bluuebunny/crossref_metadata_2025 huggingface dataset:
14α, 15α‐Epoxy‐«β»‐anhydrodigitoxigenin und 14β, 15β‐Epoxy‐«β»‐anhydrodigitoxigenin
Authors: Hofer Peter , Linde Horst , Meyer Kuno
Published: December 2004

Die Bereitung der beiden an C‐14/C‐15 epimeren Epoxide des «β»‐Anhydrodigitoxigenins und der Abbau ihrer Acetylverbindungen zu bekannten Ätiansäurederivaten wird beschrieben.
Recherches sur la formation et la transformation des esters XXXII. Sur la préparation de quelques nouveaux monoesters cyanoalcoyl‐phosphoriques et sur leur vitesse de scission à différents pH
Authors: Cherbuliez Emile , Probst H. , Rabinowitz J.
Published: December 2004

The synthesis and the rate of scission of some new cyanoalkyl‐phosphoric monoesters are described. In the case of β‐cyanoalkyl‐phosphoric monoesters, the monoester group is no more dephosphorylated in alkaline medium when the two H in the β position are substituted by alkyl groups.
Recherches sur la formation et les transformations des esters XXXIII. Etude du mécanisme de la scission alcaline des monoesters phosphoriques à l'aide de H218O
Authors: Cherbuliez E. , Dahn H. , Moll H. , Probst H. , Rabinowitz J.
Published: December 2004

By use of H2[18O] the alkaline hydrolysis of propargyl‐phosphoric acid CHCCH2OPO3H2 (which cannot undergo splitting by β‐elimination: no H on the β carbon atom) is shown to proceed mainly by splitting of the OP bond. As far as this fact may be extended to the alkaline hydrolysis of monoalkyl‐phosphoric acids in general, the use of H2[18O] allows to distinguish true alkaline hydrolysis (yielding marked phosphate) from splitting by β‐elimination (yielding unmarked phosphate). β‐Elimination is generally much faster than true hydrolysis.
Zur Reaktivität von Farbstoffepoxiden
Authors: Hopff H. , Lienhard P.
Published: December 2004

The reactivity of several dyestuffs containing epoxy groups has been examined by comparative determination of the velocity of the ring opening reaction with alkali iodides in dioxane‐water mixtures.
Sur l'équilibre liquide‐vapeur à 25° de systèmes ternaires composés d'un nitrate, d'acide nitrique et d'eau
Authors: Flatt R. , Benguerel F.
Published: December 2004

Nous avons déterminé la composition et la tension de la vapeur émise, à 25°, par des mélanges d'acide nitrique et d'eau de 50 à 60% HNO3 contenant des nitrates alcalins et alcalino‐terreux.
Sur l'hydratation des cations alcalins et alcalino‐terreux
Authors: Flatt R. , Benguerel F.
Published: December 2004

L'action différente sur la composition de la vapeur de mélanges d'acide nitrique et d'eau qu'on observe lors de la dissolution des divers nitrates des cations alcalins et alcalino‐terreux s'explique par le fait que les cations sont plus ou moins fortement hydratés.
Zur Ableitung der Gleichung für die Elektrodenspannung am Beispiel eines Redox‐Systems
Authors: Bühler H. H. , Milićević B.
Published: December 2004

To avoid possible confusion arising from inconsistent derivation of the formula for the potential of galvanic cells, as sometimes found in the literature, a derivation in terms of the thermodynamic background has been discussed. Special emphasis is laid on the case of redox‐systems.
Assoziation bei Azoverbindungen II: Einfluss der Assoziation auf das tautomere Gleichgewicht von 4‐Dimethylamino‐azobenzol‐Derivaten
Authors: Zenhäusern A. , Zollinger Hch.
Published: December 2004

The equilibrium between the two tautomeric conjugate acids of 4‐dimethyl‐amino‐azobenzene derivatives is a function of the concentration and the ionic strength of the solution.

The individual acidity constants of these two tautomeric conjugate acids have been correlated with the Hammett δϱ‐relationship.

It can be shown that the ammonium form of the first conjugate acid of 4‐dimethylamino‐azobenzene derivatives is more aggregated than the azonium form.

The δϱ‐relationships demonstrate that enhanced mesomeric interaction occurs between a ‐M substituent in the 4′‐position and the 4‐dimethylamino group, but not with the lone pair of electrons on the β‐azo nitrogen atom.
Sur les composants carbonylés de l'essence de jasmin (Jasminum grandiflorum L.)
Authors: Demole E.
Published: December 2004

The ketonic fraction isolated from jasmine oil (Jasminum grandiflorum L.) by using Girard's «P» reagent does not contain any detectable amount of a ketolactone C12H16O3, as claimed by Naves & Grampoloff. Evidence is presented showing that the major component obtained in this way is indeed (‐)‐methyl jasmonate, i.e. (−)‐methyl cis‐2‐pent‐2′‐enyl‐3‐oxo‐cyclopentylacetate. At the present time, the ketonic compounds known to exist in jasmine oil are jasmone, methyl jasmonate, benzaldehyde, vanillin and methylheptenone.
Über bicyclische Sulfonamide
Authors: Daeniker H. U. , Druey J.
Published: December 2004

Die Synthese von Verbindungen der Bicyclo[2,2,1]heptan‐, Bicyclo[2,2,2]octan‐ und 5,6; 7,8‐Dibenzo‐bicyclo[2,2,2]octan‐Reihe, die in Stellung 2 eine freie oder substituierte Sulfonamidgruppe tragen, wird beschrieben. Als Zwischenprodukte eignen sich vor allem die entsprechenden bicyclischen Sulfonsäurefluoride, die besonders gut durch Umsetzung von Vinylsulfonylfluorid nach Diels‐Alder herstellbar sind. Mit Hilfe von Protonenresonanzspektren lassen sich bei Verbindungen mit dem Bicyclo[2,2,1]heptan‐Ringsystem endo‐ und exo‐Isomere unterscheiden. Eine Reihe der beschriebenen Verbindungen zeigt zentral erregende Eigenschaften.
MO‐theoretische Berechnungen über Iminostilben und verwandte Verbindungen
Authors: Schmid R. W.
Published: December 2004

Characteristic HMO‐data have been calculated for iminostilbene, 2,3‐benzazepine and azepine. The data indicate strong localization of the benzene rings and/or double bonds. There seems to be little tendency for delocalization in the seven‐membered ring of these systems.
Photoreaktionen von Methanol mit N‐Heterocyclen 1. Mitteilung
Authors: Cerutti P. , Schmid H.
Published: December 2004

