bluuebunny/crossref_metadata_2025 huggingface dataset:
Über chelatbildende Salicylsäure‐Analoge der Thiophenreihe. II. Komplexchemische Untersuchungen
Authors: Courtin A. , Sigel H.
Published: December 2004

Acidity constants of 2‐carbethoxy‐3‐hydroxy‐5‐R‐thiophenes (R  H, CH3, phenyl, p‐biphenylyl, α‐naphtyl) and of 3‐carbethoxy‐4‐hydroxy‐2‐R‐thiophenes (R  H, CH3, phenyl) and stability constants of their complexes with some divalent metal ions have been determined. The stability of the chelates is discussed as a function of the respective bond orders of the α–β and β–β′ bonds of the thiophene ring.
Beiträge zur Chemie der Carotinoide 2. Mitteilung. Säurekatalytische Reaktionen von Isozeaxanthin
Authors: Grob E. C. , Pflugshaupt R. P.
Published: December 2004

Es wurde die säurekatalysierte Reaktion von Isozeaxanthin in Benzol‐0,01 M HCl untersucht. Für die einzelnen Reaktionsprodukte werden auf Grund chromatographischer, spektroskopischer und chemischer Eigenschaften Konstitutionsformeln vorgeschlagen.
Reaktivität von Koordinationsverbindungen XIV. Reversible O2‐Bindung an Eisen(II)‐Phtalocyanintetrasulfonsäure
Authors: Vonderschmitt D. , Bernauer Klaus , Fallab S.
Published: December 2004

Oxidation and reduction properties of iron(II) and iron(III) phthalocyaninetetrasulphonic‐acids are described. The reversible reaction of the iron(II) compound with molecular oxygen leads to a binuclear complex FeII · O2 · FeII. At a neutral pH no oxidation to the iron(III) state occurs. The stability of the O2‐complex has been determined.
Note sur la préparation de quelques isothiocyanates
Authors: Cherbuliez Emile , Weber G. , Wyss G. , Rabinowitz J.
Published: December 2004

By reacting m‐trifluoromethyl‐aniline, m‐trifluoromethyl‐benzyl‐amine and p‐fluorophenyl‐ethyl‐amine respectively with CSCl2, the authors have obtained the corresponding isothiocyanate of m‐trifluoromethyl‐phenyl, m‐trifluoromethyl‐benzyl and p‐fluorophenyl‐ethyl.
Recherches sur la formation et la transformation des esters LX. Sur la réaction des isothiocyanates avec des amino‐alcools soit libres soit estérifiés avec des acides du phosphore
Authors: Cherbuliez Emile , Baehler Br. , Jindra H. , Weber G. , Wyss G. , Rabinowitz J.
Published: December 2004

Aminoalkyl phosphoric monoesters with a primary or secondary amino group react with isothiocyanates in the presence of an alkali (2 moles of NaOH for 1 mole of the monoester and 1 mole of the isothiocyanate) to yield almost quantitatively the corresponding sodium N‐(aryl(aralkyl)‐thiocarbamyl)‐aminoalkyl phosphates; these thioureas are relatively soluble in water and generally also in methanol or ethanol.
Protonenresonanzspektren von Oximen aromatischer Aldehyde
Authors: Pejković‐Tadić I. , Hranisavljević‐Jakovljević M. , Nešić S. , Pascual C. , Simon W.
Published: December 2004

The NMR.‐spectra of 9 pairs of isomeric benzaldoximes are discussed. Syn‐anti structural assignment is possible using chemical shift data.
Photoreaktionen von Acridin und Acridinabkömmlingen Sowie von Arylketonen mit Methanol
Authors: Göth H. , Cerutti P. , Schmid H.
Published: December 2004

Beim Bestrahlen von Acridin in Methanol bzw. Äthanol entstanden neben dem 9,9′‐Biacridan (1) durch Methanol‐ bzw. Äthanol‐Addition unter C‐Hydroxyalkylierung die Verbindungen 2 und 3. Auch 9‐Methylacridin liess sich in entsprechender Weise zur Verbindung 5 umsetzen. Dieselbe Reaktion gehen 10‐Methyl‐ und 9,10‐Dimethyl‐acridiniumchlorid ein, wobei die Alkohole 6 und 7 resultieren. Beim Bestrahlen des 10‐Methylacridiniumchlorids in Äthanol entsteht auch das Dimere 9.
Sur la réaction de l'acide β‐mercaptopropionique, du β‐diéthylamino‐éthylmercaptan et de la cystéine avec divers isothiocyanates
Authors: Cherbuliez Emile , Buchs A. , Marszalek J. , Rabinowitz J.
Published: December 2004

By treating β‐mercaptopropionic acid with aryl (aralkyl) isothiocyanates in weak alkaline medium, the authors have obtained the corresponding β‐(N‐aryl(aralkyl)‐thiocarbamoylthio)‐propionic acids which, heated 2 hours at 120°, yield the corresponding 3‐aryl(aralkyl)‐4‐oxo‐2‐thiono‐tetrahydrothiazines.
Sur l'absorption des semicarbazones des cétones terpéniques dans l'ultra‐violet
Authors: Naves Yves‐René , Retamar Juan Alberto , Ricciardi Armando Italo
Published: December 2004

The UV. absorptions of semicarbazones of mono‐ and bicyclic terpene ketons are tabulated. It is possible to correlate structural features with characteristic displacements (shifts) or intensity changes of the absorption, in particular for the semicarbazones of unsaturated ketones and α‐epoxy‐ketones.
Entropiebedingte Komplexbildung Thermodynamische Daten der Komplexbildung mit dem Tripolyphosphat‐Ion
Authors: Anderegg G.
Published: December 2004

The formation of the 1:1‐complex of 10 bivalent metal ions with tripolyphosphate has been studied. The stability constants and the heats evolved by formation of the 1:1‐complexes have been determined. In all cases the complex formation is endotherm and entropically favored.
Sennosid C, ein neues Glucosid aus Cassia angustifolia (Senna). 9. Mitteilung über Anthraglykoside
Authors: Schmid W. , Angliker E.
Published: December 2004

From the leaves of Cassia angustifolia VAHL a new glycoside, sennoside C, has been isolated in crystalline form and shown by chemical means to be the 8,8′‐di‐glucoside of rhein‐aloe‐emodin‐dianthrone. This confirms the tentative formula of sennoside C by LEMLI, who deduced it by paper chromatography of the breakdown products of the aglycone. Sennoside C has the same stereochemical configuration as sennoside A.
Identifizierung der als «6β, 15α‐Dihydroxyprogesteron», «11α, 15β‐Dihydroxyprogesteron» und «12α, 15β‐Dihydroxyprogesteron» beschriebenen Steroide mit 12α, 15β‐Dihydroxyprogesteron
Authors: Dodson R. M. , Langbein G. , Muir R. D. , Schubert A. , Siebert R. , Tamm Ch. , Weiss‐Berg E.
Published: December 2004

