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Proceedings of the Chemical Society. November 1962 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue November,
1962,
Page 349-372
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PROCEEDINGS OF THE CHEMICAL SOCIETY NOVEMBER 1962 CHRISTMAS COMPETITION THEfollowing little poem is probably quite well known The Fisherman’s Prayer God grant me strength to catch a fish So large that even I When telling of it afterwards May never nsed to lie. A prize (book token for two guineas) is offered for a quatrain giving a Chemist’s Prayer. The verse may be in any metre and may concern any aspect of a chemist’s work. Entries must reach the Editor (The Chemical Society 20-2 1 Cornwall Terrace Regent’s Park London N.W.l) not later than December 31st 1962 and may be accompanied by a pseudonym for publication. It is hoped to issue a report in the January 1963issue of Proceedings. The Editor’s decision will be final.349 PROCEEDINGS MXth INTERNATIONAL CONGRESS OF PURE AND APPLIED CHEMISTRY LONDON JULY 10-17th 1963 Co~mof the second circular are now available from The Honorary Secretary XIXth International Con- gress of Pure and Applied Chemistry 14 Belgrave Square London S.W.1. This contains the names of Congress lecturers and the details regarding applica- tions to read papers at the Congress. It is stressed that such applications and abstracts of the papers must be received in London not later than January 21st 1963. Scientific Programme The scientific programme will consist of some 20 invited Congress lectures and a wide range of con- tributed papers. The papers presented in the division of Organic Chemistry will form the main theme of the Congress; but certain aspects of Inorganic Chem- istry Analytical Chemistry and Applied Chemistry will also be discussed.Each division of the Congress will comprise a number of sections and in general a proportion of these will meet concurrently. The specific topics to be discussed are given below. The abstracts of all contributed papers will be submitted to referees and only those having a direct bearing on the Congress topics can be accepted. It is moreover intended to limit the total number of papers presented at the meeting as indicated below. Scope of the Congress A. Organic Chemistry (250-300 papers) Reaction Mechanisms. Physical Methods to emphasise fundamental developments in technique and substantial applica- tions to structural problems.Stereochemistry and Conformational Analysis. Modern Aspects of Organometallic and Related Compounds. (Joint Symposium-see below.) Developments in Organic Synthesis. Biogenesis. Biologically Important Polymers. Microbiological Products and Antibiotics. Steroids and Terpenoids. B. Inorganic Chemistry (50-100 papers) Applications of the Newer Physical Methods (other than %Ray Crystallography) to Structural Inorganic Chemistry to include electron-spin resonance nuclear magnetic resonance other forms of microwave spectroscopy and polaro- graphy. Inorganic Chemistry of the Solid State. (Joint Symposium-see below.) 3 Inorganic Chemistry of the Molten State. (Especially the chemical reactions or structure of solutes in molten salts molten metals or molten non-metals.Physical properties of pure melts will not be relevant unless they have direct infiuence on the use of these melts as reaction media.) 4 Modern Aspects of Organometallic and Related Compounds. (Joint Symposium-see below.) C. Analytical Chemistry (50-100 papers) 1 Trace Analysis. 2 Separation Methods. 3 Electroanalysis. 4 Teaching of AnalyticaI Chemistry. D. Applied Chemistry (50-100 papers) 1 Adhesion particularly of Surface Coating. 2 Applied Chemistry of the Solid State. (Joint Symposium-see below.) 3 Food Packaging Materials ; Toxicological and Analytical Problems. 4 Industrial Carbon and Graphite. 5 Utilisation and Treatment of Wastes by Biological Methods.Joint Symposia Meetings in Section B2 and D2 will take the form of a joint symposium on the Pure and Applied Chemistry of Inorganic Solids. It is intended that this should deal particularly with the oxides and sulphides of the elements in relation to such matters as non-stoicheiometry and high temperature equi- libria; reaction processes in the solid state; intercala- tion compounds; reaction processes on surfaces; topochemical processes etc. and with the r6le of these in the chemistry of corrosion metal winning semiconductor chemistry etc. Joint meetings will also be held in Sections A4 and B4 and will deal particularly with the newer developments in organometallic chemistry. NOVEMBER 1962 351 EXTRAORDINARY GENERAL MEETING AN Extraordinary General Meeting was held at Burlington House on Thursday October 1Ith 1962 at 3.45 P.m.with the Resident in the Chair. me notice convening the meeting was read and after briefly to the reasons for the proposed alteration which were given in Proceedings for 1962 p. 265 the President proposed the following resolution "That the Bye-Laws of the Society be altered by substituting for Bye-Law 5 the following new Bye-Law namely "5. A list giving the names of candidates and such other particulars concerning them as the Council may from time to time prescribe shall be displayed in the Rooms of the Society for the twenty-eight days immediately prior to the meeting of the Council at which their applications for election are first considered by the council.3 The Honorary Treasurer seconded the motion which was =ITied manimouslY and the President declared the meeting closed.CHEMICAL SOCIETY COMBINED POOL OF TRUST INVESTMENTS TIE notice printed below is published at the request of the Charity Commissioners. An explanation of the purpose of the Order referred to was given in Proceedings for August page 274. CHARITY COMMISSION The Ethel Behrens Fund and The Robert Robinson Lecture Fund administered by The Chemical Society. Scheme to include the Charities in The Chemical Society Investment Pool. The Charity Commissioners have made an Order establishing a scheme for this and other purposes. Copies can be obtained by written request to the Charity Commission 14 Ryder Street London S.W.l (quoting ref.No. G.B.-129779-A) and may also be seen at that address. COMMUNICATIONS Prediction of a Stable Planar MolecuIe N(BF.J By A. D. BUCKINGHAM (INORGANIC THEUNIVERSITY CHEMISTRY LABORATORY OF OXFORD) ITis well known' that trimethylamine N(CH,), has a pyramidal structure with a CNC angIe of about 108" whereas trisilylamine N(SiH,), is believed to have a symmetrical structure in which the nitrogen and three silicon atoms are in a plane the SiNSi angle being 120". The usual explanation of this planarity in trisilylamine is that each N-Si bond con- sists of a Zrp2(N)-3sp3(Si) 0-bond together with a partial 72-bond between the 2prrO and the 3ddSi) orbitals. The purpose of this Communication is to predict that the molecule trisdifluoroborinylamine,N(BF2)3 is stable and has a planar Dshstructure.The basis of F\/ I F\B/ N\/ ' F ' (A) F this prediction is the belief that in the planar struc- ture (A) the vacant 2pnorbitals of the boron atoms form 7r-bonds with the 2po [and with the 2prr(F)] orbitals. This mbonding involving first row elements only might be expected to be stronger than in tri-silylamine and to favour the structure in which all ten atoms are in a plane. We hope to synthesise trisdifluoroborinylamineby one of the following methods (i) fluorination of boron nitride; (ii) reaction of active nitrogen with tetrafluorodiborane or by passing an electric dis- charge through a mixture of nitrogen and trifluoro- borine.Recent work2 on the reaction of active nitro- gen with trichloroborine apparently did not produce trisdichloroborinylamine,N(BCI,), but the planar form of this molecule would be overcrowded. The author is grateful to Dr. L. M. Venanzi Dr. F. G. A. Stone Dr. A. K. Holliday Mr. H. R. Leech and Dr. P. L. Goggin for discussion. (Received October 8th 1962.) "Tables of Interatomic Distances and Configurations in Molecules and Ions," Chem. Suc. Special Pubf. No. 11, ed. L. E. Sutton London 1958. a Storr Wright and Winkler Canad.J. Chem. 1962,40 1296. PROCEEDINGS The Structures of Atrovenetin and Herqueinone By I. C. PAUL,G. A. Sm (CHEMISTRY DEPARTMENT GLASGOW, THE UNIVERSITY W.2) and G. A. MORRISON COLLEGE OF ORGANIC (IMPERIAL LONDON and DEPARTMENT CHEMISTRY THEUNIVERSITY, LEEDS,2) AN X-ray crystallographic study at Glasgow has orientation of the ether ring is reversed it is apparent established the structure (I) for the ferrichloride of that a skeletal rearrangement must have occurred atrovenetin orange trimethyl ether.The structure (11) during the nitric acid degradation. Such a rearrange-previously assigned1 to atrovenetin the metabolite ment might proceed through the intermediate (VII), of Penicillium atroveneturn has therefore to be as indi~ated.~ revised to (111). The results described above have a bearing also on The ferrichloride crystallises in the monoclinic the structures of norherqueinone and its monomethyl system space group P2,,with four C22H,,0,FeC14 ether herqueinone which have been shown to units in a cell of dimensions a = 17.04 b = 9-69 possess the same skeleton as atrovenetin but to con- c = 15-66A 18 = 96" 35'.The crystal and hence molecular structure was elucidated by three-dimensional Patterson and Fourier methods 2380 independent structure amplitudes being employed. The two independent C,,H2,0~FeC14 groups con- stituting the asymmetric crystal unit are disposed as if related closely but not exactly by a glide plane parallel to (OlO) and the majority of atoms in the unit cell conform approximately to the symmetry of the space group P2,/c. This simplified the elucidation of the structure but severely hindered the refinement ;cu of atomic positions (cf. the X-ray analysis of cephalo- sporin C by Hodgkin and Maslen3).After nine rounds of structure-factor and Fourier calculations the value of R is 21-4%. In the tetrahedal FeCI,-ions the average Fe-Cl 2 bond length is 2.17 A. Further chemical evidence for the 9-hydroxyperi- naphthenone nucleus of atrovenetin is provided by the preparation of a copper derivative (IVYor equi- valent structure) m.p. 286-289" (decomp.) by treatment of atrovenetin triacetate with cuprous chloride in the presence of t-butyl perbenzoate and of the adduct (V) m.p. 242-245" obtained by allowing atrovenetin yellow trimethyl ether to react with boron trifluoride etherate. Both compounds (IV) and (V) are readily re-converted into the atro- venetin derivatives from which they are prepared by hydrolysis with dilute hydrochloric acid.9-Hydroxy- perinaphthenone also yields an adduct decomp. > 260" with boron trifluoride etherate which is regarded as analogous to compound (V). OR The structure (11) originally suggested for atro- venetin was based on the established constitution of the phenol (VI) obtained by degradation of atro- venetin with nitric acid.lV2 Since the structure of atrovenetin must now be revised to (111) in which the Barton de Mayo Morrison and Raistrick Tetrahedron 1959 6,48. a Neil1 and Raistrick Biochem. J. 1957 65 166. Hodgkin and Maslen Biochem. J. 1961 79 393. The possibility of such a rearrangement was first kindly suggested by Professor R. B. Woodward. NOVEMBER 1962 tain an extra oxygen atom in the molecule.l*b It has already been suggested that the extra oxygen atom may be situated in a tertiary position such that it blocks the aromatic system present in atrovenetin The smooth reduction of norherqueinone to atrovenetin (I1I)l with zinc and acetic acid and its acid-catalysed cleavage to isopropyl methyl ketone and norxanthoherquein (VIII)6 are adequately accommodated by structure (IX; R = R’ = H) or a tautomeric modification; other possibilities cannot be excluded however.On such a basis herqueinone is to be represented by structure (IX; R = H,R’ = Me) or (IX; R = Me R’ = H).l Either formula would account satisfactorily for the results recently obtained by Cason et aL7 in their studies on trimethylherqueinoneB. 