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Proceedings of the Chemical Society. May 1959 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue May,
1959,
Page 137-168
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PROCEEDINGS OF THE CHEMICAL SOCIETY MAY 1959 VICTOR MEYER By J. J. SUDBOROUGH VICTORMEYER was born in Berlin and he died in Heidelberg at the age of 49. His first wishes were to become an actor but at the age of 17 he joined the University of Heidelberg to work under Bunsen and shortly became his private assistant. His work was mainly the analysis of the mineral waters of South Germany. In order to widen his chemical outlook and on the recommendation of Bunsen he joined Baeyer’s laboratory in Berlin in 1867. The laboratory consisting of some 20 re-search students was recognised as one of the most famous research laboratories in Europe. His work consisted of a study of mellitic acid the constitution of disubstituted benzene compounds and of camphor and also the introduction of the carboxy-group into the molecule of aromatic compounds by the action of sodium acetate on the sodium salts of sulphonic acids.From Berlin he proceeded to the Stuttgart Polytechnic to work with Fehling. After one year there he was appointed head of the Chemistry Department of the Zurich Polytechnic where he remained for 1 3 years (1 872-1 885). According to T. E. Thorpe,l who was a fellow student with him under Bunsen his stay in Zurich constituted the most fruitful and most brilliant period in his career and before he left Victor Meyer Memorial Lecture J. 1900,77 169. he brought himself within the foremost rank of contemporary investigators. With his colleagues and students he published some 130 papers and memoirs.The work in Zurich included the study of aromatic amines and the proof that sub- stituents such as Br Cl I and NO2 take up the position ortho to the amino-group. Work was also carried out on di- and tri-substituted amines and on the structure of chloral hydrate but the most important was the study of aliphatic nitro- compounds as exemplified by the isomeric amyl compounds C5Hl1O2N one of which was shown to be amyl nitrite C,H,,.O.NO and the other a true nitro-compound C5Hll*N02. This was fol- lowed by a study of primary secondary and tertiary nitro-paraifins and the use of nitrous acid as a reagent for distinguishing the three groups. Improved methods for the preparation of hydroxylamine were discovered and its use for identifying aldehydes and ketones by the formation of oximes was elaborated.While he was in Zurich the Victor Meyer method for determining vapour densities was developed using vessels of glass porcelain and platinum-iridium and various baths e.g. boil-ing water xylene aniline ethyl benzoate amyl benzoate diphenylamine sulphur and molten 137 138 lead. The results for ferric chloride at tempera- tures below 750" gave values between those re- quired for FeCl and Fe,Cl, but above 750" corresponded with the simple formula. Similarly at high temperatures the values for iodine indicated a decomposition of I into 21. One of his most brilliant discoveries was that of tbiophen in benzene from coal-tar. This was due to an observation made during one of his lectures when it was found that the benzene used did not give the usual Baeyer or indo- phenine reaction (blue colour with isatin).It was subsequently found that the specimen used had been obtained by heating benzoic acid with lime. All samples of benzene obtained from coal-tar gave the reaction and by shaking the tar benzene with concentrated sulphuric acid products were obtained which did not give the blue colour. From the sulphuric acid a sulphonic acid was obtained and this on heating gave a volatile liquid containing sulphur and closely resembling benzene in its properties. This was named thio- phen C4H,S. Larger quantities were prepared and its properties and derivatives studied and the results published in a monograph in 1888.In 1885 he received a call to the University of Gottingen where he remained for four years. His work was mainly on benzil deoxybenzoin and oximes and the discovery of two isomeric oximes of unsymmetrical ketones. This led to a long dis- cussion with Mantzsch and Werner on the struc- ture of the isomers and to the introduction of the term stereochemistry. In 1889 an invitation came for him to succeed his old Professor-Bunsen-in Heidelberg. He tookwith him to Heidelberg Gatterman P. Jacob- son Auwers and Knoevenagel who had been him in Gottingen. As in both Zurich and with Gottingen new laboratories were promised. These adjoined the old laboratories in the Wredeplatz and were opened in 1891.The investigations carried out during the years 1889-1 897 included the following :(1) Tempera-tures of explosion of mixtures of hydrogen carbon monoxide and hydrocarbons with oxygen in sealed vessels and in open tubes. The results indicated that explosion occurs at a lower temperature in closed bulbs and that the temperature decreases as the number of carbon atoms in the hydrocarbon increases. Coating the inner surface of the bulb with silver also lowers PROCEEDINGS the temperature of explosion. (2) With Boden- stein he studied the equilibrium 2HI + I + H, in the dark at different temperatures and with W. Harris the decomposition of mercurous chloride at high temperatures with the object of deciding between the reactions Hg,Cl -+ 2HgCl and Hg,C12 -+ Hg + HgCl, and the conclusion drawn that the latter is the more probable.(3) With a number of English and American students the melting (fusion) points of many metallic salts by using a platinum-air thermo-meter by heating the salt with a metallic rod fused into it the rod being attached by a string over a pulley to a counter-weight and noting the temperature at which the rod was drawn up out of the fusing salt. (4) One of the most interesting investigations was on the iodoso- iodoxy- and iodonium derivatives of aromatic compounds carried out by Wachter Hartmann McCrae and Patterson e.g. C6H5*I0 C6H,.I0, and (C6H5),I.0H. Compounds yielding such iodon- ium compounds were benzene p-iodotoluene and o-iodobenzoic acid but not the isomeric rn-and p-acids.The iodonium hydroxides give strongly alkaline solutions and yield salts e.g. iodides and sulphates closely resembling those of silver lead and particularly thallium. When heated the iodonium iodide yields iodo- benzene (C,H,),I.I -+ 2C,H,I. (5) Another in- vestigation taken up in 1892 was the esterifica- tion of aromatic acids by the hydrogen chloride catalytic method and the influence of sub-stituents in the benzene molecule and it was my privilege to carry out the earlier experiments. Why did I go to Heidelberg? After four years at the Mason College Birmingham three years working for B.Sc. (Honours) degree of London University and one year at research under Pro- fessor w. A. Tilden the Professor urged me most strongly to study for a year or more at a German University.Unfortunately my finances did not render this possible so I spent a fifth year in Birmingham working on the addition of nitrosyl chloride to olefinic hydrocarbons. During this year the Commissioners of the 1851 Exhibition offered 14 research scholarships of &150 a year for two years and one was to be given by the Mason College. This was awarded to me and I then decided to spend two years at a German University. I consulted an old Masonian-Dr. E. F. Ehrehardt who had graduated at Munich MAY 1959 and was then on the scientific staff of Badische Anilin und Soda Fabrik at Ludwigschafen-am- Rhein-as to the best University and he strongly recommended Heidelberg which he termed the Oxford of German Universities.It had the attrac- tions of a new comparatively young and very active Director viz. Victor Meyer; also new laboratories were in course of erection and the town occupied a glorious position near the junction of the Rhine and the Neckar. In mid-October 1890 F. D. Chattaway and I started for Germany he to Munich and I to Heidelberg to work under Victor Meyer to whom I had previously written and who had agreed to accept me as a research student. Chattaway spent three or four days with me in Heidelberg and we were both enchanted with the town and its surroundings. I received a note from Professor Meyer asking me to meet him in his private room and to produce evidence that I had studied Latin.I met him for the first time and was im- mediately impressed by his strong personality- a handsome face with alert penetrating eyes and a most attractive manner. He began by saying that if he spoke German and I English we should probably understand one another. He studied my Oxford Local and London Matriculation certificates to see that I had done a little Latin and arranged to meet me in the old laboratories on the following Monday morning. When I ar-rived I was disappointed with the working bench allotted me-half a bench in one of the window recesses. After six months however I was given much better accommodation in one of the new and brighter laboratories. Meyer asked me to study the alkyl derivatives of deoxybenzoin viz.methyl ethyl benzyl and cetyl and to study the action of phosphorus pentachloride on these the products being alkylated chlorostilbenes e.g. C6H5C(CH,) :CC1C6H5. The methyl and ethyl compounds were oils but when heated gave definite crystalline compounds with the same composition. The oily and the crystalline form gave the same vapour density and the question was whether the oil was a slightly impure form of the crystalline or whether the two were stereo- isomerides e.g. for the methyl compounds C6H5-C-CHs and C6Hs-C-CHS II II C,&-C-Cl Cl-C-CcH5 During my second year the Professor was away for three months owing to a break down in his health brought on by overwork and Professor Gattermann was in charge of the laboratory where I worked.During the Professor’s absence I attempted to solve this question by preparing dichlorides and dibromides. If stereoisomeric the two forms should yield the same dichloride as only one asymmetriccarbon atomis present in themole- cule C,H5.CMeC1.CC1,C,H5 whereas they should yield distinct dibromides as two asymmetric car- bon atoms are present C,H5.CMeBr.CC6H,C1Br. The results however were inconclusive. This work formed the basis of my dissertation for the Ph.D. degree which I took in June 1892. The subjects were Chemistry Physics and Mineral- ogy and the examiners were Professors Meyer Quincke and Rosenbusch one hour for Chem- istry and half an hour each for Physics and Mineralogy. The examination took place in the main University building in the afternoon and the candidate appeared in full evening dress.I did badly in all three subjects and I was not surprised when I was awarded the degree cum Zaude i.e. 3rd Class Honours. To my surprise a week or two later I received a letter from the Secretary to the Commissioners of the 1851 Exhibition informing me that my scholarship had been renewed for a third year undoubtedly the result of V. Meyer’s report on my work during the two years. I was still further surprised when shortly afterwards Meyer offered me the post of one of his private research assistants and in October 1892 I returned for a year to work in his private laboratory. My first problem was the attempted resolution of nitrothymotinic acid a compound with six different atoms or groups attached to the carbon atoms of the benzene ring viz.H CH, C3H7 OH, C02H and NO2. Meyer’s view was that if this acid could be resolved into optically active components then the six carbon atoms of the ring could not be co-planar. An attempt to re- solve the nitro-acid by means of optically active bases had been made by my predecessor but were not successful. I tried the resolution by means of pure cultures of micro-organisms ob- tained from the Bacteriological Institute but the results were negative. Had the resolution been successful the more recent resolution of ortho-substituted diphenic acids and other compounds would have shown that Meyer’s conclusion would not be justified. PROCEEDINGS I then worked on the esterification of sub- stituted benzoic acids by the hydrogen chloride catalytic process.In the earlier experiments we used a solution of the acid in methyl alcohol saturated with hydrogen chloride and kept this overnight at room temperature but in later ex- periments we used Fischer’s method with a 3% solution of hydrogen chloride and boiling for a short time. The results showed that acids with two substituents ortho to the carboxylic acid gave no esters whereas isomeric acids with the constituents in other positions gave practically 90-100% of ester. The results were the same whether the substituents were alkyl halogeno- nitro- or carboxy-groups. This phenomenon led to the term steric hindrance.The esters are how- ever readily obtained by heating the silver salt of the acid with methyl iodide or the acid chloride with methyl alcohol. Esters are also readily formed by the catalytic method when the carboxylic group in the di-ortho-substituted acid is removed from direct attachment to the carbon atom of the ring by the interposition of CH,. COCH2. or *CH,-CH,. groups. Interesting re- sults were obtained with acids containing several carboxylic groups thus pyromellitic acid with the COzH groups in the positions 1:2:4 5 gives a tetramethyl ester the isomeric 7 :2 :3 :4-tetra-carboxylic acid a dimethyl ester and the hexa- carboxylic acid no ester. This steric effect of ortho-substituents has been used for separating a di-ortho-substituted acid from a mixture of acids also for confirming the structure of an acid supposed to be di-ortho- substituted.Experiments made by other chemists in which acids were heated with an alcohol in sealed tubes in the absence of a catalyst and in which a di-ortho-substituted acid was esterified more readily than an isomeride were used as an argument against steric hindrance. Meyer made it perfectly clear that all the Heidelberg experiments were made with hydrogen chloride as catalyst. In all the later experiments the acid was heated for a short time with a 3% solution of hydrogen chloride in the alcohol. On prolonged heating acids with ortho-substituents such as Me and OH gave small yields of esters. Experiments made between 1894 and 1897 showed that esters acid chlorides and acid amides containing two ortho-substituents are hydrolysed by water hydrochloric acid or alkalis more slowly than their isomers.Both in Zurich and Heidelberg Meyer suffered from overwork and had to take periods of absolute rest. After a period of deep depres- sion he died on August 8th 1897. Meyer received many honours during his life- time ;he was a “Geheimrat” of Baden an Honor- ary Fellow of this Society and President of the German Chemical Society. He was outstanding as a lecturer an organiser a director of research and an author. As a lecturer he was lucid and concise and had a pleasing voice; he had copious notes but did not make great use of them. All his lectures were illustrated with many experiments ; these were carefully prepared and always successful.At the end of a course the attendance was as good as at the beginning whereas in other departments the numbers gradually diminished during the course. This was largely due to the fact that a student’s attendance book was signed by the Professor at the beginning and not at the end of the course. Meyer was extremely punctual and began his lectures at 9 a.m. and on only one occasion during two years do I remember a student entering after the lecture had begun. The culprit was an Englishman and his entrance was greeted by a loud shuffling of feet of all present. As Director of the Laboratories he had every- thing working smoothly partly because most of the Professors and Privatdocenten had been with him for many years.In the laboratories he was extremely genial; he took a great interest in all students working under him; he saw them at least once a day and always remembered the stage reached and encouraged each one to look forward to a successful termination of his work. During my stay in Heidelberg the first volume of Meyer and Jacobson’s “Lehrbuch der organischen Chemie” was published and was quickly recognised as the outstanding text-book on the subject. Meyer like his predecessor Bunsen attracted F. Challenger Victor Meyer and Paul Jacobson’s “Lehrbuch der organischen Chemie.” The authors and their work J. Roy. Insf. Chem. 1958,82 164. MAY1959 many English and American students to Heidel- berg and many of these obtained positions of importance in later years.Among the English students working in the Heidelberg