The microbial transformation products described as «6β, 15α‐dihydroxy‐progesterone», «11α, 15β‐dihydroxy‐progesterone» and «12β‐dihydroxy‐progesterone» are shown to be identical and to possess the structure of 12β, 15α‐dihydroxy‐progesterone (1).
Exposition à la lumière de plaques cristallines de bromure d'argent, au cours de leur développement électrolytique
Authors: Steiger R. , Boissonnas Ch. G.
Published: December 2004

Thin polycristalline sheets of pure or doped silver bromide have been developed indirectly at the contact of a platinum wire connecting the crystal with a photographic developer. During the development, the crystals have been exposed several times to an intense flash of white or monochromatic light.
Calorimètre pour la mesure des chaleurs de mélange des liquides
Authors: Garcia J. G. Fernández , Boissonnas C. G.
Published: December 2004

A calorimeter has been designed for measuring the heat of mixing of liquid systems, which eliminates the need to correct for changes in the composition of the vapour phase on mixing. Improved accuracy has been obtained. It permits the measurements of thermic effects of the order of 0.005 joule, corresponding to temperature differences of 10−4 of a degree. Heats of mixing have been measured for the system hexadecane‐hexane, the results of which are highly satisfactory.
Synthesen in der Carotinoid‐Reihe 21. Mitteilung. Synthese von 2,2′‐Diketo‐spirilloxanthin (P 518) und 2,2′‐Diketo‐bacterioruberin
Authors: Schwieter U. , Rüegg R. , Isler O.
Published: December 2004

2,2′‐Diketospirilloxanthin and 2,2′‐diketobacterioruberin have been prepared via the corresponding 15,15′‐dehydro compounds by condensation of 15,15′‐dehydroapo‐4,4′‐carotenedial (C30) with 3‐methoxy‐(resp. 3‐hydroxy)‐3‐methyl‐2‐butanone. 2,2′‐Diketospirilloxanthin was identical with natural P 518.
Über Struktur und Aktivität der den H2O2‐ Zerfall katalysierenden Cu2+‐Komplexe IV. Katalatisches und peroxydatisches Verhalten von Cu2+‐Komplexen mit Adenin‐Nucleotiden und DNA. Metallionen und H2O2, 7. Mitteilung
Authors: Sigel H. , Erlenmeyer H.
Published: December 2004

The catalytic activity of Cu2+ complexes in the decomposition of H2O2, and the formation of ternary peroxo compounds – measured by their absorption at 360 nm– of the following ligands have been investigated: AMP (I), ADP (II), ATP (III), AMP‐N(1)‐oxide (IV), DNA

AMP = Adenosin‐5′‐monophosphat; ADP = Adenosin‐5′‐diphosphat; ATP = Adenosin‐5′‐triphosphat; AMP‐N(l)‐oxid = Adenosin‐5′‐monophosphat‐N(1)‐oxid; DNA‐Desoxyribonucleinsäure.

, PO43− and P2O74−.
Welkstoffe und Antibiotika. 35. Mitteilung. Konstitution des Diaporthins und Synthese der Diaporthinsäure
Authors: Hardegger E. , Rieder W. , Walser A. , Kugler F.
Published: December 2004

Das aus Kulturen von Endothia parasitica (MURR.) AND. isolierte, optisch aktive Welketoxin Diaporthin C13H14O5 gab mit Alkali Acetaldehyd und optisch inaktive Diaporthinsäure. deren Bruttoformel auf C11H12O5 berichtigt wurde. Die Interpretation der NMR.‐Spektren führte zu den Strukturformeln von Diaporthin (I) und Diaporthinsäure (III), welche durch Synthese der letzteren bewiesen wurden.
Etudes sur les matières végétales volatiles. CIC. Sur la structure du «diépoxyde d'allo‐ocimène»
Authors: Naves Yves‐René , Ardizio Pierre
Published: December 2004

The allo‐ocimene diepoxides described in our recent communication are trans (CHCH) as announced, and not cis/trans stereoisomers.
Biosynthese der Digitoxose in Digitalis lanata EHRH. (Vorversuch). Desoxyzucker, 39. Mitteilung
Authors: v. Euw J. , Reichstein T.
Published: December 2004

Strongly radioactive digitoxin (6) could be isolated (without dilution) in crystalline form from young plants of Digitalis lanata after their inoculation with D‐Glucose‐[6‐14C] using the wick method. Hydrolytic cleavage of this digitoxin gave digitoxigenin (11) and D‐digitoxose (7), both being isolated in crystalline form (without dilution). The genin was found to be 4 times more active, pro mole, than the digitoxose. This can be best explained when one assumes that the plant converts 1 mole of D‐glucose into 3 moles of acetic acid. After degradation of the digitoxose using NaJO4, acetaldehyde (as the crystalline p‐nitrophenylhydrazone) and formic acid (as the Pb salt) could be isolated. The acetaldehyde carried 65% and the formic acid 8,45% of the activity of the digitoxose. This is compatible with the assumption that digitoxose is formed in the plant from D‐glucose without re‐arrangement of the carbon chain. The appreciable activity of the formic acid could be derived from the relatively large proportion of radioactivity lost (ca. 38,9%), partly in the form of C1‐subunits, in the transformation of the intermediary lanosterol into digitoxigenin. This lost activity may be incorporated in unspecifically labelled D‐glucose which then re‐enters the biosynthetic pathway.
Die Struktur der Drevogenine. 2. Mitteilung Struktur von Drevogenin P. Glykoside und Aglykone, 278. Mitteilung
Authors: Sauer H. H. , Weiss Ek. , Reichstein T.
Published: December 2004

Drevogenin A was converted in several steps (acetylation, hydrogenation, dehydration, hydrogenation, the haloform reaction and energetic alkaline hydrolysis) into 3β, 11α, 12β‐trihydroxy‐5α‐etianic acid, which could be characterised by its crystalline methyl ester (15) and its tri‐O‐acetyl methyl ester (16). The same acid was obtained by partial synthesis starting from hecogenin. Taking into consideration earlier results [1], the structure of drevogenin P is proved to be 3β, 11α, 12β, 14β‐tetrahydroxy‐20‐oxo‐Δ5‐pregnene (7). Energetic hydrolysis of dihydro‐3‐O‐acetyldrevogenin A gave a mixture of 17αH‐ and 17βH‐desacyl‐kondurangogenin A, which were obtained in crystalline form after separation by chromatography. The only difference between the basic structures of the drevogenins and kondurangogenin A is the presence of a double bond in the 5‐position in the former.
Stoffwechselprodukte von Mikroorganismen. Granaticin B
Authors: Barcza S. , Brufani M. , Keller‐Schierlein W. , Zähner H.
Published: December 2004

From a strain of Streptomyces violaceoruber, ETH 11382, a new antibiotic, granaticin B. has been isolated. Granaticin B is an L‐rhodinoside of the previously described antibiotic granaticin.
Über die optische Reinheit und die Chiralität der enantiomeren α‐2H1‐Benzylamine
Authors: Gerlach H.
Published: December 2004

The optical purity and the absolute configuration of (–)‐α‐2H1‐benzylamine have been determined by NMR. analysis of a mixture of optically pure diastereoisomeric derivatives.
Katalytische Effekte bei der Reaktion von 2,4‐Dinitrofluorbenzol mit Morpholin in Benzol. 7. Mitteilung über nucleophile aromatische Substitutionsreaktionen
Authors: Becker G. , Bernasconi C. F. , Zollinger Hch.
Published: December 2004

The rates of reaction of 2, 4‐dinitrofluorobenzene with morpholine have been measured in benzene solution, with and without the addition of pyridine or 1, 4‐diaza‐bicyclo[2.2.2]octane (DABCO) as catalysts.

