April 12th 1958. The Council of the University of Sheffield has appointed Dr. B. Stevens as Lecturer in Physical Chemistry and Dr. E. Haslam as Assistant Lecturer in Chemistry at the University. Professor R.H. Stokes of the University of New England has been elected to Fellowship of the Australian Academy of Science. Mr. Maurice C. Taylor has been awarded the Honour Scroll of the Niagara Chapter of the American Institute of Chemists in recognition of his contributions to the chemical industry and service to the organisation. Dr. H. W.Thompsonhas been appointed chairman and Dr. R. S. Cahn a member and secretary of the Publication Committee of the International Union of Pure and Applied Chemistry. Dr. I. W. Wark,chief of the Division of Industrial Chemistry at the Commonwealth Scientific and In-dustrial Research Organisation has been elected General President of the Royal Australian Chemical Institute for 1957/58. FORTHCOMING SCIENTIFIC MEETINGS London Thursday December 12th at 7.30 p.m.Meeting for the Reading of Original Papers. “N-Oxides and Related Compounds. Part IX. The Electric Dipole Moments of Pyridine- and Tri- methylamine-Boron Trihydride and Trihalides,” by C. M. Bax A. R. Katritzky and L. E. Sutton. “Tetrahedral Complexes of Nickel (11) and the Factors determining their Formation. Part I. Bis (tripheny1phosphine)nickel (II) Compounds,” by L. M. Venanzi. “The Relation between Proton Dis- sociation Constants and the Stability Constants of Complex Ions,” by J. G. Jones J. B. Poole J. C. Tomkinson and R. J. P.Williams. “The Oxidation Reduction Potentials of Complex Ions,” by J. C. Tomkinson and R. J. P. Williams. Thursday January 16th 1958 at 7.30 p.m.Simonsen Lecture “Some Aspects of Sesquiterpenoid Chemistry,” by Professor D. H. R. Barton D.Sc. F.R.S. To be given in the Large Chemistry Lecture Theatre Imperial College of Science and Technology South Kensington S.W.7.(The Tilden Lecture by Professor B. Lythgoe arranged for this date will now be given on February 13th.) Aberdeen Thursday December 5th at 7.45 p.m. Lecture “Pesticides-Problems and Prospects,” by Dr. R. A. E. Galley Ph.D. A.R.C.S. D.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held at Marischal College. Birmingham Friday December 13th at 4.30 p.m. Lecture “The Chemistry of Vitamin BIZ,’’by Profes- sor A. W. Johnson M.A. Ph.D. Joint Meeting with Birmingham University Chemical Society to be held in the Chemistry Department The University.Bristol Thursday December 5th at 6.30 p.m. Lecture “Design and Operation of Waste-heat Boilers,” by Captain W. Gregson. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Chemistry Department The University. EBinkgh Thursday December 5th at 7.30 p.m. Lecture “Physical Chemistry in the Dyestuffs NOVEMBER 1957 Industry,” by Dr. D. S. Davies. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Lecture Room of the Royal Society of Edinburgh 24 George Street. Thursday January 9th 1958 at 7.30 p.m. Jubilee Memorial Lecture of the Society of Chemical Industry “The Pattern of Research in the Electrical Industry,” by Dr.H. K. Cameron. Joint Meeting with the Royal Institute of Chemistry and the Society of ChemicalIndustry to be held in the Lecture Room of the Royal Society of Edinburgh 24 George Street. Glasgow Friday December 6th at 7.15 p.m. Lecture “William Ramsay a Glasgow Man,” by Dr. A. Kent M.A. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held at the Royal College of Science and Technology. Hull Thursday December 5th at 5 p.m. Lecture “Water-repellency,” by Professor N. K. Adam Sc.D. F.R.I.C. F.R.S. Meeting arranged by the University Student Chemical Society to be held in the Organic Chemistry Lecture Theatre The University.South Wales Friday December 6th at P.m. Lecture “Some Recent Developments in the Chem- istry of Organometallic Compounds,” by Professor G. E. Coates M.A. D.Sc. F.R.I.C. Joint Meeting with the University College of Swansea Chemical Society to be held in the Chemistry Department University College Swansea. APPLICATIONS FOR FELLOWSHIP (Fello.ws wishing to lodge objections to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedings. Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Anderton Edward James M.Sc. 9 Abingdon Road Doncaster Yorks.Bain Brian MacDonald. “Oakfield,” St. Mary’s Road Leeds 7. Baron Christian Charles Andre D. ts Sc. 21 Place Bossuet Dijon France. Bendall Victor Ivor B.Sc. A.R.C.S. 18 Bilton Road Rugby Warwicks. Black Donald B.Sc. 9 The Oaks Woodside Avenue London N. 12. Boardman Kenneth Oswald M.A. 26 Townfields, Ashton-in-Makefield,nr. Wigan Lancs. Bommannavar,S.S. B-Sc. M.Sc. Science College Hubli Mysore State India. Brazier Terence Frederick. 35 Wentworth Crescent Hayes Middlesex. Burton John Stewart. 68 Warren Drive Tolworth Surrey. Cox Michael B.Sc. 9 Chantrey Road Stockwell S.W.9. Crook Leonard Robert B.Sc. F.R.I.C. c/o Wyeth Laboratories New Lane Havant Hants. Cutmore Ernest Alan. 35 4th Avenue Galon-Uchaf Merthyr Tydfil Glam.Davison Alan. 84A Pentyla Aberavon Port Talbot Glam. De Belder Anthony Norman B.Sc. Teneriffe Hamsey Road Saltdean Sussex. Dietz Roy B.Sc. 202 Twickenham Road London E.11. Emsley James William B.Sc. 2 Alderton Mount Leeds 17. Essery John Michael B.Sc. 21 New North Road Exeter. Evans John Mon B.Sc. A.R.I.C. 3 Beach Road, Rhosneigr Anglesey. Fergusson Jack Eric M.Sc. 127 Woodstock Avenue Golders Green N. W. 1 1. Fitton Peter B.Sc. 7 Travis Street Newhey Rochdale Lancs. Foster William Rees B.Sc. 248 Goldhawk Road, Shepherds Bush W.12. Golton Alan Victor M.A. D.Phi1. Chemistry Depart- ment The University Leicester. Gubbins Keith Edmund. 73 Bellemoor Road Shirley Southampton. Hamer Douglas B.Sc. Ph.D. F.R.I.C. Department of Chemistry and Pharmacy College of Technology, Belfast N.Ireland. Hessel Donald Wesley B.A. M.Sc. Ph.D. School of Tropical and Preventive Medicine College of Medical Evangelists Loma Linda California U.S.A. Hewertson Warren. Lenton Hurst Wortley Hall, University Park Nottingham. Hinterberger Hertha B.Sc, A.S.T.C 29 Beresford Avenue Bankstown New South Wales Australia. Iwase Eiichi D.Sc. Scientific Research Institute 31 Kamifujimae-cho Komagome Bunkyo-ku Tokyo Japan. Jackson William Roy B.Sc. 65 Greencroft Gardens London N.W.6. James Malcolm Burford BSc. 56 Heol Elfed Llanelly Carms. Jeffery Jonathan d’Ardern B.A. Jesus College Oxford. Jhaveri Dinbala Bhogilal M.Sc. Southpark House 64 Southpark Avenue Glasgow W.2. Johnson Anthony Francis.49 Ernest Street Merthyr Tydfil Glam. Jones David William. 