Die Photoreaktionen von Indoleniniumsalzen, Indoleninen, Indolinen und 1,2‐Dianilino‐äthan mit Methanol wurden untersucht. Aus den Indoleniniumsalzen I und III bilden sich mit Licht einer Wellenlänge < 190 mμ ohne Sensibilisator oder mit Licht der Wellenlänge 254 mμ bei Gegenwart von Sensibilisatoren die C‐Hydroxymethylverbindungen IV und VI. Aus den Indoleninen IX und XIII entstehen dabei die Oxazolderivate X und XIV. Aus den Indolinen XI und XV bilden sich mit Methanol unter denselben Bestrahlungsbedingungen X und XIV, aus 1,2‐Dianilinoäthan N, N′‐Diphenyl‐tetrahydroimidazol. Mit Alkoholen lässt sich die Stickstoff‐Kohlenstoff‐Doppelbindung in Indoleniniumsalzen und Indoleninen, am selektivsten mit Licht einer Wellenlänge > 280 mμ, reduzieren.
Zur gas‐chromatographischen Trennung aromatischer Aldehyde
Authors: Prabucki A. L. , Lenz F.
Published: December 2004

Mit Poly‐(äthylenglykolisophtalat) + Polyäthylenglykol 4000 auf Celite 545 als Säulenfüllmaterial lassen sich Gemische verschiedener substituierter Benzaldehyde, darunter die thermolabilen Vertreter 3,4‐Methylendioxybenzaldehyd und p‐Hydroxy‐benzaldehyd, gas‐chromatographisch trennen und analytisch erfassen.
Bromierung von 2‐Naphtol‐6,8‐disulfosäure: I. Kinetik der Reaktionen mit Br2 und HOBr
Authors: Christen M. , Zollinger Hch.
Published: December 2004

The kinetics of the bromination of 2‐naphthol‐6,8‐disulphonic acid with Br2 and BrOH in aqueous buffer solutions show that the rates with both brominating reagents are the same (within 20%). The rates are almost independent of the hydrogen ion concentration (pH range 3,85–5,20) and the concentration of the reactant in excess. The rate is first order with respect to the reactant in lower concentration. The reaction is base catalyzed.
Bromierung von 2‐Naphtol‐6,8‐disulfosäure: II. Kinetische Wasserstoffisotopenffekte und Reaktionsmechanismus
Authors: Christen M. , Zollinger Hch.
Published: December 2004

The bromination of the disodium salt of 2‐naphthol‐6,8‐disulphonic acid (G‐salt) with hypobromous acid in aqueous buffer solutions has a hydrogen isotope effect (kH/kD = 2.08 ± 0.10) which is independent of the reactant concentrations.
Kristallisiertes Acovenosid C Glykoside und Aglykone, 240. Mitteilung
Authors: Hauschild‐Rogat P. , Euw J. V. , Schindler O. , Weiss E. K. , Reichstein T.
Published: December 2004

Die Konstitution von Acovenosid C als β‐Gentiobiosido‐acovenosid A wird bewiesen. Unklarheit besteht noch, ob der Gentiobiosido‐Rest in 2′‐oder in 4′‐Stellung des Acovenosids A verknüpft ist. Fermentierung von Acovenosid C mit Pilzamylase führt zu Acobiosid A, welches mit Strophanthobiase zu Acovenosid A fermentiert wird.
Über eine Kombination eines Gas‐Chromatographen mit einem Massenspektrographen
Authors: Widmer Hans , Gäumann Tino
Published: December 2004

The direct combination of a gas chromatograph with a time‐of‐flight mass spectrometer is described. The advantages over the method of sampling the different gas‐chromatographic peaks are high sensitivity, high gas‐chromatographic resolution and speed of recording. The main difficulties encountered when working with small concentrations are memory effect, low abundance sensitivity and gas noise with the same frequency distribution as the flicker‐noise of thermal cathodes.
Recherches sur les arǒmes. 5e communication. Analyse de l'arǒme des framboises. I. Les constituants carbonylés volatils
Authors: Winter M. , Sundt E.
Published: December 2004

Preliminary investigations of raspberry oil have shown that carbonyls and alcohols are the most characteristic constituents.
Recherches sur la formation et la transformation des esters XXXV. Sur les esters phosphoriques primaires du type C(hal)3‐CHR‐OPO3H2
Authors: Cherbuliez Emile , Gabbai A. , Probst H. , Yazgi A. , Rabinowitz J.
Published: December 2004

Polyphosphoric acid reacts with trifluoroethanol, tribromoethanol and 1,1,1‐trichloroisopropanol to yield the corresponding phosphoric monoesters.
Über Die chemischen Bestandteile Der Mandragorawurzel 2. Die Alkaloide
Authors: Staub H.
Published: December 2004

Bei der Aufarbeitung der Mandragorawurzel mit den Methoden der Verteilungs‐ und Papierchromatographie und der Charakterisierung der Alkaloide in Form ihrer kristallisierten Pikrate wurden Hyoscyamin, Scopolamin, Atropin, Cuskhygrin und – sehr wahrscheinlich – Scopin festgestellt. Apoatropin und Belladonnin liessen sich nur papierchromatographisch nachweisen. Die chromatographisch festgestellte Existenz von Norhyoscyamin konnte durch die Analyse des Pikrats nicht einwandfrei bestätigt werden. Das Vorhandensein einer zur Pyrrolingruppe gehörenden «Base M» ist wahrscheinlich. Verschiedene kristallisierende Pikratfraktionen konnten wegen zu geringer Menge nicht identifiziert werden.
Über diuretisch wirksame Benzoesäure‐Derivate Untersuchungen über synthetische Arzneimittel, 9. Mitteilung
Authors: Jucker E. , Lindenmann A.
Published: December 2004

Es werden neuartige Hydrazide von 3‐Sulfamyl‐4‐halogen‐benzoesäuren beschrieben, die sich z. T. durch eine gute salidiuretische Wirkung auszeichnen.
Photochemische Reaktionen. 15. Mitteilung. Zur Struktur des UV.‐Bestrahlungsproduktes von Δ4, 6‐Cholestadien‐3‐on
Authors: Throndsen H. P. , Cainelli G. , Arigoni D. , Jeger O.
Published: December 2004

Δ4,6‐Cholestadien‐3‐one (1) yields on irradiation a dimeric product C54H84O2 for which structure 2a is proposed.
Über C‐substituierte Piperazinderivate Untersuchungen über Synthetische Arzneimittel, 10. Mitteilung
Authors: Jucker E. , Rissi E.
Published: December 2004

Es wird über die Darstellung verschiedener bisher unbekannter Piperazin‐2‐carbonsäureester und 2‐Hydroxymethyl‐piperazine sowie der daraus abgeleiteten α‐(2‐Piperazinyl)‐benzhydrole und 2‐Benzhydryloxymethyl‐piperazine berichtet.
Synthese von Peptid‐Zwischenprodukten für den Aufbau eines corticotrop wirksamen Nonadecapeptids. IV. Derivate der Nonapeptidsequenz Lys‐Pro‐Val‐Gly‐Lys‐Lys‐Arg‐Arg‐Pro
Authors: Rittel W.
Published: December 2004