The reaction is catalyzed by morpholine, pyridine and DABCO; the rate laws as functions of these bases are expressed by equations (2)–(4).

The reaction is considerably more sensitive to pyridine and DABCO catalysis than that of 2, 4‐dinitrofluorobenzene with the sterically identical, but more basic piperidine. These findings confirm a previously found trend of greater sensitivity to base catalysis with decreasing base strength of the reacting amine.
Über eine aussergewöhnliche Stereospezifität bei der Hydroborierung der diastereomeren (1R)‐Isopulegole mit Diboran
Authors: Schulte‐Elte K. H. , Ohloff G.
Published: December 2004

Die Umsetzung der stereoisomeren Isopulegole 1–4 mit Diboran erfolgt unter hoher Stereospezifität. Aus der nachfolgenden oxydativen Aufarbeitung resultieren die Gemische der 9‐Hydroxymenthole, in denen eines der Diastereomeren stark überwiegt. Die Konstitution von 7 Diolen (5–11) wurde ermittelt und zum Teil unabhängige Wege zu ihrer Synthese entwickelt.
Enthalpy and Entropy Changes by Formation of Different Types of Complexes
Authors: Ahrland Sten
Published: December 2004

The different types of bonding in complexes formed in aqueous solution are clearly reflected in the values of ΔH0 and ΔS0 for the complex formation reaction.
Sur l'acylation des métylfuorènes I. Benzoylation et acétylation du méthyl‐1‐fluorène
Authors: Chardonnens Louis , Dousse Roland
Published: December 2004

Benzoylation and acetylation of 1‐methylfluorene according Friedel‐Crafts in carbon disulfide with aluminium chloride yielded the corresponding 2‐acyl derivatives. By oxydation the benzoyl derivative gave 2‐benzoyl‐9‐oxo‐fluorene‐1‐carboxylic acid, cyclizable into 1,2‐phthalyl‐fluorenone.
Schmelzreaktionen mit Aluminiumchlorid 3. Mitteilung [1] Zur Kenntnis der Pyridinio‐anthrachinon‐Derivate aus der Pyridin‐Aluminiumchloridschmelze von Aminoanthrachinonen
Authors: Wick A. K.
Published: December 2004

In continuation of previous work, the behaviour of amino‐anthraquinones on fusion in pyridine ‐ aluminium chloride in the presence of oxidants is studied. Instead of dimerisation the reaction leads to salts of pyridinio‐aminoanthraquinones and further to condensed “anthraimidazopyridine” derivatives.
Die Cardenolide und Pregnan‐Glykoside der Wurzeln von Asclepias lilacina WEIMARCK. I. Isolierungen Glykoside und Aglykone, 290. Mitteilung
Authors: Sawlewicz Ludwika , Weiss Ek. , Reichstein T.
Published: December 2004

The dried roots of Asclepias lilacina contain ca. 14% glykosides, in which both cardenolides and ester glycosides of pregnane derivatives are present, the latter predominating. Uzarigenin, coroglaucigenin, and their corresponding glycosides ascleposide and frugoside, resp., were shown to be present; of these four, uzarigenin was isolated in crystalline form. The ester glycosides, some of which could be isolated in a crystalline state, are predominantly composed of the aglycones 20‐O‐acetyl‐12‐O‐benzoyl‐sarcostin and 12,20‐di‐O‐benzoyl‐sarcostin, besides which esters of desacetyl‐metaplexigenin, lineolon, and dihydrosarcostin are also present. These aglycones are mostly attached to various trisaccharides which are composed of at least two 2‐deoxy‐sugar residues. Mild acid hydrolysis gave, besides the genins, 7 sugars, namely cymarose, oleandrose, digitoxose, 3‐O‐methyl‐6‐deoxy‐D‐allose (U3), as well as 3 unknown sugars U1, U2 and U5 which are probably disaccharides. U1 and U2 were isolated in crystalline form; they are isomeric and have been named asclepobiose and lilacinobiose; they are probably composed of units similar to those in the isomeric pachybiose.
Notiz über die Isolierung quartärer Alkaloide aus Pleiocarpa tubicina STAPF
Authors: Khan Zaheer M. , Hesse M. , Schmid H.
Published: December 2004

The following quaternary indole alkaloids have been isolated from the root bark of the Apocynaceae species Pleiocarpa tubicina Stapf: huntrabrine methochloride, kopsinic acid methochloride, N(a)‐methyl‐sarpagine methochloride and macusine B chloride.
Die Massenspektren von Vitamin B1 und von einigen Modellverbindungen 6. Mitteilung über das massenspektrometrische verhalten quartärer Stickstoffverbindungen
Authors: Hesse M. , Bild N. , Schmid H.
Published: December 2004

Vitamin B1, in chloride (1) or iodide form, decomposes thermally in the mass spectrometer mainly into 2‐methyl‐4‐amino‐5‐chloromethyl(iodomethyl)‐pyrimidine and 4‐methyl‐5‐β‐hydroxyethyl‐thiazole, and partly, by loss of HCl (HI) under cyclisation, into the base 2. The mass spectrum exhibits peaks due to these products and their fragments. The mass spectra of some model compounds are discussed.
Magnetische Kernresonanz‐Untersuchungen über die struktur der Komplexe aus Nitroaromaten mit azid‐ionen 9. Mitteilung über nucleophile aromatische Subsitutionsreaktionen [1]
Authors: Caveng P. , Zollinger H.
Published: December 2004

1. NMR. spectra of solutions of tetraethylammonium azide and 2,4,6‐trinitro;benzene derivatives (methyl picrate, picryl chloride and picryl azide, respectively) demonstrate that the reactants probably form σ complexes.
Recherches dans la série des cyclitols XXXV sur des complexes molybdiques, tungstiques et boriques de cyclitols
Authors: Posternak T. H. , Janjic D. , Lucken E. A. C. , Szente A.
Published: December 2004

