bluuebunny/crossref_metadata_2025 huggingface dataset:
4,5‐Dihalogen‐O‐acetylindoxyle
Authors: Kambli Ed.
Published: December 2004

In the synthesis of 4‐chloro‐5‐bromo‐O‐acetyl indoxyl, an important substance used in locating esterase activity, difficulties arose from the formation of isomeric intermediate products. Selection of different starting compounds not only facilitates the syntheses of this dihalogeno O‐acetyl indoxyl, but also enables the production of new o‐acetyl indoxyls of equal applicability.
Étude du comportement et de l'électrolyse de solutions d'oxyde de Germanium dans des fluorures fondus
Authors: Monnier R. , Tissot P.
Published: December 2004

Pure Ge is obtained in good yield by electrolysis of GeO2 solutions in appropriate mixtures of fluorides wich melt at a temperature to 900°C. The suggested mechanism of the electrolysis consists in the dissociation of GeO2 in Ge4+ and O2− and the direct discharge of these ions at the electrodes.
Umwandlung von Krötengiften (Bufadienoliden) durch Mikroorganismen. II. 12β‐Hydroxyresibufogenin. 12. Mitteilung über Reaktionen mit Mikroorganismen
Authors: Schüpbach M. , Tamm Ch.
Published: December 2004

Incubation of resibufogenin (1) with cultures of Fusarium lini (BOLLEY) yielded the unknown 12β‐hydroxyresibufogenin (4). The structure of 4 was proved by the degradation of its diacetyl derivative 5 to methyl 3β,12β‐diacetoxy‐l4β, 15β‐epoxy‐5β, 14β, 17αH‐etianate (9) which was identical with the degradation product obtained from 14β,15β‐epoxy‐14‐anhydro‐digoxigenin diacetate (7). The latter was prepared from di‐O‐acetyl digoxigenin (8). Incubation of 14β, 15β‐epoxy‐14‐anhydro‐digitoxigenin (2) with F. lini led to the 12β‐hydroxy derivative 6, its diacetate being identical with 7. LiAlH4‐reduction of both the epoxyester 9 and the hydroxyester 12 derived from digoxigenin gave the same tetrol 10.
Metallmethylate und deren Bildungsgleichgewichte
Authors: Gut Rudolf
Published: December 2004

A pH‐scale has been defined for absolute methanol as solvent and the ionic product of methanol was evaluated (20°, μ = 1.0, N(CH3)4Cl or LiC1). The formation of methoxide complexes has been studied by titration of methanolic solutions of BCl3, AlCl3, GaCl3, InCl3, PCl3, TiCl4, ZrCl4, ThCl4, GeCl4, ZnCl2, TaCl5, NbCl5, NbOCl3, WOCl4 with lithiummethylate.
Die Glykoside von Streblus asper LOUR. 3. Mitteilung. Untersuchung der stark wasserlöslichen Anteile Glykoside und Aglykone, 260. Mitteilung
Authors: Manzetti A. R. , Reichstein T.
Published: December 2004

The highly polar cardenolide glycosides from the root bark of Streblus asper contain components which are attacked by snail glycosidases and thereby transformed into chloroform‐soluble monoglycosides. The remaining water‐soluble (chloroform‐insoluble) portion is a mixture of highly polar glycosides of mono‐ or disaccharides. 21 cardenolides could be detected in this material by paper chromatography. Of these 4 could be isolated in crystals and 8 other ones in amorphous form, giving only one spot each in paper chromatograms. One of these glycosides, Strophallosid (J), has recently been obtained from seeds of Antiaris toxicaria. The 11 other cardenolides are most probably new compounds. The main component is the crystalline glucostrebloside (M), which is not attacked by strophanthobiase although it contains terminal D‐glucose.
Die Glykoside von Streblus asper LOUR. 4. Mitteilung. Strukturbestimmung einiger stark wasserlöslicher Glykoside Glykoside und Aglykone, 261. Mitteilung
Authors: Manzetti A. R. , Reichstein T.
Published: December 2004

Tentative structures are derived for eight water‐soluble cardenolide glycosides from the root bark of Streblus asper LOUR. They are mainly based on identification by paper and thin layer chromatography of the products obtained after acid hydrolysis in micro scale, using both ‘KILIANI’ and ‘MANNICH’ conditions. In derivatives containing D‐glucose as β‐D‐glucopyranosidic end group this sugar could be split off by prolonged treatment with snail enzyme. In a few cases it was possible to perform hydrolysis in preparative scale and to show that the isolated sugar component belonged to the D‐series. Strophalloside (J) could be reduced to strophanolloside (K) with NaBH4.
Synthetische Analoge des Hypertensins. VI. α‐L‐Asp(NH2)1‐aza‐α′‐homo‐Tyr4‐Val5‐Hypertensin II und β‐L‐Asp1‐aza‐α′‐homo‐Tyr4‐Val5‐Hypertensin II
Authors: Riniker B. , Schwyzer R.
Published: December 2004

The use of the CURTIUS azide method for the synthesis of peptides is known to produce urea derivatives as side‐products due to partial rearrangement of the azide to an isocyanate. As model compounds for this type of reaction the two urea analogues of Val5‐hypertensin II mentioned in the title have been synthesised.
Optische Spaltung des 5‐Hydroxy‐DL‐Tryptophans
Authors: Rinderknecht Heinrich
Published: December 2004

A novel method for the resolution of 5‐hydroxy‐DL‐tryptophan is described. Successive treatment of N‐Benzyloxycarbonyl‐5‐benzyloxy‐DL‐tryptophan with the stereoisomeric bases quinidine and quinine precipitates directly the corresponding salts of the L‐ and D‐antipodes.
Sur les esters activés I. Aminolyse des dérivés de oximes et amidoximes
Authors: Buyle R.
Published: December 2004

O‐Acylamidoximes and acyloximes can be considered as activated esters which are useful acylating agents. A number of activated esters are compared in their action on benzylamine. Their acylating power is directly related to the acidity of the OH group of the leaving species (alcohol or oxime respectively).
Absolute Konfiguration von Terpinenol‐(4)
Authors: Ohloff G. , Uhde G.
Published: December 2004

Zur Aufklärung der absoluten Konfiguration von Terpinenol‐(4) wurde (−)‐Terpinenol‐(4) über das (+)‐Carvomenthol mit dem (−)‐Limonen verbunden. Das (−)‐Terpinenol‐(4) besitzt daher die (4R)‐Konfiguration. Für das (+)‐Terpinenol‐(4) wurde auf indirektem Wege die (4S)‐Konfiguration ermittelt.
Die synchrone Fragmentierung von γ‐Amino‐cycloalkylhalogeniden. 2. Teil. Solvolysen von 4‐Bromchinuclidin. Fragmentierungs‐Reaktionen, 12. Mitteilung
Authors: Brenneisen P. , Grob C. A. , Jackson R. A. , Ohta M.
Published: December 2004