The synthesis of derivatives of the nonapeptide sequence β11−19‐corticotropin (Lys‐Pro‐Val‐Gly‐Lys‐Lys‐Arg‐Pro) which have been used for the preparation of a nonadecapeptide, β1−19‐corticotropin, displaying corticotropic activity(1), is described in detail. Combination of acid‐labile protecting groups (BOC‐, OtBu‐ and Trityl‐) were found to be especially useful for this and subsequent work, as they can be cleaved in a very specific manner under very mild conditions.
β1–16‐Corticotropin‐methylester
Authors: Schwyzer Robert , Rittel Werner , Costopanagiotis Antigone
Published: December 2004

The synthesis of β1–16‐corticotropin methyl ester is described(14). As in previous work from these laboratories, t‐butyl‐ and t‐butoxycarbonyl groups were employed for the protection of side chain carboxyl and amino groups, respectively. This warrants excellent yields in the critical last step of the synthesis of large polypeptides: the removal of blocking groups. The compound was shown to be pure by thin layer chromatography on silicagel, by electrophoresis on paper, by amino‐acid analysis, and by digestion of the total hydrolysate with L‐amino‐acid oxidase of snake venom. The ACTH‐activity displayed was 5–10 U/mg in the in vitro assay of Saffran & Schally(4) and less than 1 USP‐U/mg in the subcutaneous test according to Sayers(5) (solution in 1% gelatin).
Phtalocyanine in wässeriger Lösung III. Säuredissoziation der Pyrrol‐NH‐Gruppe in Phtalocyanintetrasulfonsäure
Authors: Bernauer Klaus , Fallab S.
Published: December 2004

The acid NH‐dissociation of Pthalocyanintetrasulfonate has been investigated. We found, that the monomer H2PTS behaves as a moderately weak acid. The pKa‐value has been determined to 9,6. Due to steric and electrostatic hindrance of attack by hydroxide ion the reaction is surprisingly slow. The bimolecular rate constant is of the order of 3·102 l mol−1 s−1.
Odeur et Constitution. XX. Synthèses des cis‐ et trans‐Hexène‐3‐al
Authors: Winter M. , Gautschi F.
Published: December 2004

The syntheses of pure cis‐ and trans‐3‐hexenal are described. It is shown that earlier reported preparations of 3‐hexenal or β‐hexenal led in most cases to the isomeric 2‐hexenal.
Synthesen in der isochinolinreihe Zum HOFMANN'schen Abbau 1‐Phenäthylsubstituierter 1,2,3,4‐Tetrahydroisochinoline
Authors: Rheiner A. , Brossi A.
Published: December 2004

Hofmann exhaustive methylation of the analgesic 1‐p‐chlorophenethyl‐2‐methyl‐6,7‐dimethoxy‐1,2,3,4‐tetrahydro‐isoquinoline (Versidyne = I) leads to 1‐dimethylamino‐1‐(2′‐vinyl‐4′,5′‐dimethoxy‐phenyl)‐3‐(p‐chloro‐phenyl)‐propane (III), the only product formed. Its structure was proved by degradation of the dextrorotatory 1 S enantiomer of Versidyne (Ia) of known absolute configuration, yielding IIIb, the levorotatory 1 S enantiomer of III. Hydrogenation of IIIb affords (‐) 1 S 1‐dimethylamino‐1‐(2′‐ethyl‐4′,5′‐dimethoxy‐phenyl)‐3‐(p‐chloro‐phenyl)‐propane (IXb) which was also synthesized by an unambiguous route.
Recherches sur la formation et la transformation des esters XXXIX. Sur la phosphonylation des hydroxynitriles par l'oxyde phénylphosphonique
Authors: Cherbuliez Emile , Hunkeler F. , Rabinowitz J.
Published: December 2004

The phosphonylation of cyano alcohols by means of phenylphosphonic oxide is described. α‐Cyano alcohols yield exclusively the corresponding α‐carbamidoalkyl phenylphosphonic monoesters, β‐cyano alcohols yield mainly the corresponding β‐cyanoalkyl phenylphosphonic monoesters, and γ‐ and δ‐cyano alcohols yield exclusively the corresponding γ and δ‐cyanoalkyl phenylphosphonic monoesters.
Recherches sur la formation et la transformation des esters XLI. Facteurs structuraux de la labilisation de la fonction monoester phosphonique
Authors: Cherbuliez Emile , Gabbai A. , Hunkeler F. , Probst H. , Yazgi A. , Rabinowitz J.
Published: December 2004

The rate of scission of some phenylphosphonic monoesters at different pH values and at 100° is determined.
Étude de l'hydrogénation du glucose en présence d'un échangeur d'anions
Authors: Jacot‐Guillarmod A. , von Bézard A. , Haselbach C. H.
Published: December 2004

By hydrogenating glucose in the presence of an anion exchanger instead of caustic soda the undesirable CANNIZZARO reaction is limited to a considerable extent.
Etudes sur les matières végétales volatiles. CLXXXII. Sur les alcools présents dans l'huile essentielle de Bay
Authors: Lamparsky Dietmar
Published: December 2004

The bay oil contains low percentages of (+)‐3‐octanol; (−)‐l‐octen‐3‐o1; (+)‐1‐ terpinen‐4‐ol and α‐terpineol.
Methämoglobinbildung durch Röntgen‐Bestrahlung in Hämolysat und intakten Erythrocyten von verschiedenem Katalysegehalt
Authors: Heiniger J. P. , Aebi H.
Published: December 2004

Radiation induced methaemoglobin‐formation in haemolysates and in red cell suspensions of normal and acatalatic human blood has been studied under various experimental conditions.
Photochemische Untersuchungen an Farbstoffen. I: Chemismus der Phototropie von Kupferphtalocyanin‐Farbstoffen
Authors: Eigenmann G.
Published: December 2004

The photochemically induced change of colour of dyes derived from copper‐(II)‐phthalocyanine in presence of certain nitrogen‐containing crease‐resist resins was investigated by means of optical and electronspinresonance spectroscopy and by photo‐potentiometric methods. It is shown to be due to a light induced reversible one‐electron reduction of the copper (II)‐phthalocyanine.
Über die Chemie des Vitamins E. 1. Mitteilung. Die Umkehrung der Konfiguration am Kohlenstoffatom 2 von natürlichem (2 R, 4′ R, 8′ R)‐α‐Tocopherol
Authors: Schudel P. , Mayer H. , Metzger J. , Rüegg R. , Isler O.
Published: December 2004

(2 S, 4′R, 8′R)‐α‐Tocopherol with unnatural configuration at C‐2 is prepared by oxidation of natural, so called d‐α‐tocopherol (I), which has the (2R, 4′R, 8′R)‐configuration, to α‐tocopherylquinone (II), followed by recyclization of the corresponding α‐tocopherylhydroquinone (III). Experiments showed that the configuration of carbon atom 2 of natural α‐tocopherol is retained during the ferric chloride oxidation (I →II) and is predominantly inverted by zinc chloride cyclization of α‐tocopherylhydroquinone (III).
Über Reaktionen von Alkoxyradikalen. Epimerisierungen in der Steroidreihe. Über Steroide, 194. Mitteilung
Authors: Heusler K. , Kalvoda J. , Anner G. , Wettstein A.
Published: December 2004