On a isolé sous forme de son sel di‐ammonique cristallisé, un complexe épi‐inositol dimolybdique, qui a été transformé en son sel disodique C6H8O11Mo2Na2. On a préparé de même le sel disodique C6H8O11W2Na2 d'un complexe épi‐inositol ditungstique. Les poids moléculaires ont été confirmés par cryoscopie dans le sel de Glauber. Ces complexes présentent une forte mobilité électrophorétique. Il en est de même d'autres cyclitols susceptibles de contenir un groupement de 4 OH cis de conformation 1a, 2e, 3a, 5a, qui se condenserait avec les acides dimolybdique et ditungstique. Cette structure a été confirmée par le spectre de RMN. du complexe épi‐inositol dimolybdique.
Anionische Polymerisationen von 1, 3‐Cyclohexadien
Authors: Lüssi H. , Barman J.
Published: December 2004

The molecular weights obtained in the anionic polymerization of 1.3‐cyclohexadiene are exclusively determined by chain transfer with monomer. No dissociation of the ion pairs on the active chain ends seems to occur. Arrhenius plots of the intrinsic viscosities against polymerization temperature yield straight lines going through a common isocinetic point. The activation energy differences of propagation and transfer could be estimated. The extent of chain transfer depends on the solvent and counter‐ion present. The disproportionation of cyclohexadiene to benzene and cyclohexene, sometimes observed instead of the polymerization, is shown to occur if the transfer constant approaches the magnitude of unity.
Über Pyrrolizidinchemie. 8. Mitteilung [1]. Synthese von 1, 7‐Dioxopyrrolizidin
Authors: Viscontini M. , Bühler H.
Published: December 2004

Das als Zwischenprodukt der 1,7‐Dioxopyrrolizidin(I)‐Synthese dienende, sehr unbeständige 3‐Oxopyrrolidin (IV) wurde durch Ketalisierung stabilisiert. Mit Hilfe dieser Methode sind Jetzt N‐substituierte 3‐Oxopyrrolidine relativ leicht zugänglich. Die Synthese des 1,7‐Dioxopyrrolizidins (I) als Natriumenolat IX mit 3‐[3‐Oxopyrrolidinyl‐(1)]‐propionsäure‐methylester (VIII) als Edukt wird beschrieben. Das 1, 7‐Dioxopyrrolizidin (I) selbst konnte nicht isoliert werden; es scheint ebenso unbeständig zu sein wie das 3‐Oxopyrrolidin (IV).
Über die Aldolase aus Drosophila melanogaster. 12. Mitteilung über Aldolasen
Authors: Brenner‐Holzach O. , Leuthardt F.
Published: December 2004

Fructose 1,6‐diphosphate aldolase has been extracted from Drosophila m. and has been purified about 65‐fold. After precipitation with ammonium sulfate, purification on DEAE Sephadex A 50 and Sephadex G 200, we have obtained activities as high as 1350 BÜCHER units/mg protein (12,3 international units). As Drosophila aldolase is not dependent on metal ions (not influenced by EDTA) and has a broad pH optimum, it belongs to class I aldolases according to RUTTER'S classification. The KM values for both substrates FDP and F‐1‐P closely resemble those of the rabbit muscle enzyme [A], but the FDP/F‐1‐P activity ratio at substrate saturation is only 10 to 15, i.e. considerably lower than that of rabbit muscle aldolase.
Über 9β, 10α‐Steroide. 3. Mitteilung [1]. Überführung von 11‐Keto‐9β, 10α‐steroiden in 10α‐Verbindungen Synthese von 10α‐Cortison, 11‐Oxo‐10α‐progesteron, 10α‐Adrenosteron und analogen 11‐Hydroxy‐Verbindungen
Authors: Saucy G. , Müller M. , Fürst A.
Published: December 2004

Isomerisation of 11‐keto‐9β, 10α(retro)‐steroids by acid or base led to the thermo‐dynamically more stable 11‐keto‐10α‐isomers, which have not yet been described in the literature. This epimerisation at C‐9 constitutes a new route for the synthesis of 10α‐steroids. The steric factors responsible for this isomerisation are discussed.
Über einige Umwandlungsprodukte des «BLIX‐Sulfatids» und die Herstellung von quartären Dihydro‐sphingosinium‐Salzen
Authors: Kiss J.
Published: December 2004

In the sulfatide fraction of beef spinal‐cord, isolated according to the method of BLIX [9] and LEES [14], there are also sulfatides present derived from 2S, 3R‐1, 3‐dihydroxy‐2‐amino‐octadecane.
Synthese von 5‐Methyl‐3‐oxa‐A‐nor‐5β‐cholestan und 3‐Oxa‐Δ4‐cholesten‐2‐on
Authors: Heskendorn R. , Tamm Ch.
Published: December 2004

2, 3‐seco‐Δ4‐Cholestene‐2, 3‐dicarboxylic acid (5) was prepared in 30% yield from 2‐hydroxymethylene‐Δ4‐cholestene‐3‐one (1) by ozonolysis under special conditions. Pyrolysis of the pure di‐acid 5 gave A‐nor‐Δ3(5)‐cholestene‐2‐one (6), the anhydride 2 and 5‐methyl‐3‐oxa‐A‐nor‐5β‐cholestane‐2‐one (8). Pyrolysis of amorphous acidic material obtained by the ozonolysis of 1 yielded the enol‐lactones 7 and 9 as additional products. LiA1H4‐reduction of the γ‐lactone 8 gave the diol 10, which was transformed into 5‐methyl‐3‐oxa‐A‐nor‐5β‐cholestane (13) by treatment with tosyl chloride in pyridine.
Über das «pK» elektronisch angeregter Azulenium‐Kationen
Authors: Hagen R. , Heilbronner E. , Meier W. , Seiler P.
Published: December 2004

It is shown that azulenium cations in the first electronically excited state S1 are stronger acids than in the ground state S0. Their apparent pK″*, obtained from the H0‐dependence of the quenching of the azulenium cation S1 → S0 fluorescence does not correspond to a true acid‐base equilibrium in the electronically excited state S1. The pK″* values are kinetically controlled, the rate of reprotonation of azulene in the S1 state being too low to compete with the internal conversion to S0.
Die Strukturen der mittleren Ringverbidungen. XIII. Zwei neue Konformationen des Cyclodecanringes
Authors: Dunitz J. D. , Eser H. , Bixon M. , Lifson S.
Published: December 2004

The results of the X‐ray analysis of 1,1,5,5‐tetramethylcyclodecane‐8‐carboxylic acid do not correspond to a reasonable molecular structure. When used as a startingpoint for a strain‐energy minimization calculation based on semi‐empirical potential functions, they lead to two new conformations for the cyclodecane ring. It is shown that the X‐ray results can be explained by assuming that the crystal consists of a random mixture of these two conformations.
ESR.‐Spektren der Radikal‐Ionen alkylsubstituierter nicht‐alternierender Kohlenwasserstoffe
Authors: Gerson F. , Heinzer J.
Published: December 2004