The fragmentation of 4‐bromo‐quinuclidine (7) to N,4‐bis‐methylene‐piperidinium bromide (8) has been studied in six solvents. In 80% ethanol and in 70% dioxane 4‐bromo‐quinuclidine reacts 5.5 · 104 times as fast as the homomorphous compound 1‐bromo‐bicyclo[2.2.2]octane (9). The nitrogen atom therefore participates in the rate determining step.
Über die Struktur von Verrucarin A. Verrucarine und Roridine, 5. Mitteilung
Authors: Gutzwiller J. , Tamm Ch.
Published: December 2004

The antibiotic verrucarine A (C27H34O9) yields on base catalysed hydrolysis three products: (1) the sesquiterpene alcohol verrucarol (C15H22O4) (12), (2) cis, trans‐muconic acid (C6H6O4) (7), and (3) verrucarinolactone (C6H10O3) (9). The latter is the δ‐lactone of the hitherto unknown trans‐α, δ‐dihydroxy‐β‐methyl‐valeric acid (verrucarinic acid (16)). The absolute configuration of verrucarinolactone results from its degradation to (R)‐(+)‐methylsuccinic acid (21). Verrucarinolactone is a new natural isomer of mevalolactone.
Die qualitative Untersuchung der Protonierungs‐ und der Komplexbildungs‐Funktion
Authors: Anderegg G.
Published: December 2004

The importance of the complex formation function for the study of ionic equilibria in solution is discussed.
Schwingungsspektrum von Cyclododecan und Cyclododecan‐d2 zwischen 4000 und 50 cm−1. Normalkoordinatenanalyse von zwei Cyclododecanmodellen
Authors: Fuhrer H. , Günthard Hs. H.
Published: December 2004

The infrared, far infrared and RAMAN spectra of cyclododecane and the infrared and far infrared spectra of cyclododecane‐(1,1)‐d2 with D2 symmetry have been measured. For the light isotopic modification a numerical normal coordinate analysis has been carried out, using the 35‐constants potential for paraffins given by SCHACHTSCHNEIDER, and an automatic computer program for the calculation of the G‐matrix, the normal frequencies and the normal vectors.
Alkaloide aus Schizozygia caffaeoides (BOJ.) BAILL. II. Die Struktur des Schizozygins
Authors: Renner U. , Fritz H.
Published: December 2004

From chemical degradation experiments and spectroscopical data structure I is deduced for schizozygine, the major alkaloid of Schizozygia caffaeoides (BOJ.) BAILL. The given relative configuration is suggested by experiments indicating a strain‐free ring system.
Einfluss der Porenstruktur auf die Gasdiffusion in porösen Körpern
Authors: Richarz W. , Alder H. P. , Guyer A.
Published: December 2004

Es wurde an zylindrischen Probekörpern, hergestellt aus nichtporösen pulverigen Materialien unterschiedlicher Härte, die spezifische Permeabilität gemessen und mit der Porosität in Beziehung gebracht.
Circulardichroitische Messungen an gesättigten und α,β‐ungesättigten Cyclopropyl‐ketonen
Authors: Schaffner K. , Snatzke G.
Published: December 2004

The circular dichroism (CD) of saturated and α,β‐unsaturated ketones containing three‐membered rings has been measured and correlated with the configurations and conformations of these compounds.
Réarrangement thermique des oxo‐2‐oxathiadiazoles‐1,2,3,5 en dioxo‐1,1‐benzothiadiazines‐1,2,4
Authors: Eloy F.
Published: December 2004

2‐Oxo‐1,2,3,5‐oxathiadiazoles containing an aromatic substituent in the 3‐position and an aliphatic substituent in the 4‐position rearrange on heating into 1,1‐dioxo‐1,2,4‐benzothiadiazines. The mechanism of the transposition is discussed.
Die HAMMETT'sche Substituentenkonstanten für m‐ und p‐ständige Phenylazogruppen
Authors: Syz M. , Zollinger Hch.
Published: December 2004

1. HAMMETT's σ‐values for the phenylazo group in meta and para position have been determined from the acid‐base equilibrium constants of the respective phenols, anilines and benzoic acids.
De la chimie des ptérines. 11e communication. Sur une nouvelle synthèse de ptérines 7,8‐dihydrogénées et sur l'obtention inattendue de l'hydroxyméthyl‐6‐ptérine isomériquement pure
Authors: Viscontini M. , Nasini G.
Published: December 2004

Par action de l'hydrate d'hydrazine et du diméthylformamide sur la tétrahydroptérine (II) on obtient l'hydrazone de la formyl‐6‐dihydro‐7,8‐ptérine (III), qu'on oxyde ensuite facilement en hydrazone de la formyl‐6‐ptérine (IV). Un traitement acide transforme par oxydo‐réduction cette hydrazone en hydroxyméthyl‐6‐ptérine (V) isomériquement pure.
Spektren und Basizität der reinen trans‐Konfigurationen von substituierten 4‐Dimethylaminostilbenen
Authors: Syz M. , Zollinger Hch.
Published: December 2004

(1) It has been found that under normal light conditions solutions of trans‐4‐dimethylaminostilbene and a series of its derivatives contain appreciable percentages of the respective cis‐isomers; this occurs even if direct sunlight is excluded.
Zur Methylierung von 1‐Phenyl‐5‐sulfanilamido‐pyrazol
Authors: Eichenberger K. , Zürcher R. F. , Rossi A. , Wilhelm M. , Schmidt P.
Published: December 2004

By methylation of 1‐phenyl‐5‐sulfanilamido‐pyrazole in alkaline medium N1‐Methyl‐1‐phenyl‐5‐sulfanilamido‐pyrazole has been isolated, the structure of which is proved by an unambiguous synthesis.
NMR.‐Spektren von Zwischenprodukten elektrophiler aromatischer Substitutionen und Elektronen‐Donator‐Acceptor‐Komplexen
Authors: Koch W. , Zollinger Hch.
Published: December 2004

(1) The structure of the intermediates (σ‐complexes) in two bromination reactions have been studied by proton magnetic resonance spectroscopy. The structures correspond to those earlier described in the bromination of 2‐naphthol‐6,8‐disulphonic acid [1].
Etudes sur les matières végétales volatiles CXCVI. Sur la déshydratation du linalol et la préparation de β‐myrcène et de trans‐β‐ocimène
Authors: Naves Yves‐René , Bondavalli Francesco
Published: December 2004

The linalol treated by iodine at 140–150°C loses water and yields a mixture of β‐myrcene (45%) and trans‐β‐ocimene (16%).
Über die Bindung der Wassermolekel in den Verbindungen MeIISO4, 1 H2O und MeIISeO4, 1 H2O: I. Strukturuntersuchungen. (MeII = Mg, Ni, Cu, Co, Fe, Zn, Mn)
Authors: Oswald H. R.
Published: December 2004