The lead ester formed from steroidal alcohols with lead tetraacetate are thermally decomposed to oxy radicals which can either form tetrahydrofurane derivatives by direct attack on a hydrogen atom at δ‐carbon atom or, by cleavage of the α,β‐carbon bond, give rise to a carbonyl group and a carbon radical. The latter reaction is shown to be reversible in certain cases and the recyclisation can yield oxy radicals epimeric at one or both of the α and β carbon atoms.
Synthese eines 1‐Oxa‐phenalen‐Derivates mit dem chromophoren System des Biflorins
Authors: Grant Heather N. , Prelog V. , Sneeden R. P. A.
Published: December 2004

Several derivatives of 1‐oxaphenalene (II) and 1‐oxaphenalene‐7,8‐quinone have been synthesized in order to support the constitution I of biflorin by comparison of the absorption spectra.
Über die Struktur des Kopsins
Authors: Govindachari T. R. , Pai B. R. , Rajappa S. , Viswanathan N. , Kump W. G. , Nagarajan K. , Schmid H.
Published: December 2004

Die Experimente, die zur Ableitung der Formel I für Kopsin, dem Hauptalkaloid aus Kopsia fruticosa, führten, werden beschrieben.
Synthesen in der Polymyxin‐Reihe. 7. Mitteilung. Synthese des hochaktiven cyclischen Decapeptids 7α
Authors: Studer R. O. , Lergier W. , Vogler K.
Published: December 2004

The synthesis of an antibiotic substance to which we assign the structure 7α, one of the four possible formulas proposed for natural polymyxin B1, is reported. Although both synthetic and the natural product have the same antimicrobial activity towards Brucella bronchiseptica in vitro (plate test), they are not identical, as shown by the lower optical rotation of the synthetic material.
Über die Chemie des Vitamins E. 2. Mitteilung. Die Struktur des Kaliumferricyanid‐Oxydationsproduktes von α‐Tocopherol
Authors: Schudel P. , Mayer H. , Metzger J. , Rüegg R. , Isler O.
Published: December 2004

The structure of the main oxidation product of natural (2R, 4′R, 8′R)‐α‐tocopherol with potassium ferricyanide is shown to be XXIII.
Über die Chemie des Vitamins E. 3. Mitteilung. Die Totalsynthese von (2R, 4′R, 8′R)‐ und (2S, 4′R, 8′R)‐α‐Tocopherol
Authors: Mayer H. , Schudel P. , Rüegg R. , Isler O.
Published: December 2004

(2R, 4′R, 8′R)‐ and (2S, 4′R, 8′R)‐α‐tocopherol have been synthesized by WITTIG reaction of the two enantiomeric S‐(+)‐ and R‐(−)‐6‐acetoxy‐Z‐formyl‐2,5,7, 8‐tetramethyl‐chromans (I) with (3R, 7R)‐hexahydrofarnesyl‐triphenylphosphonium bromide (II), followed by hydrogenation and hydrolysis. (2R, 4′R, 8′R)‐α‐tocopherol proved to be identical in every respect with natural so called d‐α‐tocopherol. Resolution of the chroman component was achieved via the diastereomeric quinine salts of 2‐carboxyethynyl‐6‐hydroxy‐2,5,7,8‐ tetramethyl‐chroman (XVIII). followed by transformation of the enantiomers into S‐(+)‐ and R‐(−)‐I, respectively.
Das Mischpotential und seine Berücksichtigung bei der Konstruktion von elektrometrischen Flächen
Authors: Milí ević B.
Published: December 2004

For two simple examples the mixed potential is discussed and the three‐dimensional models of the voltametric and chrono‐electrometric processes with two electronexchanger pairs are given. The potential possibility of the «zero‐current chronopotentiometry» is outlined.
Ein neuer Carotinoidfarbstoff: 4′‐Hydroxykryptoxanthin
Authors: Karrer P. , Jaeger L.
Published: December 2004

Durch Oxydation von Kryptoxanthin mittels N‐Bromsuccinimid in Gegenwart von Eisessig und nachfolgende Verseifung erhält man das bisher unbekannte 4′‐Hydroxykryptoxanthin.
Welkstoffe und Antibiotika. 25. Mitteilung. Synthese der natürlichen Dehydrofusarinsäure
Authors: Steiner K. , Graf U. , Hardegger E.
Published: December 2004

Die Synthese der natürlichen Dehydrofusarinsäure (VI) gelang in guter Ausbeute durch Alkyliercing der leicht zugänglichen 5‐Methyl‐2‐picolinsäure (V) mit Allylchlorid. Die unnatürliche Δα,β‐Dehydrofusarinsäure (111), sowie die Bis‐dehydrofusarinsäure (VII) wurden nach Modell‐Versuchen am 3‐Butyl‐pyridin (Ia) gemäss Formelschema aus Fusarinsäure (I) hergestellt.
Synthese einiger Thioxanthen‐Derivate
Authors: Schindler O. , Lehner H. , Michaelis W. , Schmutz J.
Published: December 2004

The synthesis of some thioxanthene derivatives as possible metabolites of Methixerc (VI‐hydrochloride) is described. The VON BRAUN degradation of VI with cyanogen bromide leads to the demethyl derivative 9‐ [(3‐piperidyl)‐methyl]‐thioxanthene (VIII). Oxidation of Methixen with hydrogen peroxide at 20° gives a mixture of the two steroisomerie sulfoxides IX and X; they were separated by preparative paper‐chromatography. The same oxidant at 100° oxidizes Methixelz to the sulfone IV. This was also obtained by alkylation of thioxanthene‐10, 10‐dioxide (11). On oxidation with hydrogen peroxide the demethyl derivative VIII affords at 20° the sulfoxide XI (isolated in non‐uniform steric state), and at 100° the sulfone V. Alkylation of thio‐xanthene with N‐methyl‐3‐chloromethyl‐piperidine‐N‐oxide (I) leads to ‐[(N‐ methyl‐3‐piperidyl)‐methyl]‐thioxanthene‐N‐oxide (111), the constitution of which was proved by conversion to VI.
Zur Kenntnis der sogenannten «Alkalicarbonyle» I Die Kristallstruktur des Kalium‐acetylendiolats, KOCCOK
Authors: Weiss E. , Büchner W.
Published: December 2004

The structure of the yellow «potassium carbonyl», obtained from CO and K in liquid ammonia, has been shown to be potassium acetylenediolate, KOCCOK. From X‐ray powder‐diagrams a tetragonal cell containing two KOCCOK units with a = 3.93, Å, c = 12.75 Å (space group I 4/mmm) has been derived. The KOCCOK units are arranged parallel to the c‐axis with the following internuclear distnaces: K0: 2.67 and 2.78 Å; KK: 3.65 Å; C0 : 1.28 Å; CC: 1.21 Å.
Synthesen in der Isochinolinreihe Substituierte 1‐[ω‐(Nitrophenyl)alkyl]‐1,2,3,4‐tetrahydro‐isochinoline
Authors: Walter M. , Besendorf H. , Schnider O.
Published: December 2004

