bluuebunny/crossref_metadata_2025 huggingface dataset:
Die Glykoside von Vincetoxicum hirundinaria MEDIKUS. 1. Mitteilung: Isolierungen und Spaltprodukte. Glykoside und Aglykone, 316. Mitteilung
Authors: Stöckel K. , Stöcklin W. , Reichstein T.
Published: December 2004

The dried roots of Vincetoxicum hirundinaria MEDIKUS, collected in the lake of Garda area, yielded ca. 6% of a crude glycoside mixture, of which 5,16% consisted of relatively weakly polar material. After mild acid hydrolysis of the latter, 7 sugars could be identified through paper and thin layer chromatography, and paper electrophoresis. Of these D‐cymarose, L‐diginose, D‐digitoxose, and a small amount of lilacinobiose could be isolated in crystalline form. Of the other three sugars, D‐oleandrose was characterised as a crystalline derivative, whereas boivinose and canarose could only be identified through paper and thin layer chromatography, and paper electrophoresis.

Four crystalline genins (B, D, E, G) and a glycoside (F) were isolated from the genin extract. Of these, D was very unstable and therefore thus was not further investigated. B, E, and F were shown to be 15‐oxasteroids, a type of steroids so far not found in nature. Very probably, G also represents a 15‐oxasteroid. The four substances B, E, G, and F were given the following trivial names: B = anhydrohirundigenin, E = hirundigenin, G = vincetogenin, and F = hirundoside‐A. F is an oleandroside of anhydrohirundigenin. The structures of hirundigenin and anhydrohirundigenin have already been elucidated [35].
Synthese der beiden anomeren 2‐Desoxy‐D‐ribofuranoside des 2(1H)‐Pyridons
Authors: Séquin U. , Tamm Ch.
Published: December 2004

The di‐p‐toluylates IV and V of the two anomeric 2‐deoxy‐D‐ribofuranosyl‐2(1 H)‐pyridones were synthesized. IV and V were characterized by their IR.‐, UV.‐ and mass spectra. The configuration was established by NMR. spectroscopy. The specific rotations show that IV and V represent exceptions to HUDSON'Srule of isorotation.
Homoberbine, eine neue Klasse heterocyclischer Verbindungen
Authors: Brossi A. , Teitel S.
Published: December 2004

A number of rac. and optically active homoberbines have been synthesized from substituted 1‐phenethyltetrahydroisoquinolines and formaldehyde by an acid catalyzed cyclization. These homoberbines represent a new class of heterocyclic compounds which are isomeric with the homoaporphine alkaloids.
Physikalisch‐chemische, chemische und immunologische Eigenschaften der FDP‐Aldolase aus Drosophila melanogaster. 16. Mitteilung über Aldolasen [1]
Authors: Brenner‐Holzach O. , Leuthardt F.
Published: December 2004

The properties of pure aldolase from pupae of Drosophila melanogaster have been studied:

The molecular weight is about 159000 (s = 7.81 S, D = 4.55 · 10−7).

From the frictional ratio f/f0 = 1.236 the axial ratio for an oblong non hydrated ellipsoid of rotation can be calculated as b/a = 4.74.

The molecular activity is 2700 for FDP and approximately 200 for F‐1‐P.

Amino acid analysis shows significant differences between Drosophila aldolase and rabbit muscle and liver aldolases, especially in the contents of histidine, glycine, alanine and cysteine.

Hybridization with rabbit brain aldolase gives three new hybrids.

Anti‐Drosophila aldolase serum (guinea pig) does not precipitate rabbit muscle aldolase (type A) or rabbit brain aldolase (type C) in the OUCHTERLONY test.
Röntgen‐Kontrastmittel. 16. Mitteilung. Derivate von jodierten Benzoylamino‐phenyl‐ und Benzoylamino‐phenoxy‐alkansäuren
Authors: Felder E. , Pitrè D. , Fumagalli L. , Suter H. , Zutter H.
Published: December 2004

A number of new [(3‐amino‐2,4,6‐triiodo‐benzoylamino)‐phenyl‐ and ‐phenoxy]‐alkanoic acids have been synthesized for evaluation as X‐ray contrast agents. The toxicity, the bilitropism, and the urotropism of these compounds were determined.
Concerning the ‘Non‐Specific’ Far Infrared Absorption of Polar Liquids
Authors: Bulkin Bernard J.
Published: December 2004

The far infrared spectra of dimethyl sulfoxide and several aliphatic nitriles have been studied with a view towards elucidating the mechanism responsible for the intense absorption bands which have been observed in this region. Spectra of pure liquids, solid DMSO, DMSO‐d6, CD3CN, and dilute solutions in non‐polar solvents are presented. The results are discussed in terms of the possible mechanisms proposed for these absorptions.
Kernresonanzspektren des Cyclohexa‐2,5‐dien‐1‐on‐Systems (para‐Dienone)
Authors: Regel W. , von Philipsborn W.
Published: December 2004

Proton and fluorine NMR. spectra of several para‐dienones (4‐allyl‐4‐methyl‐cyclohexa‐2,5‐diene‐1‐one and its 2‐ and 3‐fluoro derivatives, a spirocyclic bis‐dienone and two dienone alkaloids) have been analysed using multiple resonance, solvent effects, and computer techniques. The relative signs of all the H, H‐ and H, F‐coupling constants of the para‐dienone system have been determined. The nature and significance of long range coupling in cyclic and openchain cross‐conjugated dienones is discussed in comparison with related systems of aromatic character.
Die Glykoside Vincetoxicum hirundinaria MEDIKUS. 3. Mitteilung: Struktur von Hirundigenin und Anhydrohirundigenin. Glykoside und Aglykone, 318. Mitteilung
Authors: Stöckel K. , Stöcklin W. , Reichstein T.
Published: December 2004

Hirundigenin can easily be converted into anhydrohirundigenin by thermal dehydration. Both substances are stable to alkali but unstable under acid conditions. Dehydrogenation of anhydrohirundigenin, using selenium at 310°, gave a mixture of 2‐methylphenanthrene (29), 1, 2‐dimethyl‐phenanthro [1,2‐b] furan (30) and 1‐ethyl‐2‐methyl‐phenanthro [1,2‐b] furan (32), all of which could be isolated in crystalline form. The last two substances are new and their structures were confirmed by synthesis. Through these results, as well as by further reactions and spectra, it could be shown that hirundigenin and anhydrohirundigenin are 16‐methyl‐15‐oxapregnane derivatives, further, that they have two epoxide rings and that they probably have the structures 7 and 11. These structures were proved by O. Kennard et. al. through X‐ray studies of p‐bromobenzoyl‐anhydrohirundigenin (13). As far as we know, 15‐oxasteroids had not yet been found in nature.
Katalytische Cyclisierung von Acetylen und substituiertem Acetylen zu aromatischen Kohlenwasserstoffen
Authors: Dändliker G.
Published: December 2004