The monohydrates of the sulphates of bivalent Mg, Ni, Cu, Co, Fe, Zn, Mn and some of the corresponding selenates have been prepared and the unit cell dimensions tabulated. All except the copper compounds have the monoclinic MgSO4·1H2O (Kieserite) structure. CuSO4·1H2O and CuSeO4·1H2O have a very similar triclinic crystal structure. The lattice parameters of CoSO4·1H2O have been determined by a least square refinement with 73 powder X‐ray reflections, and the interatomic distances and angles are given. It is shown that these monohydrates are not to be formulated as salts MeH2SO5 of a «meso sulfuric acid».
Recherches sur la formation et la transformation des esters LVII. Acides ou chlorures d'acides de PIII et alcools α‐acétyléniques: estérification sans ou avec réarrangement
Authors: Cherbuliez E. , Jaccard S. , Prince R. , Rabinowitz J.
Published: December 2004

When α‐acetylenic alcohols are reacted with acid chlorides of trivalent phosphorus in the presence of a tertiary base, the intermediate trivalent esters rearrange to pentavalent phosphorus derivatives, with formation of a new PC bond. Generally, the C3 group fixed on the phosphors has an allenic structure: ; in some cases this group tautomerizes to the corresponding acetylenic derivative: .
Die Struktur des Alstonia‐Alkaloides Villalstonin Vorläufige Mitteilung
Authors: Hesse M. , Hürzeler H. , Gemenden C. W. , Joshi B. S. , Taylor W. I. , Schmid H.
Published: December 2004

Das Alstonia‐Alkaloid Villalstonin liefert bei der Isomerisierung mit Trifluoressigsäure Villamin, welches thermisch in Pleiocarpamin(1) und Macrolin übergeht. Auf Grund chemischer Reaktionen, spektroskopischer Analysen und Vergleiche wurde für Macrolin die Struktur 13 abgeleitet. Daraus folgt für Villamin die Formel 10 und schliesslich 2 für Villalstonin.
Ist die Molekel ein Biradikal?
Authors: Baumgartner P. , Weltin E. , Wagnière G. , Heilbronner E.
Published: December 2004

Molecular orbital calculations including electron‐electron interaction indicate that the molecule
magnified image
has either a triplet ground‐state or a low lying, thermally excitable triplet state.
Decahydrochinolole, 1. Teil. Synthese und Konfiguration der epimeren 1‐Methyl‐4‐hydroxy‐trans‐decahydrochinoline
Authors: Grob C. A. , Lutz H. J.
Published: December 2004

The epimeric 4α‐ and 4β‐hydroxy‐1‐methyl‐trans‐decahydroquinolines, 1a and 2a respectively, have been synthesized from 1‐acetylcyclohexene, and their configurations and conformations determined by chemical and NMR.‐spectral methods.
Decahydrochinolole. 2. Teil. Synthese und Konfiguration von 1‐Methyl‐5‐hydroxy‐decahydrochinolinen
Authors: Grob C. A. , Kiefer H. R.
Published: December 2004

Three stereoisomers of 5‐hydroxy‐1‐methyl‐decahydroquinoline, namely the 5α‐cis, the 5α‐trans, and 5β‐trans froms, 1a,2a and 3a respectively, have been synthesized from cyclohexane‐1,3‐dione. Configurations and conformations are assigned on the basis of chemical, IR.‐and NMR.‐spectral properties.
Der oxydative Abbau von Verrucarin A, ein weiterer Strukturbeweis. Verrucarine und Roridine, 7. Mitteilung
Authors: Zürcher W. , Gutzwiller J. , Tamm Ch.
Published: December 2004

The structure of verrucarin A (1) has been confirmed by a stepwise oxidative degradation of mono‐O‐acetyl‐β‐epoxy‐verrucarin (6).
Über 9β, 10α‐Steroide 1. Mitteilung. Herstellung und Eigenschaften von 6‐Halogen‐9β, 10α‐androstan‐Derivaten
Authors: Els H. , Englert G. , Müller M. , Fürst A.
Published: December 2004

(1) The synthesis of Δ4‐,Δ1,4‐,Δ4,6‐, and Δ1,4,6‐3‐keto‐6‐halogen(F, Cl, Br)derivatives of the 9β,10α‐androstane series is described.
Organische Phosphorverbindungen XVIII. Eine neue Methode zur Knüpfung von PCP‐Bindungen (Darstellung von Di‐, Tri‐ und Tetra‐tertiären‐Phosphinen)
Authors: Maier Ludwig
Published: December 2004

Tertiary phosphines containing dialkylaminomethylgroups condense readily at elevated temperature (∼ 160°) with compounds containing a PH bond, with the formation of PCP bonds according to the general equation:
equation image
.
Die Sterine und Bufadienolide der Haut von Bufo formosus BOULENGER. Über Krötengifte, 31. Mitteilung
Authors: Iseli E. , Kotake M. , Weiss Ek. , Reichstein T.
Published: December 2004

In the skin of the Japanese toad Bufo formosus BOULENGER three sterols and 19 bufadienolides have been traced by thin layer and paper chromatography. Combining different preparative chromatographic methods a complete qualitative separation could be achieved. From 490 animals the following amounts of the 3 sterols and 16 crystalline bufadienolides were obtained (amounts in mgs): cholesterol (ca. 20000; only a fraction was purified), 7α‐hydroxy‐cholesterol (1.5, identification tentative), 7β‐hydroxy‐cholesterol (8.5), cinobufagin (40), bufalone (8.5), bufotalone (12), bufalin (353), 3‐epi‐bufalin (32), cinobufotalin (54), marinobufagin (45), bufotalin (1357), bufotalinin (13), telocinobufagin (42), desacetyl‐cinobufagin (18), desacetyl‐bufotalin (76), arenobufagin (143), hellebrigenin = bufotalidin (25), desacetyl‐cinobufotalin (18), gamabufotalin (2136). The following three were obtained in amorphous from: resibufogenin (74, identified as crystalline O‐acetyl‐derivative), argentinogenin (14) and U5 (7, not identified).
Die Konstitution von Tanghinin Glykoside und Aglykone, 268. Mitteilung
Authors: Flury E. , Weiss Ek. , Reichstein T.
Published: December 2004

Degradation of tanghinigenin 9 yields the known methyl 3‐oxo‐7,8β‐epoxy‐14β‐hydroxy‐5β‐etianate 13. This ester, after bromination followed by dehydrobromination with concomitant opening of the oxirane ring, gave methyl 3‐oxo‐8β, 14β‐dihydroxy‐etia‐4,6‐dienate 18. This same compound was obtained from scillirosidin, whose structure has already been established, following an unequivocal route. The dienone 18 from tanghinigenin gave after hydrogenation the two saturated methyl 3‐oxo‐8β, 14β,‐dihydroxy‐etianates 21 and 22, isomeric in the 5‐position. Both these compounds were products of degradation reactions carried out on scillirosidin. Together with earlier results these transformations establish the structure of tanghinigenin as 3β, 14β‐dihydroxy‐7, 8β‐epoxy‐Δ20(22)‐cardenolide 9.
Oxosynthese mit chlorierten Äthylenen
Authors: Gut G. , El‐Makhzangi M. H. , Guyer A.
Published: December 2004