The synthesis of substituted 1‐[ω‐(nitrophenyl)alkyl]‐l,2,3,4‐tetrahydro‐iso‐quinolines and their resolution into optical antipodes are described. Some of these l‐[ω‐(nitrophenyl)alkyl]‐l,2,3,4‐tetrahydro‐isoquinolines are potent analgesics.
Die sterische Anordnung der 1:2‐Metallkomplexfarbstoffe im Lichte der geometrischen Gegebenheiten
Authors: Schetty G.
Published: December 2004

Previous investigations of the 1:2‐Cr (and ‐Co) complexes have lead to the conclusion that the azo (and azomethine) dyestuffs which form 56‐rings with the metal atom are arranged perpendicularly to each other (DREW‐PFITZNER disposition). On the other hand those dyestuffs which form 6–6‐rings with the metal atom coordinate in sandwiches, thus making the formation of stereoisomeric 1 : 2‐complexes possible. The critical atomic distances and angles have been calculated and compared with the theoretical values obtained from the coordination octahedron, and found to be in good agreement with the experimental results.
Sekundäre Isotopeneffekte der Aciditätskonstanten kerndeuterierter Anilinium‐Ionen
Authors: Bernasconi C. , Koch W. , Zollinger Hch.
Published: December 2004

(1) Acidity constants of 2,3,4,5,6‐d5‐, 2,4,6‐d3‐ and 3,5‐d2‐anilinium ion, of 2,6‐d2−4‐toluidinium and 4‐d‐2,6‐xylidiniumion have been measured in aqueous solution.
Chemische Reaktionen im Massenspektrometer
Authors: Schumacher Ernst
Published: December 2004

Recent work in chemical mass‐spectrometry is reviewed.
Die Glykoside der Blätter von Digitalis canariensis L., var. isabelliana (WEBB) LINDINGER
Authors: Pavanaram S. K. , Hofer P. , Linde Horst , Meyer Kuno
Published: December 2004

Die durch Ausschiitteln eines aus getrockneten Blättern von Digitalis canariensis L., vai. isabelliana bereiteten wässerigen Auszuges mit Äther und Chloroform gewonnenen Extrakte wurden einer eingehenden Analyse unterzogen. Im Ätherauszug konnten neben den bereits in der vorangegarigenen Mitteilung beschriebenen Monosiden a, b und c und den Cardenoliden Digitoxigenin (nicht isoliert) und Uzarigenin die folgenden Substanzen kristallisiert werden : ein gelbes Pigment der Formel C16H12O3 (Methyl‐methoxy‐anthrachirion ?), ein Gitoxigenin‐Glykosid (= Substanz J), dessen Konstitution nicht abgeklart werden konnte, und γ‐Sitosterin. Letzteres ist damit zum ersten Mal in einer Digitalispflanze nachgewiesen worden. ‐ Aus dem Chloroformextrakt liessen sich die Digitanol‐glykoside Digifolein, Diginin und 14 α Digipronin in Kristallen isolieren, während Lanafolein, das nur in Spuren vorhanden war, sowohl papier‐ als auch dünnschicht‐chromatographisch nachgewiesen werden konnte. Ausserdem liessen sich zwei für D. isabelliana neue digitaloide Glykoside, nämlich Strospesid und in sehr geringer Menge ein vermutlich unbekanntes Digitalosid (= Substanz K) isolieren.
Stoffwechselprodukte von Mikroorganismen. 43. Mitteilung. Zur Kenntnis von Desferrioxamin B
Authors: Bickel H. , Keberle H. , Vischer E.
Published: December 2004

Chemical and physical properties of desferrioxamin B, the iron free ground substance of ferrioxamin B, are described.
Hydroxamatkomplexe II. Die Anwendung der pH‐Methode
Authors: Anderegg G. , L'Eplattenier F. , Schwarzenbach G.
Published: December 2004

The equilibria between acethydroxamic acid and 16 metal cations, and their complexes have been elucidated. For the results see table 1. The complex Formation of desferri‐ferrioxamine B and desferri‐ferrioxamin E, which are trihydroxamic acids, with various bivalent and trivalent metal ions have been studied in a similar manner. For the results see tables 2 and 3.
Hydroxamatkomplexe III. Eisen(III)‐Austausch zwischen Sideraminen und Komplexonen. Diskussion der Bildungskonstanten der Hydroxamatkomplexe
Authors: Anderegg G. , L'Eplattenier F. , Schwarzenbach G.
Published: December 2004

The iron transfer from sideramines to suitably chosen complexones (EDTA and similar compounds) has been studied optically. From the equilibrium constants of such exchange reactions the stability constants of Ferrioxamine B, Ferrioxaminc D1, Ferrioxamine E, Ferrichrom and Ferrichrysin have been deduced. For the results see table 5.
Über den Einbau des Kohlenstoffs der Glucose in die Harnsäure bei Drosophila melanogaster. Vorläufige Mitteilung
Authors: Brenner‐Holzach O. , Leuthardt F.
Published: December 2004

1. Uric acid was isolated from larvae of Drosophda melanogaster to which glucose‐[1‐14C] and glu∼ose‐[6‐14C] had been fed. The specific activity of the atoms 2 and 8 of the purine skeleton was considerably higher after feeding glucose‐ [6–14C] than after glucose‐ [1‐14C]. The activated formate used in building the purine ring probably derives from the C 3 of glyceric acid (glycerate → hydroxypyruvate → serine).
Le rôle du catalyseur dans la cyclisation des esters glutamiques
Authors: Hubert A. J. , Buyle R. , Hargitay B.
Published: December 2004

Lactam formation from glutamic acid diesters is subject to catalysis by carbo‐xylic acids in general and to base catalysis in alcohols. Kinetic measurements prove that catalysis by carboxylic acids is based on a push‐pull mechanism provoked by the undissociated acid molecule and that the base catalysed reaction is due to the alcoholate anion and is therefore absent in aprotic solvents. Carboxylic acids exhibit catalysis as well as ‐ at higher concentration ‐ inhibition.
Etude de structures peptidiques à l'aide de phénylisothiocyanate IV. Note sur la préparation et la purification des phénylthiohydrantoïnes dérivées de divers acides aminés
Authors: Cherbuliez Emile , Marszalek J. , Rabinowitz J.
Published: December 2004