The pentahalogenides of niobium and tantalum and some tungsten chlorides catalize the cyclotrimerization of acetylenic hydrocarbons to form aromatic compounds. Acetylene is converted into benzene at atmospheric pressure and temperatures between — 20 and 130°C. Under similar conditions methylacetylene and but‐1‐yne respectively yield a mixture of the corresponding 1,2,4‐ and 1,3,5‐substituted benzenes while with but‐2‐yne hexamethyl benzene is obtained. Cocyclization between acetylene and substituted acetylenes or diacetylene is possible; in this case mono‐ and disubstituted benzenes or biphenyl, terphenyl, and polyphenyls are formed.
Das ESR.‐Spektrum von ·CF3, erzeugt durch Photolyse von Blei (IV)‐trifluoracetat
Authors: Loeliger H.
Published: December 2004

The production of ·CF3 radicals during the photolytical decomposition of Pb (IV) trifluoracetat is demonstrated by ESR. measurements.
Die Chemie des Wieland‐Gumlich‐Aldehyds und seiner Derivate [1] 136. Mitteilung über Alkaloide [2]
Authors: Hymon J. R. , Schmid H. , Karrer P. , Boller A. , Els H. , Fahrni P. , Fürst A.
Published: December 2004

The course of the reactions involved in the process of degradation of strychnine (1) to Wieland‐Gumlich aldehyde (WGA) (2), first performed by Wieland, Kaziro & Gumlich, has been elucidated. 23‐Isonitrosostrychnine hydrochloride (9a) upon treatment with thionyl chloride undergoes a fragmentation (2nd order Beckmann rearrangement), thus furnishing N(a)‐cyanoformyl‐WGA hydrochloride (14a). On heating in an acidic medium, the latter compound is transformed — at least partially via the cyclic urethane 15 — into WGA (2), which is an important keyintermediate in the syntheses of strychnine and curare alkaloids. The compound 2 can now be obtained in high purity and good yield.

A corresponding degradation has been realized with quaternary analogues (27 → 3) as well as with 10‐chlorostrychnine (58 → 62).

10‐Chlorostrychnine (58) was prepared by chlorination of strychnine with chlorine in conc. hydrochloric acid according to Leuchs & Steinborn. As by‐products of the reaction, 10, 15‐dichlorostrychnine (59) and 10, 15, 19‐trichlorostrychnine (60) could be identified.

Starting from WGA a series of derivatives have been prepared. Special mention is made of the two epimeric methyl ethers 18 and 19. The absolute configuration at the centre 17 of WGA and of these two substances has been established by optical comparisons of 3 epimeric pairs.

The methyl ether 18, by‐product «B», is obtained if methanol is used in working up the Beckmann rearrangement products of 23‐isonitrosostrychnine hydrochloride (9a).

A second by‐product, «A», results by working up under alkaline conditions. This compound has the structure 44 with inverted configuration at centre 16. Degradation of 44 under controlled conditions leads either to WG‐diol (42) or to 16‐epi‐WG‐diol (51).

Besides «Az.rdang; and «B» a series of by‐products and intermediates (16, 17, 11a, 22. 23, 24 and 25) could be detected in the course of the process of strychnine degradation.
BIRCH‐Reduktion von [2.2] Metacyclophan
Authors: Reiner J. , Jenny W.
Published: December 2004

Metal‐ammonia‐reduction of [2.2] metacyclophan led to 5, 8, 13, 16‐tetrahydro‐[2.2] metacyclophan (II). The structure of this new ring system was confirmed by UV.‐, NMR.‐and mass spectra analyses. The NMR.‐spectrum of II in solution shows an AA′ BB′‐system for the ‐CH2CH2‐groups. This part of the spectrum is temperature dependant. It collapses and coalesces to a broad singlet at approximately 145°C. A chair‐like conformation and conformational changes of II are discussed.
Mikrobiologische Umwandlung von bicyclischen Monoterpenen durch Absidia orchidis (VUILL.) HAGEM. 1. Teil: Reduktion von Campherchinon und Isofenchonchinon. 17. Mitteilung über Reaktionen mit Mikroorganismen [1]
Authors: Pfrunder B. , Tamm Ch.
Published: December 2004

(—)‐Camphorquinone (1a) was transformed to a mixture consisting of 3‐endo‐hydroxy‐camphor (2a) (40%), 3‐exo‐hydroxy‐camphor (3a) (30%) and 2‐endo‐hydroxy‐epicamphor (4a) (30%) by an aqueous suspension of the mycelium of Absidia orchidis (Vuill.) Hagem. The composition of the reduction products was determined by the NMR. spectra. Incubation of the enantiomeric (+)‐camphorquinone (1b) under the same condition yielded 3‐exohydroxy‐camphor (3b) as single product. Since both substrates form their products immediately and in the same ratio the possibility of a posterior isomerization of 3a yielding the ketols 2a and 4a can be ruled out. For comparison the course of the chemical reduction of camphorquinone (1) to the ketols (Zn in acetic acid, hydrogenation with Raney‐Ni as catalyst, NaBH4) was investigated. Camphor was not transformed by Absidia orchidis. (—)‐Isofenchonequinone (6a) yielded upon incubation with an aqueous suspension of the mycelium of Absidia orchidis exclusively 2‐endo‐hydroxy‐epi‐isofenchone (7a). The enantiomer diketone 6b gave the same result, i. e. the ketol 7b as the only transformation product. Also with isofenchonequinone the chemical reduction to the ketols by Zn in acetic acid, hydrogenation with Raney‐Ni as catalyst and NaBH4 was studied.
Das biologische Verhalten von Fettsäuren mit Dreifachbindung. IV. Der Abbau der Crepissäure (9‐Octadecen‐12‐insäure) im Tierkörper
Authors: Bernhard Karl , Kaempf Ekkehard
Published: December 2004

Crepenynic acid (9‐octadecen‐12‐ynoic acid) fed to rats as naturally occurring triglyceride is not incorporated into brain and liver lipids, and into the depot fat only to a small amount. As a metabolite the previously unknown 4‐decynedioic acid was isolated from the urine.
Das 13C‐INDOR‐Spektrum des A3X‐Systems einer Methylgruppe
Authors: Wehrli F. W. , Simon W.
Published: December 2004