Es wurde die Hydroformylierung von 1,1‐Dichloräthylen, 1,2‐Dichloräthylen und Vinylchlorid mit Kobalthydrogencarbonyl und Dikobaltoctacarbonyl unter milden Oxosynthesebedingungen studiert. Während mit 1,2‐Dichloräthylen keine chlorierten Aldehyde gebildet wurden, konnte mit 1,1‐Dichloräthylen und Kobalthydrogencarbonyl neben 1,1‐Dichloräthan α‐Monochlorpropionaldehyd und α‐Monochloracrolein identifiziert werden. Vinylchlorid ergab in ca. 90% Ausbeute α‐Monochlorpropionaldehyd neben geringen Mengen Acrolein, Propionaldehyd und Äthylchlorid. Die Ausbeute an α‐Monochlorpropionaldehyd wird durch niedrige Temperaturen, kurze Reaktionszeiten und hohes Verhältnis von Wasserstoff zu Kohlenmonoxid begünstigt.
Synthese einiger 2‐Dialkylaminoalkoxy‐6‐alkylamino‐ und 2‐Dialkylaminoalkylamino‐6‐alkoxy‐pyridine
Authors: Büchi J. , Allisson S. , Vetsch W.
Published: December 2004

Aus 2,6‐Dichlorpyridin wurden über die 2‐Dialkylaminoalkylamino‐6‐chlorpyridine einige 2‐Dialkylaminoalkylamino‐6‐n‐butoxy‐pyridine und 2‐Dialkylaminoalkoxy‐6‐n‐butylamino‐pyridine hergestellt. Einige der hergestellten Verbindungen besitzen eine geringe motilitätsdämpfende, histaminantagonistische und lokalanästhetische Wirkung (siehe Tabelle 2), die aber eine weitere pharmakologische und klinische Prüfung nicht rechtfertigt.
Darstellung substituierter 2, 6‐Dioxo‐2, 3, 4, 6‐tetrahydro‐pyrido[2, 1‐a] isoindole. 1. Mitteilung
Authors: Viscontini M. , Kaiser W. , Leidner H. A.
Published: December 2004

N‐Phtaloyl‐β‐alanylchlorid und Essigester werden mittels Magnesiumäthylat zu N‐Phtaloyl‐β‐alanyl‐acetessigester (IVa) kondensiert, der sich leicht in wasserhaltigem Pyridin zu 1‐Acetyl‐2,6‐dioxo‐2,3,6‐tetrahydro‐pyrido[2,1‐a]isoindol (IIa) cyclisieren lässt. Mit dem gleichen Verfahren wird 1‐Acetyl‐3‐phenyl‐2,6‐dioxo‐2,3,4,6‐tetrahydro‐pyrido[2,1‐a]isoindol (IIb) hergestellt. Die Richtigkeit der Struktur IIa wird bewiesen.
Die BECKMANN‐Umlagerung und Fragmentierung von optisch aktiven α‐trisubstituierten Ketoximtosylaten
Authors: Fischer H. P.
Published: December 2004

The solvolyses of optically pure (−)‐anti‐2‐methyl‐2‐phenyl‐butyrophenonoxime tosylate and anti‐3‐methyl‐3‐phenyl‐2‐pentanonoxime tosylate in methanol and chloroform have been studied. In methanol rearrangement to amide with retained configuration of the migrating group is accompanied by fragmentation to predominantly inverted 2‐phenyl‐2‐methoxy‐butane. N‐Alkyl‐nitrilium salts are common intermediates for rearrangement and fragmentation. Since the heterolysis of N‐alkyl nitrilium ions is energetically related to SN1 reactions of alkyl halogenides or alkyl esters, the stereochemical course has been interpreted in terms of DOERING's mechanistic hypothesis for endothermic SN1 reactions.
Zur Kenntnis der Hexaalkylbenzole. 8. Mitteilung. Seitenkettenreaktionen des Hexa‐(n‐propyl)‐benzols
Authors: Hopff H. , Gati A.
Published: December 2004

Light‐activated bromination of hexa‐n‐propyl‐benzene gives hexa‐(α‐bromo‐n‐propyl)‐benzene, which can be dehalogenated to a new hydrocarbon, hexapropylidenecyclohexane.
Über die sogenannte anomale CLAISEN‐Umlagerung. 2. Mitteilung
Authors: Habich A. , Barner R. , von Philipsborn W. , Schmid H.
Published: December 2004

The mechanism of the abnormal CLAISEN rearrangement, that is the isomerisation of o‐allylphenols, has been investigated using deuterium as tracer. The incorporation and distribution of the label was followed by proton and deuterium NMR. analysis.
Alstophyllin, ein neues Indolalkaloid aus Alstonia macrophylla WALL
Authors: Kishi T. , Hesse M. , Gemenden C. W. , Taylor W. I. , Schmid H.
Published: December 2004

Aus Alstonia macrophylla WALL. wurde ein neues Alkaloid, Alstophyllin, isoliert. Auf Grund seiner Hydrolyse in ein ketonisches Spaltstück 6 und Ameisensäure sowie spektroskopischer – insbesondere massenspektrometrischer – Daten wurde ihm die Struktur 1 zuerteilt.
Polare Imprägnierung von Glaskapillaren für die Gas‐Chromatographie
Authors: Grob Kurt
Published: December 2004

According to the experience of various authors, glass capillaries used as columns for gas chromatography can be coated only with non‐polar liquids such as squalane and apiezon. This paper shows that polar liquids form a coherent film on a glass surface which has first been covered by an approx. 0.001 μ layer of carbon black. Several methods for producing these layers are described. Such pretreated glass capillaries show equal or better separation efficiencies than steel capillaries and work at lower temperatures, due to their lower adsorption activity.
Die Strukturen der mittleren Ringverbindungen. IX. 1, 8‐Diazacyclotetradecan‐dihydrobromid
Authors: Dunitz J. D. , Meyer E. F.
Published: December 2004

Crystals of 1,8‐diazacyclotetradecane dihydrobromide are orthorhombic, a = 13.58, b = 14.81, c = 8.01 Å, Z = 4, space group Pccn (D). The conformation of the 14‐membered ring has been established from three‐dimensional X‐ray analysis. It corresponds closely to an idealized conformation based on the diamond lattice.
FRIEDEL‐CRAFTS‐Reaktionen mit aromatischen äthern. 1. Mitteilung Die Herstellung von Alkoxy‐indanonen‐(1)
Authors: Marquardt F.‐H.
Published: December 2004

