bluuebunny/crossref_metadata_2025 huggingface dataset:
Stapelogenin, vermutliche Struktur. Glykoside und Aglykone, 276. Mitteilung
Authors: Eppenberger U. , Vetter W. , Reichstein T.
Published: December 2004

Stapelogenin, C21H30O4, shows a double bond and two hydroxyl groups which can be acetylated. On the grounds of UV.‐, IR.‐, and NMR‐spectra as well as mass spectra, the probable structure is that of a 3β, 12β‐dihydroxy‐(18, 20β), (14β, 20α)‐diepoxy‐Δ5‐pregnene (1). The exact position of the hydroxyl group, assumed to be 12β, is particularly unsure, as it could also be situated 11α‐ or 12α‐position.
Über einige neuartige, blutdruckwirksame Verbindungen mit Catecholamin‐ähnlicher Struktur
Authors: Daeniker H. U.
Published: December 2004

Synthesis and properties of a number of 1‐(3‐halogeno‐4‐methoxy‐phenyl)‐1‐hydroxy‐2‐amino‐propanes, a group of new hypertensive substances, are described. One racemate has been resolved, and the optically active components have been correlated with a catecholamine of known absolute configuration.
Metall‐Komplexbildung von β‐Hydroxythiophenderivaten III
Authors: Petri S. , Sigel H. , Erlenmeyer H.
Published: December 2004

The acidity constants of 2‐acetyl‐3‐hydroxy‐thiophene (III) and 3‐acetyl‐4‐hydroxy‐thiophene (IV) and the stability constants of their complexes with some bivalent metal ions have been determined. The stability of the chelates is discussed as a function of the respective bond orders of the α–β and β–β′ bonds of the thiophene ring.
Schmelzreaktionen mit Aluminiumchlorid. 2 Mitteilung. Über die Konstitution eines orangen Küpenfarbstoffs aus der Pyridin‐Aluminiumchlorid‐Schmelze von 1‐Aminoantrachinon
Authors: Wick A. K.
Published: December 2004

The structure of an orange vat dye obtained by the fusion of 1‐aminoanthraquinone in anhydrous pyridine‐aluminiumchloride has been investigated. By synthesis this dye is proved to be an “anthrimide”‐carbazole derivative of the recently described 11, 16‐dihydro‐5H‐dibenzo[c, mn]naphtho[2,3‐h]acridine‐5, 11, 16‐trione.
Synthesen in der Isochinolinreihe. Synthese und Charakterisierung von sog. «rac.‐Korpaverin»
Authors: Brossi A. , Teitel S.
Published: December 2004

The synthesis of so‐called rac.‐corpaverine (I) has been achieved. Reaction of the methobromide VI and 4‐methoxybenzylmagnesium chloride gave the S‐benzyloxytrimethoxy‐substituted derivative VII, which was catalytically debenzylated to the corresponding 8‐hydroxy derivative I. The latter has been related by O‐methylation to the known tetramethoxy‐substituted 1,2,3,4‐tetrahydroisoquinoline VIII. Physical‐chemical data for I are in full agreement with the structure. The melting points of the free base and its hydrochloride, however, differ considerably from those recently published by KAMETANI et al. [3] [4] for so‐called corpaverine.
Die Massenspektren von Schizozygin und dessen Derivaten
Authors: Hesse M. , Renner U.
Published: December 2004

Es wird der thermisch im Massenspektrometer erfolgende Abbau von Schizozygin‐methosalzen diskutiert. Die massenspektrometrischen Fragmentierungen von Schizozygin, Schizozygin‐methin, N‐Methyl‐tetrahydroschizozygin und N, N‐Dimethyl‐hexahydroschizozygin und von deren Derivaten werden auf Grund ihrer hochaufgelösten Spektren interpretiert.
Nickel‐ und Palladiumkomplexe mit Phosphinothioäthern
Authors: Degischer G. , Schwarzenbach G.
Published: December 2004