laboratories from 189 1 to 1896 may be mentioned the follow- ing W. A. Bone (afterwards Professor of Applied Chemistry at the Royal College of Science London) H. H. Cousins (Director of Agricul- ture Jamaica) Christopher Clayton (Sir) (Director I.C.I.) D. R. Boyd (Professor of Chemistry University of Southampton) Walter Harris (Principal of Stoke-on-Trent Technical College) J. T. Hewitt (Professor of Chemistry Queen Mary College London) F. Marsden (Tinctorial Expert Government of Madras) John McCrae (Director of Agriculture Govern- ment of South Africa) T. s.Patterson (Professor of Organic Chemistry University of Glasgow) J.J. Sudborough (Head of Department of General and Organic Chemistry Indian Institute of Science Bangalore) and Jocelyn F. Thorpe (Sir) (Professor of Organic Chemistry Imperial College of Science and Technology S. Kensing-ton). After leaving Heidelberg I had several letters from Victor Meyer giving me accounts of his later work on steric hindrance and wrote him giving details of my work in Nottingham. I have worked under many Professors in- cluding W. A. Tilden Charles Lapworth and W. H. Perkin jun. whom I have greatly admired but the one who impressed me most was Victor Meyer. His outstanding personality his stimulating interest in the work of his students and his retentive memory will always remain with me.TILDEN LECTURE* Some Recent Advances in the Chemistry of the D-Vitamins By B. LYTHGOE (THEUNIVERSITY, LEEDS) SINCEthe developments which I propose to discuss arise directly from the classical studies on the anti- rachitic vitamins D carried out during the nineteen- thirties it is convenient at the outset to recall the main achievements of this early w0rk.l From irradi- ated ergosterol solutions the isomeric compounds lumisterol tachysterol vitamin D (calciferol) and the suprasterols were isolated. The gross structures although not it should be noted the stereochemical C9H I7 $sHI7 Ergosterol 4Lumisterol Y HO Tachysterol Ca Ic if e rot Suprasterols ‘17 details of the first three of these isomers were de- fined by degradative studies.Other steroidal 5 :7-dienes differing only in the nature of the side chain from ergosterol were shown to undergo similar changes on irradiation and the natural vitamin D, isolated from fish-liver oils was shown to be identical with the product obtained by irradiation of 7-de-hydrocholesterol. Finally views on the sequence in which the irradiation products arose were formulated in the annexed classical irradiation scheme which represents calciferol as the product of three successive irreversible photochemical acts. The Chemistry of the Irradiation Reaction.-The position in the scheme of tachysterol formulated as the cis-6-compound (3) is logical since the first pro- duct of ring-opening should have a cis-double bond.That of lumisterol is less logical. Its formation re- quires alteration of configuration at position 9 in ergosterol; this could most readily take place by ring-opening and recyclisation rather than as a pre- lude to ring-opening.2 The classical scheme was nevertheless accepted for over twenty years its over- throw being the outcome of observations by Velluz Amiard and their co-workers3 in 1948. * Delivered before the Chemical Society at the Imperial College of Science and Technology S. Kensington London on May lst at the University Southampton on January 17th and at Trinity College Dublin on April 16th 1958. For a summary and references see Fieser and Fieser “Natural Products related to Phenanthrene,” Rheinhold Publ. Corp. Inc. New York 1949 pp.167 ei seq. Hodgkin and Sayre J. 1952 4561. Velluz Petit and Amiard Bull. Soc. chim. France 1948 11 15. Irradiation of ergosterol solutions below 20" gives little calciferol but when such irradiated solutions are warmed in the dark major amounts of calciferol are generated. The ultimate step in the formation is therefore a thermal not a photochemical process. The labile precursor precalciferol was isolated* in 1949; in warm neutral solvents it is converted re- versibly5 into calciferol which forms ca. 75 % of the resulting equilibrium mixture.6 Precalciferol is iso- meric with calciferol and contains four unsaturated centres (hydrogenation). Its ultraviolet spectrum with Amax. 262 mp (e 9OOO) is of remarkably low intensity ;for comparison calciferol has Amax 265 mp (E 18,300).For some years little further informa- tion on precalciferol was available and an acceptable structure was not proposed until 1955. Of those pre- viously suggested the least improbable assumed a geometric isomerism with one of the known 9:lO-secu-compounds so it is convenient to consider next the geometry of these compounds. The early chemical studies' showed that calciferol has double bonds situated as shown in the structure (4) which was no doubt written in this form to emphasise the relation to ergosterol. Four geo-metrical isomers of this structure are possible; the PROCEEDING s form (4) represents the cis-5-trans-7-isomer which it now seems preferable to write in the extended (s-trans) conformation (5).Two other geometrically isomeric structures are the trans-5-trans-7-form (6) and the cis-5-cis-7-form (7). Evidence on the geo- metry of calciferol was first provided by a two-dimensional crystallographic analysis of the 4-iodo- 5-nitrobenzoateYfrom which Crowfoot and Dunit2 deduced the cis-5-trans-7-structure (5). Sondheimer and Wheelerg suggested that the X-ray data might be compatible with the trans-5-trans-7-structure(6) and assigned the cis-5-trans-7-structure (5) to precal-ciferol the less intense absorption of which was ex- plained in terms of the shorter chromophore of structure (5). This suggestion is untenable for the following reasons. The synthetic model trans-triene (S) which has essentially the same unsaturated system as that of the trans-5-trans-7-structure(6) shows absorption at a longer wavelength and of greater intensity than that of calciferol.l* The trans- 5-trans-7-isomer (6) later obtained1l?l2 by iodine- catalysed stereomutation of calciferol has the ex- pected more intense light-absorption [A,,, 272 m,u (E 24,400)].The earlier crystallographic results have recently been confirmed and amplified by a three- dimensional analysis,13 which leaves no doubt that calciferol corresponds to the structure (5). The mole- cule is subject to interference between the hydrogen atoms attached to positions 7 and 19 and the inter- cyclic diene system does not lie in a plane; no doubt this provides the driving force for the cis +trans iso- merisation mentioned above.When account is taken of the light absorption Amax. 220 mp (E 10,0o0) of 1 :2-dirnethylene~ycZuhexane,~~ which contains an s-cis-diene system similar to that in calciferol the wavelength and intensity of the calciferol absorption are satisfactorily explained by the structure (5). Calciferol isomers with a cis-7-geometry are as yet unknown. The cis-5-cis-7-structure (7) which would be subject to hindrance between the hydrogen atoms at positions 6 and 15 as well as at 7 and 19 should show less intense absorption than calciferol and Braude and Wheeler15 suggested this structure might therefore represent precalciferol. This was later ruled out when it was found16 that precalciferol shows no Velluz and Amiard Compt. rend.1949 228 692. Velluz Amiard and Petit Bull. SOC. chim.France 1949 501. Verloop Koevoet and Havinga Rec. Trav. chim. 1957 76 689. (a) Heilbron R. N. Jones Samant and Spring J. 1936 905; (b) Windaus and Thiele Annalen 1936 521 160; Windaus and Grundmann ibid. 1936 524 295. * Crowfoot and Dunitz Nature 1948 162 608. Sondheimer and Wheeler Chem. and Znd. 1955 714. loHarrison Lythgoe and Trippett Chem. and Ind. 1955 507; J. 1955 4016. l1 Koevoet Verloop and Havinga Rec. Trav. chim. 1955 74 788 1125. la Inhoffen Quinkert Hess and Erdmann Chem. Ber. 1956 89 2273. l3 Hodgkin Webster and Dunitz Chern. and Ind. 1957 1148. la Bailey and Golden J. Amer. Chem. Soc. 1953 75 4780. l5 Braude and Wheeler J. 1955 320. l6 Velluz and Amiard Bull. Soc. chim. France 1955 205.MAY1959 infrared band near 895 m.-l (i.e. has no =CHJ and gives only traces of formaldehyde on ozonolysis. (I 2) (I 3) (I 4) The gross structure (3) earlier assigned to tachy- sterol has proved correct despite a proposal1s to re- place it by the structure (9). The latter is compatible neither with the formation from tachysterol and cal- ciferol of a common dihydro-compound (12) nor with the rapid formation of an adduct (at positions 6 and 9) between tachysterol and citraconic anhydride. The structure (9) belongs in fact to an isomer u-tachysterol,17 which Inhoffen and his co-workers have obtained as follows. Isomerisation with Lewis acids of either calciferol or tachysterol givesl8J9 iso-tachysterol (1 l) from which by oxidation the con- jugated trienone (10) is obtained.On reduction this furnishes u-tachysterol. The geometry of tachysterol was for long un- decided. Its rapid reaction with dienophiles pointed to the tr~ns-6-geometry,2~ but the low intensity of its ultraviolet absorption [Amax. 281 mp (E 24,600)] has been held 21 to favour the &-structure (3). Infrared evidence (bands at 957 cm.-l in both tachysterol,lg and tachystero1,'l) now points decisively to the trans-6-structure. Models show that in the conforma- tion (13) this structure is subject to interaction be- tween the hydrogen atoms at positions 6 and 15 so that the s-cis-7:s-conformation (14) may well be preferred. In this way the low-intensity light- absorption of tachysterol is accounted for; isotachy-sterol in which similar steric interactions are absent shows absorption of normal intensity having hmax.289.5 mp (E 45,300). There is now strong evidence that the old cis-tachysterol structure (3) more appropriately written in the preferred conformation (15) belongs to pre-calciferol. Havinga and his co-workersll showed that precalciferol is isomerised to tachysterol by iodine under conditions indicating a cis+trans stereomuta-tion. Velluz and his co-workers22 reached the same conclusion from a study of the monoepoxide (1 6) de- rived from precalciferol. The dienoid light-absorp- tion of the epoxide establishes that precalciferol itself is a conjugated triene. When the epoxide ring is opened with acid anionotropic change takes place giving the disecondary monotertiary trio1 (17) which as shown by light-absorption data contains an inter- cyclic diene system.HO (1 71 During the conversion of precalciferol into calciferol it seems likely that the molecule assumes the conformation (3) in which the carbon atoms 9 and 19 are close enough for an intramolecular trans- fer of hydrogen between them possibly via the cyclic transition stale (18). This remarkable reaction is un- likely to be ionic since it can take place in light petroleum and is subject neither to acidic nor basic catalysis.6 The results described above require the classical irradiation scheme (1) +-(4) to be discarded; how is it to be replaced? No generally agreed scheme is yet available although the irradiation process has been studied qualitatively by kinetic and quantum yield l7 Inhoffen Bruckner Irmscher and Quinkert Chem.Ber. 1955 88 1424. Inhoffen Bruckner and Grundel ibid. 1954 87 1. l9 Inhoffen Bruckner Grundel and Quinkert ibid. p. 1407. 2o Alder and Schumacher Fortschr. Chern. org. Naturstofe 1953 10 1 (p. 74). 21 Koch Chem. and Ind. 1942 61 273. 22 Velluz Amiard and GoBnet Compt. rend. 1955,240 2076; BuL?. SOC.chim. Frunce 1955 1341. rnea~urements,~~ and by the use of isotopically labelled intermediate^.^^ It is agreed that neither lumisterol nor tachysterol is a necessary intermediate on the path to calciferol. The first major product22 formed from ergosterol is precalciferol (yields up to 85 %) ;since this has the cis-structure earlier accorded to tachysterol the logic of the classical scheme in this of respect is restored.Irradiati~n~~ precalciferol gives in a reversible reaction tachysterol the forma- tion of which is especially favoured by light of 254 mp2* Minor amounts of lumisterol and ergosterol are also formed in this way.22,26 It is not yet clear whether lumisterol and tachysterol can also arise directly from ergosterol or in other ways. In sum-mary it appears that if intermediate excited states are neglected the simplest scheme due to Velluz and his co-workers,22 is capable of accounting for much of the observed reaction Ergosterol Precalciferol Tachysterol Calciferol Two further structural questions in the vitamin D field require discussion; the first concerns the stereo- chemistry of the four ergosterol isomers differing in configuration at positions 9 and 10.These are ergo- sterol lumisterol pyrocalciferol and isopyrocal-ciferol the last two being the products of thermal cyclisation of calciferol. isoPyrocalcifero1 was known to differ from ergosterol only at position 9 since both give a common 9 :1 1 -dehydro-compound ; isopyro-calciferol is therefore the 9p:lop-isomer (24). Lumi- sterol was formerly2'v2 thought to be the 9a:lOa- isomer but decisive new experiments due to E. R. H. Jones and his co-workers% and outlined in the formulae (19) to (24) now require this view to be revised. Oppenauer oxidation of lumisterol and acid- catalysed isomerisation of the product gives the con- jugated dienone (20) from which the enone (21) is formed by selective hydrogenation.The 6-keto-acid (22) which results from ozonolysis of the enone (the side-chain double bond being protected) is converted by a retro-Michael reaction into the tricyclic ketone (23). During this sequence configurational changes are possible (and occur) at positions 8and 10 but no change is possible at position 9. A similar sequence of reactions converts isopyrocalciferol into the same PROCEEDINGS ketone (23) so that this ketone and also lumisterol must have the 9p-configuration. Lumisterol is there- fore established as the 9/? 1Oa-and pyrocalciferol as the 9a:10a-isomer. These results bring into prominence the remark- able stereospecificity of three reactions.The thermal cyclisaton of calciferol is seen to yield only the two syn-9:10-isomers. The two syn-9 :1 0-isomers behave quite differently on irradiation from the two anti- 9 10-isomers. Whilst the anti-isomers yield precal- ciferol each syn-isomer yields a corresponding photo-compound; Dauben and F~nken~~ have identified these as valency tautomers of the parent compounds. Thus photoisopyrocalciferol (26) is transformed into isopyrocalciferol in ethyl deuter- oxide at 160" without uptake of deuterium and the derived ketone (27) is isomerised by alkali giving the conjugated dienone (28). The presence of the cyclo-butene double bond in the photo-compound (26) is shown by infrared and nuclear magnetic resonance measurements and also by the ready anhydride formation displayed by the tribasic acid (25) ob-tained from the photo-compound by ozonolysis.Photopyrocalciferol has a structure differing from that of photoisopyrocalciferol in the stereochemistry at positions 9 and 10. This account of work on the structural side may be concluded by reference to results of Dauben and his co-w~rkers~~ on suprasterol-11 which is one of the products of irradiation of calciferol. On the basis of oxidative and reductive experiments supported by 23 Rappoldt Keverling-Buisman and Havinga Rec. Trav. chim. 1958 77 328. 24 Havinga Verloop and Koevoet ibid. 1956 75 371. 26 Velluz Amiard and Goffinet Compt. rend. 1955 240 2156. 26 Rappoldt Westerhof Hanewald and Keverling-Buisman Rec.Trav. chim. 1958 77 241. 27 Kennedy and Spring J. 1939 250. 28 Castells E. R. H. Jones Williams and Meakins Proc. 1958 7. 20 Dauben and Fonken J. Amer. Chem. Soc. 1957 79 2971. 30 Dauben Bell Hutton Laws Rheiner and Urscheler ibid. 1958 80 4117. MAY1959 very effective use of ultraviolet infrared and nuclear magnetic resonance data they formulate it as the spiro-compound (30; R = CDH17). The correspond- ing dihydro-compound (30; R = CDHlD) is shown to contain a cyclupropane ring (devoid of methylene groups) in conjugation with a tetrasubstituted double bond. The cyclupropane ring is readily hydro- genolysed giving a tetrahydro-compound (32) inert to further hydrogenation. Oxidation of the hydroxyl group of dihydrosuprasterol-I1 gives a product with an unconjugated carbony1 group ; isomerisation by alumina then gives a ketone (31) in which the car- bony1 group the double bond and the cyclopropane system are all in conjugation.Related experiments on tetrahydrosuperasterol-I1 indicate that the double t R R bond in the ketone (31) is trisubstituted and semi- cyclic to a six-membered ring. These results are inter- preted in terms of the structure (30; R = C,HI7)for suprasterol-11 and its photogenesis is expressed by the formula (29 arrows). Synthesis.