353 Catalytic hydrogenation of norherqueinone fol-lowed by acetylation with pyridine and acetic an- hydride affords dihydronorherqueinone tetra-acetate m.p.209-212’. This compound which con- tains a free hydroxyl group (probably in a tertiary position) is under investigation at Leeds. For the calculations on the Glasgow University DEUCE computer programmesS devised by Dr. J. S.Rollett and Dr. J. G. Sime were employed. We are indebted to Professor J. M.Robertson F.R.S. and Professor D. H. R. Barton F.R.S.,for their interest and encouragement and to Dr. R. I. Reed for the mass-spectrometric determination of the molecular weight of compound (JV). (Received August 3Ist 1962.) Barton de Mayo Morrison and Schaeppi Chern. andInd. 1956 552. Galarraga Neill and Raistrick Biochem.J. 1955 61 456. ’Cason Correia Hutchison and Porter Tetrahedron 1962 18 839. “Computing Methods and the Phase Problem in X-Ray Crystal Analysis,” ed. Pepinsky Robertson and Speakman Pergamon Press Oxford 1961 Rollett p. 87; Sime p. 301. The Direct Measurement of the 170-Proton Spin-Spin Coupling in Water By J. REUBEN and DAVID A TZALMONA SAMUEL (THEWEIZMANN OF SCIENCE, INSTITUTE REHOVOTH,ISRAEL) THE splitting of the 170nuclear magnetic resonance line in water has not been observed previously owing to the rapid exchange of protons between molecules. Holmes et aZ.l have however recently shown that when the rate of exchange is reduced by diluting the water with a large excess of carefully purified acetone the proton magnetic resonance spectrum of HDO can be observed.We have used the same technique in order to measure the 170-proton spin-spin coupling in H20 containing2 8 atom %of 170. The derivative of the 170 absorption line of 3% solutions (by volume) of H270 in purified acetone was obtained on a Varian Associates V-4200Bwide-line nuclear magnetic resonance spectrometer operat- ing at 8-13 Mc./sec. with slow passage. As seen in the Figure the 170line is split as expected into a triplet with peak intensities in the approximate ratio 1:2 1. Adding a very small quantity of hydrochloric acid causes the peaks to merge into a single line. The spin-spin coupling constant is 73-5& 2-1c./sec. in agreement with the value of 92 f15 c./sec. calculated by Meiboom3 from the line widths measured in a study of proton-transfer in water.The central peak of the triplet in acetone solution is shifted to higher field in comparison with the 170resonance line in un- diluted water. This chemical shift caused by modi- fication of the hydrogen-bonded structure of water by the acetone was found to be 10.93 f1.4 p.p.m. j7----7 ______~ 4 Oxygen-17 nuclear magnetic resonance spectrum of Ht70 in acetone (derivative spectrum) (external reference standard ; corrected for bulk susceptibility). It thus appears that the chemical shift of oxygen is also affected by hydrogen bonding. Owing to the relaxation effect4 due to the electric quadrupole moment of oxygen-17 (spin 5/2) it is not possible to see multiplet structure in the proton resonance of Ha70.(Received September 17th 1962.) Holmes Kivelson and Drinkard J. Chem. Phys. 1962,37 150. 170-enriched water from the separation plant of the Weizmann Institute of Science normalised to the natural abundance of deuterium. a Meiboom J. Chern. Phys. 1961,34,375. Pople Schneider and Bernstein “High-resolution Nuclear Magnetic Resonance,” McGraw-Hill New York 1959, -937 y. LLI. PROCEEDINGS Reduction and Oxidation of Nitric Oxide in the System Diethyl Peroxide-Nitric Oxide Reactions of HNO By E. A. ARDENand L. PHILLIPS (EXPLOSIVES AND DEVELOPMENT MINISTRY RESEARCH ESTABLISHMENT OF AVIATION WALTHAM ESSEX) ABBEY THEreaction of diethyl peroxide with nitric oxide was to form alkyl nitrates nitro-compounds and nitro- studied by Levy,lvewho found that ethyl nitrite (66% gen.With nitroxyl the probable course of the re- yield) and traces of nitrous oxide were the only actions is similar identifiable products of reaction at 180° the nitrite . . . (2) being formed by addition of nitric oxide to the HNO + 2NO $ HN(NO)O*NO HN(NO)O.NO + H* + N + *NO . . . (3) ethoxyl radicals initially formed by pyrolysis of the For (2 3) AH = -0 peroxide. *NO + NO -+ 2N0 . . . (4) In the early stages (ca. 15%) of the pyrolysis of 9H +NO 4HNO . . . (5) diethyl peroxide in the presence of an excess of nitric *H + Et,O -+ H + MeCHO + EtO . . . (6) oxide at 95" we have found nitrogen and nitrogen dioxide in large yields which at constant initial pres- In comparison with C-nitroso-compounds free sure of peroxide increase with increasing initial nitrogen dioxide is formed here because nitric oxide nitric oxide concentration.Some results are tabu- which is present in large excess successfully com- lated. In the experiments at 95" the carbon dioxide petes for hydrogen atoms and ethoxyl radicals. The and methyl nitrite arise by reaction of nitrogen di- very small yields of nitrogen obtained at 135" are oxide with and ethanol arises by only explicable if reaction (2) is an equilibrium; reaction of ethoxyl radicals with the peroxide and similar proposals have recently been made by possibly nitroxyl. Burrell' for the reaction of nitrosocyclohexane with Yields (mm.) of products* Time Initial press. (mm.) A Temp.(hr.) Et,O NO EtO-NO MeCHO EtOH CO N NO N,O 95" 16 138 5491. 33.4 1.8 0.2 3.6 22.5 35 0.3 9 16 120 108 17.6 3.1 -0.4 3.4 t 0.1 135 0.25 136 416 23.9 6.4 2.5 -0.9 -1.5 YS 0.17 134 182 12.4 4.3 1-9 -0.3 -0-5 * In all cases also 0-2 mm. of hydrogen and small amounts of water. This experiment gave also 0.5 mm. of ethyl nitrate and 0.7rnm. of methyl nitrite. $ Present but not estimated. The observations can only be explained on the hydroxylamine nitritese,' and these can decompose basis of the reaction of nitric oxide with nitroxyl nitric oxide and by Christie8 for nitrosoalkane- (HNO) the formation of which by reaction of nitric nitric oxide reactions. Hydrogen atoms produced in oxide with alkoxyl radicals reaction (3) act as chain carriers for further reduction and oxidation of nitric oxide at 95" by steps (9,(2), Me-CH,.O*+ NO + MeCHO + HNO ...(I) (3) and (4) until termination occurs by (6); this AH -28 kcal. mole-l explains why nitrogen greatly exceeds "total" is a recognised step in the pyrolysis of organic acetaldehyde,-i.e. estimated acetaldehyde plus and must occur here. Nitroxyl is an carbon dioxide at 95". Yields of nitrogen dioxide at analogue of C-nitroso-compounds which are known 95" are rather less than twice those of nitrogen to add nitric oxide to form unstable N-alkylnitroso- because some of the former is lost in further reactions Levy J. Amer. Chem. SOC.,1953,75 1801. Levy. J. Amer. Chem. SOC.,1956,78 1780. Pedler and Pollard Trans. Faraday SOC.,1957,53,44. Phillips,J. 1961 3082.Gray Rathbone and Williams J. 1961 2620. * Brown J. Amer. Chem. Soc. 1957 79 2480; Donaruma and Carmody J. Org. Chent. 1957 22 635; Batt and Gowenlock Tram. Faraday Soc. 1959,56 682. 'Burrell J. fhys. Chem. 1962,66,401. * Christie Faraday SOC. Informal Discussion on "The Inhibition of Gaseous Free Radical Reactions," Cambridge April 1962. NOVEMBER 1962 355 e.g. H* -+-NO +HNOa EtOH + HNO -t EtO-NO+ H,O EtOH + ZNO + EtO’NO + HNO The alternative step HN(NO)O*NO4 .OH + H t NO ...(7) * * (8) . . . (9) * . .(lo) which energetically appears favourable since the enthalpy change for reactions (2) and (10) is -50 kcal. mole-l can be excluded as a main source of nitrogen because on this basis the ratios of nitrogen to “total” acetaldehyde and of nitrogen dioxide to nitrogen could not exceed unity.The possibility that Kuhn and Gunthard Helv. Chim. Acta 1960,43 607. nitrogen and nitrogen dioxide are formed by addi- tion of nitric oxide to ethyl nitrite (suggested by Kuhn and Gunthard9) followed by a rearrangement similar to reaction (3) can be discounted because when ethyl nitrite was heated with a large excess of nitric oxide for 16 hours at 95” during which less than O.I~’ of the former was pyrolysed only traces of nitrogen and nitrous oxide were formed. It is probable that the large yields of nitrogen found in the pyrolysis of the higher nitrites5 can be explained on this basis. (Received September 27th 1962.) The Occurrence of N(b)-Epimeric Quaternary Alkaloids in Hunieria eburnea Hunterburnine a-and p-Methiodide By C.C. SCOIT,G. A. SIM,and J. MONTEATH ROBERTSON DEPARTMENT GLASGOW, (CHEMISTRY THE UNIVERSITY W.2) WE recently established that hunterburnine methio- equi-inclination Weissenberg photographs only 692 dide the iodide of one of a group of isomeric quater- independent structure amplitudes could be evaluated nary alkaloids of molecular formula C20H27N202+ the low total being a consequence of the poorly developed crystals. The crystal and hence molecular isolated’ from Hunteria eburnea has the constitution and stereochemistry defined in (1).2 We have now carried out a crystal-structure analysis of the iodide of another of these alkaloids (m.p. 335”) and our results summarised in formula (11),show it to be the N(b)-epimer of (I).Spectroscopic studies and functional group analysis are fully consistent with structure We propose to rename (I) hunterburnine /3-methio- dide and to call (11) hunterburnine a-methiodide. Though synthetic N(b)-epimeric yohimban meth- iodides are known4 it is noteworthy that (I) and (11) constitute the first recognised pair of naturally occurring N(b)-epimeric quaternary alkaloids. There is an interesting pharmacological difference between (I) and @I) the latter inducing a marked lowering of blood pressure in the anaesthetised dog? Hunterburnine a-methiodide crystallises in the orthorhombic system space group P212221 with four molecules of C20H2,N20,T in a unit cell of dimensionsa = 10.97 b = 18.75 c = 9.60 A.From structure was elucidated by three-dimensional Fourier methods. Superimposed contour sections illustrating the eighth three-dimensional electron- density distribution over one molecule are shown in the Figure. The value of R is now 20 %. The ekhth three-dimensional e lectron-densit.v distribu- tion over one molecule of hunterburnine a-methiodide shown by means of superimposed contour sections drawn parallel to (001). For the calculations on the Glasgow University DEUCE computer programmes devised by Dr. J. S. Rollett5 and Dr. J. G. Sime6 were employed. We are grateful to Dr. W. I. Taylor (Ciba Pharma- ceutical Company) for supplies of material and for valuable correspondence. (Received September 3rd 1962.) Bartlett.Sklar. Smith. and Taylor. unmblished work. a Asher Robertson Sim Bartlett Skla; and Taylor Proc. Chem. Soc. 1962 72. Personal communication from Dr. W. I. Taylor. Witkop and Goodwin J. Amer. Chem. SOC.,1953,75 3371. Rollett. in “Computing Methods and the Phase Problem in X-Ray Crystal Analysis,” ed. Pepinsky Robertson and Speakman Pergamon Press Oxford 1961 p. 87. * Sime ref. 5 p. 301. PROCEEDINGS A Total Synthesis of atrone By D. J. CRISPIN and J. S. WHITEHURST (CHEMISTRY DEPARTMENT, THE UNIVERSITY OF EXETER) WE report a new straightforward synthesis of oestrone. Racemic 5,6,7,8-tetrahydro- 1 b-hydroxy- 8-methylindan-5-one1 (I)was as tetrahydropyranyl ether which,converted into enolate in benzene solution was treated m-methoxyphenethyl toluene-p-sulphonate.The pro- duct after hydrolysis and oxidation gave the di- ketone (II). The latter was cyclised smoothly with phosphorus pentoxide in phosphoric acid to yield the 17-ketone (III) m.p. 1083 Amax. (in ethanol). This compound by a reduction yields estrone stereoselectively.2 Cyclisa- tion of (11) with toluene-p-sulphonic acid in benzene yieIded 14-isoequilenin 3-methyl ether (IV).3 Boyce and Whitehurst J. 1960,4547. Hughes and Smith Chem. and Znd. 1960 1022. Birch Jaeger and Robinson J. 1945 582; Bachmann Cole and Wilds J. Amer. Chem. SOC.,1940 62 824; Johnson Petersen and Gutsche J. Amer. Chem. SOC.,1947,69 2942. The Addition of Grignard Reagents to a/%UnsaturatedKetones Catalysedby Copper Salts KHARASCN'S observation1 that in the presence of cuprous halides Grignard reagents tend to add to the carbon+arbon double bond of an ap-unsatu- rated ketone rather than to the carbonyl group has had limited practical use e.g.in introducing angular methyl group^;^ the yields are frequently poor and variable. We have now devised a procedure which geatly improves the yield. A cupric salt in solution for example cupric acetate in tetrahydrofuran (-0.1 mole relative to the ketone) together with the O Me W 0 the potassium its with 313 mp,E 32,200 two-stage 0LJ5 @ (1) MeO\ RCH2 WC"* & &I Me0 \ tho\ Satisfactory analyses and spectral data have been obtained for all these compounds. (Received September 7th 1962.) By A.J. BIRCHand M. SMITH OF MANCHESTER) (UNLVERSITY ketone is added to an excess of the Grignard reagent. Testosterone acetate with methylmagnesium iodide gives 20% yield of (I;R = Me) m.p. 129-130'; 19-nortestosterone acetate gives 83 %yield of (I; R = H) m.p. 164-1 66" ;this yield being of the same order as that obtained with the octalone (11). In all cases so far examined including the ketone (111) cis-ring junctions result exclusively. The ketonic product (64%)from the dienone (IV) is a mixture of (V) (15%) and (VI) (85%). The stereochemistry assigned to (VI) depends on its base-catalysed isomerism to the more stable stereoisomer with the a-hydrogen at the ring junction. Because of the non-rigidity of these systems no information about the conformation of the transition states can be inferred from the products.It seems likely however that the carbanion becomes attached axially to the ring originally containing the con- jugated system (cf. ref. 3). This work was carried out under the tenure of an I.C.T. Fellowship (M.S.). (Received September 12th 1962.) Kharasch and Tawney J. Amer. Chem. SOC.,1941,63,2308. Birch and Robinson J. 1943 501. Toromanoff Bull. SOC.chim. France,1962,708. NOVEMBER 1962 357 Hydrogenolysisof the Benzyl-Oxygen Bond by Boron TrifluorideSodium Borohydride By G. R. mm B. GREEN,and P. HOFER (DEPARTMENT UNIVERSITY MAINE,U.S.A.) OF CHEMISTRY OF MATNE,ORONO and D. C. AYRES and P.J. S. PAUWELS (DEPARTMENT LONDON, OF CHEMISTRY SIRJOHN CASSCOLLEGE E.C.3) Tm well-known catalytic and chemical hydrogeno- lysis methods1 for reductive cleavage of benzyl-oxy-gen bonds have recently been supplemented by several metal hydride technique^.^,^ For example the mixed hydride prepared from aluminium chloride and lithium aluminium hydride has been recom-mended3 for reduction of alkyl aryl and diary1 ketones to hydrocarbons.We now report the reductive fission of the benzyl- oxygen linkage by using boron trifluoride-sodium Ar (IV) b~rohydride.~ Both 2-naphthyt ethyl ketone and the \(I corresponding alcohol were easily reduced to 2- propylnaphthalene. Similar treatment of 3,4-methyl-PI+ cPh2-oH enedioxy-3',4',5'-trimethoxybenzophenone and an-(Ar = 3,4,5-Tri-hydropodophyllol (I) led to 3,4methylenedioxy-HO ,, methoxypheny I) phenyl-3,4,5-trimethoxyphenylmethane,m.p.58-60° and deoxypodophyllol (In respectively. In-sodium borohydride. However preliminary studies terestingly boron trifluoride-sodium borohydride indicate that diarylcarbinols (e.g. V) may yield the reduction of picropodophyllin(111) gave deoxypicro- products of dehydration rather than hydrogenolysis. podophyllin (IV). Following purification the products This investigation was supported in part by the were obtained in 58-80 % yields. National Cancer Institute U.S. Public Health Ser-Triphenylmethanol was readily converted into tri- vice and by Smith Kline and French Laboratories. phenylmethane (70% yield) by boron trifluoride- (Received August 27th 1962.) Hartung and Simonoff Org.Reactions 1953,7 263. Tweedie and Cuscurida J. Amer. Chem. SOC. 1957,79 5463. Nystrom and Berger J. Amer. Chem. SOC.,1958 80 2896; Brown and White J. 1957 3755; Bokadia Brown, Cobern Roberts and Somerfield J. 1962 1658. Prepared in. situ and used essentially as described by Pettit and Piatak J. Org. Chem. 1962,27 2127. Alternatively treating a solution of the compound and sodium borohydride in diethylene glycol dimethyl ether with boron trifluonde- tetrahydrofuran was useful with acid-sensitive substrates. The Molecular Structure of Dihydridodilr-cyclopntadienylmolybdenum By M. J. BENNETT J. A. MCCLEVERTY, M. GERLOCH and R. MASON (INORGANIC CHEMISTRY RESEARCH LABORATORIES, IMPERIAL aLLEGE OF SCIENCE AND TECHNOLOGY, LONDON S.W.7) THE preparation of the di-wcyclopentadienyl Patterson Fourier and least-squares methods the hydrides of tantalum molybdenum and tungsten has bond lengths shown in the Figure corresponding to been reported by Wilkinson et al? who on the basis the usual discrepancy index R = 0.098 for the com- of high-resolution nuclear magnetic resonance plete two-dimensional data no hydrogen being in- studies and steric considerations suggested that the cluded in the structure-factor calculations.The metal-to-ring axes are not collinear. We can now average estimated standard deviation (e.s.d.) of the report a single-crystal X-ray analysis which confirms molybdenum-carbon bond lengths is 0.04 A and the this suggestion mean carbon-carbon bond lengths and bond angles The pale yellow crystals grown by slow sublima- are 1.49 A and 107" with e.s.d.s of 0.12 A and 3" tion in vacuo are monoclinic with a = 14.30 A b = respectively.5.90 A c = 10-41A j3 = 104-0"; the space group The molecule is wedge-like the angle between the is Cc (C:). The structure has been determined by eclipsed cyclopentadienyl rings being 25" f3O. Green McCleverty Pratt and Wilkinson J. 1961 4854. 358 PROCEEDINGS A particularly significant feature of the analysis bond length is 1.1 f0.2 A the bond angle HMoH is the location by difference Fourier methods of the being 90" f10".This result is in striking agreement hydrogen atoms The mean molybdenum-hydrogen with the only previously known metal-hydrogen bond distance of ca. 1.1 A in iron carbonyl hydride as determined by broad-line proton resonance methods? The overall geometry of dihydridodi-r-cyclopentadienylmolybdenumis also consistent with the electronic model described by Ballhausen and Dahl? We acknowledge the award of a State Scholarship (M.J.B.) and thank the Department of Scientific and Industrial Research for a Research Studentship (to M.G.) and the Carnegie Trust for the Universities of Scotland for a scholarship (to J.A.McC.).