13 Church Parks Oystermouth Swansea Glam. Jones Frank B.Sc. 51 Penchwintan Road Bangor Caerns. Jones Keith B.Sc. 50 Bishopscourt Road Sheffield 8. Juby Peter Frederick B.Sc. 247 Southtown Road Great Yarmouth Norfolk. Kemp Brian Robert. 43 Woodhall Lane Welwyn Garden City Herts. Klassen Norman Victor B.Sc. Ph.D. Chemistry Depart- ment University College Gower Street London W.C. 1. Leigh Roland Albert B.A. 16 Locke Close Keresley Coventry. Lillycrop Jocelyn Eleanor. 58 Harlech Crescent Sketty Swansea Glam. Lloyd Gerald. 3 Hankey Terrace Merthyr Tydfil Glam. Long Richard Robert. Field House Castle Avenue Warblington Havant Hants. McDonald Charles Ian Ross B.Sc.35 Lome Avenue Killara New South Wales Australia. Mattocks Alan Robin B.Sc. A.R.I.C. 58 Malden Road Cheam Surrey. Morris John Howell. 377 Cowbridge Road East Canton Cardiff. Morris Roy Owen BSc. 13 Bockhampton Road, Kingston-on-Thames Surrey. Nardelli Mario. Via N. Bixio 39 Parma Italy. Nasipuri Dhanonjoy M.Sc. D.Phil. Department of Chemistry University of Manchester Manchester 13. Pope Michael Thor B.A. D.Phil. Chemistry Depart- ment Boston University Graduate School Boston 15, Mass. U.S.A. Pratesi Pietro D.Sc. Istituto Chimico Farmaceutico Universita Pavia Via Taramelli 12 Pavia Italy. Richter John Franz Paul. 59 Edeubridge Road Enfield Middlesex. Schofield Neil. 26 Kaye Lane Almondbury Hudders- field Yorks. Szelke Michael.4 Bellair Road Havant Hants. ADDITIONS TO Through alchemy to chemistry. J. Read. Pp. 206. G. Bell and Sons Ltd. London. 1957. A short history of chemistry. J. R. Partington. 3rd Edn. Pp.415. Macmillan and Co. Ltd. London. 1957. A history of industrial chemistry. F. Sherwood Taylor. Pp. 467. Heinemann. London. 1957. Oeuvres de Lavoisier. Vol. 7. Correspondance. Edited by R. Fric. Part 2. Pp. 286. Editions Albin Michel. Paris. 1957. Reports on progress in physics. Vol. 20. Edited by A. C. Stickland. Pp. 568. The Physical Society. London. 1957. (Presented by the Physical Society.) Annual review of physical chemistry. Vol. 8. Edited by H. Eyring C. J. Christensen and H. Johnston. Pp. 527. Annual Reviews Inc. Palo Alto California.1957. (Presented by the publishers.) The calculation of atomic structures based on lectures given under the auspices of the William Pyle Philips Fund of Haverford College 1955 by D. R. Hartree. Pp. 181. John Wiley and Sons Inc. New York. 1957. The spectroscopy of flames. A. G. Gaydon. Pp. 279. Chapman and Hall Ltd. London. 1957. The defect solid state. T. J. Gray et al. Pp.511. Inter-science Publishers Inc. New York. 1957. Contact catalysis. R. H. Griffith and J. D. F. Marsh. Pp. 299. Oxford University Press. Oxford. 1957. Inorganic chemistry a text-book for advanced students. E. de Barry Barnett and C. L. Wilson. 2nd Edn. Pp. 588. Longmans Green and Co. London. 1957. (Presented by the publisher.) The chemistry of borates. Part 1.P. H. Kemp. Pp. 90. Borax Consolidated Limited. London. 1956. (Presented by the publishers.) Research on spontaneous combustion of coal in mines a review H. F. Coward. (S.M.R.E. Research Report No. 142.) Pp. 80. Safety in Mines Research Establishment. Shefield. 