-Attempts to synthesise calciferol and tachysterol by methods which emphasise their nature as conjugated trienes have been made since the time when their structures were first known and recently interest in the problem has been renewed.Here attention is confined to the vitamins themselves although some progresP has been made in studies in relation to tachysterol and precalciferol. It should be mentioned that the formal total syntheses of cholesteroP2 also constitute syntheses of calciferol, precalci ferol and tach ys terol 3. All three double bonds in the conjugated system of calciferol are semicyclic to cyclohexane rings. Such double bonds are known to have a relatively high energy content,= and difficulties arise when attempts are made to introduce them by elimination reactions subject to Saytzeff-type control. These difficulties were early apparent from experiments by Burkhardt= and by Dimroth= on the synthesis of the model semicyclic triene (39) and its derivatives.The tertiary alcohol (35) is obtained from the conjugated dienone (34) formed in an aldol reaction between cyclo-hexanone and cycluhexylideneacetaldehyde (33). Elimination of water from the tertiary alcohol fails to provide the model triene (39); instead the new double bond is introduced into the endocyclic posi- tion giving the isomeric triene (36).=9% Advances in the theory of elimination reactions3’ provide a means of avoiding this difficulty. A Hof-mann elimination from the tertiary amine (38) may lead either to the fully conjugated triene (39) or to the diconjugated monoendocyclic isomer (37) ; it seemed probable that the effect of the extra conjuga- tion in the transition state leading to the fully con- jugated triene (39) would favour the formation of this isomer.This expectation was verified experi- mentally.= 31 For summary see Inhoffen “Festschrift Arthur Stoll,” Birkhauser Verlag Basel 1957 p. 519. 32 Woodward Sondheimer Taub Heusler and McLamore J. Amer. Chem. Suc. 1952 74 4223; Cornforth and Robinson J. 1953 361. a3 Wallach Annalen 1908 359 287; Brown Brewster and Schechter J. Amer. Chem. SOC.,1954 76 467. 34 Aldersley and Burkhardt J. 1938 545; Aldersley Burkhardt Gillam and Hindley J. 1940 10. 36 Dimroth Ber. 1938 71 1333 1346; Dimroth and Jonsson Ber. p. 2658. 36 For the synthesis of “isovitamin Da”by parallel methods see ref. 18. 37 Ingold “Structure and Mechanism in Organic Chemistry,” G. Bell and Sons London 1953 Chapter VIII.38 Lythgoe Trippett and Watkins J. 1956 4060. PROCEEDINGS In 1954 Wittig and SchollkopP9 described their new method of olefin synthesis from carbonyl com- pounds and alkylidenetriphenylphosphoranes.The method provides olefins of unambiguous structure and is thus exceptionally well suited to the construc- tion of semicyclic double bonds; it has provided 4 the key to advances in vitamin D synthesis. In the writer's laboratory it was first usedlO to prepare the amino-diene (42) from the phosphorane (40) and the Mannich base (41). The amino-diene was then converted40 by the Hofmann method into the model triene (39) identical with that prepared by the earlier route. We hoped that some of the cis-isomer (43) of the amino-diene (42) might be formed along with the latter since both geometric forms of olefins can sometimes be obtained39 from Wittig reactions but here formation of the cis-isomer was apparently 17 prevented by the bulky dimethylamino-group.The cis-amino-diene (43) would of course provide a method of preparing the cis-triene (47) which has an ~~~ unsaturated system identical with that of calciferol. That the triene (39) had the trans-configuration was shownlO by its rapid reaction with maleic an- hydride giving the acid (44)which is an analogue of the adduct (45) similarly formed (in a slow reaction) from calciferol. A third and most convenient method of preparing the trans-triene (39) was available in the Wit t ig reaction bet ween methylene trip hen ylp hos- phorane and the conjugated dienone (34).As ex-pected from its origin% in an aldol reaction this di- enone has the trans-c~nfiguration.~~~~~ Adequate means of constructing semicyclic double bonds being thus available the problem of obtaining the central cis-double bond in the triene system of calciferol remained for study. One solution was foundm in the well-known@ ultraviolet irradiation method of converting trans- into cis- ag-unsaturated ketones. Irradiation of the trans-dienone (34) gave the cis-dienone (46) which was then converted by a Wittig reaction into the model cis-triene (47). As ex-pected this showed light-absorption very similar to that of calciferol and less intense than that of the trans-triene (39).Like calciferol it reacted slowly with maleic anhydride giving a stereoisomer of the adduct (44). R yJ+p R OAc -p OHC' (48) These reactions were then extended43 to provide a partial synthesis of calciferol from the aldehyde (48; R = C,H,,) whichis a product of the oxidative degradation of calcifer01.~~ In previous workla this 3s Wittig and Schollkopf Chern. Ber. 1954 87 1318. 4oA similar preparation of the triene has been reported by Inhoffen Bruckner Domagk and Erdmann Chem. Ber. 1955 88 1415. 41 For examples of the formation of cis-enones in aldol reactions see Bentley and Firth J. 1955 2403; cf. Milas and Priesing J. Amer. Chem. Soc. 1957 79 3610. 42 The view (Milas and Priesing J. Amer. Chem. Soc. 1957 79 6297) that the crystalline product from 4-methoxy- cyclohexanone and cyclohexylideneacetaldehydeis a mixture of cis-and trans-formsis supported by no reliable evidence.43 Harrison and Lythgoe Proc. 1957 261 ;J. 1958 837. ** Paal and Schulze Ber. 1902 35 168; Lutz and Jordan J. Amer. Chem. Soc. 1950 72,4090; Buchi and Yang ibid. 1957 79 2318. 46 Windaus and Riemann 2. physiol. Gem. 1942 274 206; ref. 7(a). MAY 1959 aldehyde had been condensed with 4acetoxycycZu- hexanone giving a mixture of the two epimers of the trans-dienone (49; R = C9H17). Irradiation of the mixed epimers gave a mixture of the cis-isomers (52) which were converted into trienes by a Wittig reac- tion. The epimeric products separated* as 3 :5-di-nitrobenzoates provided after hydrolysis calciferol (53; R = CgH17) and 3-epicalciferol (51; R = C9H17) isolated as the p-nitrobenzoate.This p-nitrobenzoate has also been obtainedM by ir-radiation of 3-epilumisterol (50) which confirms its structure. In experiments commencedP7 at about the same (50) A time as those of the writer's group Inhoffen and his colleagues studied an alternative route to the vitamins D in which the Wittig reaction is used for the synthesis of the trans-5-isomers of the vitamins. They showed@ that the trans-isomers obtained11J2 from the vitamins by isomerisation with iodine are partially reconverted into the cis-forms by irradia- tion in glass so that a synthesis of a trans-isomer constitutes a synthesis of the corresponding vitamin. Initial experimentsg7 on the synthesis of trans-5-cal- ciferol used as starting material the mixed epimeric trans-dienones (49; R = CgH,,) which were pro- tected as tetrahydropyranyl derivatives.Reaction with methylenetriphenylphosphorane gave corres- ponding mixed epimeric trienes as an oil but removal of the protecting groups failed owing to the sensitivity to acids of the trans-triene system. In later the mixed acetyl derivatives of the epimeric trans- dienones (49; R = CgH17) were subjected to a Wittig reaction hydrolysis of the product then providing crystalline material which was regarded as a mixture of the epimers (54 and 56; R = CgH17); the optical- rotation data show that the proportion of trans-5- calciferol(56; R = C9H17) is low and its separation from the synthetic material has not so far been re ported.In the vitamin D series however as an- nounced very recently,50 Inhoffen and hisco-workers 62) HO"o", have successfully separated both epimers of the trans-dienone (55; R = C,H,,) and by means of Wittig reactions have obtained from them trans-5- calciferol (56; R = C8H17) and its epimer (54; R = C8H1 7)* f' Inhoffen Quinkert and SchutzSl converted the bicyclic ketone (57) obtained from vitamin D by ozonolysis into the diene (58); partial ozonolysis of this dime gave the ab-unsaturated aldehyde (48; R = C8H17) identical with material obtained by de gradation of vitamin D,. Since this aldehyde formed the starting material for the above synthesis of trans- 5-calcifero13 it is clear that a synthesis of the bicyclic * (Added in proqf) Similar work in the vitamin Dz,field has now been accomplished by Inhoffen Irmscher Hirschfeld Stache and Kreutzer Chem.Ber. 1958 91 2309. t (Added in proof.) As pointed out by Tnhoffen and his collaborators (Chern. Ber. 1958 91 2309) this .separation yields epicalciferyl 3 :5-dinitrobenzoate as a 1:1-complex with calciferyl 3 :5-dinitrobenzoate; the complex IS however resolved after conversion into the p-nitrobenzoates (ref. 46). 46 Harrison Hurst and Lythgoe unpublished work. 47 Inhoffen Kath and Bruckner Angew. Chem. 1955 67 276. c8 Inhoffen Quinkert and Hess Naturwiss. 1957 44 11; Inhoffen Quinkert Hess and Hirschfeld Chem. Ber. 1957 90 2544. Inhoffen Kath Sticherling and Bruckner Annalen 1957 603 25.50 Lecture by Inhoffen reported in Angew. Chem. 1958,70 576. 61 Inhoffen Quinkert and Schiitz Chern. Ber. 1957 90,1283. 148 ketone (57) would complete a new total synthesis of vitamin D through the intermediates bicyclic ketone (57) -+ c$-unsaturated aldehyde (48; R = CIH1,)-+trans-5-calcifero13+vitamin D,. 0 (57) The synthesis has now been completed50 in a notable manner. Inhoffen and earlier pre- pared the acid (60) from the Hagemann ester (59) and ethyl /3-chloropropionate ;addition of hydrogen cyanide and hydrolysis then gave the dibasic acid (61). Details of the subsequent steps are not yet avail- able but the acid (61) was apparently resolved and converted into the dibasic ester (62). Reference com- pounds were available from a degradations3 of vitamin D, ozonolysis and reduction of which gave the bicyclic alcohol (63); further degradation by OH (68) standard methods then gave successively the alde- hydes (64and 65; R = Ac) and finally the hydroxy- ketone (66).The same hydroxy-ketone (66) was obtained syntheticallys0 by cyclising the dibasic ester (62). It wasconverted by a Grignard reaction into the tertiary PROCEEDINGS alcohol (69); hydroxylation and glycol fission then gave geometrical isomers of the unsaturated aldehyde (65; R = H). The isomer shown was reduced with lithium in ammonia to the aldehyde (64;R = H) which had the required configurations at positions 17 and 20. A Wittig reaction converted the aldehyde into the unsaturated alcohol (68) which was then hydrogenated to the alcohol (67).This alcohol had previouslyM been oxidised by chromic oxide-pyridine to the trans-fused bicyclic ketone (57) so completing the synthetic chain. The syntheses so far available make use of photo- chemical reactions and although this in no way detracts from their interest it is ironical to reflect on the ease with which if ultraviolet light is used cal-ciferol may be obtained from ergosterol. In my view therefore a purely chemical method of synthesis 6H (69) would have its interest especially since it might con-firm independently the cis-5-trans-7-geometry of the vitamins which the photochemical methods do not. Pursuing this aim,it has been shown in model experi- ments& that the bicyclic lactone (70) which contains a preformed cis-double bond can be converted into s8 Inhoffen and Prim ibid.1954 87 684. 6a Inhoffen Quinkert Schutz Friedrich and Tober ibid. 1958 91 781. 54 Inhoffen Quinkert Schutz Kampe and Domagk ibid. 1957 90 66l. 66 Harrison and Lythgoe J. 1958 843. MAY1959 the cis-triene (47) previously obtained by the photo- chemical route. This was carried out by a selective attack on the primary hydroxyl group of the diol(71) which was first converted by Landauer and Rydon’sSO reagent into the monobromide and then into the phosphonium bromide (72). The derived Wittig re- agent gave with cyclohexanone the cis-dienol (73) which was oxidised by manganese dioxide to the cis- dienone (46).This was transformed into the cis-triene (47) by a Wittig reaction. Landauer and Rydon J. 1953 2224. Similar methods may I hope provide a chemical synthesis of vitamin D,. I acknowledge gratefully the valuable help of my collaborators in work mentioned in this lecture; particularly of Dr. S. Trippett in earlier stages and of Dr. I. T. Harrison in later stages. I would also thank for their past encouragement Sir Ian Heilbron whose early work on calciferol stimulated my in- terest in this field and Sir Alexander Todd who directed my first steps in synthetic chemistry. COMMUNICATIONS The Reactivity of Anions towards Acylating Agents By M. GREEN and R. F. HUDSON (QUEENMARYCOLLEGE, LONDON E.l) VARIOUSempirical equations relating the rate constant for a substitution to some characteristic property of the reacting anion have been proposed recently.lp2 The following typical reactivity order for a series of anions participating in bimolecular (S,2) displacements is similar to that for the corresponding oxidation-reduction potentials:2 S20 > SCN > I > N >OH > Br > C1 > AcO > H20.This cor- relation may be attributed to the relatively weak (p/2) bonding in the transition state so that changes in the activation energy follow the solvation energies and ionisation potentials of the ions. In kinetic studies of the reactions of acyl halides we have established an entirely different rate order for the reaction of anions with ethyl chloroformate in aqueous solution.Representative values of some of the rate constants (ka are given in the Table. Rates of reaction of anions with ethyZ chloroformate in 85:15 water-acetone (v/v) at 25”. Cl.C02Et Reagent and k2 concn. (N) concn. (N) (1. mole. min.-l) 0.011 0.014 0.010 0.005 0.005 0.0055 0.005 0.030 F-0.085 0.24 N3-0.015 17-5 NO2-0.030 32.2 PhOH 0.025 (pH 7) 90-6* Acetoxime 0.028 (PH 7) 506 x lo3* Acetoxime 0.028 (pH 6) 501 x lo3* OH-0.020 169 tS2032-0.030 (PH 7) 0.60 * Calc. from concn. of anion. t Reaction at Et group. [Chloride bromide iodide cyanate thiocyanate Scott and Swain J. Amer. Chem. SOC.,1953 75 146. a Edwards ibid. 1954 76 1540; 1956 78 1819. Bruice and Lapinski ibid. 1958 80 2265.chlorate and nitrate ions have no effect (within experimental error) on the rate of reaction.] It is not proposed to analyse this rate order theoretically here but the following points are made. (1) Only ions derived from first-row elements are reactive under these conditions. This shows the im- portance of the bond-forming energy in the transi- tion state which probably resembles a tetrahedral intermediate. (2) Acetoxime (pK ’L 12.5) is ca. 3 x lo3 times more reactive than the hydroxide ion and the phenoxide ion (~K,‘L10) is almost as re- active as the latter. Similar observations have recently been made in the reactions of p-nitrophenyl esters of carboxylic acids.3 This “abnormal” reactivity of highly basic oxy-anions is characteristic of the ion and not of the bond type in the transition state since it is also observed in phosphorylati~n~ and in acid- base cataly~is.~ The different nucleophilic orders for alkylation and acylation may find various mechanistic applica- tions e.g.the prediction of (a) the reaction centre when the substrate contains alternative electrophilic groups6 and (b) the nature of the product when the anion contains alternative nucleophilic atoms. For example the thiocyanate ion gives alkyl thiocyanates with alkyl halides and acyl isothiocyanates with acyl halides in non-aqueous solvents. RSCN + X-+-SCN--+ R(C0)NCS + X-Rx RCOX We acknowledge financial support from the Central Research Fund of the University of London. (Received March 17th 1959.) Dostrovsky and Halmann J.1953 503. Bell and Higginson Proc. Roy. Soc. 1949 A 197 141. * Harper and Hudson J. 1958 1356. 