The authors describe modified procedures for the synthesis of phenylthiohydantoins derived from α‐amino acids, applied to 16 amino acids. With the exception of the phenylthiohydantoins containing a free NH2, CONH2, COOH or hetero‐cyclic group belonging to the starting amino acid, they can be purified by sublimation. The yield of chromatographically pure product vary between 54 yo (threonine) and 92% (tyrosin); with asparagine, the yield did not exceed 49%.
Recherches sur la formation et la transformation des esters XLII. Sur la phosphorylation de différents types d'alcools, et particulièrement d'alcools non saturés
Authors: Cherbuliez Emile , Cǒak‐Antić Sl. , Schwarz M. , Rabinowitz J.
Published: December 2004

Tertiary alcohois and terpenic alcohols cannot be phosphorylated by means of polyphosphoric acid or phosphorus pentoxide even in the presence of a tertiary base.
Synthese von Zwischenprodukten für den Aufbau corticotrop wirksamer Polypeptide. V. Derivate des Pentapeptids H · Val‐Lys‐Val‐Tyr‐Pro · OH (β20–24‐Corticotropin) und des diastereoisomeren Peptids H · Val‐lys‐Val‐Tyr‐Pro · OH
Authors: Schwyzer R. , Riniker B. , Kappeler H.
Published: December 2004

Various syntheses of L‐Valyl‐Nϵ‐t‐butoxycarbonyl)‐L‐lysyl‐L‐valyl‐L‐tyroxyl‐L‐proline t‐butyl ester (IX) are described. Condensations involving dicyclohexyl carbodiimide and either p‐phenylazo‐benzyloxycarbonyl‐L‐valyl‐(Nϵ‐t‐butoxycarbonyl)‐L‐lysine (VII), carbobenzoxy‐L‐valyl‐(Nϵ‐t‐butoxycarbonyl)‐L‐lysine (XI), or carbo‐benzoxy‐L‐valyl‐L‐tyroxine (I) produce about 25 per cent racemisation of the C‐terminal amino acids. Carbobenzoxy‐L‐valyl‐(Nϵ‐t‐butoxycarbonyl)‐D‐lysyl‐L‐valyl‐L‐tyrosyl‐L‐proline t‐butyl ester (XIIa) was isolated as a cristalline compound with the same m. p. as the «all‐L»‐isomer. Configurations were determined by teh action of trypsin on lysyl peptides and by the action of L‐amino‐acid oxidase on acid hydrolysates.
Über die Geschwindigkeit der Aminolyse von verschiedenen neuen, aktivierten, N‐geschützten α‐Aminosäure‐phenylestern, insbesondere 2,4,5‐Trichlorphenylestern
Authors: Pless J. , Boissonnas R. A.
Published: December 2004

A comparison of the ate of aminolysis of many substituted phenyl esters of N‐protected α‐amino‐acids shows that the 2,4,5‐trichlorophenyl esters are promising new active derivatives for the synthesis of peptides.
Synthèse de la Sér4‐oxytocine, de l'Ala4‐oxytocine, de la Sér5‐oxytocine et de l'Ala5‐oxytocine
Authors: Guttmann St. , Boissonnas R. A.
Published: December 2004

Ser4‐oxytocin and Ala4‐oxytocin have been synthesized and found to possess biological properties not very different from those of isotocin. Ser5‐oxytocin and Ala5‐oxytocin have also been prepared and found to be almost inactive. An hypothesis concerning the mode of fixation of oxytocin on its receptor is presented.
Synthèse de l'Orn8‐vasopressine et de l'Orn8‐oxytocine
Authors: Huguenin R. L. , Boissonnas R. A.
Published: December 2004

Orn8‐vasopressin and Orn8‐oxytocin have been synthesized and their biological activities compared with those of arginine‐vasopressin and lysine‐vasopressin and of arginine‐vasotocin and lysine‐vasotocin, respectively. The replacement of the arginine or lysine residues by an ornithin residue to not considerably affect the oxytocic and pressorie activities.
Tricyclo[2,2,2,02,6]octan und Tricyclo[2,2,2,02,6]oct‐7‐en Konjugation in Cyclopropyl‐äthylenen. Bicyclo[2. 2. 2]octan‐Reihe, 6. Mitteilung
Authors: Grob C. A. , Hostynek J.
Published: December 2004

3,5‐Dibromo‐tricyclo[2.2.2.02,6]octane (3), which is obtained by homoconjugative addition of bromine to bicyclo[2.2.2]octa‐2.5‐diene (1), is shown by NMR.‐spectroscopy to be a mixture containing ca. 72% of the trans stereoisomer 13 and ca. 28% of a cis stereoisomer, presumably the exo‐cis from 11. Upon treatment with zinc in dimethylformamide these tricyclic dibromides 3 revert to the diene 1. Hydrogenation over nickel produces bicyclo[2.2.2]octane (15) and a small amount of tricyclo‐[2.2.2.02,6]octane (4), which has been synthesized from bicyclo[2.2.2]octan‐2‐one (16) by a Bamford‐Stevens reaction. In addition to the diene 1, Cope‐elimination of 2‐(dimethylamino‐N‐oxido)‐bicyclo[2.2.2]‐oct‐5‐ene (9) produces small amounts of the abnormal 1,3‐elimination product tricyclo[2.2.2.02,6]oct‐7‐ene (5). The latter compound has been prepared in high yield by a Bamford‐Stevens reaction on bicyclo[2.2.2]oct‐2‐en‐5‐one (23). In tricyclo[2.2.2.02,6]oct‐7‐ene (5) the plane of the double bond symmetrically bisects the cyclopropane ring. Strong conjugation of the cyclopropyl‐ethylene system is indicated by the UV.‐absorption maximum at 206 mμ (log ϵ = 3.71), which shows a bathochromic shift of 23 mμ with respect to cyclohexene.
Einfluss der Kammersättigung in der Dünnschichtchromatographie
Authors: Honegger C. G.
Published: December 2004

1. Es wird eine neue, einfache Schmalkammer zur aufsteigenden Dünnschicht‐chromatographie beschrieben.
Sur les aldéhydes β‐acétyléniques Synthèse de l'hexyne‐3‐al
Authors: Winter M.
Published: December 2004

β‐Hexynal and some of its derivatives have been prepared.
Organische Phosphorverbindungen VII. Zur Kenntnis der Reaktion von Phenylphosphin mit Schwefel
Authors: Maier Ludwig
Published: December 2004

Bei der Umsetzung von Phenylphosphin mit Schwefel im Molverhältnis 1:1 bildet sich Phenylphosphinsulfid, dem die Thionostruktur C6H5P(S)H2 und nicht die isomere Thiolstruktur C6H5P(SH)H zukommt. Phenylphosphinsulfid ist instabil und zersetzt sich unter Bildung von Tetraphenyl‐cyclo‐tetraphosphin‐monosulfid, [(C6H5)P]4S, Schwefelwasserstoff und Phenylphosphin.
Recherches sur la formation et la transformation des esters XLIV. Sur l'action de l'oxyde phénylphosphonique sur des alcools non saturés, des hydroxy‐éthers, des alcools cycliques et le phénol
Authors: Cherbuliez Emile , Čolak‐Antić Sl. , Gabbai A. , Hunkeler F. , Gowhari M. , Rabinowitz J.
Published: December 2004