(Received October 2nd 1962.) Bishop Down Emtage Richards and Wilkinson J. 1959,497. * Ballhausen and Dahl Acra Chem. Scand, 1961,15 1333. Aminostannanes Stannylamines and Stannazanes By K. JONES and M. F. LAPPERT (DEPARTMENT FACULTY UNIVERSITY OF CHEMISTRY OF TECHNOLOGY OF MANCHESTER) ALTHOUGHthe silylamines and silazanes are well- with many multiple-bonded compounds to afford known,l the analogous germanium and tin com-novel classes of tin compounds.Trimethylstannyl pounds have received little attention; and the first dimethylcarbamate dimethyldithiocarbamate and Sn-N derivatives have only recently been obtained. NN-dimethy1-N'-phenylurea and thiourea have beer We now report the preparation and characterisa- adequately characterised (see Table). The reactions tion (see Table) of some other aminostannanes two leading to their formation are essentially insertions stannazanes a tristannylamine and a cyclostan-into the Sn-N bond. Preliminary qualitative experi- nazane the polynuclear species were prepared by ments indicate that similar additions can be realised transamination-elimination methods.We have also with a much wider range of reagents and also with found that dimethylaminotrimethylstannane reacts these reagents and amino-derivatives of elements TABLE* 4-4-Compound B.p./mm. o Compound B.p./mm. a o Compound B.p./mm. % (M.p.) " (M.p.) 9 (M.p.) 2 5 3 SII(NM~,)~ 51"/0*15 1 Me,Sn.NPh 128"/0-1 1 (Me,Sn),NEt 93"/15 2 BunSn(NMea 67"/0*1 1 Me 2SnW Me 2) 2 138"/760 1 Me,Sn-NMePh 82"/0.1 1 (Me3Sn),N 70"/0-2 3 Me,Sn(NPr*,) 66"/0*05 1 Me,Sn.NHPh 77"/0.05 1 Me,Sn<(NEt.SnMeJ,>NEt 104"/0-054 Bun2Sn(NMe,) 72"/0*05 1 Et,Sn-NMe 76"/9 1 Me3Sn.0C0.NMe (156") 5 Ph,Sn(NMe,) 128"/0*2 1 Bun,Sn.NMe 86"/0.1 1 Me,SnSCS-NMe (63") 5 Me3Sn.NMe2 126"/760 1 Me3Sn.NPri 63"/8 1 Ph,Sn-NMe 166"/0*1 1 Me,SnN Ph-CO-NMe 103"/0.5 6 Mc3Sn-NBun 74"/2-5 1 (Me,Sn),NMe 64"/3 2 All compounds have been analysed and characterised also by physical constants and by their infrared spectra; they were obtained in good yields (> 65 %).t Methods 1 R,-,SnCl + nLiNR'R"; 2 Me,SnNMe + RNH,; 3 Me,SnNMe + NH,; 4 Me,Sn(NMe,) + EtNHz; 5 Me,SnNhle + CX,; 6 Me,SnNMe + PhNCO. cf. Fessenden and Fessenden Chem. Rev. 1961 61 361. Thomas Canad. J. Chem. 1961,39 1386; van der Kerk Luijten and Janssen Chimia 1962 16 10; Abel Brady and Lerwill Chem. and Znd. 1962 1333. Wiberg and Rieger G. P. 1 121 050. NOVEMBER 1962 other than tin. Indeed Breederveld has recently ob- served that carbon dioxide and carbon disulphide react similarly with dialkylamin~trimethylsilanes.~ M-N M L-i &A B-A-N= The essential characteristic of the reagent AB appears to be that it should be susceptible to attack by nucleo- philes but not electrophiles (for example we observed Breederveld Rec.Trav. chim.,1962,81 216. no reaction with unsubstituted olefins although enol acetates reacted) whilst the amino-derivative appears to be most reactive when the negative end of the di- pole of the M-N bond is well displaced towards the nitrogen (see scheme). We are grateful to Pure Chemicals Ltd. for their generous support of this work. (Received September 3rd 1962.) 1,5-Tmnsannular Shift of Hydrogen in Cycloheptatriene and Related Compounds By A. P. TER BORG,H. KLOOSTERZIEL, and N. VANMEURS (KONINKLIJKE/SHELL-LABORATORIUM, AMSTERDAM) 7-DEUTEROCYCLOHEPTA-1,3,!%TRIENE (94% iSOtOpiC purity) rearranges when heated at 100-140” to a mixture of deuterocycloheptatrienes.Mass-spectral data ruled out an intermolecular redistribution of hydrogen.Four simple mechanisms can be visualised for an intramolecular rearrangement involving the shift of one hydrogen atom and one or more double bonds A shift from 7 to a to B to y and to 7 a & and y at random. The aliphatic nuclear magnetic resonance signal for the starting material consists of a triplet (1 2 1; by H,-Ha coupling) of triplets (1:l:l; by H,-D coupling) with a total intensity of 1.06. The first additional feature to appear is a triplet characteristic of a methylene group flanked by two a-protons.The 7 to a and the 7 to random shift are thus ruled out since they would give rise to a doublet and a triplet + doublet respectively. The decision between the 740- and 7-to-y shifts was arrived at by integration of the total spectrum which revealed that in the early stages of the reaction the intensity of the 7 signal grows at the expense of the y signal by a 7-to-y shift of protiurn the deuterium appears in the y position decreasing the intensity of the y signal [(I) + (II)]. Since the complete set [(Q-(IV)] of 7to y shifts (X = D) involves only one rate constant (with statistical factors) if secondary isotope effects are disregarded the distribution of protons over the various positions during the rearrangement is uniquely determined.Nuclear magnetic resonance data tally with the depicted scheme but not with the other mechanisms mentioned. The occurrence of this 1-5 transannular shift can be understood from the non-planar model of cycloheptatriene*. The energy and entropy of activa- tion are 31 kcal./mole and -10 cal.deg.-l mole-l (indicative of a rigid transition state). The energy of activation for the reaction (I) + (II) (X = Ph) in which the trienic and aromatic systems enter into conjugation is 4 kcal./mole less. The rates of the isomerisations of the other phenylcycloheptatrienes in which the phenyl group remains in conjugation with either the rearranging dienic part ((11) + (111)J or the nonparticipating enic part [(Ill) -$(IW] are however similar to the rate of (deutero)cyclohepta-triene itself.1,5-TransannuIar shifts are also involved in the isomerisations of cycloheptatrienecarboxylic esters and acids (the Biichner acids). The double bond which is not directly involved in the 1-5 shift need not be present. Thus cyclohepta-1,3-diene derivatives including dihydrotropones also appear to show 1-5 shifts. (Received September 3rd 1962.) * Since the infrared spectrum of 7-deuterocycloheptatrieneshows the presence of two species one with “axial” D and one with “axial” H a planar carbon-skeleton has to be rejected (C. la Lau and H. de Ruyter unpublished results). PROCEEDINGS Stable Radicals Derived from Azo-1-pyrroline 1-Oxides By A. R. FOWTERand R. H. THOMSON (UNIVERSITY OF ABERDEEN) REDUCI-IVE cyclisation of 3-methyl-3-nitrobutyl cyanide yields a base formulatedl as (I); spectro-scopic studies support the N-oxide structure (in chloroform solution) but the compound reacts in both forms.2 Oxidation of the base with alkaline ferricyanide or neutral pmnanganate did not give a stable free radical as did porphyrexine3 (11) but afforded instead an orange-red diamagnetic crystal- line solid m.p.203" C,,H,,N,O, h,,,. 240 435 590 mp (log E 3.68 4-50 3-22) having no infrared absorption > 3000 cm.-l. When hydrogenated over platinum oxide this solid rapidly absorbed one mol. of hydrogen with loss of colour (quickly restored on exposure to air) whereas over Raney nickel four mol. were slowly taken up to give the cyclic amidine (III).l The red product is therefore the azo-compound (IV).The leuco-compound which may have either the hydrazo- (V) or the azine structure (VI) can be isolated as the dihydrochloride ClzHz2N402,2HC1 picrate or oxalate. c >(+&-NH<+)( Y (v) Y 0-O- or oN-Nc)( Fil O Y W Nr O 0-(VII) ONa' HO (VI) OH Reagents 1 H,-Pt. 2 0,. 3 Na in tetrahydrofuran. 4 0,-HO-. 5 [Fe(CN),I3-HO-. 6 H,-Ni. If an aqueous solution of the dihydrochloride is exposed to air in the presence of a strong base (e.g. sodium hydroxide) it becomes bright blue changing gradually through green and yellow to red from Buckley and Elliott J. 1947 1508. a Forrester and Thomson unpublished work. which solution the azo-compound can be isolated quantitatively.The blue solution is paramagnetic (electron spin resonance signal4) ;rapid evaporation in vacuo affords a blue solid which is aIso paramag-netic and appears to be stable indefinitely in absence of oxygen. The blue solid was also obtained by reaction of the azo-compound (IV) with sodium under nitrogen in tetrahydrofuran or 1,2-dimethoxy- ethane the solution changing slowly from red to green to blue (cf. ref. 5). We interpret these reactions as a series of one-electron changes which proceed from the dianion of (VI) through a blue mesomeric radical-ion represent- ed by (VII) to the azo-compound (IV) and vice versa. The radical-ion inhibits the polymerisation of styrene is reduced by ascorbic acid and dithionite and oxidised by iodine and ferricyanide.It de-hydrogenates quinol and hydrazobenzene but has no effect on bibenzyl or dihydroanthracene in boiling methanol. Several homologous azopyrroline 1 -oxides which behave in the same way have been prepared but homologues of compound (I) which possess an a-hydrogen atom (e.g. VIII) do not yield azo-compounds on oxidation. Instead nitrogen and a little nitrous oxide are evolved the major product being a y-keto-nitrile. The probable course of events is shown in the annexed scheme. -0 NH-OH HO: *H OH I O N + NHp+ -N2(+N20) 0 We thank Varian Associates Ziirich for tbe electron spin resonance spectrum Mr. P.Kelly for mass-spectrometric analysis and the D.S.I.R. for a studentship (to A.R.F.). (Received,September 17th 1962.) Piloty and Schwerin Ber.1901 34 1870 2354; Piloty and Vogel Ber. 1903,36 1283. Interpretation of the hyperbe structure is in progress. Kauffmann and Hage Angew. Chem. 1961,73,680. NOVEMBER 1962 36 1 Reduction of Nitro-compounds by Triethyl Phosphite A New Cyclisation Reaction By J. I. G. CADOGAN and M. CAMERON-WOOD (KING'S COLLEGE LONDON, STRAND W.C.2) RECENTLY~ it was shown that aromatic C-nitroso- compounds are readily deoxygenated by triethyl phosphite and the reaction was utilised to reduce 2-nitrosobiaryls to carbazoles. The utility of the re- action is reduced however by the low yields obtained in the reduction of the precursory 2-nitrobiaryls to the nitroso-compounds. It has now been shown that the nitro-compounds themselves can be similarly reduced by boiling triethyl phosphite.Thus reaction of 2-nitrobiphenyl with triethyl phosphite (4 mol.) at 160" under nitrogen gave after 9 hours carbazole (m.p. and mixed m.p. 239-243") in 82.5 % yield. 4-Bromo-2'-nitrobiphenyl similarly gave 2-bromo- carbazole (7703 while pyrido [I ,2-b]indazole2 (I) (m.p. and mixed m.p. 78-79') was obtained in almost theoretical yield from 2-o-nitrophenyl-pyridine. The reaction is capable of extension to related systems e.g. phenazine has been obtained from re- action of triethyl phosphite and 2-nitrodiphenyl- amine benzocinnoline from 2,2'-dinitrobiphenyl and from benzocinnoline di-N-oxide azobenzene from NO2 r;r azoxybenzene and 2-phenylindole (m.p.and mixed m.p. 188-189') from both cix-and trans-Znitro- stilbene. Drs. R. A. Abramovitch and C. W.Rees are thanked for gifts of compounds. This investigation was supported by a D.S.I.R. Special Research Grant. (Received August 29rh 1962.) Bunyan and Cadogan Proc. Chem. SOC.,1962,78. Abramovitch and Adams Canad. J. Chem. 1961,26 4684. The Pentacyanonitrosylferrate(II)Anion By I. BERNAL and E. F. HOCKINGS (RCA LABORATORIES, PRINCETON,NEWJERSEY U.S.A.) MAGNETIC susceptibility measurements on aqueous solutions of the pentacyanonitrosylferrate(n) anion showed1 it to contain one unpaired electron and from this and other results Grfith Lewis and Willcinson concluded that the iron was bivalent. Recently,2 Griffith has concluded that the complex contains a neutral nitrosyl ligand.However this is in contrast to similar compfexe~~,~ in which the nitrosyl ligand can better be formulated as NO+. The reduction under nitrogen at a mercury cathode of a solution of disodium pentacyanonitro- sylferrate in NN-dimethylformamide (with tetra-butylammonium iodide as a supporting electrolyte) yielded a blue solution which exhibited strong electron-spin resonance absorption (Figure). This indicates that the species generated was paramagnetic with an electronic ground state that was orbitally non-degenerate. The three absorption lines are of equal intensity and approximately evenly spaced and arise from interaction of the unpaired electron with the nitrogen nucleus in the nitrosyl ligand.Similar nitrosyl-nitrogen interactions have been ob-served in pentacyanonitrosylchromate(~~)~ and in bis-(NN-dimethy1dithiocarbamato)nitrosyliron(n) P The non-equivalent cyano-nitrogen is not expected to give rise to hyperfine splitting.6 Polarographic methods have shown7 that the reduced species re- tains all the ligands of the original anion and that reduction is a one-electron process. Addition of an electron must give a 3d7 configuration which in C, symmetry becomes (e)4(ba)2(bl)1 with an electronic ground state 2B,.This accords with the observed elect r on-spin resonance. The optical spectrum showed one absorption band Griffith Lewis and Wilkinson J. 1958 3993. Griffith Quart. Rev. 1962 16 188. Lewis Irving and Wilkinson J.Inorg. Nuclear Chem. 1958 7 32. Eernal and Harrison J. Chem. Phys. 1961,34 102. Gray Bernal and Billig J. Amer. Chem. Soc. 1962 84 3404. Weissman and Gamer J. Amer. Chem. SOC.,1956,78 1072. 