150 PROCEEDINGS New Iron-Acetylene-Carbonyl Complexes By J. R. CASE,R. CLARKSON, E. R. H. JONES,and M. C. WHITING (THEDYSON LABORATORY, PERRINS OXFORD) IT has recently been shown' that the acidic For these complexes we propose formula (111) i r on- h y d r oc a r b on y 1-ace t y 1e ne c~mplexes~~~ which implies that the ethylenic linkage is not bonded H [RC= CR',Fe,(CO),] possess structures in which a central grouping (A) is attached to two linked (OC),Fe residues. In addition to confirming this contention Hock and Mills4 have now proved by X-ray analysis that in the solid this grouping is asym- metrically placed (cf.I) the two iron atoms being therefore nonequivalent. It remains to be decided (a) whether a similar geometry is maintained in solution and if so (6)whether the symmetrical configuration (11) represents a potential energy maximum suffici- ently high to allow e.g. the isolation of suitably substituted derivatives in diastereoisomeric forms. Chemical evidence reported below suggests an affirmative answer to question (a). Oxidation of these complexes in acidic media Cpreferably with ferric chloride) leads to loss of one iron atom as Fe++ and the formation of a series of complexes RCrCR',Fe(CO), isolated in the cases where (i) R = R' = H Me Et or Ph and (ii) R = H and R' = Me Et Bu or Ph. All these eight compounds are stable and the simpler of them are volatile.When R = R' = Me further oxidation with cold concentrated nitric acid gave dimethylmaleic an- hydride. to the metal atom. In agreement with this view treatment of the simplest complex with cyclo-pentadiene resulted in a normal Diels-Alder reaction giving the almost colourless adduct (IV). Treatment with zinc and acetic acid converted the compound (111; R = R' = H) into a colourless dihydro- derivative which gave succinic acid on oxidation. These new complexes are thus simply cyclic acyl derivatives of hydridocarbonyliron analogous to the compound5 AcMn(CO),. Their reactions and question (b) above are now under investigation in these laboratories. (Received February 19t/z,1959.) Clarkson Jones Wailes and Whiting J.Amer. Chem. SOC.,1956 78 6206. Reppe and Vetter Annalen 1953 582 133. Wender Friedel Markby and Sternberg J. Amer. Chem. Soc. 1955 77 4946 ; 1956 78 3621. Hock and Mills Proc. Chem. Soc. 1958 233. Coffield Kozikowski and Closson J. Org. Chem. 1957 22 598. Mundulone By B. F. BURROWS, N. FINCH,W. D. OLLIS,and I. 0. SUTHERLAND (THE UNIVERSITY BRISTOL) THEbark of Mundulea sericea yields as the principal extractive a colourless compound C2,H2,06 m.p. 180" which we have called mundulone. It is probably identical with "Mundulea substance A" which was isolated earlier1 but was then given the formula C25H2406-Mundulone [cc]~~,,- 11.5" (in CHCI,) contains one methoxyl group one alcoholic hydroxyl group [vmax. 3600 3395 (in CHCI,)] and one con- jugated carbonyl group [Vmax.1631 cm.-' (in CHCI,)]. It forms a monoacetate m.p. 190" mono-benzoate m.p. 164" and monomethanesulphonate m.p. 206". Catalytic reduction of mundulone [Am,, 244 (E 42,600) 252 (E 42,100) 309 (E 16,800) and 312 m,u (E 16,100) (in EtOH)] gave dihydro-mundulone m.p. 200" [Amax. 244 (E 32,000) 252 (E 32,400) 309 mp (E 18,000) (in EtOH)] and these spectral changes indicate that the reducible double bond in mundulone is remote from the main chromo- phoric system. Mild alkaline hydrolysis of mun-dulone gave munduletone C2,H,,0,.0Me m.p. 160" and formic acid. Munduletone contained an o-hydroxycarbonyl function [vmax. 1641 cm.-l (in CHCl,) 1 and methylation of its phenolic hydroxyl group gave its methyl ether m.p.150" [vmax. 1666 cm.-l (in CHCI,)]. It was shown that mundul- etone is in fact a deoxybenzoin which required mundulone to be an isoflavone thus locating the Rangaswami and Narayana J. Sci. Znd. Res. India 1955 14 B 105. MAY 1959 fourth oxygen in a pyrone ring. The other two oxygen atoms are shown to be ethereal in the sequel. Mundulone was proved to be an isoflavone because it was resynthesised from munduletone by heating it with ethyl orthoformate-pyridinepiperidine.2 Biogenetic reasoning led us to examine the possibility that mundulone (C2& might be an iso- flavone (C15) bearing two isoprene residues (2 x C5) and one methoxyl group and later experiments demonstrated that this was the case. Demethylation of mundulone by hydrobromic-acetic acid followed by oxidation with alkaline peroxide gave mun-duloxic acid C12HIdO5 m.p.195 ",whose character- isation as a salicylic acid [vmax 1650 cm.-l (in Nujol)] showed that one isoprene group was associated with each of the two benzene rings in mundulone. This was proved by peroxide oxidation of dihydromunduletone methyl ether m.p. 128" prepared from dihydromundulone by hydrolysis and methylation. This produced a mixture of two acids m.p. 145" C12H130,~OMe (69 %yield),andm.p. 118" C12H,,0,*OMe (62 % yield) so that these acids each contain one of the benzene rings of the isoflavone structure. The acid C12H1304*OMe was the methyl ether of munduloxic acid. The other acid m.p. 118" [Amax. 259 mp (E 14,500) (in EtOH); vmax 1679 cm.-l (in Nujol)] was demethylated and gave a salicyclic acid [vmax 1650 cm.-l (in Nujol)] which was identified as dihydro-p-tubaic acid (I; R = H) by direct comparison with a specimen prepared from rotenone.Thus the acid m.p. 118" was dihydro-p- tubaic acid methyl ether. Similarly oxidation of munduletone methyl ether gave munduloxic acid methyl ether and an acid m.p. 11 1 ",C12Hl10,~OMe in which the double bond was styrenoid [Amax. 244 mp (E 25,600) (in EtOH)]. This acid m.p. 11 1 " [vmax. 1733 1688 1640 cm.-l (in CHCI,)] was re- duced to the acid (I; R = Me) so that it must be j3-tubaic acid methyl ether (II; R = Me). Oxidation of dihydromunduletone by alkaline peroxide gave a compound mp. 106" Cl,H1503*OMe which must be the phenylacetic acid corresponding to the benzoic acid (I;= Me).These experiments establish the R positions of the double bond and the methoxyl group and lead to the partial structure (111) for mundulone. The elucidation of the structure of mundulone was thus reduced to the determination of the structure of munduloxic acid which involves the undefined (C5H1202) residue in the partial structure (111). Munduloxic acid C12H1405 is a salicylic acid [vmax. 1650cm.-l (in Nujol)] forming a monomethyl ether m.p. 145" [vmax. 1708 1680 cm.-l (in Nujol) 1724 cm.-l (in CHCI,)] and a monomethyl ether * Sathe and Venkataraman Current Sci. (India) 1949 18, Haller J. Amer. Chem. SOC.,1931 53 733. Bowden Heilbron Jones and Weedon J.1946 43. Nickl Chem. Ber. 1958 91 1372. methyl ester [vmax. 3600 3450 1714 cm. (in CHCI,)] characterised as a monoacetate n1.p. 92.5" and a monomethanesulphonate m.p. 102". Thus munduloxic acid contains the hydroxyl group which corresponds to the hydroxyl group in mundulone and since its ultraviolet spectrum and those of its derivatives show that it is a 2,4-dioxygenated benzoic acid this leads to the partial structure (IV) for munduloxic acid. Mundulone is not easily changed by acidic reagents and its methanesulphonyl derivative is stable under solvolytic conditions so that its hydroxyl group is not tertiary or benzylic. However alkaline treatment of methyl munduloxate methyl ether methane-sulphonate gave an acid m.p. 105" C12H,10,*OMe which was isomeric with /3-tubaic acid methyl ether (II; R = Me) but was still styrenoid [Amax.238 mp (E 38,600) (in EtOH)]. Oxidation of munduloxic acid by permanganate gave acetone and oxidation of its methyl ether with the Jones reagent4 gave an uncon- jugated ketonic acid Cl,Hl104*OMe [vmax. 1730 1690 1670 cm.-l (in Nujol); Amax. 247 (E SOW) 295 mp (E 3700) (in EtOH)]. (V 0 These facts lead to one structure cv) for mun- duloxic acid and the structure of mundulone is therefore (VII). Synthetical evidence confirming this structure was provided by a re-investigation of the reaction of 2-methylbutyn-2-01 and methyl resorcyl- ate. In addition to the p-tubaic acid (II; R = H) isolated previou~ly,~ chromatography yielded an iso- meric acid m.p.136". The synthetic /3-tubaic acid 373. gave a methyl ether (11; R = Me) identical with the acid m.p. lll” obtained by oxidation of mundul- etone methyl ether. The other acid m.p. 136” gave a methyl ether (VI) identical (ultraviolet and infra- red spectra m.p.) with the anhydro-derivative m.p. 105”,of munduloxic acid methyl ether. Mundulone is an isoflavone of novel complexity. PROCEEDINGS It is the first natnrally occurring 2,2-dimethyl- chroman-3-01 and it is the first CI5 plant-phenolic with isoprene groups associated with both the A and the B ring. Its structure has implications concerning biosynthesis of isoflavones. Satisfactory analytical data are available for all compounds described in this communication.(Received April 13th 1959.) Biogenesis of Papaverine by A. R. BATTERSBY and B. J. T. HARPER (THEUNIVERSITY, BRISTOL) NORLAUDANOSOLINE (11; R = H) and similar l-benzyl-l,2,3,4-tetrahydroisoquinolines are regarded in biogenetic theory as key intermediates for many of the large group of isoquinoline a1kaloids.l Elucidation of the biogenesis of a benzylisoquinoline alkaloid must therefore come early in our wider study of alkaloid biogenesis and papaverine (rU) was selected as a convenient case. produced in the oxidation step was inactive. Ozono- lysis of the acid (V) yielded one of the atoms marked *C as formaldehyde and the other was isolated as carbon dioxide on decarboxylation. Within the limits of experimental error the original activity of the papaverine is thus shown to be divided equally between the two carbon atoms marked * a result Full arrows indicate conversion in the laboratory.Broken arrows indicate postulated route in the plant. Papaver somniferurn plants were fed with DL-which establishes the biogenesis of papaverine from [2-14C]tyrosine(I) and the isolated papaverine was two molecules of tyrosine. purified to constant activity as the picrate; this Kleinschmidt and Moths4 have now reported activity is taken as 1-0 and the activities of the experiments on another benzylisoquinoline alkaloid degradation products are calculated relatively to it. narcotoline which indicate that two molecules of They are shown as figures under the formula. Reduc- tyrosine are involved in the biogenesis.However tion of the papaverine methiodide with potassium generally labelled tyrosine was used as the precursor borohydride2 yielded laudanosine (11; R = Me) and the difficulty of interpreting such an experiment which by Hofmann degradation was converted into led the authors to the view that conclusive evidence This was oxidised and the amino- must come from the use of specifically labelled pre- the methine (JY). acid fraction was further degraded by Hofmann’s cursors. The foregoing work on papaverine provides method to yield the acid3 0;the veratric acid (VI) this conclusive proof. (Received March 5th 1958.) Winterstein and Trier “Die Alkaloide,” Borntraeger Berlin 1910 p. 307; Robinson “The Structural Relations of Natural Products,” Clarendon Press Oxford 1955 and refs.therein. Garratt B.Sc. Thesis Bristol 1956; Mirza J. 1957 4400. a Kondo and Mori J. Pharm. SOC.Japan 1931 51 615. Kleinschmidt and Mothes Z. Naturforsch. 1959 146 52. MAY1959 153 Complex Hydrides and Alkyls of Ruthenium and a Hydride of Osmium By J. CHATT and R. G. HAYTER CHEMICAL LIMITED LABORATORIES, (IMPERIAL INDUSTRIES AKERSRESEARCH THE FRYTHE HERTS.) WELWYN AFTER discovery of the very stable trans-planar (PEt,)2PtHC1,1*2we have looked for similar complex hydrides of octahedral configuration. For maximum stability we have employed chelate ligands and examined complexes of the formula [(chelate),MX,] (X = halogen M = Ru and 0s) as parent sub- stances. The known complexes of this type e.g.[{o-C,H,(ASM~~),),MX,],~ appear to have trans- configurations and could not be reduced to hydrides but a new series of cis-isomers derived from ruthen- ium halides are reduced by lithium aluminium hydride to halogeno-hydrides of the type trans-[(chelate),RuHX]. The chelate groups employed in this way are C2H,(PMe2), C,H,(PEt,), and o-c,H,(AsMe,),. The complex hydride derived from the diarsine is unstable but those derived from the diphosphines are stable enough to be handled in air. They are colourless or pale yellow diamagnetic solids decomposing with melting in the temperature range 120-220". They are rather less stable than their platinum analogues trans- [(PR,),PtHX]. Organic solvents dissolve them readily and they decompose slowly in hygroscopic solvents.The solid hydrides also decompose slowly in contact with moist air but can safely be stored in dry nitrogen. They dissolve in dilute ammonia and can be reprecipitated unchanged by acid provided the operation is done quickly. They also react with the appropriate halogen acid to re- generate the original cis-[(diphosphine),RuX,] which in the case of the chlorides are soluble in water. The infrared spectra of the hydrides have a strong sharp band in the region 1800-1950 cm.-l which can be assigned to the Ru-H stretching mode of vibration (see Table). It is to be noted that changing the halogen from chlorine to iodine raises the Ru-H frequency and so the Ru-H bond strength contrary to expectation on the basis of the trans- effects of the halogens and the observed sequence in the platinum series.2 The configurations of the hydrides were deter- mined from their dipole moments and nuclear mag- netic resonance spectra.The dipole moments are high e.g. [{C2H,(PEt~2}2RuHI] has a moment of 5-73 D; but using the platinum(I1) compounds as models we estimate that this is not unreasonable and that the cis-isomer should have a moment of about 8 D. The chemical shift of the proton resonance of the Ru-hydrogen atom in trans- [{C,H,(PEta,},RuHX] Stretching frequency (vRu-H cm.-l) of the Ru-H bond in the series of complexes trans- [(chelate),RuHY] in hexane (h) or benzene (b) at 20". (Y = halogen or alky1.)* Chelate c1 Br C2H4(PMe&2 1891 h 1895 h 1898 h C2H4(PEt 2) 2 1938 h 1945 h 1948 h -o-C,H,(AsMe~ 1804 h -Me Et Prn C2H4(PPh&2 1884 b 1873 b 1867 b in * VR-H occurs at 2195 cm.-l in tran~-[(PEt~)~PtHCl] CC1 at 20".with water as standard is f27.1 p.p.rn. (X = Cl) +26.3 p.p.m. (X = Br) and +24.6 p.p.m. (X = I) the highest tver reported. These proton resonances consist of five sharp equally spaced bands with in-tensities roughly in the ratio 1 :4 6:4 1 consistent with the coupling of the hydrogen nucleus to four equivalent phosphorus nuclei each of nuclear spin i. We failed to obtain the cis-isomer of [(C2H,(PPha2),RuC12] and the trans-isomer could not be reduced. However in contrast to the trans-com- plexes of the other ligands except o-c,H,(AsMe,), it reacts with aluminium alkyls to give halogeno- alkyls of the type [(C2H,(PPh~,}2RuRC1] (R = Me Et Prn) which are converted by lithium aluminium hydride into the alkyl hydrides [{C,H,(PPh2),},RuHR].These are the first alkyl derivatives of ruthenium to be reported and the first alkyl hydrides of any transition metal. A preliminary investigation of the corresponding iron and osmium complexes indicate that it is more difficult to obtain hydrides and alkyls of corresponding type from these two elements. However one osmium halogeno-hydride probably [(C2H,(PPh2)2}20sHCl] has been obtained in small yield. It is characterised by a strong sharp band at 2046 an.-' in the infrared spectrum of the solid and is more stable than the complex ruthenium halogeno- hydrides.The authors are greatly indebted to Dr. L. A. Duncanson and Miss I. Bates for the infrared spectra and to Dr. L. E. Orgel for the nuclear magnetic resonance spectra. (Received March 16th 1959.) Chatt Duncanson and Shaw Proc. Chem. Soc. 1957 343. Idem. Chem. and Ind. 1958 859. a Nyholm J. 1950 851;Nyholm and Sutton J. 1958 567 572. PROCEEDINGS A Stereospecific Synthesis of an Optically Active Allene By S. R. LANDOR and R. TAYLOR-SMITH (WOOLWICH LONDON, POLYTECHNIC S.E.18) ONLY three reports of the resolution of allenesl and -1.323" (homogeneous) respectively. The (+)-recently one of partial asymmetric synthesis2 have alcohol and thionyl chloride were added dropwise to been published. We have converted an optically boiling dioxan and after reaction hydrogen chloride active acetylenic alcohol into an optically active was removed by addition of pyridine.The pro- allene by an essentially stereospecific method. duct 1 -chloro -3,4,4 -trimethylpenta -1,2 -diene The Grignard reagent obtained from 3,4,4-tri- CMe,*CMe=C= CHCl (47 % yield) was shown by methylpent-l-yn-3-01,~ CM%*CMe(OH)*C=CH by its infrared spectrum to be free from acetylenic alcohol; it had [all5 + 39-48' (homogeneous) and ethylmagnesium bromide was converted by phthalic anhydride into the (&)-hydrogen phthalate m.p. strong bands at 1950 and 730 cm.