The natural abundance 13C INDOR spectrum of the A3X system of the methyl group in a substituted toluene was investigated at a very small value of the perturbing rf field H2. The relative line intensities can be explained in terms of a redistribution of the equilibrium spin populations due to the polarizing field H2. The double resonance method is suggested for accurate determination of the chemical shift of 13C in medium‐size compounds where the carbon atom under consideration couples with only one set of magnetically equivalent hydrogen nuclei.
Synthèse d'isocarbostyriles et de chloro‐1‐isoquinoléines
Authors: Eloy F. , Deryckere A.
Published: December 2004

A partir d'acides cinnamiques substitués on a préparé les styrylisocyanates correspondants qui, par cyclisation thermique, ont fourni des isocarbostyriles que l'action de l'oxychlorure de phosphore transforme en chloro‐1‐isoquinoléines. Ce procédé de synthèse s'est montré supérieur aux méthodes connues.
Mechanismus der Bildung und des Zerfalls von Amidkomplexen, I Kupfer (II) und N, N′‐Diglycylpropylendiamin
Authors: Wagnerová D. , Kaden Th. , Zuberbühler A.
Published: December 2004

The kinetics of the formation and dissociation of the copper (II) complex with N, N′‐Diglycyl‐propylendiamine has been studied. In the formation reaction an intermediate was observed, the structure and reactivity of which is discussed. The rate of dissociation of the complex is proportional to [H+]2. This is explained by a rapid proton addition to one of the amino groups, followed by the slow reaction of a second proton with the coordinated amide group. The effect of acetate buffer, which increases the dissociation rate, is discussed.
Über Derivate von 9, 10‐Methaniminomethano‐ 9, 10‐dihydroanthracen
Authors: Blaser R. , Imfeld P. , Schindler O.
Published: December 2004

Im Unterschied zur BECKMANN‐Umlagerung des Oximes I, welche zum Nitril II führt, resultiert aus dem SCHMIDT‐Abbau des Ketones IV das tetracyclische Amid V. Dessen Konstitution ist gesichert durch die Überführung in XII. LiAIH4‐AlCl3‐Reduktion von V liefert das tetracyclische Amin IX.
Massen‐ und Ladungsverteilung bei der Spaltung von 249Cf mit thermischen Neutronen. Vorläufige Mitteilung
Authors: Flynn K. F. , von Gunten H. R.
Published: December 2004

The distribution of mass and charge in the thermal‐neutron‐induced fission of 249Cf has been investigated by radiochemical determination of the fission yields of 25 mass chains and one shielded nuclide (independent yield). The mass distribution is asymmetric, as in all known cases of low‐energy fission. The fission yield data indicate a value of 6 ± 1.5 for v, the average number of neutrons emitted per fission. The division of nuclear charge, as indicated by the independent yield of 136Cs, is consistent with the equal charge displacement hypothesis characteristic of low‐energy fission.
Derivate des 5, 6‐Dihydro‐p‐dithiin‐2, 3‐dicarbonsäureanhydrids, II: N‐Amino‐imide und cyclische Hydrazide
Authors: Schweizer H. R.
Published: December 2004

5. 6‐Dihydro‐p‐dithiin‐2. 3‐dicarboxylic anhydride reacts with hydrazine to form the N‐amino‐imide; the six‐membered cyclic hydrazide is formed only in minor amounts. 1‐Substituted and 1. 1‐disubstituted hydrazines form exclusively N‐amino‐imides. All N‐amino‐5.6‐dihydro‐p‐dithiin‐2. 3‐dicarboximides have fairly strong, bright greenish‐yellow colours, but are of no practical value as dyes or pigments.
Zusammensetzung und strukturelle Eigenschaften des „zweiwertigen”︁ Kobaltcyanids
Authors: Güdel H. U. , Ludi A.
Published: December 2004

The products obtained by mixing aqueous solutions of cobalt (II) chloride and potassium or hydrogen cyanide are nonstoichiometric compounds Co(CN)x, yH2O whith x between 2.2 and 2.4 and y between 1.75 and 2.15. They have a cubic face‐centered unit cell with a = 10.20 ± 0.02 Å and Z between 6.8 and 7.1 (Z = number of units Co (CN)x yH2O per cell). Infrared spectra show that there is zeolitic as well as coordinated water present. The coordination units derived from reflectance spectra in the ultraviolet and visible region are (CoIII)C6 and CoIIN6‐xOx. There exists a close structural relationship between Co(CN)x, yH2O and the stoichiometric compound Co3[Co(CN)6]2, zH2O. Comparison of calculated with experimental density shows that there must be holes in the threedimensional CoCNCo‐framework, which can be occupied by water molecules.
Über die Oxydation von Manganoxidhydroxid
Authors: Giovanoli R. , Leuenberger U.
Published: December 2004

The oxidation of γ‐MnOOH (manganite) in oxygen and its disproportionation in HNO3 lead topotactically to β‐MnO2. The oxidation of synthetic α‐MnOOH (groutite) in oxygen depends on its cristallite size; finely divided crystals oxidise rapidly to Mn5O8 which usually is stable but yields β‐MnO2 by further oxidation. Larger crystals of disperse synthetic α‐MnOOH are topotactically transformed to γ‐MnO2. In HNO3 α‐MnOOH disproportionates into γ‐MnO2 and Mn2+. Though strictly topotactical, the reaction α‐MnOOH → γ‐MnO2 is not single‐phase as might be expected. The discontinuity in the function: JAHN‐TELLER distortion vs. reaction rate, may simply be interpreted as the crosspoint of two different functions attributed to the crystal species α‐MnOOH and γ‐MnO2, respectively. This distortion confirms the presence of Mn3+ in manganite and nsutite. The wide variety of possible X ray powder patterns of the phase γ‐MnO2 is explained by the superposition of, (i) cristallite size broadening, (ii) intergrowth structure effects on the profile, and (iii) BRAGG angle shifts due to substitution of part of Mn4+ by Mn3+.
Extension de la méthode du «logarithme limite» [1] pour la détermination de la composition et de la constante de stabilité des complexes
Authors: Marcantonatos M. , Monnier D.
Published: December 2004

A study of the conditions of applicability to weak complexes of the relation log x = v log V + log (βv,cCc) = f(logV), where V and C are variable and constant total concentrations of the constituants of the complexe, shows that for conditions other than C ≫ V, another function φ(log V) accounts better for the formation equilibrium of the complexe.

From f(log V) and φ (log V) a relation t(log V) is derived whose simple analysis permits the determination of the composition and the stability constant of weak complexes.