Ethenic alcohols, ethynic tertiary alcohols, hydroxy ethers, cyclic alcohols, araliphatic alcohols, and phenol react very easily with phenyl phosphonic oxide to yield the corresponding phosphonic monoesters.
Etudes sur les matières végétales volatiles CLXXXVIII. Sur l'absorption d'alcools terpéniques aliphatiques dans l'ultra‐violet, de 185 à 225 mμ
Authors: Naves Yves‐René , Frei Charles
Published: December 2004

The ultra‐violet spectra of a number of aliphatic terpene and sesquiterpene alcohols together with their ydrogenated derivatives have been measured between 185 and 225 mμ.
Über Protonenresonanz‐Spektren von Pteridinen III. Zur Struktur von 9‐Acetonylxanthopterin und Erythropterin
Authors: von Philipsborn W. , Stierlin H. , Traber W.
Published: December 2004

Proton magnetic resonance spectra of 9‐acetonylxanthopterine (I) and erythropterine (II) are reported. Based upon these data and UV.‐spectroscopic evidence, it is shown that these compounds exist in the tautomeric forms Ib and IIb, respectively.
Über Pterinchemie. 8. Mitteilung. Struktur und Protonenresonanz‐Spektren einiger Xanthopterinderivate
Authors: Merlini L. , von Philipsborn W. , Viscontini M.
Published: December 2004

Im Zusammenhang mit der Struktur des Schmetterlingspigmentes Erythropterin wurden einige Xanthopterinderivate untersucht und die Tautomeriefragen mittels NMR.‐ und UV.‐Spektren abgeklärt.
Etude des composés d'addition des acides de LEWIS XIX. Sur les composés formés par les 2‐ et 4‐hydroxyacétophénones avec TiCl4 et ZnCl2
Authors: Göhring J. , Rossetti G. P. , Susz B. P.
Published: December 2004

The preparation of complex compounds between ZnCl2 or TiCl4 and p‐hydroxy‐, o‐hydroxy‐ and hydroxy‐2‐methyl‐5‐acetophenone is described. Some of these compounds have been isolated as intermediate complexes of Fries rearrangements catalyzed by TiCl4. ZnCl2 forms addition compounds whereas with TiCl4 elimination of HCl occurs. The IR, absorption spectra are examined and prodable structures proposed for the compounds. The electronic acceptor group ‐OTiCl2 is found to be weaker than TiCl4 and about as strong ZnCl2 when dative bonds are formed.
Ringschlussreaktionen des Butadiendioxids mit Hydrazinen zu neuen Derivaten des Pyrazolidins und Piperidazins
Authors: Meyer H. R. , Gabler R.
Published: December 2004

The reaction of butadiene dioxide (dl‐and meso‐) with various hydrazines led to 1: 1‐adducts having either pyrazolidine or piperidazine structures. Using N,N′‐di‐substituted hydrazines, pyrazolidine derivatives were obtained with yields of 70–80%, whereas hydrazine itself reacted with DL‐butadiene dioxide to give about 20% of trans‐4,5‐dihydroxypiperidazine and a small quantity of trans‐7,8‐tetrahydroxy‐10‐azaquinolizidine. The five ring closure reaction seems to be a general and preparativeloy interesting pyrazolidine synthesis. The structure of a representative of the 5‐ and of the 6‐ring system was proven by their conversion into open chain diamines. The constitutions of these diamines were established by independent synthesis or by conversion into known compounds. The assignation of the other 1: 1‐adducts to the pyrazolidine or to the piperidzaien series respectively was carried out by mean of NMR‐analysis.
Über die Stereochemie der cyclischen Additionsprodukte von Butadiendioxid mit Hydrazinen
Authors: Koch W. , Zollinger Hch.
Published: December 2004

1) Derivatives of piperidazine and pyrazolidine have been investigated by NMR.‐spectroscopy.
Hircinol, eine antifungisch wirksame Substanz aus Knollen von Loroglossum hircinum (L.) RICH
Authors: Urech J. , Fechtig B. , Nüesch J. , Vischer E.
Published: December 2004

Aus Knollen von Loroglossum hircinum (L.) Rich., welche mit dem Pilz Rhizoctonia versicolor Müller et Nüesch infiziert worden sind, wird das fungistatisch wirksame Hircinol, C15H14O3, in Ausbeuten von 250–400 mg pro kg Knollengewebe isoliert. Die Knollen enthalten ferner pro kg ca. 150 mg einer fungistatisch unwirksamen Substanz A. Beide Verbindungen scheinen dem Orchinol, einem aus Orchis militaris L. isolierten Pilzabwerhrstoff, chemisch nahe zu stehen. Substanz A hat sich als identisch mit dem von Hardegger und Mitarb. beschirebene Loroglossol erwiesen.
Synthesen in der Polymyxin‐Reihe. 8. Mitteilung. Synthese des hochaktiven cyclischen Decapeptides 7 γ und sein Vergleich mit natürlichem Polymyxin B1
Authors: Vogler K. , Studer R. O. , Lanz P. , Lergier W. , Böhni E. , Fust B.
Published: December 2004

Es wird über die Synthese des cyclo‐Decapeptides 7γ berichtet. Als Ergebnis unserer Bemühungen zur Strukturaufklärung von Polymyxin B2 durch Synthese wird festgestellt, dass keine der möglichen Formeln 8α, 8γ, 7α und 7γ, die durch Abbau hergeleitet wurden, mit der Struktur von Polymyxin B1 übereinstimmen, obwohl 7α und 7γ eine bemerkenswerte antimikrobielle Aktivität in vitro in vivo aufweisen.
Reaktionen von Steroid‐Hypojoditen VII. 3‐Oxo‐1,11α‐oxido‐Δ1‐steroide. Über Steroide, 204. Mitteilung
Authors: Meystre Ch. , Kalvoda J. , Anner G. , Wettstein A.
Published: December 2004

The homolytic cleavage of 11‐hypoiodites of 3‐oxo‐11α‐hydroxy‐steroids, generated from the corresponding hydroxy compounds by treatment with lead tetraacetate and iodine, has been investigated. The main reaction products are enol ethers containing the 3‐oxo‐1, 11α‐oxido‐Δ1‐grouping.
Über eine neuartige Basen‐katalysierte Umlagerung der Nitroso‐Gruppe
Authors: Daeniker H. U.
Published: December 2004

By treatment with bases in methanolic solution N‐substituted N‐nitroso‐amino‐acetonitriles (I) undergo an internal rearrangement of the nitroso group to yield α‐isonitroso‐aminoacetonitriles (II). The structures of the rearrangement products are proved by their physico‐chemical properties, by chemical degradation to known products, and by transformation into a number of derivatives. Similar compounds in which the nitrile group of I is replaced by other activating groups do not rearrange to compounds analogous to 11, but lead in part to SCHIFF bases. Mechanisms for all these reactions are proposed.
Etudes sur les matières végétales volatiles CXCIISur la composition des huiles essentielles d'ylang‐ylang
Authors: Naves Yves‐René , Ardizio Pierre
Published: December 2004