-l but no ultra- 136-138" in up to 90% yield [Hickman and violet absorption maximum indicating the allene Kenyon's method^,^ using pyridine or triethylamine structure.It absorbed 3 mols. of hydrogen with loss gave only -30% yields]; crystallisation of the of >90 % of the optical activity (the residual activity brucine salt from acetone and removal of the may be due to stereospecific formation of optically brucine then gave the (+)-and the (-)-hydrogen active 2,2,3-trimeth~lpentane~). O, phthalate m.p. 120-121 of maximum [~]~~,+72" Conversion of the optically active acetylenic -74" (in acetone). The optically active alcohols alcohol into a highly active allene supports the were obtained from the esters by reduction with SNi' mechanism3 [with an intermediate This appears to be lithium aluminium hydride at O" this method avoid- CM%*CM~(C~ZCH)*O*SOC~]. ing alkyl-oxygen fission and the infrared spectra the first stereochemical correlation of an allene with showing that the acetylene bond was unaffected.a tetrahedral-carbon compound and should lead to Combined ester fractions severally of + 46" assignment of absolute configuration to allenes. and -40" gave alcohols of [x]lSD+ 1.584" and (Received March 16th 1959.) Maitland and Mills Nature 1935 135 994; J. 1936 987; Kohler Walker and Tishler J. Amer. Chem. SOC.,1935 57 1743; Wotiz and Palchak ibid. 1951 73 1971. Jacobs and Dankner J. Org. Chem. 1957 22 1424. Bhatia Landor and Landor J. 1959 24. Hickman and Kenyon J. 1955 2051 ;1957,4677. Cf.McKenzie et al. J. 1905 187 1373; 1906 89 688; 1909 95 544. The Carbon Skeleton of Lagosin (Antibiotic A 246) By M. L. DHAR and M. C. WHITLNG V. THALLER (DYSON LABORATORY, FERRINS OXFORD) and RAGNAR STINA STALLBERG-STENHAGEN RYHAGE and EINAR STENHAGEN FOR MASS SPECTROMETRY INSTITUTET, (LABORATORY KAROLINSKA STOCKHOLM INSTITUTES CHEMISTRY and UPPSALA) OF MEDICAL GOTEBORG RECENTLY partial structure (I) was proposedl for fragment presumably containing a carbonyl group "antibiotic A246," lagosin.We now present evi- and several hydroxyl groups was isolated after ex- dence which defines the greater part of the carbon traction with butanol. It was treated successively I i with sodium borohydride hydriodic acid and phos- OCO*C~gHg,-*,Oo C(0H)-phorus aluminium-nickel alloy and alkali and methanol and sulphuric acid. A mixture of a high- CH,CH.CH(OH). [CH=CH],CH-CMe-CH(OH) boiling ester and a similar y-lactone was thus ob- (1) tained the latter being removed by chromatography skeleton of this compound and allows the expansion on alumina.The ester fca. 140 mg. from 5 g. of the of this structure to (11). antibiotic) was shaken in hydrogen in the presence of When subjected to periodate oxidation in acidic platinum and then subjected to gas chromatography solution lagosin gave a product which as on a Reoplex 400 column at 202.5" (when run at previously stated,l yielded on alkaline hydrolysis optimal conditions the column had an efficiency of 12 13 -dihydroxy -2 -methyltetradeca-2 4 6:8 :10 -5000 plates). The ester from lagosin proved to be a pentaenal as the main neutral fragment. The acidic very complex mixture. The quantitatively largest Dhar Thaller and Whiting Proc.Chem. SOC.,1958 148. MAY1959 155 component (approx. 30% of the total) formed a lagosin and alkali,* presumably by retroaldol fission sharp symmetrical peak with a retention time of allows the location of a 1-hydroxy-n-hexyl group in 9.2 minutes (methyl stearate had a retention time of a position a to the carboxyl residue. This is obviously 13.1 minutes under the same conditions). This com- consistent with the structure of the CIQreduction ponent was isolated rechromatographed on the same product. column and examined in the mass spectrometer. The Evidence citedl for a Cql formula for lagosin to mass spectrum gave the molecular weight as 3 12 and some extent conflicts with C30 and CS5formulae it showed high peaks due to fragments of m/e = 158 advanced for the obviously related antibiotics and 228.Earlier experience on branched-chain esters2 filipin3 and fungichromin.* Rigorously and in-suggested a methyl dialkylacetate structure with C dependently of earlier work the isolation of C, and and Cll alkyl groups. A specimen of methyl 2-hexyl- CIQfragments disallows formulae below C34 while tridecanoate was prepared for comparison by a the fact that no acidic product is obtained on oxida- nialonic ester synthesis the two alkyl halides being tion with neutral periodate eliminates molecular n-CSHllCH(OH) I \I \I \i \i \r \r \i \i \/ \I \i 0-CO*CH-C- C- C -C-C- C- C -C -C -C-C I 1C6H30-,409 CH,CH.CH(OH)-[CH= CH],-CH= CMeCH(OH)C(OH) = I (11) (Only hydrogen and oxygen attached to the C, residue) prepared from crystalline sorbic and undec-10-enoic formula in the range C35-C37 for lagosin.As the acid. The synthetic ester and that obtained from published absorption intensities for these antibiotics lagosin had the same retention time in gas chromato- e.g.,E(1% 1 cm.) = 1330 and 1430 respectively at graphy and their mass spectra were also identical ca. 3560 A; are similar to or lower than that (1491 except for very weak peaks in that derived from at 3558 A) for lagosin we believe that they may have lagosin attributable to residual impurities. larger molecules than has been suggested. The C,Hll-C-O grouping was already known One of us (M.L.D.) thanks the Commissioners for to be present;l the formation of hexanaldehyde from the 1851 Exhibition for a Fellowship.(Received April 7th 1959.) Ryhage and Stenhagen unpublished work. * Although we had strongly suspected that it was formed under these conditions this aldehyde was only isolated as its 2 4dinitrophenylhydrazone after we had heard that it had been similarly obtained from fungichr omh6 Whitfield Brock Ammann Gottlieb and Carter J. Arner. Chem. Soc. 1955 77 4799. Tytell McCarthy Fischer Dolhofer and Charney Antibiotics Annual 1954-5 716. Cope personal communication. Microwave Spectrum and Structure of Cyanamide By J. K. TYLER and J. SHERIDAN L. F. THOMAS (DEPARTMENT THE UNIVERSITY OF CHEMISTRY BIRMINGHAM) IN condensed phases and in solution cyanamide in Mc./sec. for H,N-CN (B + C,) = 19,995-1f1 appears to be mainly HzNCN,1b2 but apart from (B -C,) = 263.7 f0-1;for HDNCN (B + C,) an indication of the H-H separation in the solid = 18,861.4 f 1 (B -C,) = 347-8 f 1; for from proton magnetic resonance,2 no internuclear D2N.CN (Bo + Co) = 17,899.7 f1 (Bo -Co) = distance or even the precise symmetry of the mole- 412-5 5 0.5.Spectra of vibrationally excited mole- cule has previously been determined. Attempts cules appear in addition to those of the ground made here in 1953,3 to measure microwave absorp- states. The relative intensities of these spectra at the tions of cyanamide failed on account of its low 1 -f 202,1 -+ 2, and 1 11 +2, transitions show volatility. We have now observed at cell-tempera- that the nuclear-spin statistics applicable in keten4 tures near 60° Q-and R-branch rotation spectra of are also obeyed in cyanamide.Accordingly the H,NCN HDN-CN and D2NCN between 17,900 equilibrium state of the molecule appears to be and 40,300 Mc./sec. The spectroscopic constants are planar with C, symmetry about an axis containing Davies and Jones Trans. Faraday SOC.,1958 54 1454. Moulton and Kromhout J. Clzem. Phys. 1956 25 34. Heath G. A. unpublished work. Johnson and Strandberg J. Cizein.Phys. 1952 20 687. I56 PROCEEDINGS the N-C-N chain. These intensities also suggest that leads to improbably low values of dcN. The N-H at least one deformation mode of cyanamide has a distance appears very short but models in which dNH lower frequency than any previously assigned,l and is appreciably lengthened by a decrease of the angle further studies are being made.HNH below 120"are improbable on account of the From the quadratic Stark effect of the 0, -+lo large values of d, which then result. Accordingly transition a preliminary value of 4.3 D is obtained the parameters corresponding to an angle HNH of for the dipole moment of H,NCN in quite good 120" or slightly less are the most acceptable. The agreement with the moment in s~lution.~'~ nitrogen-nitrogen distance is certainly very close to 2.507 A. The results agree reasonably with predic- The spectra show effects of nuclear quadrupole tions based on findings for the related substance coupling which almost certainly involves both 14N f~rmamide,~ the structure H,+N=C=N-doubtless nuclei. Higher-resolution studies and work on being important.From Cox and Jeffrey's bond-species containing 15N,are now going forward with order-length curve,8 the total bond-number of the a view to analysis of these splittings refinement of carbon atom in cyanamide is about 4.4. A better values of rotational constants and determination of assessment of structure will be possible when work centrifugal distortion constants. on further isotopic forms is complete. The data are consistent with the annexed sets of Note added in proof.-Since writing this note we structure-parameters. havelearnt that Dr. D.J. Millen and Mr. G. Topping Angle have independently obtained very similar results. Dr. J. M. Dowling has also suggested to us from HNH dNH 'NC dCN dNC + dCN unpublished work on formamide the possibility of (assumed) (A) (A) (A) (A) a non-planar H,NC group with inversion.Any such 119" 0.94 1.296 1.212 2.508 inversion would have to occur very easily and the 120" 0.93 1.328 1.178 2.507 details so far seem best explained in the manner 121O 0.93 1.361 1-14 2.505 given. Increasing the angle HNH above 120"thus quickly (Received March 23rd 1959.) Schneider J. Arner. Chem. SOC.,1950 72 761. Devoto and Di Nola Guzzettu 1933 63,495. Kurland and Wilson J. Chem.Phys. 1957,27 585. Cox and Jeffrey Pruc. Roy. SOC.,1951 A 207 110. The Structure of a Complex of Empirical Formula Co,(CO),HC iCH and its Relation to a Proposed Structure for Cobalt Octacarbonyl By 0. S. MILLSand G. ROBINSON (THEUNIVERSITY 13) MANCHESTER THEreaction of acetylene with Co,(CO) can lead to 7.3, b = 8-60 c = 12.4 A 01 = 91" 54' p = the formation of a complex Co,(CO),HC CH,l the 115" 24' and y = 98" 54'.The observed density structure of which has been recently described, p = 1.86 g.ml.-l determined by flotation in carbon whilst more energetic conditions3 lead to a complex tet rachloride-methylene iodide together with the of empirical formula Co,(CO),HC; CH. Neither the above unit-cell dimensions indicate two molecules known chemical reactions of the latter nor its infra- per unit cell (the calculated molecular weight is 393). red spectrum leads to an unambiguous structural Application of the N(z) test4 to the projection data formulation. h01 favours the centrosymmetric space group Pi. We have recently examined single crystals of the This conclusion has been confirmed by the sub- nonacarbonyl complex which were kindly supplied sequent analysis.The space group hence affords no by Dr. H. W. Sternberg. Some 1100 general reflexions information about the symmetry of the molecule. have been estimated visually from equi-inclination The positions of the metal atoms have been Weissenberg photographs taken with Co-Ka radia-established both by the use of direct methods applied tion. The crystals are triclinic and have unit-cell to the two-dimensional data5 and with less am- parameters (for the Delauney reduced cell) of a = biguity from a three-dimensional Patterson synthesis ; Greenfield Sternberg Friedel Wotiz Markby and Wender J. Arner. Chem. Soc. 1956,78 120. Sly ibid. 1959 81 18. Sternberg Shukys Donne Markby Friedel and Wender ibid.in the press. Howells Phillips and Rogers Actu Cryst. 1950 3 210. Robinson M.Sc. Thesis 1958 University of Manchester. MAY1959 they are separated by ca. 2-5 A and this rules out those structures which do not include metal- metal bonds.5 The light-atom structure has been deduced from successive Fourier syntheses of elec- tron density in three dimensions in a manner similar to that reported in the analysis6 of the hydridocar- bonyliron-but-Zyne complex. The first Fourier syn- thesis was computed with phases based upon the two cobalt atoms alone and in successive calculations 4,8 19 and 20 light atoms were incorporated. In all cases the peaks due to the oxygen atoms were clearly larger than the carbon peaks.The structure has been partially refined by a least-squares method during which the value of R = CI F,-F I/cIF I has de- creased from 29 % to 15 %. A difference synthesis has established the absence of unexplained peaks of magnitude greater than 1 electron A-3. The structure (A) is of approximate mirror sym- metry C,. Each cobalt is surrounded by five carbon A (4 atoms in a square pyramid configuration. The struc- ture is obtained by joining two such pyramids along a basal edge and folding the whole along the join until the correct Co-Co distance ensues and the trigonal axes of each Co(CO) group coincide the CO groups thus lying in the eclipsed position. This structure is thus the first example of two metal atoms bridged by a carbon atom of a ring here a lactone Hock and Mills.Proc. Chern. Suc.. 1958. 233. ring. The positions of the oxygen atoms in the ring are clearly defined and bond-lengths within the molecule are reasonable at this stage of refinement. Another important structural feature of (A) is that the two metal atoms and the bridging carbon atoms are not coplanar. It appears that in view of the rela- tion between the nonacarbonyl complex and dicobalt octacarbonyl Co,(CO), the generally accepted structure of the latter in which these atoms are assumed to be ~oplanar,~~~~~ should be reviewed in favour of structure (B). It is interesting that dicobalt octacarbonyl can take up a further molecule of carbon monoxide to form an unstable complex Co,(CO) in which the additional group presumably is attached at least initially in the vacant trigonal bridging position.1° Similar geometric symmetry would presumably also apply to the catalytically active ion Fe,(C0),2-11.We are continuing refinement of structure (A). 0 \ P (8) We thank the Department of Scientific and Industrial Research for a grant towards X-ray apparatus Messrs. Esso Research Ltd. for a grant towards expenses and the staff of the Computing Machine Laboratory University of Manchester for permission to use the Mercury Computer. (Received April lst 1959.) Cable Nyholm,'and Sheline J. Aher. Chern. Suc. 1954,76,3373. * Friedel Wender Shufler and Sternberg ibid. 1955,77 3951. Cavalca and Bassi Ricerca Sci.,1953,23 1377.lo Sternberg Markby and Wender J. Arner. Chern. Soc. 1956,78,5704. Simultaneous Unimolecular and Bimolecular Reactions in Nucleophilic Substitution By G. KOHNSTAM and B. SHILLAKER A. QUEEN (UNIVERSITY LABORATORIES, SCIENCE SOUTHROAD,DURHAM) THEborder-line region which marks the transition been described in two general ways. Some workers from reaction by the bimolecular mechanism SN2 consider that the individual molecular acts of sub- to reaction by the unimolecular mechanism SNl,has stitution occw via a single intermediate transition state which requires some covalent participation by the reagent;l such a process must be regarded as bimolecular.2 Others have suggested that a variety of transition states may be available to the reacting system and that some of the substitutions occur uni- molec~larly,~ but no unambiguous evidence for this concurrence of the two mechanisms has been reported so far.It has now been demonstrated that S,l and SN2processes operate simultaneously in the attack of azide ions on 4-methoxybenzyl chloride (RCI) viz. RC1 + N,-+RN + C1-. The reaction was examined in 70% aqueous acetone where hydrolysis also occurs but this side reaction proceeds exclusively by mechanism SJ i.e. through the rate-determining ionisation of RC1. This conclusion is based on the great similarity of the solvolytic behaviour with that of diphenylmethyl chloride a compound which is known to react uni- molecularly in aqueous solvents:5 the ratio of the heat capacity of activation to the entropy of activa- tion4 is the same for the hydrolysis of both com- pounds and the two reactions occur at about the same rate and are affected in an almost identical manner by (a)changes in the solvent composition or (b) addition of “common-ion” salts and “non-common-ion7’ salts containing weakly nucleophilic anions (e.g.,sodium perchlorate).These results show that the effect of azide ions on the rate of ionisation of RCl can be assumed to be the same as their effect on the overall rate of decomposition of diphenyl- methyl chloride since the latter compound is sterical- ly unfavourable to bimolecular attack by nucleophilic reagents. PROCEEDINGS Initial first-order rate coeficients (in sec.-l) .for the reaction of 4-methoxybenzyf chloride with 70% aqueous acetone and sodium azide at 20”.[NaN,] -0.0198 104kh 2.706 2.493 l@ki* 2.706 2.879 104k 2.706 3.555 kallka -0.363 * By analogy with experiments chloride. 