Applications are given to 1:1, 1:2, 2:2 composition.
Darstellung und spektroskopische Untersuchungen von Kupferkomplexen mit verschiedenen Mikrostrukturen. II Stereochemie und Elektronentransferspektren von Halogeno‐Stickstoffbasen‐Kupfer (II)‐Komplexen
Authors: Ludwig W. , Gasser F.
Published: December 2004

Es werden die Elektronenspektren oberhalb der Ligandenfeldübergänge von CuL2X2‐Komplexen unidentater Stickstoffbasen mitgeteilt. Es wird der Zusammenhang zwischen Stereometrie und den Elektronentransferübergängen beschrieben und diskutiert, sowie ein Vorschlag für die Indizierung der Absorptions‐ und Reflexionsspektren gemacht. Die Untersuchungsergebnisse machen wahrscheinlich, dass neben den ligandinternen π → π*‐Übergängen bei den Pyridinbasen‐Komplexen Elektronentransferübergänge vom Typ X → M, aber keine «inversen» Elektronentransferübergänge M → π* (L) auftreten.
L'hydrolyse acide des diazocétones alcoylées: Formation d'ions α‐acylcarbonium secondaires
Authors: Dahn H. , Ballenegger M.
Published: December 2004

Hydrolysis of secondary diazoketones CH3COCN2R (R  Me, Et, isopropyl) by aqueous perchloric acid is characterized by rate‐determining protonation demonstrated by solvent isotope effects kD2O/kH2O = 0,4–0,6 and by the intervention of general acid catalysis. The product determining step, yielding keto‐alcohols and keto‐olefines, is independent of added nucleophiles; this is interpreted as resulting from the intermediate formation of (more or less free) αhyphen;ketocarbonium is ions. The hydride shift observed wih III (R = isopropyl) supports this interpretation. The difference between hydrolysis of primary and of secondary diazoketones is discussed.
Synthese von trans‐7‐Methyl‐2,16‐dioxo‐eicosen‐(14)
Authors: Joss U. , Schaltegger H.
Published: December 2004

The synthesis of trans‐7‐methyl‐2,16‐dioxoeicosen‐(14) dicarbonyl‐compounds is described.
Calicen Hochpolare Dicyan‐diphenyl‐derivate [1] [2]. Vorläufige Mitteilung
Authors: Prinzbach H. , Woischnik E.
Published: December 2004

Three dicyano‐diphenyl‐calicenes have been synthesized. Judged by the dipole moments, the uv. and nmr. data, there is appreciable charge separation in the ground states.
La migration de groupes carboxamides lors de la transposition benzilique d'amides α,β‐dicarbonylés. 24e Communication sur les réductones et les composés tricarbonylés‐1,2,3 [1]
Authors: Dahn H. , Karoui S.
Published: December 2004

Under the conditions of the benzilic acid rearrangement, α,β‐diketobutyryl‐di‐phenylamide (Ia) and ‐N‐methylanilide (Ib) are transformed into tartronic acid derivatives (VI), which decarboxylate to lactamides VII. It is proved by 14‐labelling of Ia, that the reaction takes place by carbonamide group migration.

The reaction was followed kinetically by polarography at a fixed potential; at low pH the velocity is proportional to [OH⊖], at higher pH it becomes independent of [OH⊖], which is explained by complete transformation of I into its hydrate‐anion. The equilibrium between I and its hydrate was measured by UV.‐spectroscopy.
Cinétique du coupage de la fluorescence du p‐terphényle en solution
Authors: Cosandey‐Tenthorey Maurice , Haralambof Vladimir
Published: December 2004

The quenching effect in a solution of p,‐terphenyl in toluene has been studied for an aliphatic and an aromatic ketone. The rate constant of the quenching effect has been determined by three methods, and found to be independent of the choice of the particular method. FÖRSTER'S resonance theory can be applied successfully.
ESR.‐Messungen an Radikal‐Anionen Trimethylsilyl‐substituierter Hetero‐π‐Systeme
Authors: Gerson F. , Krynitz U. , Bock H.
Published: December 2004

The ESR. spectra of the radical anions of trimethylsilyl‐substituted derivatives of p‐benzoquinone, phenylketone, diimine, p‐benzoquinone‐diimide, aniline and p‐phenylenediamine are reported. In most cases the coupling constants of 29Si isotopes in natural abundance have been measured. The comparison of the ESR. data for the radical anions of the trimethylsilyl derivatives with those for the radical anions of the corresponding parent hydrocarbons and/or alkyl‐substituted compounds provide additional evidence for the overall electron withdrawing effect of the trimethylsilyl substituent (Si←Cπ and Si←nπ delocalization).
Synthèse de C‐glycosides dérivés du pyrazole et de l'isoxazole. Communication préliminaire
Authors: Trochet J. M. J. , Jotterand A. , Le‐Hong N.
Published: December 2004

Bromination of 2.3:4.5‐di‐O‐isopropylidene‐aldehydo‐D‐arabinose p‐nitrophenyl‐hydrazone affords the corresponding hydrazidic bromide. Similarly, chlorination of 3‐O‐benzyl‐1,2‐O‐isopropylidene α‐D‐xylo‐pentodialdo‐1,4‐furanose oxime leads to the corresponding hydroxamoyl chloride. These two compounds constitute useful new synthetic intermediates in carbohydrate chemistry. For example, they may be ethynylated, then cyclised respectively to pyrazolyl‐ and isoxazolyl‐C‐glycosides.
Cyclization of the Enol Esters of o‐Acyloxyphenyl Alkyl Ketones, IV. A kinetic study of the steps of the KOSTANECKI‐ROBINSON reaction
Authors: Széll T. , Kovács K. , Zarándy M. S. , Erdőhelyi Á.
Published: December 2004

In a study of the KOSTANECKI‐ROBINSON reaction of 2,4‐diacetoxy‐6‐hydroxy‐propiophenone the rate constants and the order of each step have been approximately determined and compared. Mechanism for the reaction is suggested.
Höhere, kondensierte Ringsysteme. 5. Mitteilung[1]. Makrocyclen mit überbrückten 9, 10‐Dihydrophenanthreneinheiten
Authors: Paioni R. , Jenny W.
Published: December 2004

Starting from 2, 7‐diacetyl‐9, 10‐dihydrophenanthrene, 2, 7‐dichloromethyl‐9, 10‐dihydrophenanthrene was synthesized through a serie of a new compounds. By a modified Wurtz reaction the dichloromethyl compound led to hexahydro‐[23] (2,7) phenanthrenophane and decahydro‐[25] (2,7) phenanthrenophane. [23] (2,7) phenanthrenophane was obtained by dehydrogena tion of hexahydro‐[23] (2,7) phenanthrenophane with Pd/C. The structure of these new ring systems was confirmed by UV.‐, NMR.‐ and mass spectroscopy.
Photofragmentierung von Cyclohexa‐1,3‐dien‐5,6‐dicarbonsäure‐anhydriden [1]
Authors: Kitzing R. , Prinzbach H.
Published: December 2004