1957. (Presented by the publishers.) Production of heavy water. Edited by G. M. Murphy, H. C. Urey and I. Kirshenbaum. Part 1 by J. 0.Maloney et af. Part 2 by M. L. Eidinoff et a/. (National Nuclear Energy Series. Manhattan Proiect Technical Section. Division 111. Vol. 4F). Pp. 394. McGraw-Hill Book Company Inc. New York. 1955. Polythene the technology and uses of ethylene polymers. Edited by A. Renfrew and P. Morgan. 37 contributors. Pp. 567. Iliffe and Sons Limited. London. 1957.Turner Gerald Patrick Anthony B.A. 49 Draycott Place London S.W.3. Vaughan Dennis Joseph. 24 Walter Street West Bromwich Staffs. Wain Brian Jack A.R.I.C. Salem View Belmont Road Stroud Glos. Walsh Donald Kyffin. 367 Cregagh Road Belfast N. Ireland. Walton Annette B.Sc. 12 Allington Avenue Lenton Nottingham. Wells Edward Joseph. 42 Lambert Road Bardwell Park Sydney Australia. Wilson Keith B.Sc. Chemistry Department The University Hull. Winterbottom Eric. Station House Barnby Dun nr. Doncasher Yorks. Wormald Christopher John. The Bushes Lowdale Lane Hart Station Hartlepool Co. Durham. Wright John Christopher. 44Lindum Road Cleethorpes Lincs. Wynne Francis B.%. Jocelyn Place Dundalk Co. Louth. THE LIBRARY Houben-Weyl’s Methoden der organischen Chemie.4th Edn. Vol. 11/1. Stickstoffverbindungen 11. Amine I. Herstellung. Edited by E. Miiller. Pp. 1,172. Georg Thieme Verlag. Stuttgart. 1957. Some aspects of the chemistry and toxic action of organic compounds containing phosphorus and fluorine. B. C. Saunders. Pp. 231. University Press. Cambridge. 1957. Ion exchangers in organic and biochemistry. Edited by C. Calmon and T. R. E. Kressman. 37 contributors. Pp. 761. Interscience Publishers Inc. London. 1957. Calcium metabolism. J. T. Irving. (Methuen’s Mono- graphs on Biochemical Subjects.) Pp. 177. Methuen and CO.Ltd. London. 1957. Excited states in chemistry and biology. C. Reid. Pp. 215. Buttenvorths Scientific Publications. London. 1957. Biochemistry of the amino-acids.A. Meister. Pp. 485. Academic Press Inc. New York. 1957. A textbook of brewing. J. de Clerck. Translated by Kathleen Barton-Wright. Vol. 1. Pp. 587. Chapman and Hall Ltd. London. 1957. Cereal laboratory methods with reference tables com- piled by the Committee on Revision of the American Association of Cereal Chemists Inc. 6th Edn. Edited by E. C. Swanson. Pp. 528. American Association of Cereal Chemists Inc. Minnesota. 1957. Hochfrequenztitration die chemische Analyse mit Hochfrequenz ohne galvanischen Kontakt zwischen Losung und Elektrode. K. Cruse and R. Huber. (Mono- graphien zu Angewandte Chemie und Cltemie-lngenieur-Teclznik No. 69.) Pp. 198 Verlag Chemie GMBH. Weinheim. 1957. Complexometric titrations. G. Schwarzenbach.Trans- lated by H. Irving. Pp. 132. Methuen and Co. Ltd. London. 1957. (Presented by the publishers.) Carotene its determination in biological materials. V. H. Booth. Pp. 119. W. Heffer and Sons Ltd. Cam- bridge. 1957. Applications of infra-red spectroscopy symposium organjsed by the London Section of the Society of Chemical Industry 1956. (Sections variously paginated.) Society of Chemical Industry. London. 1957. (Presented by the publishers.) Chemical engineering in the coal industry an inter- national conference organised by the National Coal Board at Cheltenham 1956. Edited by F. W. Sharpley. Pp. 141. Pergamon Press. London. 1957.
ISSN:0369-8718
DOI:10.1039/PS9570000301
出版商:RSC
年代:1957
数据来源: RSC
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