The products resulting from condensation of veratrole and α,β‐unsaturated acids in polyphosphoric acid are the corresponding 1‐indanones. With pyrogallol trimethyl ether and with resorcinol dimethyl ether the nature of the products of these condensations varies according to the α,β‐unsaturated acid employed. Usually it will be a phenyl vinyl ketone, which agrees with the results given in the literature for the reaction with anisole. The ability of the various aromatic ethers to form indanones by this condensation is discussed on the basis of the π‐electron density in the different positions of the aromatic ethers.
Die Cardenolide von Parquetina nigrescens (AFZEL.) BULLOCK. Glykoside und Aglykone, 270. Mitteilung [1]
Authors: Berthold R. , Wehrli W. , Reichstein T.
Published: December 2004

Six crystalline (A, C, E, H, J and K) and six amorphous (α, γ, A1, D, D′, and G) but paperchromatographically homogenous cardenolides were isolated from the wood of Parquetina nigrescens (AFZEL.) BULLOCK (= Periploca nigrescens AFZEL.) after fermentation with glucosidases. The presence of twelve more cardenolides was observed in paperchromatograms. Three of the mentioned compounds could be identified with known substances: A = strophanthidin (already isolated by SCHENKER et al. [3] from similar material), H = strophadogenin = 16β‐hydroxystrophanthidin and J = convallatoxin. A1, C, D, E, and K are new compounds whose structures will be reported in the following publication. The structures of α, γ, D′ and G are as yet unknown.
Die Konstitution von Verrucarin J. Verrucarine und Roridine, 9. Mitteilung [1]
Authors: Fetz E. , Böhner B. , Tamm Ch.
Published: December 2004

The antibiotic verrucarin J (C27H32O9) yields on base catalysed hydrolysis verrucarol (3), cis,trans‐muconic acid (5) and 5‐hydroxy‐3‐methyl‐2‐pentenoic acid lactone (6). 6 is a secondary reaction product of the genuine cis‐5‐hydroxy‐3‐methyl‐2‐pentenoic acid (10). In the antibiotic the three fragments 3, 5 and 10 are united to form a macrocyclic triester. Their sequence is deduced on the basis of the partial hydrolysis of verrucarin J leading to the dihydroxyester 11. Structure 1 is assigned to verrucarin J.
Komplexone XXXVIII. Reaktionsenthalpie und ‐entropie bei der Bildung der 1:1‐und 1:2‐Metallkomplexe von Methyliminodiessigsäure
Authors: Anderegg G.
Published: December 2004

The enthalpy changes involved in the metal complex formation with methyliminodiacetate‐ion have been determined, using a direct calorimetric method. The thermodynamic data obtained are used to calculate the chelate effect with the EDTA‐homologous (−OOCCH2)2 = N(CH2)nN = (CH2COO−)2 as ligand.
Synthese von in 10‐Stellung basisch substituierten 9,9‐Dialkylacridanen
Authors: Molnar I. , Wagner‐Jauregg Th.
Published: December 2004

Es wird über die Synthese von in 10‐Stellung basisch substituierten 9,9‐Dialkyl‐acridanen nach drei Methoden berichtet. Unter den hergestellten Verbindungen zeigen das N‐Methyl‐3′‐aminopropyl‐9,9‐dimethyl‐acridan (SD 735) und das entsprechende N‐Dimethyl‐Analoge (SD 25) im Tierversuch Antireserpin‐Wirkung und bei der klinischen Prüfung thymoleptische (antidepressive) Eigenschaften.
Synthèse de l'Ala1‐Ala6‐Arg8‐vasopressine et de l'Ala1‐Ala6‐Lys8‐vasopressine, ainsi que de la (déamino‐Ala)1‐Ala6‐Arg8‐vasopressine et de la (désamino‐Ala)1‐Ala6‐Lys8‐vasopressine
Authors: Huguenin R. L. , Guttmann St.
Published: December 2004

Ala1‐Ala6‐Arg8‐vasopressin, Ala1‐Ala6‐Lys8‐vasopressin, (Deamino‐Ala)1‐Ala6‐Arg8‐vasopressin and (Deamino‐Ala)1‐Ala6‐Lys8‐vasopressin were prepared by condensation of a tripeptide azide or, respectively, a propionyl‐dipeptide azide with a hexapeptide amide, both fragments having been synthesized by methods excluding racemization. These peptides represent analogues of arginine‐vasopressin, lysinevasopressin and of their deamino derivatives, in which the ring is open and the sulphur atoms are replaced by hydrogen atoms. The new peptides were found to be devoid of any biological activity and did not inhibit the corresponding natural hormones. The significance of this observation is discussed.
Synthèse de la Gly8‐oxytocine, de l'Ala8‐oxytocine et de la But8‐oxytocine
Authors: Jaquenoud P.‐A.
Published: December 2004

Gly8‐oxytocin and Ala8‐oxytocin have been synthesized according to the 3+6 scheme, and But8‐oxytocin to the full recurring scheme, active esters having been used almost throughout for the formation of peptide bonds. The comparison of their biological activities with those of oxytocin, Val8‐oxytocin and Ile8‐oxytocin, shows that omission of the aliphatic side chain of the amino‐acid in position 8 strongly depresses the activities. Nevertheless an ethyl group (But8‐oxytocin) and even a methyl group (Ala8‐oxytocin) are sufficient to confer to the, molecule a high degree of activity.
Synthesen in der Isochinolinreihe Zur partiellen Ätherspaltung 6,7‐dimethoxy‐substituierter 3,4‐Dihydro‐isochinoline und Isochinoline
Authors: Bruderer H. , Brossi A.
Published: December 2004

The selective ether cleavage observed with 6,7,8‐trimethoxy‐substituted 3,+‐dihydroisoquinolines and isoquinolines under the influence of 20% hydrochloric acid takes place in the analogous 6,7‐dimethoxy series with concentrated hydrobromic acid at 100°. This constitutes an easy route to 6‐methoxy‐7‐hydroxy‐isoquinoline derivatives.
Reversible Umlagerung eines cis‐2‐Vinyl‐cyclopropylformaldehydes zu einem Dihydrooxepin. Vorläufige Mitteilung
Authors: Rey Max , Dreiding André S.
Published: December 2004

Evidence is given for a fast reversible 2‐vinylcyclopropylformaldehyde‐dihydro‐oxepine rearrangement. Bicyclo[3.1.0]hex‐2‐ene‐6‐endo‐formaldehyde and 2‐oxa‐bicylo[3.2.1]octa‐3,6‐diene coexist in a 7:3 equilibrium, which is pulled in the direction of the enol ether by a cycloaddition with tetracyanoethylene, and in the direction of the aldehyde by interaction with LiAlH4, Ag2O or NaHSO3. Decomposition of the pure hydrogensulfite adduct of the aldehyde refurnishes the 7:3 mixture.
Réactions du diazométhane. I. Transformation de la fonction N‐phénylthio‐carbonyle (C6H5SCO‐NH‐R) avec production d'isocyanate (OCNR) par élimination bimoléculaire
Authors: Baudet P. , Calin M. , Cherbuliez E.
Published: December 2004