The photochemical elimination of the anhydride function («C2O3») from the dihydrobenzenoid anhydrides 6a‐6c is described. Some applications and limitations of this double bond producing reaction are given. A formal correlation between ease of «C2O3» elimination upon irradiation and upon electron impact respectively is indicated.
Zur Stabilität und Struktur der CuI‐Komplexe des Imidazols und Histamins. Chemie des einwertigen Kupfers in homogener, polarer Lösung. 1. Mitteilung
Authors: Sigwart C. , Kroneck P. , Hemmerich P.
Published: December 2004

Univalent copper is stabilized in aqueous medium by the non‐protophilic ligand CH3CN, allowing ligand displacement reactions to be investigated as if a stable CuI‐hydrate did exist. Under these conditions the formation of CuI‐complexes with imidazole and its derivatives has been studied in polar solution in the absence of CuII. Imidazole (ImH) acts upon CuI as a bidentate ligand forming polynuclear chains according to the equation
equation image

Histamine reacts in the same way, i. e. the coordination number of CuI does not exceed 2; by comparison of the complexes of CuI with histamine and its N‐methyl‐derivatives it is shown that no six‐membered chelate – which sterically would be possible – is built up. Trigonal as well as tetrahedral coordination of CuI – i. e. chelate formation – in dilute polar solutions are confined to π‐ or d‐acceptor ligands, e. g. bipyridine or methionine. Conclusions are drawn from this on the requirements for redox‐active copper in proteins.
Über Oxidhydroxide des vierwertigen Mangans mit Schichtengitter. 1. Mitteilung. Natriummangan (II, III)manganat(IV)
Authors: Giovanoli R. , Stähli E. , Feitknecht W.
Published: December 2004

The preparation of Na4Mn14O27, 9H2O (hitherto named manganomanganite or δ‐MnO2) by oxidation of a fresh Mn(OH)2 suspension in aqueous NaOH by molecular oxygen, and its probable structure are described. It is a double layer manganate (IV) structure resembling other manganates such as chalcophanite. Orthorhombic unit cell parameters are, a0 = 8,54, b0 = 15,39, c0 = 14,26 Å. In diluted nitric acid topotactical transition to manganese (III) manganate (IV), Mn7O13.5H2O (unit cell: a0 = 2,84, c0 = 7,27 Å; primitively hexagonal), and by prolonged digestion to nsutite, γ‐MnO2, occurs.
Säurekatalysierte Isomerisierung von (−)‐a‐Copaen‐epoxid
Authors: Ohloff G. , Pawlak M.
Published: December 2004

Die Epoxy‐Verbindung 2 des (−)‐α‐Copaens (1) geht bei der Behandlung mit schwachen Säuren unter molekularer Umlagerung in zwei Alkohole (3 und 5) der (−)‐α‐Muurolen‐Reihe über, während sich der dritte (4) vom (+)‐δ‐Cadinen ableitet. (−)‐3β‐Hydroxy‐T‐muurolol (5) ist ebenso wie der entsprechende Ketoalkohol 6 mit den beiden Naturprodukten identisch.
Zur Kinetik des Diffusionsvorgangs bei Adsorptionsuntersuchungen nach dem Zweielektrodenverfahren
Authors: Schmidt E. , Siegenthaler H.
Published: December 2004

Die Kinetik des Transports der adsorbierbaren Spezies bei Adsorptions‐messungen nach dem Zweielektroden‐Dünnschichtverfahren wird anhand eines linearen Diffusionsmodells untersucht. Es wird die Lösung des zugehörigen Differentialansatzes angegeben und die Beziehung zwischen den an beiden Elektroden herrschenden Flüssen diskutiert. Ein Verfahren zur Errechnung des Flusses an der Messelektrode aus Momentanwerten des Flusses an der Generatorelektrode durch Reihenentwicklung wird angeführt. Es wird nachgewiesen, dass die Existenz eines zeitlichen Grenzwerts des Integrals über den Messelektrodenfluss die Existenz eines identischen Grenzwertes des Generatorflussintegrals impliziert.
Über Pterinchemie. 29. Mitteilung. Hydroxylierung der Phenylreste in Phenylalanylpeptiden mittels Tetrahydropterin unter physiologischen Bedingungen
Authors: Viscontini M. , Mattern G.
Published: December 2004

Die Ausbeuten an Tyrosinen bei der Hydroxylierung von Peptiden, in denen das Phenylalanin eingebaut ist, sind gegenüber jenen bei der Hydroxylierung von freiem Phenylalanin bedeutend geringer. Besonders herabgesetzt wird die Bildung von o‐bzw, m‐Tyrosin. Wir nehmen an, dass dies auf die sterische Hinderung der Phenylgruppe im Komplex zurückzuführen ist, in dem Eisen als Zentralatom und Tetrahydropterin, Sauerstoff und Peptid als Liganden vorliegen.
Thermische Lactonisierung von Estern γ‐Brom‐α, β‐ungesättigter Carbonsäuren zu Δα‐Butenoliden. Direkte γ‐Bromierung von α, β‐ungesättigten Säuren
Authors: Löffler A. , Norris F. , Taub W. , Svanholt K. L. , Dreiding A. S.
Published: December 2004

By heating with iron powder at 120–150° some γ‐bromo‐α, β‐unsaturated carboxylic methyl esters, and, less smothly, the corresponding acids, were lactonized to Δ7alpha;‐butenolides with elimination of methyl bromide. The following conversions have thus been made: methyl γ‐bromocrotonate (1c) and the corresponding acid (1d) to Δα‐butenolide (8a), methyl γ‐bromotiglate (3c) and the corresponding acid (3d) to α‐methyl‐Δα‐butenolide (8b), a mixture of methyl trans‐ and cis‐γ‐bromosenecioate (7c and 7e) and a mixture of the corresponding acids (7d and 7f) to β‐methyl‐Δα‐butenolide (8c). The procedure did not work with methyl trans‐γ‐bromo‐Δα‐pentenoate (5c) nor with its acid (5d).

Most of the γ‐bromo‐α, β‐unsaturated carboxylic esters (1c, 7c, 7e and 5c) are available by direct N‐bromosuccinimide bromination of the α, β‐unsaturated esters 1a, 7a and 5a; methyl γ‐bromotiglate (3c) is obtained from both methyl tiglate (3a) and methyl angelate (4a), but has to be separated from a structural isomer. The γ‐bromo‐α, β‐unsaturated esters are shown by NMR. to have the indicated configurations which are independent of the configuration of the α, β‐unsaturated esters used; the bromination always leads to the more stable configuration, usually the one with the bromine‐carrying carbon anti to the carboxylic ester group; an exception is methyl γ‐bromo‐senecioate, for which the two isomers (cis, 7e, and trans, 7d) have about the same stability.