0-0312 0.0399 2.427 2-320 2.982 3.063 4.070 4.336 0.338 0.369 on diphenylmethyl The data in the Table show that sodium azide reduces the rate of hydrolysis (kh) and increases the rate of ionisation (ki).This can only arise from the competition of azide ions and water for the carbon- ium ion R+ and therefore demonstrates the uni- molecular formation of RN,. The rate of ionisation is however always less than the overall rate of de- composition (k),and it must therefore be concluded that RN is also produced by the alternative bi- molecular meuhanism.In agreement with these con- clusions the fraction of RN formed unimolecularly [kal/ka = (ki -kh)/(k -kh)] is constant within the limits of experimental error. Any attempt to exclude the bimolecular contribution would require the im- probably high value of 8 x for the ionic-strength constant.’ Experiments aimed at finding further examples of simultaneous S,l and SN2reactions are in progress. (Received April 6th 1959.) Grunwald Jones and Winstein J. Amer. Chem. SOC.,1951 73 2700. Ingold “Structure and Mechanism in Organic Chemistry,” G. Bell and Sons London 1953 p. 315. Gold J. 1956 4633; Gold Hilton and Jefferson J. 1954 2756; Crunden and Hudson J. 1956 501. Bensley and Kohnstam J. 1957,4447. Ref. 2 p. 325. de la Mare and Hughes J.1956 845. Bateman Church Hughes Ingold and Taher J. 1940 979. New Tetrahedral Complex Cations with Phosphine Oxide Ligands By F. A. COTTON R. BARNES E. BANNISTER and R. H. HOLM OF CHEMISTRY INSTITUTE (DEPARTMENT MASSACHUSETTS OF TECHNOLOGY CAMBRIDGE 39 MASS. U.S.A.) ONE finds in the literature numerous examples of sterically forced configurations of complex ions. We now report a new instance which provides access to a number of complex cations whose spectral and magnetic properties are of interest. Triphenylphosphine oxide has long been known1 to form complexes with various metal halides giving e.g. (Ph,PO),CoCl, (Ph,PO),ZnBr ; other trialkyl- and triaryl-phosphine oxides behave similar- lyY1and we have considerably extended the number of such compounds known and are investigating Pickard and Kenyon J.1906,89 262. their magnetic and spectral characteristics. Presum- ably here the halide ions are ligands so we have tried using metal salts with anions lacking donor properties i.e. ClO,- BF4- SiF2- Br0,- etc. Using perchlorates we have isolated a number of compounds of the type [(Ph,PO),M](ClO,) or 3. it appears that in general for metal ions of the first transition series the steric requirements of the Ph,PO ligand exclude all but the tetrahedral con- figuration in the cation. Thus we presume that in the [(Ph,P0),Fel3+ ion the 04Fe configuration is that of MAY1959 a regular tetrahedron. With Co2+,which is known to form other tetrahedral complexes we again conclude that for steric reasons alone the [(Ph,PO)4Co]2+ ion must be tetrahedral.In the latter case there is cor- roboration from the absorption spectrum [the ion has the deep blue-purple colour characteristic of tetrahedral CO(II) complexes] and from the magnetic moment of the analogous deep blue tri-(p-dimethyl- aminopheny1)phosphine oxide complex which has also been made (,a = 4.76 B.M.). While with Fe3+ Co2+,and Zn2+ the isolation of tetrahedral complexes is not too surprising since these ions are known to form other tetrahedral com- plexes the isolation of a tetrahedral Ni(I1) complex is novel. We believe the cation in the yellow salt [(Ph3PO),Ni](C10,) to be tetrahedral for several reasons (1) As in other cases no other configuration seems to be sterically possible; (2) The absorption spectrum is in accord with what we should expect from theory taking Dg x 400 cm.-l in our calcula- tions.(3) The magnetic susceptibility follows the Curie-Weiss law [p = 2-842/(T -s>] with 8 equal to -10”~ and p equal to 3-51 B.M. The [(Ph,PO),Ni J2+ ion is as far as we how the first truly tetrahedral* cationic complex of Ni(Ir). Venanzi and his co-workers2 have shown that the complexes (Ph,P),NiX, where X = Cl I and prob- ably Br are “tetrahedral” with respect to the orienta- tion of the nickel-ligand bonds but of course the true symmetry of the P,NiX grouping can only be C,,or lower. This is amply reflected in the low mag-netic moments which indicate that the T,,fF) ground state expected in a regular tetrahedron is split up with an orbital singlet probably lying lowest.Gill Nyholm and P. Pauling? have obtained the tetrahedral ions NiCl,,- NiBr,,- and Ni142- the codiguration being stable only in the crystals and the magnetic moments of these are 3-5-3-9 B.M. It has been reported that We9 has placed Ni2+ ions in tetrahedral holes in glasses and the magnetic moments under these conditions are reported* to be 3.8-3.9 B.M. We have also isolated pale blue Cu(N0&,4Ph3P0 the constitution of which is under investigation. This work is supported in part by the United States Atomic Energy Commission. CReceived April lst 1959.) * There may be slight distortion due to the Jahn-Teller effect. a E.g.Venanzi J. Inorg. Nuclear Chem. 1958 8 137; J. 1958 719. Gill Nyholm and P. Pauling Nature 1958 182 168. Quoted by Nyholm J. Inorg. Nuclear Chem. 1958 8 420. The Crystal Structure of Di-(2-thioimidazolidine)cadmium Thiocyanate By L. CAVALCA and G. FAVA M. NARDELLI CHEMISTRY INSTITUTE (STRUCTURAL LABORATORY OF CHEMISTRY UNIVERSITY ITALY) OF PARMA CADMIUM THIOCYANATE forms a complex compound Cd[SC(NHCH,-),]ANCS), with 2-thioimidazolid- ine (ethylenethiourea) which crystallises in mono- clinic system with space group C2/c(Cg, No. 15) and a = 15.60 A b = 8-17A c = 11.51 A = 95” 41’. The unit cell contains four mo1ecules.l The positions of the cadmium and sulphur atoms were determined by means of P(U,W) and P(U,Y) Patterson projections.The structural study was com- pleted mainly by means of po(X,Z) and po(X,Y) Fourier projections and of C,(X,Z) Sl(X,Z) and The cadmium atoms lie in special positions on two-fold axes. The co-ordination around the metal atom is octa- hedral because each thiocyanate group is bonded by its ends to two cadmium atoms. The co-ordination polyhedra are formed by two sulphur atoms from two thioimidazolidine molecules two sulphur atoms from two thiocyanate groups and two nitrogen atoms from two other thiocyanate groups. The poly- hedra are linked as illustrated. The structure of this compound is remarkably {pa + IplI)(X,Z) generalised projections. With only different from that of the analogous thiourea corn- the observed reflexions taken into account the re- pound in which the co-ordination is still octahedral liability factors are R(hOZ) = 0.19 R(h1Z) = 0-14 but the linkage between the co-ordination polyhedra R(hk0) = 0.27 R(hk1) = 0-23.occurs through the sulphur atoms of thiourea. Each Nardelli and Chierici Gazzetta 1958 88 248. of these atoms forms two co-ordinative bonds while the thiocyanate group is bonded only by the nitrogen atom.2 Nardelli Braibanti and Fava ibid. 1957,87,1209. PROCEEDINGS Di-(2-thioimidazolidine)lead(11)thiocyanate is iso- structural with the analogous cadmium compound.f (Received March 9th 1959.) Synthesis of Chrysanthenone by the Photoisomerisation of Verbenone By J. J. HURST and G. H. WHITHAM (DEPARTMENT UNIVERSITY OF CHEMISTRY OF BIRMINGHAM) IRRADIATION in cyclo- of a solution of verbenone (I) hexane with ultraviolet light gives a good yield of the isomeric ketone (11).The latter shows infrared bands (in CCI,) at 1785 (cyclobutanone) and 3030 and 1660 cm.-l (trisubstituted double bond) and its ultraviolet spectrum is compatible with that of a fi-unsaturated ketone showing interaction between the double bond and carbonyl group.' Structure @I)has been assigned to chrysanthenone a terpene ketone isolated from a species of Chrysan-Cookson and Wariyar J. 1956,2302. Kotake and Nonaka Annalen 1957,607 153. themum,2 and the properties of the photo-isomer of verbenone are consistent with the published data for chrysanthenone.Eg. reduction with lithium alumin- ium hydride gave an unsaturated alcohol whose 3,5-dinitrobenzoate had m.p.114-1 16",undepressed on admixture with an authentic specimen;3 the infra- red spectra (in CCl,) of the two samples were identical. Oxidation of the unsaturated alcohol with pyridinechromium trioxide regenerated ketone (11). We thank Professor M. Stacey F.R.S. for encouragement; one of us (J.J.H.) is indebted to the University of Birmingham for a research scholarship. (Received March 30th 1959.) We are grateful to Dr. H. Nonaka Osaka City University for the specimen for comparison. The Use of a Thiol-Disulphide Interchange in the Detection of Thiols By B. SAVILLE BRITISHRUBBER RESEARCH 48-56 TEWINRD., (THE PRODUCERS' ASSOCIATION WELWYN CITY,HERTS.) GARDEN DURING studies on thiol-disulphide interchange it was noticed that the equilibria between various thiols and di-p-nitrophenyl disulphide in basic solvents lie well to the right of the equations RSH + 02N.C6H4.S.S.CsH4.N02 + 02NC,H4-SH + RS-S*C,H4-N02 RS.S.C6H4.N02+ RSH + RS-SR 4-02N.C6H4*SH The important requirement appears to be that the acid strength of the thiol (RSH) be less than that of p-nitrothiophenol whose pK can be assumed to be lower than the value of 7.2 quoted' forp-nitrophenol.Thiols whose pK values are > 7 should be effective in displacing p-nitrothiophenol from the disulphide. Since these reactions occur in basic media the p-nitrothiophenol formed will be mainly ionised to p-nitrothiophenoxide ion which is strongly yellow (cf.p-nitrophenoxide). These observations suggested a simple colour reaction for the detection and possible determination of thiols. A convenient reagent is made by dissolving the disulphide (1 -0g.) m.p. 18 1 O (from iodine oxida- tion of sodium p-nitrothiophenoxide2 and crystallisa- tion from glacial acetic acid) in hot redistilled ethanol (1 1.). When cold the practically colourless reagent (20 ml.) gives yellow colours with 0.1 mg. of ethanethiol propanethiol 2-hydroxyethanethiol mercaptoacetic acid 2-furylmethanethiol 2-diethyl- aminoethanethiol toluene-w-thiol p-nitrotoluene- o-thiol benzenethiol and cysteine on the addition of a drop of morpholine piperidine or triethylamine. Cyanide ion also gives the colour. (Received April 16th 1959.) Martin and Butler J.1939 1366. Waldron and Emmet Reid J. Amer. Gem. Soc. 1923,45,2401. MAY1959 161 ~~ ~ NEWS AND ANNOUNCEMENTS Foreign Members of The Royal Society.-At a meeting of The Royal Society on April 23rd the following were elected Foreign Members of the Society Professor Melvin Calvin The University of California Berkeley California U.S.A. Distin-guished for his researches into the mechanism of photosynthesis. Professor Gerhard Domagk The University of Munster ; and Director Research Laboratories for Experimental Pathology and Bacteriology Farben- fabriken Bayer Wuppertal-Elberfeld Germany. Distinguished for his researches leading to the dis- covery of Prontosil the first chemotherapeutic agent against septic infection.Professor Jan Hendrick Oort The State University of Leiden The Netherlands. Distinguished for his contributions to the knowledge of galactic structure of stellar distribution and of stellar dynamics. Professor Axel Hugo Teodor Theorell The Nobel Medical Institute Stockholm Sweden. Distinguished for his work in the field of enzyme chemistry particularly in relation to oxidation in animal tissues. British Association for the Advancement of Science. -The 121st Annual Meeting of the British Associa- tion for the Advancement of Science will be held in York from September 2nd to 9th 1959 under the Presidency of Sir James Gray C.B.E. M.C. F.R.S. Professor of Zoology in the University of Cambridge. The title of his Presidential Address will be “The Proper Study of Mankind is Man.” No scientific qualifications are required for membership and all who are interested in science and its impact upon society can join the Association and attend the Meet- ing without any formalities.Adults can become Associate Members for a fee of two guineas; students and school children for ten shillings. Copies of the preliminary programme can be obtained from the Secretary British Association for the Advancement of Science 18 Adam Street Adelphi London w.c.2. The Royal Institute of Chemistry.-At the 81st Annual General Meeting of the Institute held in Manchester on April 17th 1959 Mr. E. Le Q. Herbert was elected President for two years (1959-61) and took over this office from Dr.D. W. Kent-Jones (President 1955-57) who had been Acting President since the death on December 19th 1958 of Professor W. Wardlaw C.B.E. (elected President for 1957-59). Dr. C. W. Herd Professor Charles Kemball and Mr. Clifford Paine were elected Vice-presidents for 1959-61 in succession to Professor H. V. A. Briscoe Dr. John Idris Jones and Professor R. G. W. Norrish F.R.S. who had completed their two years of office. Dr. Norman Booth Professor Charles Gray and Dr. Frank Hartley are due to continue as Vice-presidents until 1960. Professor Harold Burton was re-elected Honorary Treasurer for the ensuing year. Seven of the twenty-one General Members of the Council had completed their period of service and on the result of a postal ballot the following were declared elected to serve for three years (1959-62) Mr.E. H. Coulson Dr. D. C. Garratt Professor Sir Christopher Ingold F.R.S. Professor H. N. Rydon Dr. Charles Simons Professor R. L. Wain and Dr. David Woodcock. The new District Members of the Council for 1959-60 are Mr. L. Balmforth Mr. F. D. M. Hocking Dr. S. J. Fletcher Dr. R. E. Parker Mr. C. C. Skou Dr. M. B. Watson Mr. P. N. Williams and Dr. W. Wilson. The other twelve District Members were serving in 1958-59 and have been re-elected for a further year. Society of Chemical Industry.-The President of the Society Sir Robert Robinson O.M. F.R.S. will complete his term of office at the Annual General Meeting of the Society on July loth 1959 in Glasgow.Council of the Society has appointed Monsieur E. J. Solvay of Brussels to succeed Sir Robert Robinson as President. Monsieur Solvay is a direct descendant of the discoverer of the ammonia soda process which bears his name. Salters’ Institute of Industrial Chemistry.-Profes- sor A. R. J. P. Ubbelohde Professor of Thermo- dynamics at the Imperial College of Science and Technology has been appointed Director of the Salters’ Institute of Industrial Chemistry on the retirement of Sir AIfred Egerton on June 30th 1959. van ’t Hoff Fund.-The Committee of the van ’t Hoff Fund for the endowment of investigations in the field of pure and applied chemistry invites applications for grants from the fund. The amount available for next year is about 1,750 Dutch guilders.Applications should be sent by registered post to Het Bestuur der Kon. Ned. Akademie van Wetenschappen bestemd voor de Commissie van het “van ’t Hoff Fonds,” Trippen- huis Kloveniersburgwal 29 Amsterdam before December lst 1959. The purpose for which the grant is required the reasons for the application and the amount desired must be stated. Grants from the Fund for 1959 were awarded to Ir. M. Doucet (Ukkel Belgium) Dr. P. Jacquignon (Paris) Professor Dr. F. L. J. Sixma (Amsterdam) and Dr. E. Taschner (Gdansk Poland). Symposia etc.-A Symposium on “Physical Chemical and Biological Methods in the Study of 162 PROCEEDINGS High-Molecular Weight Carbohydrates,” sponsored by the Society will be held at the University of Edinburgh on July 12-14th 1960.Full details will American Chemical Society. This is the first time the Dexter Award has been conferred outside the United States. be circulated to Fellows of the Society. A Symposium on “Steric Aspects of the Chem- istry and Biochemistry of Natural Products” is being arranged by The Biochemical Society to be held in the Senate House on June 30th at 11 a.m. Arrange- ments have been made for those attending the meet- ing to have lunch at University College. Tickets for the lunch (price 5/6d.) are available from Mrs. Sherriff The Lister Institute Chelsea Bridge Road London S.W.3. Deaths of Fellows.-We regret to announce the deaths of the following Fellows Dr. Abraham Burawoy (1 1.4.59) of Manchester University; Dr.Maurice Copisarow (15.4.59) of Manchester; Dr. John Vargas E’re (7.4.59) formerly of the Distillers’ Company of Epsom; Dr. Eric Berkeley Higgins (8.4.59) of Catomance Limited Welwyn Garden City; Mr. Edwin Charles Lacey (March 1959) of West Norwood; Mr. James Henry Pizey (9.4.59) former Consulting Chemical Engineer of Bexhill-on- Sea; Mr. Edmund Milton Rich (14.4.59) formerly Education Officer L.C.C. of Beckenham; Dr. Leonard James Spence C.B.E. F.R.S. (14.4.59) formerly Keeper of Minerals at the British Museum (Natural History) of Battersea ; Dr. Reginald Killmaster Stratford (20.4.59) Scientific Adviser to Imperial Oil Limited Sarnia Ontario ; Mr. George William Gerald Tatam (4.3.59) of Broadstairs; and Mr. George Watson Young (22.2.59) of West Hartlepool.Personal.