Diazomethane transforms N‐(phenylthio‐carbonyl)‐amino acid esters or amides into the corresponding N‐carbonyl derivatives, similarly it converts N‐(phenylthio‐carbonyl)‐butyl‐1‐amine into butyl‐isocyanate. Solvents with a high dielectric constant (e. g. nitromethane, ethanol) favour this transformation. The analogous but N‐substituted N‐(phenyloxy‐carbonyl)‐amino acid esters are not modified by diazomethane. This new reaction appears to proceed by a bimolecular elimination (E2), where the transition state leads very rapidly to the formation of an isocyanate on the one hand and thio‐anisole on the other.
3‐Hydroxy‐1,2,4‐benzotriazin‐1‐oxid‐7‐carbonsäure und verwandte Verbindungen
Authors: Brenneisen K. , Thumm O. , Benz J.
Published: December 2004

The chloride of 3‐chloro‐1,2,4‐benzotriazine‐1‐oxide‐7‐carboxylic acid has been prepared, and from this a number of derivatives of 3‐hydroxy‐1,2,4‐benzotriazine‐1‐oxide‐7‐carboxylic acid were synthesized by stepwise substitution of the two halogen atoms. This acid chloride has further been used for linking dye components containing amino groups, and for the synthesis of reactive dyes whose suitability for dyeing cellulose and wool has been examined.
Die Zusammensetzung der Neutrallipide aus normalen Hirnen alter Menschen
Authors: Lesch Peter , Meier Sylvia , Bernhard Karl
Published: December 2004

The chemical composition of lipids from six human brains (60–73 years) is reported. The total lipids out of cortex, white matter, diencephalon and cerebellum, pons, and medulla oblongata have been isolated and the neutral lipids have been separated in cerebrosides, sphingomyelines, and lecithins. The highest amount of pure lipids is found in the white matter, the lowest in the cortex. The relation of neutral lipids to acid lipids as well as the amount of cholesterol are about equal for all regions. The white matter shows more cerebrosides and sphingomyelines than the cortex, the opposite being the case for lecithins. The differences are strongly significant. The fatty acids out of the different pure lipid fractions have been analysed as esters by gas chromatography. Stearic and lignoceric acid, and cerebronic and hydroxy nervonic acid respectively are main components of cerebrosides, with only little differences for the different brain regions. The fatty acids of sphingomyelines consist mainly of stearic and nervonic acid; in the white matter these two acids are present about in the same quantity, whereas stearic acid dominates in the cortex and the other sections. Lecithins contain above all palmitic and oleic acid. The amount of the latter in the white matter is higher than that of palmitic acid.
Organische Phosphorverbindungen XXII. Darstellung und Eigenschaften von diprimären α,ω‐Bis‐phosphino‐alkanen
Authors: Maier Ludwig
Published: December 2004

The preparation and properties of diprimary α,ω‐bis‐phosphino‐alkanes of the general structure H2P(CH2)n PH2 (n = 1, 2, 3, 4) are described. Their reactions with N‐hydroxymethyl‐dialkylamines and with olefins, which yield ditertiary α,ω‐bisphosphino‐alkanes, (R2NCH2)2P(CH2)nP(CH2NR2)2 and R2P(CH2)nPR2, respectively, are also reported. The physical properties of two new α,ω‐bis‐dialkylphosphinyl‐alkanes have been determined.
Metallionen und H2O2. VI. Über Struktur und Aktivität der den H2O2‐Zerfall katalysierenden Ni2+‐Komplexe
Authors: Zell R. , Sigel H.
Published: December 2004

The catalytic properties in H2O2 decomposition of Ni2+‐chelates of the following ligands have been investigated: ethylenediamine, diethylenetriamine, triethylenetetramine, 2,2′‐bipyridine, pyrophosphate and ethylenediamine‐N, N, N′, N′‐tetra‐acetic acid, and of the following peptides and peptide‐like ligands: glycylglycine, N,N′‐diglycyl‐ethylenediamine, N, N′‐diglycyl‐1, 5‐diaminopentane and polymyxin B.
De la chimie des ptérines. 15e communication. Hydroxylation non‐enzymatique de la phénylalanine en tyrosine à l'aide de ptérines tétrahydrogénées
Authors: Bobst A. , Viscontini M.
Published: December 2004

The non‐enzymatic hydroxylation of phenylalanine to tyrosine has been effected by atmospheric oxygen in aqueous solution in the presence of 5,6,7,8‐tetrahydropterines, FeII or FeIII, and EDTA, in a phosphate buffer at pH 6,9. A possible reaction mechanism is discussed.
Synthese von in 2‐Stellung substituierten 2‐Amino‐ und 3‐Amino‐1‐indanonen
Authors: Allisson S. , Büchi J. , Michaelis W.
Published: December 2004

An examination has been made of the reaction of secondary amines with 2‐bromo‐1‐indanones II substituted at position C‐2, and with 2‐substituted indenones III. 2‐Bromo‐2‐methyl‐1‐indanone (IIa) and dimethylamine yielded a mixture of the corresponding 2‐ and 3‐amino‐methylindanones IVa and Va. 2‐Bromo‐2‐methyl‐6‐chloro‐1‐indanone (II b) and morpholine gave a mixture of the 2‐ and 3‐aminocompounds IVe and Ve.
Macralstonin
Authors: Kishi T. , Hesse M. , Vetter W. , Gemenden C. W. , Taylor W. I. , Schmid H.
Published: December 2004

Das aus Alstonia macrophylla Wall. (A pocynaceae) isolierte «dimere» Indolalkaloid Macralstonin lässt sich durch verdünnte Salzsäure in die Villalstonin‐Spaltbase Macrolin (8) und das ebenfalls aus Alstonia macrophylla isolierte Alkaloid Alstophyllin (2) spalten. Daraus und auf Grund spektroskopischer Untersuchungen (UV.‐, IR.‐, NMR.‐, Massenspektren) wird für Macralstonin die Struktur 1 abgeleitet.
Die Struktur des Alkaloides Pleiomutin: massenspektrometrische Analyse und Partialsynthese
Authors: Hesse M. , Bodmer F. , Schmid H.
Published: December 2004

Für Pleiomutin, ein «dimeres» Indolalkaloid aus Pleiocarpa mutica BENTH., wird auf Grund des Massenspektrums, seiner Hydrolyse zu Pleiocarpinin (3) und seiner Partialsynthese aus 3 und Eburnamin (7) die Konstitution 1 abgeleitet.
Über Dibenz[b,f]‐azocin‐Derivate
Authors: Schindler O. , Blaser R. , Hunziker F.
Published: December 2004

Aus o‐Aminodibenzyl (I) und o‐Amino‐cis‐stilben (IV) wurden mit Phosgen die Isocyanate II bzw. VIII hergestellt. Diese wurden als Harnstoffe V bzw. VII charakterisiert. Mit AlCl3 in Dichlorbenzol behandelt, ging II in das Azocin III über, während aus VIII das Indolon IX entstand.
Organische Phosphorverbindungen XXIII. Sekundäre Phosphinselenide, eine neue Klasse von organischen Phosphorverbindungen
Authors: Maier Ludwig
Published: December 2004