'Kolthoff and Toren J. Amer. Chem. SOC..1953,75 1197. PROCEEDINGS at 16,500 cm.-l (E = 1500) and possibly another in the region of 25,000 cm.-l (E -5000) but the latter was not clearly resolved. The spectrum can be com-pared with that of the dithiocarbamatoiron complex r The electron -spin resonance spectrum of [Fe(CN),N0l3-at 9.492 Klwclsec. For the central line g = 2.0253. as the compounds are isoelectronic and have the same effective symmetry. The dithiocarbamate showed a band at 17,100 cm.-l (E = 1200). As the nitrosyl group dominates the overall ligand field,5 the optical absorption spectrum should be similar for the two compounds particularly since the transitions in question do not involve orbitals of 4 character.The presence of the axial cyano-group in the reduced anion acts only as a perturbation on the energy levels observed for the dithiocarbamato-complex. The transition observed in the pentacyanonitrosylferrate-(11) at 16,500 cm.-l is assigned as b (u*)-+e (n*). The electron-spin resonance spectrum shows that the unpaired electron is delocalised between the iron and the NO ligand. The nitrogen hyperfine splitting constant for [Cr(CN),NOIS- was about one third of that found for [Fe(CN),NO]* showing that the extents of delocalisation depend upon whether the metallic orbitals concerned are non-bonding or anti- bonding.The available data suggest that these metal-nitrosyl complexes should be considered as molecular species with electrons delocalised to different extents rather than containing charged ligands. (Received August 20th 1962.) The Absolute Configurationof Calycanthine By S.F. MASON (CHEMISTRY DEPARTMENT OF EXETER) UNIVERSITY X-RAY diffraction studies1 have established the structure of calycanthine as (I) apart from the absolute configuration. The optical rotatory power of the molecule measured in the present work as the circular dichroism in the region of the long-wave- length absorption band at 3100 8( (Figure) indicates that (I) represents the absolute configuration. Me (1) Optically calycanthine consists of two aniline chromophores with an angle1 of 61" between the planes of the aromatic rings the intersection of the planes making an angle of 28" with the two-fold axis of each aniline residue.The long-wavelength absorp- tion band of mono- and para-di-substituted benzene derivatives is due to a transition which is polarised in the plane of the aromatic nucleus perpendicular to the two-fold axis as is shown by the polarised spectra2 and by studiesS of the intensity variation with substitution. Correlation interactions give for any particular excitation of aniline two transitions in calycanthine one polarised perpendicular and the other parallel to the two-fold rotation axis of the molecule. Moffitt's coupled-oscillator theory,' which does not require correction5 for the present case indicates that the two associated transitions of calycanthine should have rotational strengths of equal magnitude and opposite sign and that the transition with the smaller dipole strength should have the lower energy.The calculated dipole strengths of the parallel and the perpendicular transitions of calycanthine are in the ratio 1.4:1 if it is assumed that the long-wave- length excitation of the aniline residues is polarised in the aromatic plane perpendicular to the C-N bond direction; and the ratio is increased if allowance is made for the effect of the o-alkyl substituent in each aniline residue on the transition moment direction. The perpendicular transition has therefore the Hamor and Robertson J.1962 194. Albrecht and Simpson J. Chem. Phys. 1955,23 1480; J. Amer. Chem. Soc. 1955 77,4454.. Platt J. Chem. Phys. 1951 19 263. Moffitt,J. Chem. Phys. 1956,25,467. 6 Moffitt Fitts and Kirkwood,Proc. Nat. Acad. Sci. 1957 43 723. NOVEMBER 1962 363 I-------l-4 lower energy and the high- and the low-frequency circular dichroism bands observed under the long- wavelength absorption band of calycanthine (Figure) are due to the parallel and the perpendicular transition respectively. The higher- and the lower-frequency circular di- chroism bands have rotational strengths of negative and positive sign respectively and these signs are given by coupled-oscillator theory“ for the parallel and the perpendicular transition respectively if calycanthine has the absolute configuration (I).The author is indebted to Dr. J. Harley-Mason for a sample of calycanthine and to the Royal Society Imperial Chemical Industries Limited and Messrs. Albright and Wilson Ltd. for the components used to construct the circular-dichroism spectrophoto- The electronic absorption spectrum (A) and the meter. circular dichroism (B) of calycanthine in ethanol. (Received September 9th 1962.) A New Procedure for the Protection of Amino-groups By A. T. KADERand C. J. M. STIRLING (THE QUEEN’S OF BELFAST) UNIVERSITY ELIMINAnor f cert in /%groups (e.g. OR,l S02R, formate (I) and aniline with N-ethanolic potassium OCOR4) from sulphones occurs readily hydroxide (1-1 mol ) gave the ethoxy-sulphone (111) NRsSO,A~,~ under basic conditions.We have now found that and the salt (IV) which with acid gave aniline (88 %). p-Me~C,H4~S02-CH,CH2~OCOCl + PhNH - (1) 5. p-MeC6H4-S0,CH,CH2-OC0.NHPh I (ID A r-p-Me-C,H,-SO,CH,CH,.OEt K+ -0.CO.NHPh (I111 (Iv) similar elimination of carbamoyloxy-groups affords In applications to peptide synthesis the protected a simple method for the protection of amino-groups. amino-acid (V)was converted into the p-nitrophenyl The sulphone (11) obtained from the chloro- ester and thence into the protected dipeptide estefl X-NHCH2CO*NH-CH2C02H X-NHCHR.CO*NH*CHR’C02Et (VIII) (iii)/ CVI) NH2CH2*CO-NH.CH2C02Et J (X = p-MeC,H4.S0,CH,.CH2-O-COI) Stirling Chem. and Ind. 1960 933.Kader and Stirling J. 1962 3686. Stirling,J. 1962 3676. Mamalis and Rydon J. 1955 1049. Cf. Bodanszky and du Vigneaud J. Amer. Chem. SOC.,1959 81 5688. (VI) which under appropriate conditions gave the free peptide the protected peptide acid or the un- blocked peptide ester as in the following examples (i) Treatment with N-aqueous ethanolic sodium hydroxide (3 mol.; 1 hr. at 20") removed the pro- tecting group and hydrolysed the ester group yield- ing the free peptide (VII). Glycylglycine glycyl-L- alanine L-alanylglycine and L-alanyl-L-alanine have each been obtained by this route all stages giving at least 77% of crystalline product. Dipeptides which contained L-alanine residues had specific rotations within 1O of literature values? (ii) Hydrogenation of the ester (VI; R = R' = H; CH,Ph for Et) in t-butyl alcohol7 over palladium-charcoal gave the protected peptide acid (-11) (89 %).(iii) Treatment PROCEEDINGS of the ester (VI; R = R' = H) with N-ethanolic sodium ethoxide (1 mol.; 15 min. at 20")gave gIycyl- glycine ethyl ester (92 %) as the N-(2,4-dinitrophenyl) derivative.8 The chloroformate (I) which is easily prepared from 2-hydroxyethyl p-tolyl sulphone has m.p. 48" and is stable. Related methods for the protection of hydroxyl thiol and carboxyl groups are being studied. We thank Dr. J. Grimshaw for valuable discus- sions which led to this investigation and the Ministry of Education of The Republic of Iraq for a scholarship (to A.T.K.). (Received September 12th 1962.) Erlanger and Brand J.Amer. Chem. Soc. 1951,73 3508. Crofts Markes and Rydon J. 1959 3610. Cf. Rydon and Smith J. 1955 2542. Evidence for Carbon-1 Protonation of l-Nitro-4,6,8-trimethyIazulene By JANOSSCHULZE and F. A. LONG (DEPARTMENT CORNELL ITHACA, OF CHEMISTRY UNIVERSITY N.Y. U.S.A.) THE early calculations and experiments of Heil- bronner and his co-workersl*a indicated that protona- tion of 1-substituted azulenes would normally occur at position 3. However it was pointed out that steric considerations might sometimes lead to carbon-1 protonation and Heilbronner suggested this as a at position 3 enough so that tritium or deuterium can be introduced at position 3 with use of acidic media.4?5 The neutral molecules of 1-nitroazulene and 1-nitro-4,6,8-trimethylazulenegive quite similar ultra- violet spectra both in non-polar solvents and in possibility for the 1,s-dimethylazulenium cation (I)? water.However the spectra of solutions in 70% r I 7+ We present evidence of a similar situation with the 1-nitro-4,6,8-trimethylazuleniumion (11). This is of interest since nuclear magnetic resonance ultra- violet and mass-spectrometric studies indicate that 1 -nitroazulene preferentially protonates on the nitro- group even though it also protonates very slightly aqueous perchloric acid which completely proto- nates both molecules and from which both can be recovered unchanged after neutralisation are very different. The spectrum of the 1-nitroazulenium ion is very similar to that of cations of azulenes which protonate on the substituent group e.g.1-formyl- and 1-trifluoroacetyl-azulenes. In contrast the spectrum of the 1 -nitro-4,6,8-trimethylazulenium ion is very like those of cations of azulenes which pro- tonate on carbon e.g. azulene and trimethylazulene. The implication is that the nitro-group does not participate in the resonance structure for the ion of the trimethyl compound; this is the expected conse- quence of the formation of structure (11). Further