ESR.‐spectra of the radical‐anions and the radical‐cations derived from two alkyl‐substituted, non‐alternant hydrocarbons, acepleiadiene (APH2) and 3,5,8,10‐tetramethyl‐cyclopenta[ef]heptalene (TMCP) have been recorded and analysed. The large differences in the total widths of the spectra of the corresponding ions (APH2⊖: 32; APH2⊕: 57; TMCP⊖: 69 and TMCP⊕: 36 Gauss) are well accounted for by the simple HMO model. The excellent agreement between the experimental and the theoretical values allows one to make a reliable assignment of the coupling constants to sets containing equal numbers of equivalent protons.
Über die Konstitution des Macralstonidins. 124. Mitteilung über Alkaloide
Authors: Waldner E. E. , Hesse M. , Taylor W. I. , Schmid H.
Published: December 2004

The alkaloid macralstonidine, which was originally isolated from Alstonia macrophylla WALL. by T. M. SHARP in 1934, has the molecular formula C41H48O3N4. The hydrolysis of this dimeric alkaloid yielded the macroline derivative 5, N(a)‐methyl‐sarpagine (6) and formaldehyde. Partial acid cleavage under deuterating conditions gave 5‐d9, 6‐d3 and decadeuterated macralstonidine. On the basis of spectral data, particularly an analysis of the mass spectra of macralstonidine and its decadeutero derivative, structure 2 has been elucidated for this alkaloid.
Synthese der 2,5‐Diole des A‐nor‐5α‐Cholestans und A‐nor‐5β‐Cholestans
Authors: Heckendorn R. , Tamm Ch.
Published: December 2004

Treatment of A‐nor‐Δ3(5)‐cholestene‐2‐one (1) with alkaline hydrogen peroxide gave 3β,5‐epoxy‐A‐nor‐cholestane‐2‐one (2) and the epoxylactone 3 (BAEYER‐VILLIGER reaction). LiAlH4‐reduction of 2 yielded A‐nor‐5β‐cholestane‐2β,5‐diol(4) (main product) and A‐nor‐5β‐cholestane‐2α,5‐diol (5). LiAlH4‐reduction of 1 led mainly to A‐nor‐Δ3(5)‐cholestene‐2α‐ol (8). Catalytic hydrogenation of 8 gave the known A‐nor‐5α‐cholestane‐2α‐01 (10), A‐nor‐5β‐cholestane‐2α‐01 (11) (main product), A‐nor‐5β‐cholestane (9) and A‐nor‐5β‐cholestane‐2‐one (12). By LiAlH4‐reduction of the ketones 12 and 13 the two additional alcohols 14 and 15 were obtained.
Opposid, vermutliche Struktur. Glykoside und Aglykone, 302. Mitt.
Authors: Hausschild‐rogat P. , Weiss E. K. , Reichstein T.
Published: December 2004

The hypothetical structure 1 is proposed for opposide (C29H44O11), a new glycoside from the seeds of Acokanthera oppositifolia (LAM.) CODD. Opposide is derived from the new aglycone gratogenin, which is most probably the 1β, 3β, 5β, 11α, 14β‐pentahydroxy‐card‐20:22‐enolide (8) (C23H34O7) and which is bound glycosidically through position 3 to the α‐pyranosidic form of 6‐desoxy‐L‐talose. The hydrolysis of opposide by HCl in acetone gave an anhydrogenin (C23H32O6) instead of the intact aglycone. In analogy to the reaction sequence observed by VOLPP and TAMM for ouabagenin, the structure of the anhydrogenin is deduced to be that of a 3β, 5β, 14β‐trihydroxy‐1α, 11α‐epoxy‐card‐20:22‐enolide (6). The above mentioned structures are based on the course of acetylation and especially on NMR.‐spectra.
Rac. cis‐ und trans‐ 1, 2‐Dimethyl‐4‐hydroxy‐6, 7‐dimethoxy‐1, 2, 3, 4‐tetrahydro‐isochinolin, Synthese und Stereochemie
Authors: Grethe G. , Uskokovice M. , Williams T. , Brossi A.
Published: December 2004

The synthesis of rac. cis‐ and trans‐1,2‐dimethyl‐4‐hydroxy‐6,7‐dimethoxy‐1,2,3,4‐tetrahydro‐isoquinoline (respectively 8 and 9) is described. The relative configuration of these amino alcohols was determined by a detailed analysis of nmr.‐ and ir.‐spectra. The comparison of the nmr.‐spectra of 8 and 9 with that of gigantine reveals the non identity of these compounds.
Neues über 1,3‐Cycloadditionen
Authors: Huisgen Rolf
Published: December 2004

Em Wort aufrichtigen Dankes gilt tüchtigen und begeisterten jungen Wissenschaftlern, die an den skizzierten Arbeiten mitwirkten. Mit der Chemie der Nitril‐ylide befassten sich die Herren Dr. H. STANGL, Dr. H. J. STURM, Dr. R. RAAB, Dip1.‐Chem. K.BUNGE und Dr. R. SUSTMANN, Die Ringöffnungen der Aziridine wurden untersucht von Dip1.‐Chem. W. SCHEER, Dr. G. SZEIMIES, Dr. L. SZABÓ und Herrn H. HUBER.
Photoreactions of Aromatic Molecules
Authors: Havinga E. , de Jongh R. O. , Kronenberg M. E.
Published: December 2004

1. Aromatic substitutions can generally be effected by simple photochemical methods.
Schmelzreaktionen mit Aluminiumchlorid 4. Mitteilung [1]. Thermische Analyse des Systems Pyridin‐Aluminiumchlorid
Authors: Wick A. K.
Published: December 2004

The phase diagram of the technical important fusion system pyridine‐aluminiumchloride was determined by classical thermo‐analysis, proving the existance of a hitherto unknown pyridine‐aluminium chloride 2:1 complex.
Die Kinetik der Murexid‐Komplexbildung mit Kationen verschiedenen Koordinationscharakters
Authors: Geier G.
Published: December 2004

The kinetics of the reaction of murexide with different divalent metal ions of class A and B have been measured by the temperature‐jump‐relaxation method. The second‐order formation rate constant increases in the sequence Ni2+ < Co2+ < Mn2+ < Zn2+ < Cd2+ ˜ Cu2+ ˜ Ca2+ < Sr2+ < Ba2+ < Pb2+.