The preparation and properties of secondary phosphine selenides, R2P(Se)H(R = i‐C4H9, C6H5), a new class of organophosphorus compounds, are described.
Über die Chiralität der enantiomeren 4‐Methylcyclohexylidenessigsäuren
Authors: Gerlach H.
Published: December 2004

The chirality of the enantiomeric 4‐methylcyclohexylideneacetic acids has been determined by a mechanistic correlation with (−)‐isoborneol.
Zur thermodynamisch‐phänomenologischen Beschreibung der Färbevorgänge I. Diskontinuierliches Modellsystem
Authors: Milićević B. , McGregor R.
Published: December 2004

The essential characteristics of a simple, discontinuous model system for mass transfer between two phases are discussed. It is shown that for dyeing processes that conform to this model it is possible, with the aid of the methods of non‐equilibrium thermodynamics, to give an unambiguous definition of the concepts «rate of dyeing» and «affinity of dyeing», at any stage of dyeing. It is clear from the derived phenomenological equations that dyeing systems rarely reach a true equilibrium state (i.e. a stationary state of zero order), but that in general an osmotic or a DONNAN equilibrium is attained.
Untersuchungen über den Mechanismus der beiden Azosynthesen von SUCKFÜLL & DITTMER. 18. Mitteilung zur Kenntnis der Azokupplungsreaktion
Authors: Christen M. , Funderburk L. , Halevi E. A. , Lewis G. E. , Zollinger Hch.
Published: December 2004

15N‐Tracer techniques have been employed to investigate the reactions of aryldiazonium ions with aryldiazosulphonates and with aryldiazotates (SUCKFÜLL‐DITTMER azo syntheses), in which unsymmetrical azo compounds and o‐hydroxyazo compounds respectively are formed as the main products, with concomitant elimination of molecular nitrogen.
FRIEDEL‐CRAFTS‐Reaktionen der C7‐, C8‐ und C12‐Cycloalkane mit Kohlenmonoxid
Authors: Hopff H. , von Rütte R.
Published: December 2004

The reaction of cycloheptane, cyclooctane, and cyclododecane with carbon monoxide under pressure in the presence of anhydrous aluminium chloride has been investigated. Cycloheptane leads to acetylcyclohexane and trans‐2‐methyl‐cyclohexane carboxylic acid as main products. Cyclooctane yields 3‐ and trans‐4‐acetyl‐methylcyclohexane and various dimethylcyclohexane carboxylic acids. From cyclododecane a mixture of numerous ketones has been obtained besides a mixture of acids.
Sur les esters activés III. Nouvelle synthèse des dioxo‐2,5‐pipérazines et étude de leurs propriétés chimiques
Authors: Buyle R.
Published: December 2004

By reacting an α‐amino acid N‐carboxyanhydride with an amidoxime the dioxopiperazine derived from the parent amino acid is formed in quantitative yield. In this way the dioxopiperazine of glutamic acid, which is not otherwise accessible, has been prepared.
Massenspektren einiger SCHIFF'schen Basen des Pyridin‐2‐aldehyds
Authors: Schumacher Ernst , Taubenest Richard
Published: December 2004

Photographically recorded high‐resolution mass spectra of some SCHIFF bases of pyridine‐2‐aldehyde are presented. Fragmentation patterns of the primary ions formed under electron impact are discussed in connection with a proposed four‐membered cyclic transition state.
Über die Reaktion substituierter Thioxanthenoxide mit Säuren
Authors: Schindler O. , Michaelis W. , Gauch R.
Published: December 2004

9‐[(N‐Methyl‐3′‐piperidyl)‐methyl]‐thioxanthene‐10‐oxide (I) on treatment with boiling concentrated hydrochloric acid gives mainly 9‐[(N‐methyl‐3′‐piperidyl)‐methylene]‐thioxanthene (IV) together with small amounts of 9‐[(N‐methyl‐3′‐piperidyl)‐chloro‐methylene]‐thioxanthene(II), 9‐hydroxy‐9‐[(N‐methyl‐3′‐piperidyl)‐methyl]‐thioxanthene (III) and 9‐[(N‐methyl‐3′‐piperidyl)‐methyl]‐thioxanthene (V). Treatment of I with acetic anhydride yields only IV.
Sensibilité au choc des explosifs chimiques solides. A propos d'une note récente d'A. J. A. van der Wyk
Authors: Cruchaud M.
Published: December 2004

La sensibilité au choc d'un explosif chimique solide n'est pas, comme l'a pensé A. J. A. VAN DER WYK, déterminée par sa chaleur spécifique.
Die Glykoside der Samen von Stapelia gigantea N. E. Br. Glykoside und Aglykone, 275. Mitteilung
Authors: Eppenberger U. , Kaufmann H. , Stöcklin W. , Reichstein T.
Published: December 2004

The seeds of Stapelia gigantea are very rich in ester glycosides (ca. 5,9%). Mild acid hydrolysis gave a mixture of sugars which, after paper chromatography and electrophoresis, was found to be probably composed of cymarose, oleandrose, digitoxose, arabino‐2,6‐dideoxyhexose (= canarose) and pachybiose. The mixture of the raw genins gave after alkaline hydrolysis a mixture of about nine deacyl genins (C, D, E, F1, F2, F3, G, H, J); the acids split off during hydrolysis were not identified. The nine deacyl genins are probably closely related pregnane derivatives. The main component (E), C21H30O4, was obtained in crystalline state, and was named stapelogenin. Its probable structure is reported in the following publication.
Zur Synthese des Ecdysons. II. Mitteilung über Insektenhormone Synthesen von 2β, 3β‐Dihydroxy‐6‐keto‐A|B‐cis‐Steroiden
Authors: Wiechert R. , Kerb U. , Hocks P. , Furlenmeier A. , Fürst A. , Langemann A. , Waldvogel G.
Published: December 2004

Experiments towards a synthesis of ecdysone (1) ([22R]‐2β, 3β, 14, 22, 25‐pentahydroxy‐5β, 14α‐cholest‐7‐en‐6‐one) have led to 2β, 3β‐dihydroxy‐6‐keto‐5α‐steroids. These could be epimerized to the corresponding 5β‐series. The proposed configurational assignments are supported by physical data and chemical correlation.
Zur Synthese des Ecdysons. III. Mitteilung über Insektenhormone. Synthesen von 2β, 3β, 14α‐Trihydroxy‐6‐keto‐Δ7‐A|B‐cis‐Steroiden
Authors: Furlenmeier A. , Fürst A. , Langemann A. , Waldvogel G. , Kerb U. , Hocks P. , Wiechert R.
Published: December 2004