The ylang‐ylang oils «extra» «first» «second» and «third» have been analysed by vapor phase chromatography and compared with absolute oils described in 1959. The contents in geranyl acetate are far lower than advocated by KATAGUE&KIRCH.It is firmly established that the sesquiterpenes are artefacts, the findings of GLICHITCH&NAVES(1932)on the relative rates of distillation of benzyl benzoate and sesquiterpenes being confirmed.
Note sur la catalyse acide de la réaction des phosphobétaïnes avec le benzaldéhyde
Authors: Fliszár S. , Hudson R. F. , Salvadori G.
Published: December 2004

The catalysis by benzoic acid of the reaction between carbethoxymethylene‐tri‐phenylphosphorane and benzaldehyde, reported by KUCHARDT et al. for benzenic solutions, is reduced by changing the solvent from benzene to chloroform, and by increasing the temperature. These observations are interpreted by specific hydrogen bonding in the transition state, which also explains the lower activation energy of the reaction in chloroform.
Eine einfache neue Synthese für Säureanhydride
Authors: Rinderknecht Heinrich , Ma Victoria
Published: December 2004

A novel method for the synthesis of acid anhydrides is described. Condensation of two molequivalents of a triethylammonium salt of an aliphatic or aromatic acid with one molequivalent of phosgene in an inert solvent at low temperature furnishes excellent yields of anhydrides.
Strahlungschemie von Kolhenwasserstoffen 10. Mitteilung Let‐Effekte in Toluol
Authors: Hoigné J. , Burns W. G. , Marsh W. R. , Gäumann T.
Published: December 2004

Liquid toluene was irradiated with 60Co γ‐rays, with protons of energies from 1.8 down to 0.5 MeV and with α‐particles of 1.5 and 0.7 MeV with a dose of 10 and 30 Mrad at 20‐25°C. The G‐values increased with increasing LET from 0.11 to 0.58 for hydrogen, from 0.95 to 1.55 for polymers, from 0.055 to 0.061 for bibenzyl, from 0.034 to 0.042 for bitolyls, 0.020 to 0.066 for benzyltoluene and 0.028 to 0.051 for benzyldihydrotoluene. The isomer ratio of the six bitolyls changed appreciably but the ratio of the three benzyltoluenes remained constant. The yield vs. LET dependence shows different characteristics for the different products formed. The competition of reactions of first and second order with respect to primary reactive species are discussed. The results approve the hypothesis that benzyltoluene is mainly formed by a second order reaction of reactive primary particles in the spurs. If this molecule formation would be due to a radical recombination, then a small spur‐radius must be accepted for this reaction.
Anorganische Dünnschicht‐Chromatographie 9. Mitteilung Dünnschichtchromatographische Trennung von Sulfaten und Polythionaten
Authors: Seiler H. , Erlenmeyer H.
Published: December 2004

Thin laver chromatography is applied to the separation and identification of several oxoacids of sulfur and some polythionic acids.
Über die Hydroxidhalogenide Me2(OH)3Cl, ‐Br, ‐J zweiwertiger Metalle (Me = Mg, Ni, Co, Cu, Fe, Mn)
Authors: Oswald H. R. , Feitknecht W.
Published: December 2004

The preparations of the 3:1 hydroxide halides Me2(OH)3Cl, ‐Br and ‐I of Mg, Ni, Cu, Co, Fe and Mn are described, and the corresponding X‐ray data registered. The following structures were found: Layer structures: (a) C6 type [α‐Mg2(OH)3Cl, α‐ Ni2(OH)3CI, α‐Co2(OH)3Cl, α‐Fe2(OH)3CI, α‐Mn2(OH)3Cl]; (b) Botallackite type [α‐Cu2(OH)3Cl (= synth. Botallackite), Cu2(OH)3Br, Ni2(OH)3Br, α‐Co2(OH)3Br, Fe2(OH)3Br, Cu2(OH)3I, Ni2(OH)3I, Co2(OH)3I, Fe2(OH)3I, Mn2(OH)3I].
Synthèses d'analogues structuraux de l'élédoïsine. 2me partie: Préparation de tétrapeptides, pentapeptides et hexapeptides intermédiaires
Authors: Sandrin Ed. , Boissonnas R. A.
Published: December 2004

The preparation of new tetrapeptides, pentapeptides and hexapeptides, which constitute intermediates in the synthesis of Eledoisin analogues, is described.
Flavosemichinon‐Metallchelate: Modelle zur Erklärung der «active site» in den mitochondrialen Flavoenzymen. Zum Verhalten des Riboflavins gegen Metallionen III
Authors: Hemmerich P.
Published: December 2004

The behaviour of half reduced isoalloxazine (flavocoenzyme) systems, riboflavin and analogues, has been studied acidimetrically and spectrophotometrically in aqueous solution, in the presence or absence of non‐redox d‐metal ions. The metal has been found to combine selectively with the flavin semiquinone anion, forming deep red radical chelates with cornproportionation of the ligand system. Colour and reactivity of native metal‐containing flavoenzymes might be explained satisfactorily by this. Reference has been made to biological conclusions advanced elsewhere.
Les spectres de masse dans l'analyse. 3e communication. Les spectres de masse des hydrocarbures monoterpéniques
Authors: Thomas Alan F. , Willhalm B.
Published: December 2004

The mass spectra of cis‐ and trans‐p‐menthane, 5 menthenes, 5 saturated bicyclic hydrocarbons C10H18, and 22 terpenes C10H16 have been measured. Only the spectra of cis‐ and trans‐alloocimene were indistinguishable from one another; all the other substances gave specific fragmentation patterns that can be used in their identification.
Novobiocin V. Synthesen und Reaktionen von Acyl‐noviosylhalogeniden
Authors: Vaterlaus B. P. , Spiegelberg H.
Published: December 2004

A number of arylglycusyl halides were synthesised and their usefulness for glycosidation with respect to synthesising novobiocin explored. The key intermediate, the 2,3‐O‐carbonyl‐noviosylchloride (10) is described.
Valenzisomerisierung und Fragmentierung von Cyclodecatertraenen. Cyclodecapolyene, 3. Mitteilung
Authors: Grob C. A. , Schiess P. W.
Published: December 2004

Degradation of the N‐oxides and quaternary salts of the cis and trans forms of 1,6‐bis‐dimethylamino‐cyclodeca‐3,8‐dienes (4 b) and (4 c), respectively, afforded mixtures of hydrocarbons C10H12 separable by gas chromatography after hydro‐genation. In both cases a mixture of decalins, n‐butykyclohexane,n‐butylbenzene, cyclodecane and an unidentified tricyclic hydrocarbon C10H16 were obtained. However, COPE elimination yielded mainly trans‐decalin (66%), HOFMANN elimination mainly the cis isomer (58‐74%).