Thermodynamic data obtained from kinetic and equilibrium studies, respectively, are in good agreement. The results are compared with the characteristic rate constants for H2O‐exchange in the inner coordination sphere of these metal ions, which follow the same sequence. The rate constants of the reaction of murexide with various trivalent metal ions, including the lanthanides, are also discussed in terms of current ideas on metal complex formation.
Etudes sur les composés organométalliques IV [1] Stabilité et nature des liaisons de quelques complexes organostanniques
Authors: Affolter Jean , Jacot‐Guillarmod André , Bernauer Klaus
Published: December 2004

The complexes between different diorganotin cations and substituted 1, 10‐phenanthrolines in aqueous solution containing acetate ion have been investigated. Diorganotin cations can co‐ordinate two acetate ions. One of these may be replaced by a 1, 10‐phenanthroline derivative. A comparison of the different equilibrium constants shows that the acid hardness of diorganotin cations is markedly modified if the organic groups bound to the tin are α,β‐unsaturated.
Über ein‐ und zweiphasige Reduktion von γ‐MnO2 durch Zimtalkohol
Authors: Giovanoli R. , Bernhard K. , Feitknecht W.
Published: December 2004

The reduction of γ‐MnO2 with cinnamic alcohol in xylene at 90° leads (1) to γ‐MnOOH in a double phase reaction with germination if the α‐MnO2 is extremely disperse, and (2) to α‐MnOOH in a strictly topotactical (single phase) reaction without germination if the γ‐MnO2 is relatively well crystallised. The hexagonality of the densest packed oxygens is not a linear function of the reduction rate but shows a discontinuity when about half of the Mn4+ are reduced, which is consistent with results of GABANO. The αMnOOH obtained by this reaction shows still the selective and asymmetric X‐ ray and electron reflection broadening of the reactant. Hence, the authors consider the product to possess an intergrowth structure of a Groutite matrix with statistically and layerwise distributed Manganite microdomains, according to a model proposed by DE WOLFF for α‐MnO2. The domains are supposed to have the size of one cell only in the b direction, and of a few cells in the a direction, and to be present in relatively small concentration.
Das biologische Verhalten von Fettsäuren mit Dreifachbindung: III. Der Abbau der Taririnsäure
Authors: Bernhard Karl , Yekundi Kushal , Kaempf Ekkehard
Published: December 2004

Octadec‐6‐ynoic acid (tariric acid) fed to rats as triglyceride is incorporated both into depot fat and liver lipids. As a metabolite the so far undesdribed dec‐4‐ene‐6‐ynedioic acid, HOOC(CH2)2CHCHCGC(CH2)2COOH, was isolated from the urine.
Réactions du diazométhane III. Etude de la réaction d'insertion entre diazométhane et phénylcarbamates: comportement de la N‐(phénoxy‐carbonyl)‐aniline et de la N‐(p‐nitrophénoxy‐carbonyl)‐aniline
Authors: Baudet P. , Calin M.
Published: December 2004

Diazomethane reacts with N‐(p‐nitrophenoxy‐carbonyl)‐aniline giving on the one hand p‐nitroanisole and phenylisocyanate, the latter being transformed into N‐phenyl‐β‐propiolactam, and on the other hand N‐(p‐nitrophenoxy)‐acetanilide by insertion. N‐(phenoxy‐carbonyl)‐aniline does not react. The insertion reaction seems to depend on the heterolysis of the bond between the oxygen of the p‐nitrophenoxy group and the carbamic carbonyl function, which is strongly polarized (existence of a mesomeric nitro‐phenoxonium). The insertion is equally influenced y the nature of the radical R attached to the carbamic nitrogen: with R = CH2COOC2H5 the reaction yields only isocyanate, with R = C6H5 it yields at the same time the isocyanate and the insertion product.
Zur Chemie von GS 13005, einem neuen insektiziden Phosphorsäureester
Authors: Rüfenacht K.
Published: December 2004

The synthesis of the new insecticidal dithiophosphoric acid ester GS 13005 as well as of intermediates, by‐products, and degradation products is described.
Über siliciumaromatische Verbindungen II. 5‐ Trimethylsilyl‐isophtalsäure und Trimethylsilyl‐terephthalsäure
Authors: Hopff H. , Gallegra P.
Published: December 2004

5‐Trimethylsilyl‐isophthalic acid (III) and trimethylsilyl‐terephthalic acid (II) have been prepared and converted into some derivatives.
Oxetane von A‐nor‐Steroiden: 2α, 5‐Oxido‐A‐nor‐5α‐cholestan, 2β, 5‐Oxido‐A‐nor‐5β‐cholestan und 2α‐Äthyl‐2β, 2′‐oxido‐A‐nor‐5α‐cholestan
Authors: Heckendorn R. , Tamm Ch.
Published: December 2004

Treatment of 2β‐tosyloxy‐A‐nor‐5α‐cholestane‐5‐ol (2) with t‐butoxide in t‐butanol gave 2α, 5‐epoxy‐A‐nor‐5α‐cholestane (3) in quantitative yield.

When A‐nor‐5β‐cholestane‐2α, 5‐diol (4) was treated with tosyl chloride in pyridine 2β‐chloro‐A‐nor‐5β‐cholestane‐5‐ol (7) and 2α‐tosyloxy‐A‐nor‐5β‐cholestane‐5‐ol (8) were obtained. Whereas the chloride 7 was resistant to t‐butoxide the tosylate 8 was transformed into an 1 : 1 mixture of 2α, 5‐epoxy‐5β‐cholestane (10) and 2ξ‐t‐butoxy‐A‐nor‐5β‐cholestane‐5‐ol (11). In 2α‐tosyloxy‐A‐nor‐5α‐cholestane‐5‐ol (12) substitution occurred as the only reaction.

Both oxetanes 3 and 10 isomerize after heating above 50° and in polar or protic solvents to form A‐nor‐Δ3(5)‐cholestene‐2α‐ol (6) and ‐2β‐ol (14) respectively. Also, 2, 5‐diols are encountered.

2α‐Ethyl‐2β, 2′‐epoxy‐A‐nor‐5α‐cholestane (23) was synthesized starting from A‐nor‐5α‐cholestane‐2‐one (17). The intermediates were the ester 16, the diol 18, the hydroxy‐tosylate 19 and the chlorhydrin 20. The spirocyclic oxetane 23 was reduced by LiAlH4 in dioxane (not in ether). By chromatography on silica gel 23 was isomerized to the homoallylic alcohol 21 and transformed into 2‐methylene‐A‐nor‐5α‐cholestane (24) by fragmentation.

The IR. and NMR. spectra of the new oxetanes were compared with those of a series of known oxetanes.
Fluorénacènes et fluorénaphènes Synthèses dans la série des indéno‐fluorènes XI [1]. Trans‐Fluorénacène et dérivés méthylés
Authors: Chardonnens Louis , Salamin Luc
Published: December 2004

On décrit la préparation, à partir de la dibromo‐2, 5‐téréphtalophénone et de quelques‐uns de ses dérivés méthylés, par déshydrobromation accompagnée d'une double cyclisation, de la trans‐fluorénacène‐dione (dioxo‐6, 12‐dihydro‐6, 12‐indéno [1, 2‐b] fluorène) et de quelques dérivés méthylés. Ces dicétones polycycliques sont colorées en orangé, rouge ou violet, et cuvables. Leur réduction selon WOLFF‐KISHNER fournit les hydrocarbures correspondants.
Die Strukturen der mittleren Ringverbindungen. XVI. Cyclooctan‐cis‐1, 2‐dicarbonsäure
Authors: Bürgi H. B. , Dunitz J. D.
Published: December 2004