The synthesis of the tetracyclic skeleton of ecdysone with correct stereochemistry and substitution is described. 22,25‐Didehydroxy‐ecdysone and methyl (20S)‐2β,3β‐dihydroxy‐6‐oxo‐5β‐pregn‐7‐ene‐20‐carboxylate have been prepared. The latter is a key intermediate in the synthesis of ecdysone.
Zur Katalyse der Umvinylierungen
Authors: Lüssi H.
Published: December 2004

It is shown that the vinyl interchange reaction between vinyl acetate and carboxylic acids proceeds by an acid catalysed addition of mercuric acetate to the vinyl double bond; the corresponding organomercuric intermediate has been isolated and identified.
Über Pyrrolizidinchemie 6. Mitteilung. Konfiguration der HARINGTON'schen(±)‐β‐Hydroxyglutaminsäure und der daraus hergestellten (±)‐3‐Hydroxypyrrolidon‐2‐carbonsäure
Authors: Viscontini M. , Odasso G. , Freitag W.
Published: December 2004

Für den von HARINGTON synthetisierten (±)‐β‐Hydroxy‐glutaminsäure‐äthylester wird die erythro‐Konfiguration bewiesen. Der daraus gewonnene (±)‐3‐Hydroxy‐prolin‐äthylester ist dementsprechend ein trans‐Derivat.
Die Strukturen der mittleren Ringverbindungen. X. 1, 6‐trans‐Diaminocyclodecan‐dihydrochlorid, monokline Modifikation
Authors: Huber‐Buser Effi , Dunitz J. D.
Published: December 2004

The structure of the monoclinic modification of 1,6‐trans‐diaminocyclodecanedihydrochloride has been determined, and refined by full‐matrix least‐squares analysis of three‐dimensional X‐ray data. The cyclodecane skeleton is very similar to that found previously in the triclinic modification, but the substituents are attached to different types of carbon atoms. The two crystal modifications thus correspond to different conformational isomers.
Nigrescigenin, Identifizierung mit Sarmentosigenin A Glykoside und Aglykone, 281. Mitteilung
Authors: Brandt R. , Kaufmann H. , Reichstein T.
Published: December 2004

“Sarmentosigenin A” has been identified with nigrescigenin. The latter is the older and thus valid name for this 3β, 5β, 11α, 14β‐tetrahydroxy‐19‐oxo‐card‐20:22‐enolide.
Die Isolierung zweier neuartiger Indol‐Derivate aus dem Mycel von Claviceps paspali STEVENSet HALL
Authors: Fehr Th. , Acklin W.
Published: December 2004

Investigation of the dried mycelium of Claviceps paspali STEVENS et HALL has led to the isolation of two new neutral metabolites, paspalin, C28H39O2N, and paspalicin, C31H35O4N, both of which contain a 2,3‐disubstituted indole nucleus.
Über Pterinchemie. 17. Mitteilung. Neuer Beitrag zum Studium eines von Tetrahydropterinen aktivierten Enzymmodelles der Hydroxylierung
Authors: Viscontini M. , Leidner H. , Mattern G. , Okada T.
Published: December 2004

Anhand neuer experimenteller Ergebnisse wird für den Mechanismus der von Tetrahydropterin und Fe2+ bzw. Fe3+ katalysierten Hydroxylierung des Phenylalanins zum o‐, m‐ und p‐Tyrosin eine neue Hypothese formuliert, wobei zwei wichtige Punkte hervorgehoben werden: 1. Diese Hydroxylierung ist keine «gemischte» Oxydation, wie wir sie selbst früher postulierten; 2. N‐Oxide sowie Tetrahydropterin‐und HO‐Radikale treten vermutlich als Zwischenprodukte der chemischen bzw. enzymatischen Hydroxylierung auf.
Zum Mechanismus der Autoxydation von Vanadium (IV)‐Komplexen
Authors: Kaden Th.
Published: December 2004

The stoichiometry and the kinetics of the autoxidation of vanadium(IV)‐picolinic acid complexes are studied. Oxygen is reduced to H2O2, a stable peroxovanadate being formed as end product.
Über eine neuartige Substitutionsreaktion am Chinoxalinsystem: nucleofuge Carbonamid‐ und Carbonester‐ Gruppen
Authors: Dahn H. , Moll H.
Published: December 2004

The oximes or arylhydrazones of quinoxaline‐2‐carboxylic acid and its esters or amides substituted in position 3 by an aromatic acyl group are easily cyclized to form condensed isoxazole or pyrazole derivatives, respectively. In the reaction, the oxime oxygen or hydrazone nitrogen acts as a nucleophile; the eliminated carboxyl, carboxylic ester or carboxamide group is partly found as formic acid and CO. The reaction may proceed by an addition‐elimination mechanism.
Über Pyrrolizidinchemie. 7 Mitteilung. Herstellung von L‐Prolin und trans‐3‐Hydroxy‐DL‐prolin durch elektrochemische Reduktion der entsprechenden Pyrrolidon 2‐carbonsäuren
Authors: Viscontini M. , Bühler H.
Published: December 2004

Die Darstellung von (teilweise racemisiertem) L‐Prolin und von trans‐3‐Hydroxy‐DL‐prolin durch elektrochemische Reduktion von 5‐Oxo‐L‐pyrrolidin‐2‐carbonsäure (oder deren Äthylester) bzw. von trans‐3‐Acetoxy‐5‐oxo‐DL‐pyrrolidin‐2‐carbonsäure‐äthylester wird beschrieben.
Die Konstitution von Roridin D. Verrucarine und Roridine, 12. Mitteilung
Authors: Böhner B. , Tamm Ch.
Published: December 2004

The antibiotic roridin D (C29H38O9), a companion of roridin A, yields on base catalysed hydrolysis verrucarol (3) and the hitherto unknown 2, 3‐epoxy‐2‐anhydrororidinic acid (4) (C14H18O7). Roridin D is a macrocyclic diester to which structure 1 is assigned. In roridin D an epoxy group replaces the hydroxyl group of roridin A.
Katalytische Effekte bei den Reaktionen von 2,4‐Dinitrofluorbenzol und 2,4‐Dinitrochlorbenzol mit p‐Anisidin in Benzol. 5. Mitteilung über nucleophile aromatische Substitutionsreaktionen
Authors: Bernasconi C. F. , Zollinger Hch.
Published: December 2004

(1) The rates of the reactions of 2.4‐dinitrofluorobenzene and 2.4‐dinitrochlorobenzene with p‐anisidine have been measured in benzene solution, with and without the addition of pyridine and 1.4‐diaza‐[2.2.2]‐bicyclooctane (DABCO) as catalysts.
Resorption, Retention, Ausscheidung und Verteilung von PhyllochinonMenachinon‐4 und α‐Tocopherolchinon im Vergleich zum α‐Tocopherol bei der Ratte
Authors: Gloor U. , Wiss O.
Published: December 2004

(1) Phylloquinone (K), menaquinone‐4 (MK‐4) and α‐tocopherolquinone (α‐TQ) were compared with d,l‐α‐tocopherol as regards absorption, retention and distribution in various organs.