The N‐bromosuccinimide bromination of the α,β‐unsaturated carboxylic acids 1b, 3b, 4b, 5b and 7b is shown to give results entirely analogous to those with the corresponding esters. In this way γ‐bromocrotonic acid (1 d), γ‐bromotiglic acid (3 d), trans‐ and cis‐γ‐bromosenecioic acid (7d and 7f) as well as trans‐γ‐bromo‐Δα‐pentenoic acid (5d) have been prepared.

Iron powder seems to catalyze the lactonization by facilitating both the elimination of methyl bromide (or, less smoothly, hydrogen bromide) and the rotation about the double bond.

α‐Methyl‐Δα‐butenolide (8b) was converted to 1‐benzyl‐(9a), 1‐cyclohexyl‐(9b), and 1‐(4′‐picoly1)‐3‐methyl‐Δα‐pyrrolin‐2‐one (9 c) by heating at 180° with benzylamine, cyclohexylamine, and 4‐picolylamine.

The butenolide 8b showed cytostatic and even cytocidal activity; in preliminary tests, no carcinogenicity was observed. Both 8b and 9c exhibited little toxicity.
Push‐pull‐Cyclobutadiene
Authors: Neuenschwander M. , Niederhauser A.
Published: December 2004

Two push‐pull‐cyclobutadienes 10b and 10c are prepared by reaction of two eq. of the corresponding acetylenes having electrondonating and electronaccepting groups (4) with one eq. of HBF4 to cyclic cyanine salts, followed by elimination of HBF4 with KOC(CH3)3. These cyclobutadienes, stable in cristalline form at room temperature respectively for a short time (10b RCH3) or for several days (10c ROCH3), are extremely reactive in solution towards various nucleophiles and electrophiles. Cleavage of the nascent cyclobutenes leads to butadienes. The cyclobutadienes 10 dimerise thermally to cyclooctatetraenes 18.
Komplexone XLIII. Die Komplexe des dreiwertigen Antimons mit Polyaminocarboxylaten
Authors: Anderegg G. , Malik S.
Published: December 2004

If a strong base is added to solutions containing complexes of trivalent antimony with aminopolycarboxylates, these ligands are displaced, and oversaturated solutions of antimony (III) hydroxide are formed. This reaction has been used to investigate the formation of complexes of SbIII with the following ligands: N′‐hydroxyethyl‐ethylenediamine‐N,N,N′‐triacetate ion, ethylenediamine‐N,N,N′,N′‐tetraacetate ion, 1,2‐diaminocyclohexane‐N,N,N′,N′‐tetraacetate ion, and diethylenetriamine‐N,N,N′,N″,N″‐pentaacetate ion.
Komplexone XLIV. Die Komplexe der Anionen der Triäthylentetraminhexa‐Essigsäure mit Calcium(II), Kupfer(II) und Zink(II)
Authors: Linden W. v. D. , Anderegg G.
Published: December 2004

Using pH‐methods ‐ direct titration according to Schwarzenbach, and ligand‐ligand exchange ‐ the stability constants of the complexes of divalent calcium, copper and zinc ions with the anions of triethylenetetramine hexaacetic acid have been determined. The complications arising by the interpretation of the experimental measurements of pH‐values below 3.5 are discussed. These factors are normally not taken into account, and often wrong values of the equilibrium constants have been communicated.
Die Komplexbildungstendenz des dreiwertigen Antimons in wässeriger Lösung
Authors: Anderegg G. , Malik S.
Published: December 2004

The formation of the complexes of trivalent antimony ion with the following ligands has been investigated with pH measurements: D‐tartaric acid, L‐tartaric acid, catechol, catechol‐3,5‐disulfonic acid, 2,3‐dihydroxybenzoic acid, mercaptoacetic acid, rac‐thiomalic acid, meso‐, rac‐dithiotartaric acid, and mercapto‐ethanol. Using the determined equilibrium constants, a classification of the ligands with respect to their ability to sequester the cation studied is given. In a discussion in which data of the literature are also included the structure of the tartar emetic, the possibility of a volumetric determination of the antimony, some problems concerning the coordination number, and the structure of the complexes are examined.
Über En‐synthesen mit Singulett‐Sauerstoff [1] II. Die Farbstoff‐sensibilisierte Photooxygenierung von (—)‐Thujopsen und die Stereochemie der dargestellten Thujopsanole
Authors: Ohloff G. , Strickler H. , Willhalm B. , Borer C. , Hinder M.
Published: December 2004

The dye‐sensitized photooxygenation of (–)‐thujopsene (1) leads to two allyl hydroperoxides 16 and 17 (ratio 2:1). From the structure of the corresponding alcohols 2 and 3 it is possible to demostrate the complete stereospecificity of the addition of 1Δg‐oxygen to the acceptor system. In this way it is shown that 1 exists in only one conformation in solution. The production of the rearranged product 23 can be explained by Hock fission from the allyl hydroperoxides 16 or 17 following the Criegee mechanism. Under the epoxidation conditions 1 is converted mainly to the two new odorous substances (–)‐3‐thujopsanone (4) and (–)‐3‐isothujopsanone (5). A series of sesquiterpenes with the thujopsane skeleton is also described, all of which have been intercorrelated.
Photochemical Reactions. Part 58 [1]. On the mechanism of the rearrangement of the triplet‐excited α, β‐unsaturated δ‐diketone 3, 7‐dioxo‐4, 4‐dimethyl‐17 β‐acetoxy‐Δ5‐androstene
Authors: Domb S. , Schaffner K.
Published: December 2004

In einer vorangehenden Arbeit [2] wurde gezeigt, dass sich das triplettangeregte α, β‐ungesättigte δ‐Diketon 1 in die beiden stereoisomeren Cyclopropyl‐diketone 2 und 3 umlagert. Neue Resultate vermitteln nun einen näheren Einblick in die mechanistischen Aspekte dieser Photoreaktion. Die Bestrahlung der 4α‐Trideuteromethyl‐Verbindung 7 in Dioxan mit 2537 Å lieferte nach einem Umsatz von ≧ 30% die an C‐4 sterisch äquilibrierten Photoisomerenpaare 8a, b und 9a, b während im regenerierten Ausgangsmaterial (7) die C(4)‐Chiralität erhalten blieb. Dieser Befund spricht gegen eine konzertierte Umlagerung und ist indikativ für einen schrittweisen Reaktionsablauf.
Darstellung und Eigenschaften verschiedener 3‐Benzazocine, eine Klasse potentieller Analgetika
Authors: Pecherer B. , Stumpf J. , Brossi A.
Published: December 2004

In continuation of our study on new types of analgesics, we synthesized various hexahydro‐3‐benzazocines. The synthesis of these compounds, starting from well‐known intermediates, is described in this paper. The compounds do not exhibit biological activities worthy of further exploration.
Stoffwechselprodukte von Mikroorganismen 80. Mitteilung [1] Aranciamycin
Authors: Keller‐Schierlein W. , Sauerbier J. , Vogler U. , Zähner H.
Published: December 2004

Aranciamycin is a new antibiotic isolated from cultures of a strain of Streptomyces echinatus. The orange‐yellow acidic compound, C27H28O12, is a glycoside of an aglycone, aranciamycinone, and a 6‐deoxyhexose monomethyl ether.