Crystals of cyclooctane‐cis‐1, 2‐dicarboxylic acid are monoclinic, a = 10.37, b = 8.52, c = 11.95 Å, β = 103.65°, space group P21/c, with 4 molecules in the unit cell. The structure has been solved with the help of direct methods and refined by full‐matrix least‐squares analysis of three‐dimensional intensity data. The cyclooctane ring is found to occur in the same, approximately mirror‐symmetric (‘boat‐chair’), conformation as was previously found for the trans‐isomer.
3,6,9,10‐Tetrahalogenphenanthrene. Eine neue Cycloarylierungsreaktion von DDT‐Derivaten
Authors: Weis C. D.
Published: December 2004

A simple synthesis of tetrachlorophenanthrene starting from DDT has been realized. 1,1,1,2‐tetrachloro‐2,2‐bis‐(4‐chlorophenyl)‐ethane (I) and its rearranged product 1,1,2,2‐tetrachloro‐1,2‐bis‐(4‐chlorophenyl)‐ethane (V) and other analogs substituted by halogen in the para‐position undergo a cycliarylation yielding 3,6,9,10‐tetrahalogenophenanthrenes. Partial dechlorination of this tetrachlorophenanthrene yields 3,6‐dichlorophenanthrene. Oxidation gives 3,6‐dichloro‐9,10‐phenanthrenequinone, and chlorosulfonation leads to 3,6,9,10‐tetrachloro‐2,7‐bis‐(chlorosulfonyl)‐phenanthrene. The mechanism of this cyclization reaction in presence of LEWIS acids is discussed and compared with the cyclization of DDT derivatives to yield fluorenones.
Synthese von 2‐Oxa‐6‐thia‐adamantan. Vorläufige Mitteilung
Authors: Ganter C. , Wicker K.
Published: December 2004

The synthesis of 2‐oxa‐6‐thia‐adamantane and some of its derivatives is described.
Multiple aromatische sigmatropische Umlagerung von γ, γ‐Dimethylallyl‐phenyläther
Authors: Scheinmann F. , Barner R. , Schmid H.
Published: December 2004

The rearrangement of γ,γ‐dimethylallyl phenyl ether (1), contrary to previous reports, gives a mixture of 4‐(γ,γ‐dimethylallyl)‐phenol (2), 2‐(α,β‐dimethylallyl)‐phenol (3) and 2,2,3‐trimethylcoumaran (4). The ratio of the reaction products is dependent on the solvent and the reaction temperature. The mechanism for the reaction is discussed in terms of multiple sigmatropic rearrangements.
Über ein neues Glykosidierungsverfahren Synthese von Epipodophyllotoxin‐β‐D‐glucopyranosid. 21. Mitt. Über mitosehemmende Naturstoffe [1]
Authors: Kuhn M. , Von Wartburg A.
Published: December 2004

A new method for the synthesis of glycosides is described. Epipodophyllotoxin (4) reacts with 2,3,4,6‐tetra‐O‐acetyl‐β‐D‐glucopyranose in the presence of BF3‐etherate at low temperature to yield tetra‐O‐acetyl‐epipodophyllotoxin‐β‐D‐glucopyranoside (6). This compound, which is sensitive to acid and base, can be converted into the free glucoside 8 by zinc acetate catalysed methanolysis. Glycosidation of podophyllotoxin (1) occurs under the same conditions but is associated with an inversion at C‐1 of the aglycone moiety, leading also to the acetylated epi‐glucoside 6. It is assumed that the glycosidation proceeds through a common carbonium ion intermediate (12), generated from 1 and 4 respectively by the action of BF3. The intermediate 12 is substituted by the pyranose component from the less hindered side, giving exclusively 1‐epi derivatives (e.g. 6). The glycosidation reaction is also highly stereoselective with respect to the glycosidic linkage. The stereochemistry of this bond is determined by the configuration at C‐1 of the pyranose compound employed for the glycosidation. Further experimental evidence for the proposed mechanism consists in the glycosidation of diphenylmethanol (14) to the corresponding β‐D‐glucoside 15. Scope and limitation of the new glycosidiation method are briefly discussed.
Massenspektrometrische Untersuchung von Pleiocarpamin‐Derivaten. 9. Mitteilung über das massenspektrometrische Verhalten quartärer Stickstoffverbindungen [1]
Authors: Leuzinger F. , Hesse M. , Schmid H.
Published: December 2004

Mass spectrometric analysis of quaternary nitrogen compounds has shown that three principal thermal processes occur, namely dealkylation, Hofmann degradation and substitution. Only in the cases of dealkylation and the Hofmann degradation has direct chemical evidence been previously obtained. The first part of this paper presents mass spectrometrical and chemical evidence for the pyrolytic formation of a substitution product, e. g. 5.

By means of different deuterated derivatives the mechanisms of fragmentation of the mavacurine derivative ϵ2‐dihydromavacurine methochloride (8) and of the corresponding Hofmann base (14) have been formulated.
Zusammensetzung der Neutrallipide und deren Fettsäuren aus Walhirnen. III. Hirne von Grindwalen (Globicephala melaena)
Authors: Lesch Peter , Neuhaus‐Meier Sylvia , Bernhard Karl
Published: December 2004

The lipids from the brain of six pilot whales were extracted and separated into different fractions. The grey matter contains 8% cerebrosides, 6% sphingomyelines, 21% ethanolamine cephalines, 26% lecithines and 22% cholesterol; the white matter 22, 8, 17, 12 and 25%, respectively. We analysed the fatty acid composition of each fraction.

In comparison to the human brain, the brain of the pilot whale contains more glycerophos‐phatides and less sphingolipids, in comparison to the fin whale, more cerebrosides.
Herstellung von Iminen durch Gasphasen‐Pyrolyse: N‐Methyl‐äthylidenimin
Authors: Meier J. , Akermann F. , Günthard Hs. H.
Published: December 2004

N‐methyl‐ethylidenimine (CH3CHNCH3) was obtained by pyrolysis of 2‐methylaziridine in a gas phase flow system, using quartz as a catalyst. Pyrolysis of aziridine gave mainly N‐methyl‐methylenimine (CH2NCH3). Under the conditions used in this work, pyrolysis of both compounds surprisingly showed cleavage of the CC‐bond in the three‐membered ring. No monomeric ethylidenimine (CH3CHNH) could be isolated by pyrolysis of trimeric ethylidenimine (2,4,6‐trimethyl‐hexahydro‐1,3,5‐triazine), whereas N‐vinyl‐ethylidenimine (CH3CHNCHCH2) could be identified as one of the pyrolysis products. NMR. data for N‐methyl‐ethylidenimine and N‐vinyl‐ethylidenimine are given for identification purposes.
Tricyclische CuII‐ und NiII‐Chelate aus 2,2‐Bis‐(2‐hydroxyarylazo)‐biphenyl bzw. ‐diphenylsulfid
Authors: Schetty G. , Eder M.
Published: December 2004