evidence comes from nuclear magnetic resonance spectra all taken on a Varian A60 apparatus. The peak assignments given for the neutral molecule are entirely consistent with spectra Heilbronner and Simonetta Helv. Chim.Acra 1952 35 1049. Heilbronner "Non-Benzenoid Aromatic Compounds," ed. Ginsburg Interscience Publishers New York 1959 Ch. v. Chopard-dit-Jean and Heilbronner Helv. Chim. Ada 1952 35 2170. Heilbronner and Meuche Helv. Chim. Acta to be published. Unpublished work this laboratory. NOVEMBER 1962 for similar azulenes. The spectra for the cation in CF,-CO,H and CF,CO,D are however different from those obtained for other azulenes.6 The several azulenes which protonate at position 3 invariably produce a methylene peak near 6 = 4.0 p.p.m. rela- tive to an internal tetramethylsilane standard the overall spectra being clearly similar to that of azulenium ion itself.g These methylene peaks are absent from spectra of solutions in deuterium acids showing the ready exchange of the position-3 hydro- gen atoms.For substituted azulenes which protonate at the substituent group e.g. 1-nitroazulene a methylene peak is not observed. The spectrum of l-nitr0-4,6,8-trimethylazulenein trifluoroacetic acid shows an unusual peak at 6 = 6.66 p.p.m. which disappears when the solvent is deuterated. This peak is shown by integration to be due to one hydrogen atom. The obvious explanation is that protonation is preferentially at position 1 leading to structure (II). The unusual position of the peak can be qualita- tively explained as due to a strong deshielding effect of an adjacent nitro-group and to the absence of shielding from a second hydrogen atom such as is present when protonation is on the unsubstituted position 3.’ The spectrum in CF,-C02D does not show a peak due to protons at position 3 implying proton exchange at this site presumably due to a slight tendency to protonate at position 3 also.The nuclear magnetic resonance spectrum of 9,lO-dimethyl-1,Zbenzanthracene in CF,CO,H-H,O-BF shows that the proton addition occurs at carbon 9.8 The stabilisation of the resulting cation (111) is very similar to that here suggested for cation (11.) Furthermore 1 -nitro-4,6,8-trimethylazuleneis un- usually basic relative to 1-nitroazulene itself. The latter is half-protonated (on oxygen) at an H, value of -4.7.5 At this acidity position 3 is still virtually unprotonated. The nitrotrimethyl compound is half- protonated at H, = -2-3.This enhanced basicity is far larger than expected from the addition of three methyl groups and suggests an added contribution from the steric relief of forming structure (IT). The authors acknowledge the generous gift of a sample of l-nitro-4,6,8-trimethylazuleneby Profes- sor K. Hafner of the University of Marburg and financial assistance from the Atomic Energy Commission. (Received August 24th 1962.) Danyluk and Schneider J. Amer. Chem. SOC.,1960,82 997. The protons of the seven-membered ring of most simple amlenium cations lead to signals which are very close to each other. 1-Nitro- l-carboxy- and 1-fonnyl-amlenium cations however show one separated (1 p.p.m.) signal at lower field. Integration shows that the signal is due to one proton.6 This signal is probably due to a deshielding effect of the electron-withdrawing substituent at position 1 on the proton at position 8.Deshielding on a proton at position 1 would be expected to be substantially larger. MacLean van der Waals and Mackor Mol. Phys. 1958,1 247. Biosynthesis of Narcotine By A. R. BA’ITERSBY and D. J. MCCALDIN (THE BRISTOL) UNIVERSITY IT has been proposed that the phthalideisoquinoline alkaloids are biosynthesised from a benzylisoquino- line residue and a one carbon unit or alternatively that ring D (cf. e.g. I) and its attached carbon atoms are derived from a hydrated prephenic acid by re- arrangement? Activity from uniformly labelled tyrosine is known to be incorporated into narcotine (I) and narcotoline? and Gear and Spenser have demonstrated the incorporation of two units deriv- able from specifically labelled tyrosine into hydra- stine;4 these results point against the latter hypothesis and are in keeping with the former.The following experiments on narcotine (I) provide direct evidence in favour of the former proposal. DL-[2-14C]Tyrosine was fed to Papaver somniferum plants (variety “Schlanstedt”) to yield radioactive alkaloids and the isolated narcotine (I;1-00C*)was degraded5 to cotarnine (11) and opianic acid (111). The latter was virtually inactive (0.02 C*).Methyla-tion6 of the former gave the methiodide (IV; 0.97 C*) which was degraded to isolate the carbon atoms from positions 1 and 3. Within experimental error each carried one half of the original activity (0.51 0.51 C* respectively).Robinson “The Structural Relations of Natural Products,’’ Clarendon Press Oxford 1955. Wenkert Experientia 1959 15 165. Kleinschmidt and Mothes 2.Nuturforsch. 1959 14b 52. Gear and Spenser Nature 1961 191 1393; J. Amer. Chem. SOC.,1962,84 1059. Ahluwalia Kochhar and Ray J. Indian Chern. Suc. 1932,9 215. Roser. Annalen 1888 249 156. PROCEEDINGS [1-14C]Norlaudanosoline7 (Vl was also incor- porated into narcotine and degradation as above <zq!Me gave inactive opianic acid (HI) and the methiodide (IV;0.99C*). The latter was shown to be specifically this centre). Me01 labelled at the aldehyde group (0.94 C* located at \ OMe The origin of the lactone-carbonyl group has been <'mNk3 investigated by feeding sodium P4C Iformate.Cleavage of the resultant radioactive narcotine gave Me (lv)Meo Ho opianic acid (I11;0.48 C*) which was decarboxylated and the carbon dioxide was isolated as barium car- bonate (0.13 C*). It is thus demonstrated that the lactone-carbonyl group is derivable from the pool of C compounds in the plant. Further experiments are in progress involving [methyl-14C]methionine and "Xw labelled protoberberine derivatives as precursors. H (Received September 28th 1962.) Battersby and Binks Proc. Chem. SOC. 1960 360. A New Aluminium-Nitrogen System J. IDRISJONESand W.S. MCDONALD (NATIONAL D.S.I.R. TEDDINGTON) CHEMICALLABORATORY ATlow temperatures certain aluminium compounds of the type AIX3 (where X = hydrogen alkyl aryl or halogen) combine with amines to form 1:1 mole-cular addition compounds f R3N -I-AlX -R3N4kX3 (I).When heated,l-' those adducts having hydrogen on nitrogen and hydrogen alkyl or aryl on aluminium lose hydrogen or hydrocarbon and form successively polymers (R2NAlX2) (11) and (RNAIX) (111) and finally the three-dimensional wurtzite structure of aluminium nitride AlN. In contrast the aluminium- chlorine bond is very stable and no condensation occurs when there are alkyl or aryl groups on nitrogen.s Nor is it possible to eliminate hydrogen halide thermally or chemically when there is hydro-gen on nitrogen ;9 indeed H3N:AlC13 is reported to be stable at its boiling point 42O0.lo Compounds (R,NAlX& (TI) have been charac- terised as low polymers (m= 2,3 or 4) and nitrogen- bridged cyclic structures with tetrahedral co-ordination of aluminium and nitrogen have been suggested.8 All the polymers (111) previously reported* are claimed to have macromolecular structures consist- ing of a two- or three-dimensional framework of alternating tetra-co-ordinated aluminium and nitro- gen atoms.There is no indication of the formation of a cyclic trimer analogous to the well-known boron-nitrogen (borazole) system. Such a trimer with its three-co-ordinate aluminium and nitrogen would require some T bonding to stabilise the ring. Laubengayefl claims that "there is no evidence for nbonding to set up multiple bonds between alumin- ium and nitrogen atoms." We now report the preparation of a series of crystalline tetramers (ITI) related to the tetrameric borazynes recently reported from this Laboratory-l1 The essential difference between our approach to the synthesisof these oligomers and that of Laubengayer Wiberg Angew.Chem. 1953,65 16. a Davidson and Brown J. Amer. Chern. SOC. 1942 64 316. Bahr Fiat Review of German Science 1939-1946 24 Inorg. Chem. p. 155. Wiberg and Noth 2.Naturforsch. 1955 10 231. Laubengayer Smith and Ehrlich J. Amer. Chem. SOP., 1961 83 542. * Ruff and Hawthorne J. Amer. Chem. Soc. 1960,82 2141; 1961 83 535; Ruff ibid. 1961 83 1798. Fetter and Bartocha Canad. J. Chem. 1961 39 2001. Laubengayer Chem. SOC. Special Publ. No. 15 1961 p. 85. * Jones and Hughes unpublished work.lo Renner Z. anorg. Chern. 1959 298 22. l1 Turner and Warne Proc. Chem. SOC. 1962 69. NOVEMBER 1962 et aL5 is that we used the molecular addition com- pounds derived from aromatic amines and a triaryl- rather than trialkyl-aluminium or dialkyl-aluminium halide and operated in dilute solution. (Since this paper was submitted Laubengayer er alla have reported on the behaviour of the methylamine adduct of triphenylaluminium but make no claim to the preparation of a crystalline tetramer.) In boiling benzene or toluene the adducts from triphenylaluminium and primary amines undergo decomposition eliminating benzene However the course of the reaction is governed by the nature of the mine. The addition compounds from alkyl- and aralkyl-amines and aromatic amines bearing ortho-substituents decompose with elimination of 1 mole of benzene per mole of triphenylaluminium and yield crystalline dimers (Ph,AINHR),.Compounds of this type have been obtained from methylamine n-propylamine benzylamine o-toluidine and 2,6- dimethylaniline. However the adducts from aro- matic amines having no ortho-substituent-aniline m-toluidine p-toluidine p-anisidine p-chloroaniline and p-iodoaniline-yield 2 moles of benzene and the tetramers (PhAlNAr),. Of the adducts we have examined the only exception to the above generalisa- tion is that from t-butylamine which appears to be stable even in boiling toluene. Clearly both elec- tronic and steric factors are operative in the synthesis of the oligomers (11) and (111).The composition of the tetramers has been firmly established by elemental analysis and molecular- weight determination ebullioscopically in benzene. They are colourless crystalline solids which cannot be sublimed without decomposition and having high (> 300”) indefinite melting points. They are extremely sensitive to oxygen and moisture. X-Ray measurements on single crystals of phenyl- imido phenyl aluminium tetramer (PhAlNPh)4 have been carried out by Dr. T. R. R. McDonald who reports :Tetragonal dipyramidal(4/m) a 20.0 f0-1 c 10.90 f0.05 A Dm 1.20 Dc (for 4 tetramer mole- cules) 1.19. Space group Z4,/a (No. 88 C46h) requiring that the molecular symmetry is 3 (inversion tetrad). Of the various structures for this tetramer which might reasonably be considered only the tub con-formation of the eight-membered ring (IV) and the cubic structure (V) have the necessary;? symmetry.