The aglycone, C20H16O8, is composed of a 1, 8‐dihydroxyanthraquinone nucleus, to which a fourth carbocyclic six‐membered ring is condensed, bearing a tertiary C‐methyl group, a tertiary and a secondary hydroxyl group, a secondary methoxyl group, and a carbonyl group. A partial formula of the aglycone is given.

Aranciamycin as well as its aglycone are strongly inhibitory against gram‐positive bacteria on synthetic media. The antibiotic activity is considerably decreased by the addition of amino‐acid combinations and pyruvate to the test medium.
Untersuchung des UV. Spektrums von Acenaphtylen durch Beobachtung des durch ein elektrisches Feld induzierten Dichroismus
Authors: Seibold K. , Zahradnik R. , Labhart H.
Published: December 2004

The absolute direction of transition moments and the change of the dipole moment upon transition to excited states of acenaphthylene are determined from the influence of an electric field on the optical density of a solution. The results agree well with predictions from PPP‐calculations. In the lowest excited state the dipole moment is antiparallel to the ground state dipole moment.
The electron spin resonance spectrum of the triphenylsilyl radical formed by the X‐irradiation of monocrystalline triphenylsilane
Authors: Geoffroy M. , Lucken E. A. C.
Published: December 2004

The electron spin resonance spectrum of X‐irradiated monocrystalline triphenylsilane has been studied at room temperature. The main radical species present is the triphenylsilyl radical, formed both as isolated radicals and pair‐wise trapped radicals. For the radical pairs the analysis of the dipole coupling tensor indicates an inter‐radical distance of 7.36 Å. The 29Si hyperfine tensor has been determined, and the values discussed in terms of the electronic structure of the triphenylsilyl radical.
Schmelzreaktionen mit Aluminiumchlorid 5. Mitteilung [1] Nebenreaktionen bei der Carbazolierung von Di‐(1‐anthrachinonyl)‐amin in Pyridin‐Aluminiumchlorid‐Schmelzen
Authors: Wick A. K.
Published: December 2004

Some by‐products of the carbazolation of di‐(1‐anthraquinonyl)‐amine in aluminium chloride‐pyridine fusions rich in aluminium chloride are shown to result from pyridiniosubstitution and higher condensation of the 1, 2; 7, 8‐diphthaloyl‐carbazole primarily formed.
Fluorénacènes et fluorénaphènes Synthèses dans la série des indéno‐fluorènes, XV [1] Méthyl‐5‐dihydro‐10, 12‐indéno [2, 1‐b]fluorène
Authors: Chardonnens Louis , Häger Josef
Published: December 2004

Starting from α‐methylchalcone and diethyl ketone the title compound, II, has been synthesized in 6 steps (overall yield 26%). As an intermediate compound the gold yellow 10, 12‐dioxoderivative of II was also obtained.
Muscarine and Muscarine Isomers in Selected Inocybe Species
Authors: Catalfomo Philip , Eugster Conrad Hans
Published: December 2004

The distribution and relative concentrations of muscarine and its isomers in Inocybe species were determined. Notable was the finding that I. cinnamomea A. H. Smith, I. geophylla Karst, and I. lacera (Fr.) Quél. contained concentrations of epi‐muscarine equal to or‐higher than muscarine itself.
Synthesen in der Polymyxinreihe. 12. Mitteilung. Die Synthese von Polymyxin D1
Authors: Studer R. O. , Lergier W.
Published: December 2004

The synthesis of the cycloheptapeptide XI (Figure 1), corresponding to the structure proposed by T. Suzuki et al, for the antibiotic Polymyxin D1 is reported. This synthetic compound proved to be identical in all respects with natural Polymyxin D1.
New Methods for the Synthesis of Oxygenated Carotenoids
Authors: Surmatis J. D. , Walser A. , Gibas J. , Schwieter U. , Thommen R.
Published: December 2004

Six keto carotenoids (4, 5, 6, 11, 12, and 22) were synthesized from intermediates which were prepared from the condensation products of mesityl oxide and acetoacetic ester. Compounds 4 and 22 can serve as precursors for zeaxanthin, while 5 can be used as an intermediate for xanthophyll. Echinenone and canthaxanthin were prepared by a new approach from vitamin A. Two new types of keto carotenoids with the keto functions incorporated into the unsaturated chain were prepared.
Lattice Energy, Lattice Constant, and Thermodynamic Properties of γ–Al2O3
Authors: Borer W. J. , Günthard Hs. H.
Published: December 2004

Basierend auf bekannten thermodynamischen Daten von α‐Al2O3 (Korund) und der Phasenumwandlung α‐Al2O3→ γ‐Al2O3 werden eine Reihe von Konsequenzen für die Natur der γ‐Phase diskutiert. Es wird gezeigt, dass die Annahme einer unterkühlten Flüssigkeit für die γ‐Phase mit zuverlässigen Daten schwer verträglich ist. Andererseits sind diese Daten konsistent mit einer ungeordneten kubischen Struktur der γ‐Phase, die für alle Temperaturen bis zum Schmelzpunkt des α‐Al2O3 in Bezug auf dieses als thermodynamisch unstabil betrachtet werden kann. Die bisher bekannten Daten der Phasenumwandlung γ→α weisen insgesamt auf einen kinetisch kontrollierten Prozess hin, obwohl sie wechselseitig nicht konsistent sind. Es wird der Coulomb‐Anteil der Gitterenergie von‐γ‐al2O3 numerisch berechnet und eine Gitterkonstante von 7,883 Å (25°25) für die ungeordnete spinellartige γ‐Al2O3 Struktur aus thermodynamischen Daten abgeleitet.
Synthese von Diazoketonen aus Acylaminosäuren unter Verwendung von gemischten Anhydriden bzw. N, N′–Dicyclohexyl‐carbodiimid
Authors: Penke Botond , Czombos József , Baláspiri Lajos , Petres Jolán , Kovács Kálmán
Published: December 2004