Tricyclic CuII and NiII chelates are produced from some 2,2′‐bis‐(2‐hydroxyaryl‐azo)‐biphenyls and ‐diphenyl sulphides. From their electron spectra it is concluded that in the Ni complexes of the azo‐biphenyl dyestuffs the central atom is coordinated in a different way (probably planar) from that in the corresponding Cu complexes. On the other hand, the valences of both metals in the azo‐diphenyl sulphide complexes seem to have the same steric arrangement. This arrangement is probably the same as that of the CuII ion in the azobiphenyl dyestuffs, which could be tetrahedral.
Menschliches Calcitonin. III. Struktur von Calcitonin M und D
Authors: Neher R. , Riniker B. , Rittel W. , Zuber H.
Published: December 2004

Human calcitonin M and its dimer calcitonin D, two highly active peptides isolated from C cell tumours, were subjected to sequence studies using chemical and enzymatic methods. For calcitonin M, containing 32 amino acid residues, the following structure was derived: magnified image

Though the disulphide bridge between position 1 and 7, and the C‐terminal proline amide of human calcitonin M are the same as in porcine α‐thyrocalcitonin, many amino acid residues ‐ 18 in all ‐ are different throughout the molecule. Arginine and tryptophan are absent; on the other hand, lysine and isoleucine are to be found at position 18 and 27 respectively. Methionine changes its place from position 25 to 8 adjacent to the disulphide bridge. Experimental evidence indicates that calcitonin D represents the antiparallel dimeer of calcitonin M.
Die Struktur der Hydrate von Co3[Co(CN)6]2 und Cd3[Co(CN)6]2
Authors: Ludi A. , Güdel H. U.
Published: December 2004

The crystal structures of Co3[Co(CN)6]2, 12 H2O (a, = 10.210 ± 0.005 Å) and Cd3[Co(CN)6]2, 12 H2O (a = 10.590 ± 0.005 Å) have been determined by X‐ray powder methods. According to the measured density the unit cell contains 1 1/3 formula units with 4 Co2+ (Cd2+) in 4a, 2 2/3 Co3+ in 4b, 16 C and 16 N in 24e, 8 H2OI near 24e, (96k) and 8 H2OII near 8 c (192 l). Structure factor calculations based on the space group Oh5 ‐ F m 3 m lead to the following final values of the reliability index R: 0.038 (Co3[Co(CN)6]2, 12 H2O) and 0.037 (Cd3[Co(CN)6]2, 12 H2O). The interatomic distances for the cobaltous compound (in parentheses for the cadmium compound) are: Co3+‐C: 1.88 Å (1.89); C‐N: 1.15 Å (1.17); Co2+‐N: 2.08 Å (2.24); Co2+‐OI: 2.10 Å (2.27); shortest OI‐H‐OII‐bonds: 2.89 Å (2.82). Co3+ is octahedrally coordinated by six carbon atoms, the divalent metal ion by four nitrogen atoms and two water molecules. The two different metal ions are connected by M2+‐N‐C‐Co3‐bonds to a threedimensional network. The infrared and electronic spectra are shown to be in agreement with the results of the structure analyses of these compounds. The observed positions of the OH‐stretching vibrations lead to a hydrogenbond‐length of 2.8–2.95 Å.
Un nouveau mécanisme réactionnel en série aromatique: Addition ‐ substitution
Authors: Aubort J.‐D.
Published: December 2004

Reactions of three disubstituted sodium phenolsulfonates with bromine are examined in various conditions. In aqueous medium, two reactions may occur: bromodesulfonation (an electrophilic substitution) or/and formation of corresponding p‐benzoquinones. In methanol, only bromodesulfonation is observed. Formation of p‐benzoquinones is explained by a solvolytic displacement on the quinoloid product of bromine addition on phenolsulfonate.

A reaction scheme is proposed, which explains the observed effects of substrate structure and reaction medium.
Umbellamin, ein neues «dimeres» Indolalkaloid 130. Mitteilung über Alkaloide [1]
Authors: Morita Y. , Hesse M. , Schmid H.
Published: December 2004

Umbellamine (f; C41H48N4O4), a «dimeric» indole‐indoline alkaloid, was isolated from the root bark of Hunteria umbellata (K. SCHUM.) HALL. F.; it is probably identical with the alkaloid hunterine (structure unknown) of NeUSS & CONE [14]. Thermolysis yielded (+)‐eburnamenine (II), whereas a detailed mass spectrometric study of I, of its O‐methyl and O‐acetyl derivatives, and also of the derived diol V revealed the presence of a phenolic hydroxy‐pseudoakuammigine group as second part, the benzene nucleus of the latter being linked to the C‐14 atom of the eburnamenine component (present in the dihydrom form).

The n.m.r. study of umbellamine and of its derivatives showed that the phenolic hydroxy group is either at C‐10′ or C‐11′ and that the dihydroeburnamenyl residue is connected to C‐11′ or C‐10′ of the pseudoakuammigine residue. A choice between these alternatives was possible by investigation of the hydroxylated base IX arising from the latter component, and obtained in small quantities by treatment of umbellamine with zinc or tin in acid. Its constitution, deduced by uv., n.m.r. and mass spectrometry, suggested that the hydroxy group is fixed at C‐11′. If this is correct, the dihydrocburnatnenyl residue is linked to C‐10′ of the pseudoakuarnmigine residue. Thus we propose formula I for umbellamine.
Umwandlung von 3‐Oxo‐17‐äthylendioxy‐19‐mesyloxy‐δ1,4‐androstadien in dreifach ungesättigte A‐homo‐19‐norsteroide Über Steroide, 215. Mitteilung
Authors: Wieland P. , Anner G.
Published: December 2004

4‐oximino‐17‐ethylenedioxy‐A‐homo‐δ1(10),2,4a‐19‐nor‐androstatriene is formed by treatment of 3‐oximino‐17‐ethylenedioxy‐19‐mesyloxy‐δ1,4‐androstadiene with sodium hydroxide. An analogous reaction occurs with the corresponding semicarbazone, but under the same conditions 3‐hydrazino‐17‐ethylenedioxy‐19‐mesyloxy‐δ1,4‐androstadiene leads to 17‐ethylenedioxy‐A‐homo‐δ2,4,5(10)‐19‐norandrostatriene.
Über eine neue Ringschlussreaktion mit 3‐Dimethylaminopropyl‐carbinolen zu Oxolanen. Mitteilung über Grignard‐Reaktionen mit Halogenalkylaminen [1]
Authors: Marxer A.
Published: December 2004

A new ring‐closure reaction is described, consisting in the treatment of basic carbinols of types 2, 8, 13, 16, with sodamide or sodium hydride, and adding to the sodium salts formed an alkyl halide. Oxolanes of types 5, 9, 14, 17, 20, are formed.
Dünnschichtchromatographie als Hilfsmittel in der Radiochemie. 3. Mitteilung [1]. Trennung von 99Mo und 99Tc
Authors: Seiler H.
Published: December 2004

The separation of 99Tc from neutron irradiated ammonium molybdate by thin‐layer chromatography is described.