\ \ / / N-AI’ ,N-Al’ ’(IV) ‘ (v) ‘ The tub conformation would suggest a system of alternating single and double bonds in the ring13s14 since only this conformation permits such an arrange- ment of bonds without strain. However the available X-ray evidence strongly favours form (V) rather than (IV). Recently,15 the “octaphenylcubane” structure has been advanced for tetraphenylcyclobutadiene dimer. Significantly the X-ray diffraction data for this system are similar to those reported above for our tetramer. (Received July 30th 1962.) l2 Laubengayer Wade and Lengnick Znorg.Chem. 1962 1 632. l3 Person Pimental and Pitzer J. Arner. Chenz. Soc. 1952 74 3437. l4 Wiegers and Vos Acta Cryst. 1961 14 562. l6 Freedman and Petersen J. Amer. Chem. Soc. 1962 84 2837. NEWS AND ANNOUNCEMENTS Library.-The Library will be closed for the Christmas holiday from 5 p.m. on Saturday December 22nd to 9.30 a.m. on Friday December 28th 1962. Liaison Officer.-Dr. B. P. Stark has agreed to serve as a Chemical Society Liaison Officer at CIBA (A.R.L.) Ltd. Duxford in place of Dr. G. Winfield. Election of New Fellows.49 Candidates whose names were published in Proceedings for September have been elected to the Fellowship. Deaths.-We regret to announce the deaths of the following Fellows Dr. T. N.Ghosh (14.5.62) of the Bengal Immunity Research Institute Calcutta; Mr. H. F. Hills (27.9.62) of Sanderstead a Fellow for over 60 years; Mr. A. Kalnins (8.9.62) formerly of the University of Adelaide; Sir Zrvine Masson (22.10.62) a former Honorary Secretary (1921- 1924); Dr. P. Schellenberg (15.7.62) of the Institute for Organic Chemistry Stuttgart; Dr. E. P. Taylor (22.9.62) Head of the Chemical Research Depart- ment Allen and Hanburys Ltd. Ware. Visit to Rhodesia and Nyasaland.-Professor F. L. Warren Head of the Department of Chemistry and Chemical Technology University of Natal Pieter- maritzburg visited the University College of Rhodesia and Nyasaland during September under the auspices of the Chemical Society. He gave two lectures in the Department of Chemistry on “Struc- tural Studies in the Senecio Alkaloids” and “The Alkaloids of the Amaryllidaceae and their Biological Synthesis.” Whilst in Salisbury he visited the Kutsaga Laboratory of the Tobacco Research Board and the Mazoe Citrus Estate of the British South Africa Company.Royal Society Leverhulme Visiting Professors- The Royal Society and the Leverhulme Trust announce the establishment of a scheme for the appointment of two Visiting Professors to India each year. Each Visiting Professor shall visit a university or research institution in India for a period of about four months. It is hoped that in this way a contdbu- tion to higher education in India can be made. In implementing the scheme a committee in India will nominate the universities or other institutions to be visited appointments will be made by the Council of the Royal Society the finance and administrative arrangements being provided by the Leverhulme Trust Fund.The first appointments will be made so that the Visiting Professors can be in India between October 1963 and February 1964. Title Journal of the American Chemical Society Journal of Physical Chem- istry Journal of Organic Chem- istry Journal of Chemical and Engineering Data Chemical Reviews Journal of Chemical Docu- men tation Chemical and Engineering News Analytical Chemistry Journal of Agricultural and Food Chemistry Inorganic Chemistry Biochemistry Journal of Medicinal and Subscript ion classification Domestic or Foreign Domestic or Foreign Domestic or Foreign Domestic or Foreign Domestic or Foreign Domestic or Foreign Domestic or Canada Foreign Domestic or Canada Foreign Domestic or Foreign Domestic or Foreign Domestic or Foreign Pharmaceutical Chemistry Domestic or Foreign Industrial and Engineering Chemistry* I&EC plus 1 quarterly IUC plus 1 quarterly (Int’l) I&EC plus 2 quarterlies I&EC plus 2 quarterlies (Int’l) I&EC plus 3 quarterlies IdiEc plus 3 quarterlies (Int’l) Domestic or Canada Foreign Domestic or Canada Foreign Domestic or Canada Foreign PROCEEDINGS American Chemical Society.-Fellows may obtain forms of application for membership of the American Chemical Society together with details of the prices of publications at Member’s rates from the General Secretary.Under a reciprocal agreement Fellows of the Chemical Society may subscribe to the journals pub- lished by the American Chemical Society at a dis- count of 10% from the non-member’s rates postage extra. 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The rates for the 1963 edition are as follows Single copy at Educational rate .. $350.00 (This applies to hospitals medical schools colleges universities.) Single copy at Industrial rate .. .. $700.00 (This applies to industrial firms government agencies public libraries research institutes not affiliated with hospitals or medical schools and research institutes who perform services for industry.) Fellows wishing to receive the Index Chemicus on behalf of their University or firm should apply to the General Secretary stating whether they are claiming the Educational or Industrial rate.The Society will act as their agent. Symposium.-A Symposium on the Chemistry and Biochemistry of Fungi and Yeasts will be held in Dublin on July 18-20th 1963 (not in June as stated in Proceedings 1962 p. 310). Further enquiries should be addressed to Professor T. S. Wheeler Department of Chemistry University College Science Buildings Upper Merrion Street Dublin Ireland. Personal.-The University of Sheffield has made the following appointments in Chemistry Dr. H. M. Atherton Lecturer; Miss T. S. Godfiey I.C.I. Research Fellowship; Dr. J. N. Murreff,Honorary Lecturer; and Dr. G. A. Taylor Assistant Lecturer.Montpellier University has conferred the degree of Hon. D.Sc. on Professor D. H. R. Burton. Dr. M. G. J. Beets has been appointed Managing Director of International Flavors and Fragrances (Nederland) N.V. Hilversum. Dr. E. T. Borrows formerly with Bataafse-Internationale Chemie Maatschappij has been appointed director of research with John Wyeth and Brother Ltd. at Havant. Professor E. Bzmcel has been appointed Assistant Professor of Organic Chemistry at Queen's Univer- sity Kingston Ontario Canada. Dr. D. D. Chapman has taken up an appointment as a research chemist with the Eastman Kodak Co. Rochester N.Y. Dr. William B. Cook of Montana State College Bozeman is currently on leave carrying out research in the Organic Chemistry Laboratories at Cambridge University.Dr. W. David English has joined the staff of Astropower Inc. California. Dr. R. A. E. Galley Manager and Director of Research at Woodstock Agricultural Research Centre has been appointed Director of Shell Research Ltd. Dr. G. J. Gittens formerly of Chelsea College of Science and Technology has joined the Chemistry Division A.E.R.E. Harwell. Mr. B. Haynes formerly Senior Lecturer at the Central College of Further Education Eastham is now a Principal Lecturer at Kingston College of Technology. Dr. J. G. Heathcote has been appointed Senior Lecturer in Biochemistry at the Royal College of Advanced Technology Salford. Dr. J. B. Jepson has been appointed to the newly- established Readership in Biochemistry at the Middlesex Hospital Medical School.Mr. E. B. Jones is now at the College of Liberal Arts University of Arizona. The American Chemical Society has appointed Dr. R.L. Kenyon director of publications for applied Journals. Dr. A. Koebner has been appointed to the Board of Solway Chemicals Ltd. as Research Director. Dr. J. Leslie has accepted a one-year appointment as Assistant Professor of Chemistry at Washington College Maryland. Mr. R. J. Loveluck has retired from his appoint- ment with Imperial Chemical Industries Limited Dyestuffs Division Grangemouth. Dr. A. R.Mathieson of the University of Leeds has been appointed Professor and Head of the Department of Chemistry Ahmadu Bells Univer- sity Zaria Northern Nigeria.Mr. I. D. Rattee has been appointed to the Chair of Colour Chemistry and Dyeing at the University of Leeds in succession to Professor W. Bradley who retired owing to ill health in September 1961. Mr. H. G. Rickard has been appointed Works Manager at the Ardeer Factory of I.C.I. Nobel Division. Dr. B. W. Rockett is now at Duke University Durham U.S.A. Dr. K. Singer at present Senior Lecturer has been appointed to the Readership in Chemistry at the Royal Holloway College. Dr. J. C. Tebby formerly of Stanford University California is now at the Department of Pharma-ceutical Chemistry U.C. Medical Centre San Francisco. Dr. A. J. Wicken formerly at King's College Newcastle upon Tyne is now at the Biochemistry Department Lincoln College University of Canter- bury New Zealand.The title of Professor in Pharmaceutical Chem- istry has been conferred on Dr. L. Saunders in respect of his post at the School of Pharmacy University of London. Dr. B. 2". Sutcfife Demonstrator in Chemistry University of Keele has accepted a Post-Doctoral PROCEEDINGS appointment in the Co-operative Computing Labora- DECHEMA (Deutsche Gesellschaft fur chemisches tories of the Massachusetts Institute of Technology. Apparatewesen) as their Honorary Delegate for Dr. A. J. V. Underwood has been appointed by Great Britain. FORTHCOMING SCIENTIFIC MEETINGS London Thursday December 13th 1962 at 6 p.m. Meeting for the Reading of Original Papers “The Cleavage of Aryltricyclohexylstannanes by Iodine in Carbon Tetrachloride,” by R.W. Bott C. Eabom and J. A. Waters. “The Mechanism of Electrophilic Substitution in Heterocyclic Chemistry. Part I. Hydrogen Exchange of Lutidine and Collidine. Part 11. The Nitration of Collidine Methosulphate,” by A. R. Katritzky and B. J. Ridgewell. “The Free-radical Hydroxylation of Benzenoid Compounds,” by W. T. Dixon J. R. Lindsay Smith and R. 0. C. Norman. To be held in the Rooms of the Society Burlington House W.l. (Abstracts of papers can be obtained from the General Secretary.) Aberdeen Wednesday December 12th 1962 at 8 p.m. Lecture “The Synthesis of Certain Pesticides,” by Dr. B. J. Heywood F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Medical Physics Lecture Theatre Marischal College.AberYstwYth Thursday December 6th 1962 at 5 p.m. Lecture “Champagne,” by Professor F. Mackenzie M.A. D.ks.1. Joint Meeting with the University College of Wales Chemical Society to be held in the Edward Davies Chemical Laboratory. Belfast Thursday December 6th 1962 at 7.45 p.m. Lecture “Catalytic Superactivity of Metal Wires,” by Dr. A. J. B. Robertson M.A. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Department of Chemistry David Keir Building Queen’s University. Bristol Thursday December 6th 1962 at 6.30 p.m. Lecture “Modem Methods of Aluminium Produc- tion,” by A. R. Carr B.Sc.A.R.I.C. and Dr. C. E. Ransley F.I.M. Joint Meeting with the Royal Insti- tute of Chemistry and the Chemical Engineering Group of the Society of Chemical Industry to be held in the Department of Chemistry The Univer- sity. Durham (Joint Meetings with the Durham Colleges Chemical Society to be held in the Science Laboratories The University.) Monday December 3rd 1962 at 5 p.m. Lecture “Unusual Co-ordination Numbers of the Transition Metals,” by Professor R. S. Nyholm D.Sc. F.R.S. Monday December loth at 5 p.m. Lecture “Emerging Patterns in the Chemistry of Gallium,” by Professor N. N. Greenwood Ph.D. F.R.I.C. Edinburgh Thursday December 6th 1962 at 7.30 p.m. Lecture “Solid-state Polymerisation,” by Professor C.H. Bamford M.A.,Sc.D.F.R.I.C. Joint Meeting with the Royal Institute of Chemistry and the Society of Chemical Industry to be held in the Heriot-Watt ColIege. Exeter Friday December 7th 1962 at 5.15 p.m. Lecture “The Benzidine Rearrangement,” by Sir Christopher Ingold D.Sc. F.R.S. To be given in the Washington Singer Laboratories Prince of Wales Road. Keele Thursday December 6th 1962 at 8.15 p.m. Lecture “Some Aspects of Di- and Tri-terpene Syn- thesis,” by Dr. J. A. Barltrop. Joint Meeting with the Royal Institute of Chemistry to be held in the Department of Chemistry The University. Leicester Monday December 3rd 1962 at 4.30p.m. Lecture “Aromatic Fluorine Compounds,” by Pro- fessor M. Stacey D-Sc. F.R.S. Joint Meeting with the University Chemical Society to be held at the Department of Chemistry The University.NOVEMBER 1962 Manchester Tuesday December 4th 1962 at 4 p.m. Lecture “The Chemistry of Bacterial Walls and Membranes,” by Professor J. Baddiley D.Sc. F.R.S. Joint Meeting with the University Chemical Society to be held in the Large Chemistry Theatre The University. Reading Friday December 14th 1962 at 7.30 p.m. Lecture “Tracer Techniques in Inorganic Analysis,” by Dr. F. Morgan. To be given in the Zoology Lecture Theatre The University. St. Andrews and Dundee Tuesday December 4th 1962 at 5 p.m. Lecture “A Few Chemical Problems Connected with Cancer Chemotherapy,” by Professor F. Bergel D.Sc. F.R.S. To be given in the Chemistry Depart- ment Queen’s College Dundee.Southampton Wednesday December 5th 1962 at 7 p.m. Lecture “Platinum Group Metals,” by E. C. Davies. 371 To be given at the College of Technology Ports- mouth. Friday December 7th at 5 p.m. Lecture “The Reactivity of Solids,” by Dr. F. S. Stone. Joint Meeting with the Royal Institute of Chemistry to be held in the Chemistry Department The University. Swansea Monday December loth 1962 at 4.30 p.m. Lecture “The Shapes and Spectra of Small Mole- cules,” by Professor A. D. Walsh Ph.D. F.R.I.C. Joint Meeting with the Student Chemical Society to be held in the Chemistry Lecture Theatre University College. Tees-side Wednesday December 5th 1962 at 8 p.m. Lecture “Organometallic Co-ordination Complexes of Some Group I1 and I11 Elements,” by Professor G.E. Coates M.A. D.Sc. Joint Meeting with the Royal Institute of Chemistry the Society of Chem- ical Industry and the Society for Analytical Chem- ists to be held at the William Newton School Norton. EDGAR CLAY BRITTON 189 1-1 962 EDGARC. BRITTON,Dow Chemical Company re- search consultant former President of the American Chemid Society and a winner of the Perkin Medal industrial chemistry’s highest award died on July 3 1 st in a Midland Michigan hospital. Director of Dow’s E. C.Britton Research Labora- tory until his retirement in 1956 Dr. Britton had continued as a research consultant on a company- wide basis until his death. He was awarded the Perkin Medal in 1956 recog- nising his many outstanding contributions to industrial organic chemical development.Among the contributions forming the basis for the award were Dr. Britton’s early work on the synthesis of phenol which provided this vital raw material in abundance for producing numerous aids to agricul- ture; his synthesis of eight of the essential amino- acids nature’s protein building blocks; and other notable accomplishments which contributed to the production of synthetic dyes pharmaceuticals syn- thetic rubber silicon resins and great numbers of chemical compounds utilised in other kinds of chemical production. Born in Rockville Indiana October 25th 1891 Dr. Britton attended Wabash College and the Uni- versity of Michigan receiving an A.B.and a Ph.D. from the latter school. Both schools also awarded him honorary degrees of Sc.D. He was an instructor in organic chemistry at the University of Michigan until he joined Dow’s organic research staff in 1920 as a research chemist. In 1932 Dr. Britton became Director of the Dow organic research laboratory which was renamed the E. C. Britton Laboratory in 1953. He served as National President of the American Chemical Society in 1952. ADDITIONS TO THE LIBRARY Schoffler-Weis compact German and English diction- ary. Revised by E. Weis and E. Weis. Pp. 626. Harrap. London. 1962. Dictionary of commercial chemicals. Compiled by F. D. Snell and C. T. Snell. 3rd edn. Pp. 714. Van Nostrand. Princeton N.J. 1962. The radiochemical manual.Part 1 Physical data a collection of data for users of radioisotopes. Compiled by the Radiochemical Centre Amersham Bucks. Pp. 102. Radiochemical Centre. Amersham. 1962. Shock waves in chemistry and physics. J. N. Bradley. Pp. 370. Methuen. London. 1962. Introduction to thermodynamics of irreversible pro- cesses. I. Prigogine. 2nd edn. Pp. 119. Interscience. New York. 1961. Tables of Einstein functions :vibrational contributions to the thermodynamic functions. J. Hilsenrath and G. G. Ziegler. (NBS Monograph No. 49.) Pp. 257. U.S. Govt. Printing Office. Washington. 1962. (Presented by the Society of Chemical Industry.) Ionization constants of acids and bases a laboratory manual.A. Albert and E. P. Scrjeant. Pp. 179. Methuen.London. 1962. Hyperconjugation. M. J. S. Dewar. Pp. 184. Ronald Press. New York. 1962. Advances in inorganic chemistry and radiochemistry. Edited by H.. J. Emeleus and A. G. Sharpe. Vol. 4.Pp. 344. Academic Press. New York. 1962. Advanced inorganic chemistry a comprehensive text. F. A. Cotton and G. Wilkinson. Pp. 959. Interscience. New York. 1962. Sulfur bonding. C. C. Price and Shigeru Oae. Pp. 208. Ronald Press. New York. 1962. Hydroboration. H. C. Brown. Pp. 290. W. A. Benjamin. New York. 1962. The dithiocarbamates and related compounds. G. D. Thorn and R. A. Ludwig. Pp. 298. Elsevier. Amsterdam. 1962. cis-trans-Isomeric carotenoids vitamins A and aryl- polyenes. L. Zechmeister. Pp. 251. Springer-Verlag. Vienna. 1962. The photosynthesis of carbon compounds.M. Calvin and J. A. Bassham. Pp. 127. W. A. Benjamin. New York. 1962. Horizons in biochemistry. A. Szent-Gyorgyi dedica- tory volume. Edited by M. Kasha and B. Pullman. Pp. 604. Academic Press. New York. 1962. Molecular biochemistry. E. M. Kosower. Pp. 304. McGraw-Hill. New York. 1962. Advances in applied microbiology. Edited by W. W. Umbreit. Vol. 4. Pp. 251. Academic Press. New York. 1962. Introduction to immunochemical specificity. W. C. Boyd. Pp. 158. Interscience. New York. 1962. Micromanometric analyses. D. D. van Slyke and J. Plazin. Pp. 85. Williams and Wilkins Co. Baltimore. 1961. Combifling speed with accuracy in routine analysis. 13. C. Wilkinson. Pp. 17. British Coke Research Assoc. Lo-don.1962. (Presented by the publisher.) Analytical chemistry of polymers. Edited by G.M. Wine. (High polymers. Vol. 12. Parts 2 and 3.) Inter- science. New York. 1962. Polymers and resins their chemistry and chemical engineering. B. Golding. Pp. 744. Van Nostrand. Princeton N.J. 1959. Chemicals from petroleum an introductory survey. A. L. Waddams. Pp. 179. John Murray. London. 1962. (Presented by the publisher.) Paint Testing Manual Physical and chemical examha- tion of paints varnishes lacquers and colors. H. A. Gardner and G. G. Sward. 12th edn. Pp. 553. Gardner Lab. Inc. Maryland. 1962. Handbook of adhesives. Edited by I. Skeist. Pp. 683. Reinhold. New York. 1962. (Presented by the publisher.) Chemical processing of reactor fuels.Edited by J. F. Flagg. (Nuclear Science and Technology Series Vol. 1.) Pp. 530. Academic Press. New York. 1961. An introduction to the physical chemistry of iron and steel makina. R. G. Ward. h.238. Edward Arnold. London. 1962. ~ The science of surface coatinm. Edited by H. W. -Chatfield. Pp. 594. E. Benn. London. 1962. Riegel’s industrial chemistry. Edited by J. A. Kent. Pp. 963. Reinhold. New York. 1962. Recent advances in food science. Edited by J. Haw-thorn and J. M. hitch. 2 Vols. Buttenvorths. London. 1962. Lipids and their oxidation proceedings of the 2nd Symposium on Foods held at Oregon State University Corvallis 1961. Edited by H. W. Schultz E. A. Day and R. 0. Sinnhuber. Pp. 442. AVI Publishing Co. Inc. Westport Connecticut.1962. Progress in industrial gas chromatography. Vol. 1. Proceedings of the third annual Gas Chromatography Institute held at Canisius College Buffalo New York April 4-6th 1961. Edited by H. A. Szymanski. Pp.235. Plenum Press. New York. 1961. Free radicals in inorganic chemistry papers presented at the symposium on inorganic Free Radicals and Free Radicals in Inorganic Chemistry at the 142nd Meeting of the A.C.S. Division of Inorganic Chemistry Atlantic City New Jersey 1962. (Advances in Chemistry Series No. 36.) Pp. 175. American Chemical Society Washing- ton. 1962. Spectroscopy report of the conference organised by the Hydrocarbon Research Group of the Institute of Petroleum held in London 1962. Edited by M. J. WelIs. Pp. 304.Institute of Petroleum. London. 1962. NEW JOURNALS Azerbaijankii Khimicheskii Zhurnal from 1961. Trudy Instituta Khimii Akademiia Nauk Azerbaijan- skoi S.S.R. from 1961 19. Doklady Akademii Nauk Azerbaijanskoi S.S.R.,from 1961 17. Trudy Instituta Khimicheskikh Nauk S.S.R. Akademiia Nauk Kayakhskoi S.S.R. from 1960 5.
ISSN:0369-8718
DOI:10.1039/PS9620000349
出版商:RSC
年代:1962
数据来源: RSC
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