Aus Benzyloxycarbonyl‐ und t‐Butyloxycarbonyl‐aminosäuren werden über gemischte Anhydride oder mittels N, N′‐Dicyclohexyl‐carbodiimid durch Reaktion mit Diazomethan Diazoketone hergestellt, wobei die in der Literatur [6] [7] erwähnte Oxazolonbildung nicht beobachtet wird. Durch Wolff'sche Umlagerung der Diazoketone lassen sich optisch aktive Peptide mit β‐Aminosäureresten leicht herstellen.
Isolierung und Strukturaufklärung von Chaetocin
Authors: Hauser D. , Weber H. P. , Sigg H. P.
Published: December 2004

The structure and absolute configuration of Chaetocin, a metabolite of the fungus Chaetomium minutum with antibacterial and cytostatic activity has been elucidated by chemical and X‐ray methods.
Die Photoelektron‐Spektren der Monohalogenacetylene
Authors: Haink H. J. , Heilbronner E. , Hornung V. , Kloster‐Jensen Else
Published: December 2004

The photoelectron spectra of the four monohaloacetylenes XCCH with X  F, Cl, Br, I have been recorded. The first four bands of these spectra are assigned (in order of increasing ionization potentials) to the following states: band 1: 2Π3/2(1), 2Π1/2(1); band 2: 2Π3/2(2), 2Π1/2(2); band 3: 2Σ+(3); band 4: 2Σ+(4). A correlation diagram based on a simple ZDO‐MO model shows that the observed band positions and the size of the splits due to spin‐orbit coupling can be satisfactorily explained in terms of such a model. It is found that the orbital energies AX of the postulated halogen npλ(X)‐basis orbitals are a linear function of the ionization potentials I(X) of the free atoms X. The validity of the ZDO‐MO‐model is confirmed by the excellent qualitative agreement between the observed and predicted spacings of the vibrational fine structure of the π‐bands.
Le diméthyl‐ et le diéthyl‐tétracarbonylosmium Synthèse et réactivité
Authors: L'Eplattenier F. , Pélichet Mlle C.
Published: December 2004

The sodium salt Na2[Os(CO)4] has been obtained in high yields by the reduction of either OsH2(CO)4 or Os3(CO)12 with sodium sand in the presence of catalytic amounts of 2, 2′‐bipyridyle. The reaction of Na2[Os(CO)4] with alkylating agents such as methyl and ethyl iodide produces OsR2(CO)4 (R = CH3, C2H5). NMR. and IR. spectra indicate a cis‐octahedral structure of symmetry C2v for these new alkyl compounds. Bromine breaks one osmium‐carbon bond in cis‐Os(CH3)2(CO)4 to give cis‐OsCH3Br(CO)4, whereas in cis‐Os(C2H5)2(CO)4 both ethyl groups are easily displaced by bromine to give cis‐OsBr2(CO)4. Under CO pressure and at elevated temperature cis‐Os(CH3)2(CO)4 is converted to Os(CO)5 and ethane. With cis‐Os(C2H5)2(CO)4 two CO are inserted in osmium‐carbon bonds to give . NMR. and IR. data suggest a cis‐configuration for this derivative and the possibility of the presence of rotational isomers.
Synthesen von cis‐ und trans‐1,2,3,4,4a, 10a‐Hexahydro‐1,4‐benzodioxino[2,3‐c]‐pyridinen
Authors: Berthold R. , Niklaus P. , Stoll André P. , Troxler F.
Published: December 2004

Cis‐ and trans‐1,2,3,4,4a,10a‐hexahydro‐1,4‐benzodioxino[2,3‐c]pyridines have been synthetised and their structures established by NMR.‐spectroscopy.
Reaction of 2‐Methylnorborn‐2‐ene with N‐Bromosuccinimide [1]
Authors: Jefford C. W. , Wojnarowski W.
Published: December 2004

The reaction of 2‐methylnorborn‐2‐ene with N‐bromosuccinimide produced exo‐3‐bromo‐2‐methylenenorbornane and 2‐methyl‐3‐bromonortricyclene in a 3:1 ratio. No 2‐bromomethyl‐norborn‐2‐ene was found. Most of the unreacted olefin was found to be isomerized to 2‐methylenenorbornane.

The hydrolysis of 2‐methyl‐3‐bromo‐nortricyclene with silver acetate in a 50% mixture of acetone and water afforded the corresponding alcohol and acetate. Exo‐3‐bromo‐2‐methylenenorbornane on similar treatment gave the exo‐3‐hydroxy‐2‐methylene‐norbornane and 2‐hydroxymethyl‐norbornane and 2‐hydroxymethyl‐norborn‐2‐ene and their corresponding acetates in a 3:2 ratio.

An ionic rather than a radical mechanism is proposed for the bromination reaction. In the solvolysis reactions of the resulting bromides the nature of the ionic intermediates is discussed.
Inter‐ und intramolekulare Umlagerung der Sulfogruppe in 2‐Naphtol‐1‐sulfonsäure
Authors: Fisher P. B. , Zollinger H.
Published: December 2004

The isomerisation of 2‐naphthol‐1‐sulfonic acid (potassium salt) into 2‐naphthol‐6‐sulfonic acid has been studied using labelled sulfuric acid (H235SO4). In 40 to 50% aqueous sulfric acid the reaction takes place exclusively by an intermolecular mechanism (protio‐desulfonation and resulfonation). In glacial acetic acid, in the presence of an excess of sulfuric acid, the rearrangement is partly intramolecular. With an equimolar amount of sulfuric acid the rearrangement is completely intramolecular. This reaction is first order with respect to 2‐naphthol‐1‐sulfonic acid and zeroth order with respect to excess of sulfuric acid. A mechanism for the reaction is proposed.
Contribution à la connaissance des o‐menthols et des o‐menthones (carquéjanols et carquéjanones). 3e communication
Authors: Ferretti‐Alloise Maria Giulia , Jacot‐Guillarmod André , Naves Yves‐René
Published: December 2004

The alcohols (+)‐carquejanol, (−)‐neocarquejanol, (−)‐isocarquejanol, and (−)‐neoisocarquejanol are described, and their conformations and configurations are studied by IR., NMR. and mass spectroscopies. Isocarquejanol is a mixture of conformers approximatively 50:50 with, respectively, axial and equatorial OH.
Chaleurs d'adsorption de quelques cycloalcanes sur du silicagel par chromatographie gaz‐solide
Authors: Jeanneret C. , Stauffer H. P. , Fernandez‐Garcia J. G. , Boissonnas C. G.
Published: December 2004

Heats of adsorption on silicagel, for different cycloalcanes, have been measured by gas‐solid chromatography. The experiments were carried out between 180 and 210°C. Values based on the corresponding retention times and temperature parameters for cyclopentane, cyclohexane, cycloheptane, and cyclooctane were found to be 7.5, 8.3, 10.0 and 11.5 kcal/mole, respectively.