-Sir Christopher Ingold has been elected a Fellow of the Imperial College of Science and Technology London. Dr. W. Idris Jones has been nominated for the Presidency of the Institution of Chemical Engineers. Professor John Read Professor of Chemistry St. Salvator’s College University of St. Andrews has been chosen for the 1959 Dexter Award adminis- tered by the Division of History of Chemistry of the Mr. R. L. D. Ellis has resigned his post at Ewe11 County Technical College to become Principal of Isleworth Polytechnic. Dr. Joseph de Heer Associate Professor of Chemistry at the University of Colorado U.S.A. has been awarded a Guggenheim Fellowship for the academic year 1959-60. He will carry out research in quantum chemistry at the University of Uppsala Sweden.In addition he hopes to pay brief visits to centres of Theoretical Chemistry in other European countries. Professor E. Lieber has been appointed Professor and Chairman of Chemistry of Roosevelt University Chicago as from September lst 1959. He will leave his present post of Professor of Chemistry DePaul University at the end of August. Dr. J. R. Morton has been appointed I.C.I. Fellow in Chemistry at the University of Birmingham. Dr. John T.Stock Associate Professor of Chem- istry at the University of Connecticut U.S.A. has been appointed Professor of Analytical Chemistry in that University. Dr. R. A. Bottomley Research Director of Mauri Brothers & Thomson Limited Sydney is visiting the U.S.A.and Canada for three months. He will arrive in this country in the middle of July for a six weeks’ stay before continuing his studies on the Continent. Mr. P. J. Gay has been appointed Technical Director of Hangers Paints Associated Companies. Mr. W.E. Huggett has resigned his post as General Manager of the Carrington Works of Petrochemicals Ltd. to take up a position with Constructors John Brown Ltd. Dr. T. T.Jones has been promoted to the new position of Research Scientist at Monsanto Chem- icals Ltd. to assist their research and development programmes in the field of polymers. Dr. A. C. Pepper has been appointed Managing Director of Alexander Duckham & Co. FORTHCOMING SCIENTIFIC MEETINGS London Thursday June 4th at 7.30 p.m.Meeting for the Reading of Original Papers. “Kinetics and Orientation of Some Epoxide Ring Opening Reactions,” by N. B. Chapman N. S. Isaacs and R. E. Parker. “Aromatic Reactivity. Part 111. Cleavage of Substituted Phenyltrimethyl- silanes by Sulphuric Acid in Acetic Acid-Water,” by F. B. Deans and C. Eaborn. “The Heats and Entropies of lonisation of Some Aromatic and N-Heteroaromatic Amines,” by J. J. Elliott and S. F. Mason. To be held in the Rooms of the Society Burlington House W.l. Coffee will be served in the Library from 7 p.m. (Abstracts of the Papers are available from the General Secretary.) Birmingham Tuesday July 14th to Friday July 17th 1959. International Symposium on Fluorine Chemistry.The Programme has now been circulated and registrations are required before June 13th 1959. Registration forms are available from the General Secretary. MAY1959 Oxford (Joint Meetings with the Oxford University Alembic Club to be held in the Inorganic Chemistry Lecture Theatre.) Monday June 8th at 8.15 p.m. Lecture “Graphite and its Crystal Compounds,” by Professor A. R. Ubbelohde D.Sc. F.R.S. Monday June 15th at 8.15 p.m. Lecture “Electron Deficient Compounds and Valence Theory,” by Professor R. E. Rundle (Iowa State College). OBITUARY NOTICES WILLIAM STONE 1857-1958 MR. WILLIAMSTONE,of Albany W.l died on October 25th at the age of 101. William Stone was born at Bath on January 14th 1857 his father being a successful solicitor of that city and its town clerk.He was educated at Clifton and obtained a science scholarship to Peterhouse Cambridge. There in spite of his attention to his scientific studies he seems to have found time for all the other activities enjoyed by undergraduates of the day. He considered these very important and none more so than the doings of the “Volunteers”. After a course at Wellington Barracks (a memory he cherished) he was made the Captain of the Cam- bridge University Rifle Corps. He kept as apparently most undergraduates did in those days his own wine cellar and entertained lavishly in his rooms. When he came down in 1878 with first-class honours in the Natural Sciences Tripos he also brought the remnant of his cellar 20 dozen bottles of wine.He next set about establishing himself in London Society. To this end he joined several learned societies and also seven London clubs. He always advocated this procedure as much more worth-while for young men coming down from the university than the more frivolous application of their time and money then usual. He was elected a member of the Chemical Society on April 17th 1879 and on his one hun- dredth birthday was its senior member as he was of the Linnean Society the Royal Geographical Society and the Zoological Society. He also belonged to the Royal Institution and these memberships brought him into contact with the leading scientists of the day many of whom he knew well personally. He was also the senior member of the Athenaeum the Oxford and Cambridge Club the United Univer- sities’ Club the Reform Club the Garrick Hurling- ham and the Bachelors’ Club.On attaining his majority he entered into a substantial patrimony and this enabled him to travel an occupation for which he had a great passion. In 1882 he was in Egypt and travelled up to Khartoum on a donkey taking a fortnight for the journey. He paid many visits to India in the early days of the railways there and was successful as a big game hunter. He went to China and since a favourite hobby was the collection of butterflies was able to secure many rare specimens while inspecting the Great Wall. He ventured into politics in 1885 and contested unsuccessfully the Northern Division of Wiltshire.This enterprise greatly extended his circle of friends but he never repeated it. In 1893 he purchased his first set of chambers in Albany-D.6-and there he received many visits from Cecil Rhodes who in- terested him both romantically and financially in his projects for South Africa. It was in Albany during this period that he lead the well-to-do care-free bachelor existence of a “man-about-town”. He took a great interest in the stage and it was his boast that he had not missed a first night for 40 years. An incident which he was fond of recalling occurred in 1896. His friend Sir Alfred Welby then commanding The Greys was ordered to be present at the Coronation of the Tsar Nicholas I1 and in- vited Willie Stone to accompany him.His memory of those times was prodigious and the stories of his more frivolous life in consequence very entertain- ing. He had however more serious pursuits and of these Albany absorbed much of his attention. He was elected by the proprietors as a trustee in 1895 and became chairman of the trustees in 1909 a position he held till 1941. With a group of the younger proprietors he succeeded in rescuing Albany from almost certain disaster at the turn of the century. He acquired other and larger sets of chambers for his own occupation and also as he so often insisted to prevent any of the property being acquired by less desirable owners who might put their own profit before the interests of Albany. He finally settled in the chambers A.1 which had once housed Sir Beerbohm Tree and Sir Squire Bancroft to become the oldest member of yet another historical institution enjoying his 100th birthday there in full possession of his faculties a charming survival from a vanished age. (Reprinted,with permission from The Times.) PROCEEDINGS FREDERIC JOLIOT 1900-1958 FREDERIC was born on March 19th 1900 son JOLIOT of a Paris merchant. In 1920 he gained admission to the &ole de Physique et de Chimie de la Ville de Paris whose director at that time was Paul Langevin. This was the school in which some twenty years before Pierre and Marie Curie had discovered radioactivity and separated the first radioactive elements. In 1924 after graduation and military service Joliot joined a large steel manufacturing company as production engineer.In a very short time he won the appreciation of his superiors and was promised a brilliant future in industry. But academic research was more attractive to him and in 1925 he accepted a position as “prkparateur” (assistant) in the Institut du Radium offered him by Madame Curie on the recommendation of Langevin. Although he spent only a few months in industry he always emphasised the importance of this experience in his general education. In 1926 he married Irkne Curie his laboratory colleague by whom he had two children Helbne and Pierre. In 1930 he obtained his Doctor’s degree with a thesis on “The electrochemistry of radioactive elements.” Although by this time several publications had appeared in collaboration with Irhe Curie it was during the years 1930 to 1936 that this collaboration became particularly fruitful.This was an exciting time of peaceful competition between a small number of laboratories then working on radioactivity. Each result obtained in Paris was followed up in Cambridge and in Berlin and vice versa. Thus the note of Frederic and Irbne Joliot published on January 18th 1932 “On the emission of protons of high velocity by hydrogenated sub- stances under the influence of very penetrating y-rays” induced Chadwick to make some additional experiments and led to his discovery of the neutron (Nature 1932 February 17th). This in turn led the Joliots to the correct determination of the relative masses of neutron and proton.Some months later Anderson discovered the positron and Chadwick Blackett and Occhialini attributed some electrons of “wrong” curvature ob- served by the Joliots in the Wilson cloud chamber to this new particle. This led the Joliots to make their important contributions to the problems of materiali- sation of photons and annihilation of positrons. Then in January 1934 came the discovery of artificial radioactivity. The promising young couple became world famous scientists. Joliot and his wife were awarded the Nobel prize in 1935 and in the same year he was appointed Maitre de Confkrences in Electrochemistry at the Sorbonne. Two years later came his appointment as Professor at the College de France in a specially created chair of “Nuclear Chem- istry” and as head at the Laboratoire de Synthese Atomique of the Centre National de la Recherche Scien tsque.Joliot rapidly equipped the new laboratories with a 7 Mev cyclotron and a van der Graaf and a Lauritsen type accelerator. These new sources added to the large stock of natural radioactive elements patiently built up by Madame Curie Joliot and his wife. In 1938 much work was done in several labora- tories on “transuranium” elements supposedly pro- duced from uranium by neutron bombardment. The results were sometimes odd. Irhe Joliot-Curie and Savitch found (May 1938) that one of the radio- active products formed is chemically closer to lanthanum than to possible “transuranium ele-ments.” Hahn and Strassman then found some elements chemically indistinguishable from barium and cerium and concluded in their famous article (Naturwiss.,1939 January 6th) that as chemists they would deduce that a splitting of uranium had taken place but that having worked in close collaboration with physicists and on the basis of the evidence in hand they “cannot decide to make this jump that would contradict all previous experience of nuclear physics.” As soon as Joliot got to know Hahn and Strassman’s results he decided to make a decisive physical experiment to establish the reality of uranium fission.The experiment is so typical of Joliot’s way of thinking that it seems worthwhile to recall it. Joliot argued that since the mass-defect is much larger in the middle of the Periodic System than for uranium should fission occur the frag- ments produced would share a large amount of kinetic energy even if some is given up in the form of /3-and y-rays.He evaluated this energy to be 25-30 Mev per fragment which is sufficient to allow the fragment to traverse a thin layer of uranium and to still have a range of a few centimetres in air. Accordingly he enclosed a (Rn-Be) neutron source in a brass cylinder covered by a thin layer of uranium oxide and surrounded by a concentric Bakelite cylinder with an air gap of 3 mm. He found indeed that if and only if both the uranium and the source were present some radioactive products were de- posited on the Bakelite cylinder.The same effect was observed if uranium was replaced by thorium. After MAY 1959 165 having thus established the existence of fission re- actions Joliot expressed the opinion that simul- taneously with the fission an “evaporation” of neutrons was to be expected. This paper was sub- mitted to the Academy of Sciences on January 20th 1939 four days after Frisch had sent his letter to Nature giving a different “physical” proof of the reality of fission. Immediately Joliot and his co-workers Halban and Kowarski began to exploit the discovery. In February 1939 Joliot demonstrated fission in a Wilson cloud chamber. In March Joliot Halban and Kowarski gave a proof of neutron emission and determined (with Dodk) its energy.In April they determined the number of neutrons emitted per fis- sion (3.5 &-0-7)and indicated that there was a definite possibility of producing a self-sustained chain reaction which as Joliot pointed out four years earlier in his Nobel Lecture was a pre-requisite for the utilisation of nuclear energy. A convergent chain reaction was demonstrated in September. The war clamped secrecy on this work and it was only in 1949 that a sealed letter deposited in October 1939 with the Acadkmie des Sciences was opened and revealed that Joliot and his co-workers had known ten years previously how to obtain a di- vergent chain reaction using either isotopically en- riched uranium or a heavy-water moderator and an inhomogeneous pile structure.Patents were applied for some together with Francis Perrin for utilisation of all these techniques in pile construction. Later the inventors made a gift of these patents to the C.N.R.S. and to the Atomic Energy Commissariat. The defeat of France in 1940 and the German Occupation put a stop to this work. Joliot sent Halban and Kowarski to England with all their data and the world stock of heavy water obtained from Norway. He himself remained in France to protect his laboratory and to take part in the struggle against the Germans. Indeed during the whole German occupation Joliot was extremely active in the French Resistance Movement. It was at that time that he joined the Communist Party which for him com- bined two of his ideals-the quest for social justice and patriotism.He refrained from working on fission but took an active part in research on biological and medical applications of isotopes. After the Liberation Joliot spent most of his time and resources on organisation and promotion of French Science. In August 1944 the first de Gaulle government entrusted himwith the reorganisation of the Centre National de La Recherche Scientifique (C.N.R.S.). As head of the C.N.R.S. he not only created its present structure but also fixed the whole pattern for the development of French Science. In January 1946 Joliot left the C.N.R.S. to take up the newly created position of High Commissioner for Atomic Energy. In this post and in collaboration with Ir&ne Joliot-Curie Francis Perrin Auger Kowarski Goldschmidt Gueron and others he laid the foundation for the whole development of atomic energy in France.On December 15th 1948 the first French pile became critical. Only people who know the situation of French industry and research at that time can realise what an achievement this was. The old Fort de Chgtillon where the C.E.A. laboratories were housed soon became too small. Joliot selected a new site in Saclay and began to equip it. This activity was interrupted in 1950 when the govern- ment considered that political positions taken by Joliot were incompatible with his position as High Commissioner. During these years in the C.N.R.S. and in the C.E.A. Joliot gave a full measure of his abilities as an organiser and as a leader of men.His enthusiasm for Science and the work to be done was contagious. It is difficult to describe the enthusiasm and the atmosphere of companionship that reigned during this period in the Commissariat. On leaving the C.E.A. Joliot returned to the College de France and divided his time between teaching the training of research workers and his activities as President of the World Peace Movement. He was an extraordinary teacher capable of pre- senting simply and lucidly the essential points of the most involved scientific matters. Unforgettable to me will be his lectures on the history of nuclear physics in which he analysed the psychological reasons which made one man (sometimes himself) miss the correct interpretation of an observation while another did not.Joliot held very definite opinions concerning the social responsibility of scientists. He believed they should insist that their discoveries be utilised only for the benefit of mankind. War particularly atomic war being the worst evil that could befall humanity the overriding duty was to prevent it whatever the personal consequences might be. In 1955 Joliot fell seriously ill the first manifesta- tion of the illness that was to prove fatal to him. He had hardly recovered from this first attack when he received a new and severe blow the death of his wife (March 1956) which left unfinished the new Nuclear laboratory in Orsay a manifold extension of the Old Institut du Radium. Although he knew that his time and forces were limited Joliot agreed to succeed his wife in her chair at the Sorbonne and to complete the new labora- tories.At the close of the school year 1957-58 he was tired but nobody could foresee that the end was so near. He himself was full of plans for personal work to be started as soon as the Orsay Laboratory was finished. Joliot indeed was an “artisan” of science and in his last public lecture in May 1958 he gave way to his nostalgia of the time when a scientist working alone making use of his brains and his hands could make important contributions to science without large equipment without a large team and without the laboratory becoming a factory. Outside the realms of science and its effects on mankind Joliot found relaxation in painting and his favourite sports tennis fishing skiing and judo.His family life was a happy one. It was during the summer holidays in August 1958 spent as usual with his children in Britanny that he collapsed and was rapidly taken back to Paris. There despite urgent medical attention he died on August 14th 1958. PROCEEDINGS Member of the Paris Academy of Sciences and of Medicine Foreign Member of the Royal Society of the Soviet Academy and of ten other Academies honorary doctor of nine Universities Joliot retained the natural simplicity ease of approach and fascinating personality of his younger days. Although most of his work was in the field of nuclear physics his broad knowledge bright intel- ligence and keen interest in all aspects of science made discussion with him always stimulating even in fields remote from his proper domain of interest.His early death leaves the scientific world very much poorer and it is a blow from which French science will take long to recover. M. MAGAT. APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objections to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedings. Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Abu-Hamdiyyah Mohammad B.Sc. Chemical Research Laboratory The Arab Potash Co. Ltd. P.O. Box 33, Jericho Jordan.Bain Peter James Stratford. 64 Hayter Road Wrexham Denbighshire. Baldwin Margaret Elizabeth B.Sc. Chemistry Depart- ment Bedford College Regent’s Park N.W.l. Baliga Bantwal Trivikrama M.Sc. Department of Chemistry McMaster University Hamilton Ontario Canada. Barton John Alfred. 527 Hitchin Road Luton Bedford- shire. Baxter Olive Pearl Allen B.Sc. 1 Caenwood Road Cross Roads Kingston 5 Jamaica W.I. Birchall John Michael B.A. 77 Palatine Road Didsbury Manchester 20. Bond F. Thomas B.S. Gilman Hall University of California Berkeley 4 California U.S.A. Carr Malcolm David M.Sc. Chemistry Department University of Canterbury Christchurch N.Z. Claxton Thomas Arthur B.Sc. 249 Leigham Court Road Streatham S.W.16. Dobson Doreen Florence B.Sc.79 Thurleigh Road London S.W.12. Drewett Robin. “Cariads,” Lewis Lane Chalfont Heights Chalfont St. Peter Bucks. Edwards Philip Neil M.Sc. Chemistry Department Manchester University Manchester 13. Evans John Reginald. 7 The Rise Beaufort Ebbw Vale Mon. Galbraith Michael Neil. “Medway,” P.O. Box 10 Moss Vale N.S.W. Australia. Garratt Sheila B.Sc. 49B Fernbank Road Redland Bristol 6. Goble Anthony George Ph.D. “The Tapestries,” Mornington Road Ashford Middx. Gopinath Kottil Wallapil Ph.D. Department of Chemistry Presidency College Madras 5 India. Hamlow Harlan Patrick M.S. Chemistry Department University of California Berkeley 4 California U.S.A. Hargreaves George Barritt Ph.D. A.R.C.S. D.I.C., A.R.I.C. 417 Belchers Lane Little Bromwich Birming- ham 9.Holden Kenneth George B.S. Department of Chemistry University of California Berkeley 4 California U.S.A. Hollas John Michael B.Sc. Chemistry Department University College Gower Street W.C. 1. James Edward Arnold B.Sc. 117 Appledore Road Gabalfa Cardiff. Johnston Graham Allen Ross. 12 Greengate Road Killara Sydney N.S.W. Australia. Koch Heinz Frank M.S. Baker Laboratory Cornell University Ithaca New York U.S.A. Lacan Marijan Ph.D. Laboratory of Organic Chem- istry University of Zagreb Krsnjavoga 15 Yugoslavia. Livett Richard Herbert. 23 Seymour Road Slough Bucks. Mackor Eduard L. Koninklijka/Shell-Laboratorium, Badhuisweg 3 Amsterdam-N. Holland. Masamune Tadashi Ph.D. Department of Pharma-ceutical Chemistry University of Wisconsin Madison Wisconsin U.S.A.Meldrum Bruce Robert B.Sc. 123 Queenscliff Road Queenscliff,N.S.W. Australia. Miller John Rennie B.A. 93 Barton Road Cambridge. Mortimore Roger Harry. 18 Dorking Road Epsom Surrey. Nealey Richard Howard MSc. 106 Spruce Street Lawrence Mass. U.S.A. Oddy John Raymond B.A. B.Sc. 35 Falkner Square Liverpool 8. Otvos Laszlo. Laboratory for Stereochemical Researches P.O. Box 70 Budapest XIX Hungary. Ostrowski Alexander Andrzej B.A. 63 Vineyard Hill Road Wimbledon S.W.19. Page Sally Grace M.Sc. 51 Aynsley Terrace Opawa Christchurch S.E.2 N.Z. Parekh Narendra Laxmikant BSc. Tulsi Vihar 70 Marine Drive Bombay 1 India. Pino Piero D.Chem. via Cesare Battisti 11 Pisa Italy.Pragnell Michael John. 7 Cottesmore Gardens Leigh- on-Sea Essex. hgh Harold. University Chemical Laboratory Lens- field Road Cambridge. Rajappa Srinivasachari M.A. Ph.D. 53/6 Edward Elliot Road Madras 4 India. MAY 1959 ~~ Richards John Keith. 26 Normanton Road South Croydon Surrey. Roberts Glyn Parry B.Sc. Ty Maw Bodelwyddan Nr. Abergele N. Wales. Robey Timothy Lester Townsend B.Sc. A.R.C.S. 33 Park Road Hampton Hill Middx. Rye Robin Tilley Brooke B.A. M.Sc. 7 Lyndhurst Gardens London N.W.3. Still Ian William James B.Sc. 8 Lansbury Street, Alexandria Dunbartonshire. Story Paul Richard B.S. 228 N. Riverside Drive Ames, Iowa U.S.A. Strachan Robert Gibb B.S. 1145 West Fifth Street Plainfield New Jersey U.S.A.Sykes Peter Job BSc. 64 Peckover Drive Pudsey Y orks . Szabo George. 21 Handen Road Lee S.E.12. Thesing Jan Dr.rer.nat. Frankfurterstr. 250 Darmstadt Germany. Trustcott Ruth Marion. 58 Oxford Road Birmingham 13. Waite David. 20 Maybridge Crescent Worthing Sussex. Way Jack Kenasley B.Sc. 58 Nansen Avenue Oakdale Poole Dorset. Weller Brion B.A. 46 Kingsleigh Road Heaton Mersey Stockport Cheshire. Wells Peter Robert Ph.D. A.R.I.C. Chemistry Depart- ment Iowa State College Ames Iowa U.S.A. Williams Dudley Howard B.Sc. 5 Glenholme Road Farsley Pudsey Yorks. Williams Roger Owen. 33 Oakfield Road Cwmbran Mon. Wilson Donald Victor B.Sc. 6 Leeds Road Harrogate Y orks . Zauli Carlo D.Chem. Department of Chemistry, University College Gower Street London W.C.1. ADDITIONS TO THE LIBRARY Peter Griess Leben und Wirken eines grossen Farbstoffchemikers. A. Wingler. Pp. 39. Farbenfabriken Bayer Aktiengesellschaft Leverkusen. Leverkusen. 1959. (Presented by the publishers.) Thudichum chemist of the brain. D. L. Drabkin. Pp. 309. University of Pennsylvania Press. Philadelphia. 1958. Aluminium in the chemical and food industries; issued by the British Aluminium Co. Ltd. 2nd edn. Pp. 135. British Aluminium Co. Ltd. London. 1959. (Presented by the publishers.) Nuclear magnetic resonance applications to organic chemistry. J. D. Roberts. Pp. 118. McGraw-Hill Book Company Inc. New York. 1959. Crystal structures. R. W. G. Wyckoff. Supplement 1V additions to chapters IX X XIII-XV (1959).“Loose leaf” pages. Interscience Publishers Inc. New York. 1959. Structure reports ;supplementary volume and cumula- tive index for 1940-1950. Edited by A. J. C. Wilson N. C. Baenziger C. S. Barrett J. M. Bijvoet J. Wyart, and J. M. Robertson. Vol. 14. Pp. 215. N.V.A. Oosthoek’s Uitgevers MIJ. Utrecht. 1959. Solubilities inorganic and metal-organic compounds a compilation of solubility data from the periodical literature. A. Seidell. 4th edn revised and continued by W. F. Linke. Volume I. A-Tr. Pp. 1487. D. Van Nostrand Company Inc. Princeton N.J. 1958. Reiburg und Schmierung fester Korper. F. P. Bowden and D. Tabor. Translation of 2nd edn. into German by E. H. Freitag. Pp. 430. Springer-Verlag. Berlin. 1959. (Presented by the publishers.) The principles of electrophoresis.R. Audubert and S. de Mende. Translated by A. J. Pomerans. Pp. 142. Hutchinson Scientific and Technical. London. 1959. (Presented by the publishers.) Electrophoresis theory methods and applications. Edited by M. Bier. 16 contributors. Pp. 563. Academic Press Inc. New York. 1959. Gmelins Handbuch der anorganischen Chemie. 8th edn. Fluor. Erganzungsband. System-nummer 5. Pp.258. Verlag Chemie GmbH. Weinheim. 1959. Nouveau traite de chimie minerale. Edited by P. Pascal. Volume 11. Arsenic antimoine bismuth. P. Bothorel R. Dolique L. Domange and P. Pascal. Pp. 850. Masson et Cie. Paris. 1958. (Presented by the publishers.) Nouveau trait6 de chimie minkrale. Edited by P. Pascal. Vol. 12. Vanadium niobium tantale protactin- ium.G. Bouissibres M. Foex M. Haissinsky A. Morette and R. Rohmer. Pp. 692. Masson et Cie. Paris. 1958. (Presented by the publishers.) Nouveau trait6 de chimie minerale. Edited by P. Pascal. Volume 14. Chrome complexes du chrome molybdbne tunsthe hkteropolyacides. J. Amiel J. Aubry A. Chrttien C1. Duval R. Duval W. Freundlich L. Malaprade and P. Pascal. Pp. 1014. Masson et Cie. Paris. 1959. (Presented by the publishers.) Nouveau trait6 de chimie minkrale. Edited by P. Pascal. Vol. 19. Ruthbnium osmium rhodium iridium pal- ladium platine. R. Charonnat G. Ciepka M. Delepine C1. Duval and P. Poulenc. Pp. 953. Masson et Cie. Paris. 1958. (Presented by the publishers.) Isotopic analysis of plutonium and uranium by mass spectrometer.A. H. Turnbull and D. F. Dance. Issued by the United Kingdom Atomic Energy Authority Research Group. (A.E.R.E. C/R 2776). Pp. 4. Atomic Energy Research Establishment. Harwell. 1958. (Pre- sented by the publishers.) The reactions of zironcium and zirconium based alloys with nitric and nitric-hydrofluoric acids. F. S. Martin and B. 0. Field. Part 1. Hazardous aspects. Part 2. Dissolu- tion rates. Issued by the United Kingdom Atomic Energy Authority Research Group. (A.E.R.E. C/R 2692.) Pp. 14. Atomic Energy Research Establishment. Hanvell. 1958. (Presented by the publishers.) Cahiers de synthkse organique methodes et tableaux d’application. J. Mathieu and A. Allais. Edited by L. Velluz. Volume V. Pp. 394. Masson et Cie.Paris. 1959. (Presented by the publishers.) Analyse der Fette und Fettprodukte einschliesslich der Wachse Harze und verwandter Stoffe. Edited by H. P. Kaufmann. I. Allgemeiner Teil. 11. Spezieller Teil. 2 vols. Pp. 18 16. Springer-Verlag. Berlin. 1958. Organic Chemistry Monographs. Aspects of the organic chemistry of sulphur. F. Challenger. Pp. 253. Butterworths Scientific Publications. London. 1959. (Presented by the author.) Radioaktive Isotope in der Biochemie. E. Broda. Pp. 326. Franz Deuticke. Vienna. 1958. The chemistry of drugs. N. Evers and D. Caldwell. 3rd edn. Pp. 415. Ernest Benn Limited. London. 1959. (Presented by the publishers.) Inside the living cell. J. A. V. Butler. Pp. 174. George Allen & Unwin Ltd. London.1959. (Presented by the author.) I68 The constituents of tobacco smoke an annotated bibliography. Edited by H. R. Bentley and E. G. N. Berry. (T.M.S.C. Research Papers. No. 3.) Pp. 49. Tobacco Manufacturers’ Standing Committee. London. 1959. (Presented by the publishers.) Standard methods for testing petroleum and its products (excluding engine test methods for rating fuels) issued by the Institute of Petroleum. 18th edn. Pp. 835. Institute of Petroleum. London. 1959. Solid propellent and exothermic compositions. J. Taylor. Pp. 153. George Newnes Limited. London. 1959. (Presented by the publishers.) Analytical chemistry some new techniques. A. G. Jones. Pp. 268. Butterworths Scientific Publications. London. 1959. The development of titrimetric analysis till 1806.E. R. Madsen. Pp. 237. G.E.C. Gad Publishers. Copenhagen. 1958. Analytical applications of diaminoethanetetra-acetic acid. T. S. West and A. S. Sykes. Pp. 106. British Drug Houses Ltd. Poole Dorset. 1959. (Presented by the publishers.) EDTA titrations an introduction to theory and practice. H. A. Flaschka. Pp. 138. Pergamon Press. London. 1959. The chemical analysis of foods and food products. M. B. Jacobs. 3rd edn. Pp. 970. D. Van Nostrand Com- pany Inc. Princeton N.J.1958. Nomenclature of inorganic chemistry definitive rules for nomenclature of inorganic chemistry; 1957 report of the Commission on the Nomenclature of Inorganic Chemistry. Issued by the Inorganic Chemistry Section of the International Union and Pure and Applied Chem- istry.Pp. 93. Butterworths Scientific Publications. London. 1959. ASTM standards on paint varnish lacquer and related products (with related information) prepared by ASTM Committee D-1 on Paint Varnish Lacquer and Related Products. Specifications methods of testing, definitions of terms. Pp. 1030. American Society for Testing Materials. Philadelphia. 1958. Sadtler Standard Spectra. Chemical Classes alpha- betical list. 1959. Pp. 40. Samuel P. Sadtler & Son Inc. Philadelphia. 1959. Sadtler Standard Spectra. Sadtler AlphabeticaI Supple- ment ;Sadtler Numerical Supplement and Sadtler Mole- cular Formula Supplement-1 st quarter 1959. Sadtler Midget Edition Spectra 13,751-14,200. “Loose leaf” pages.Samuel P. Sadtler & Son Inc. Philadelphia. 1959. Handbook of chemistry and physics a ready-reference book of chemical and physical data. 40th edn. Edited by C. B. Hodgman R. C. West S. M. Selby et al. Pp. 3456. Chemical Rubber Publishing Co. Cleveland Ohio. 1958. (Presented by the publishers.) Tables of constants and numeral data affiliated to the International Union of Pure and Applied Chemistry. 8. Selected constants; oxydo-reduction potentials. G. Charlot D. BCzier and J. Courtot. Prepared under the aegis of the Commission of Electrochemical Data of the Analytical Chemistry Section and subsidised by the International Commission of Tables of Constants and by the National Centre for Scientific Research. Pp. 41. Pergamon Press.London. 1958. Tables of constants and numerical data affiliated to the International Union of Pure and Applied Chemistry. 9. Selected constants; optical rotatory power. 11. Triter-penoids. J.-P. Mathieu and G. Ourisson. Subsidised by the International Commission of Tables of Constants and by the Central National de la Recherche Scientifique. Pp. 302. Pergamon Press. London. 1958. Organic peroxides in radiobiology (les peroxydes organiques en radiobiologie). R. Latarjet et al. Edited by M. Haissinsky. Colloquium on organic peroxides formed by radiations and their role in radiobiology organised by the Institut du Radium Paris 1957. Pp. 153. Pergamon Press. London. 1958. CIBA Foundation symposium on the biosynthesis of terpenes and sterols held 1958.Edited by G. E. W. Wolstenholme and M. O’Connor. Pp. 311. J. & A. Churchill Ltd. London. 1959. The physical properties of polymers :comprising papers read at the Silver Jubilee Symposium organised by the Plastics and Polymers Group held London 1958. (S.C.I. Monograph No. 5.) Pp. 293. Society of Chemical In- dustry. London. 1959. (Presented by the publishers.) NEW JOURNALS International Journal of Radiation Biology from 1959 1. Journal of Applied Polymer Science from 1959 1. Journal of Biochemical and Microbiological Tech- nology and Engineering from 1959 1. Journal of Chemical and Engineering Data from 1959 4. Journal of the Karnatak University (science numbers only) from 1958,2. Journal of Medicinal and Pharmaceutical Chemistry from 1959 1.Tetrahedron Letters from 1959 No. 1.
ISSN:0369-8718
DOI:10.1039/PS9590000137
出版商:RSC
年代:1959
数据来源: RSC
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