A new terdentate ligand bis‐(diphenylphosphinoethyl)‐sulfide (PSP) and a new quadridentate ligand 1, 2‐bis‐(diphenylphosphinoethylthio)‐ethane (PSSP) (structures see page 1928) have been synthesized and their NiII‐ and PdII‐complexes have been studied. There is good evidence that the metal has coordination number five in some of these complexes containing halogen (Cl, Br, J).
Fluorénacènes et fluorénaphènes Synthèses dans la série des indéno‐fluorènes X. Exo‐cis‐fluorénaphène
Authors: Chardonnens Louis , Chardonnens Henri
Published: December 2004

On décrit une nouvelle synthèse, réalisée en 9 étapes à partir de la propiophénone avec un rendement global de 8,2%, du dihydro‐5,8‐indéno[2,1‐c]fluorène ou exo‐cis‐fluorénaphène. Dans l'avant‐dernière étape, on obtient la dicétone correspondante ou exo‐cis‐fluorénaphène‐dione.
Dicarbonate und Dicarbamate des DL‐Threits und des Erythrits
Authors: Meyer H. R.
Published: December 2004

DL‐Threitol dicarbonate and erythritol dicarbonate were prepared by the reaction of butadiene dioxide (DL and meso) with carbon dioxide. Treated with aqueous ammonia the dicarbonates gave the corresponding dicarbamates.
Stereospezifische Synthese und Isomerisierung der 10‐Chlor‐decahydroisochinoline. Decahydroisochinoline. IV. Teil
Authors: Grob C. A. , Wohl R. A.
Published: December 2004

Treatment of cis‐ and trans‐10‐hydroxy‐N‐methyl‐decahydroisoquinoline, (3a) and (10a) respectively, or N‐methyl‐Δ9,10‐octahydroisoquinoline (4 a) with hydrogen chloride in acetic acid affords the thermodynamically more stable trans‐isomer of 10‐chloro‐N‐methyl‐decahydroisoquinoline (1a). On the other hand ring closure of β‐(cyclohexen‐1‐yl)‐ethylamines 11a or 11b with aqueous formaldehyde in the presence of chloride ions leads to the 10‐cis‐chlorides 2a or 2b in a kinetically controlled reactions.
Reaktionen des Hexachlordibenzyls II
Authors: Weis C. D.
Published: December 2004

1, 1, 2, 2‐Tetrachloro‐1, 2‐bis‐(4‐chlorophenyl)‐ethane (hexachlorodibenzyl) heated with 4‐chlorobenzoic acid or benzoic acid undergoes pyrolytic cleavage yielding the corresponding benzoylchlorides and trans‐tetrachlorostilbene.
Die Strukturen der mittleren Ringverbindungen. XI. Cyclooctan‐1, 2‐trans‐dicarbonsäure
Authors: Dobler M. , Dunitz J. D. , Mugnoli A.
Published: December 2004

Crystals of 1, 2‐trans‐cyclooctane‐dicarboxylic acid are monoclinic, a = 14.76 Å, b = 11.89 Å, c = 12.98 Å, β = 111.25°, space group C/2c with 8 molecules in the unit cell. The structure has been solved by direct methods and refined by full‐matrix least squares analysis of three‐dimensional intensity data. The cyclooctane ring is found to occur in an approximately mirror‐symmetric (‘boat‐chair’) conformation.
Verfeinerung der Kristallstruktur von 1,4‐trans‐Diaminocyclohexan‐dihydrochlorid
Authors: Dunitz J. D. , Strickler P.
Published: December 2004

The previously described structure of 1, 4‐trans‐diaminocyclohexane dihydrochloride has been further refined by full‐matrix least‐squares analysis with an improved weighting scheme.
Die Solvolyse von exo‐ und endo‐3‐Chlor‐bicyclo[3.2.1]octan
Authors: Grob C. A. , Weiss A.
Published: December 2004

The rates of solvolysis of exo and endo 3‐chloro bicyclo[3.2.1]octane 1a and 2a have been measured in 80 vol.% aqueous ethanol. The axial endo chloride reacts 263 times as fast as the equatorial exo epimer. This remarkably large rate difference is ascribed to sterically accelerated ionisation of the axial endo epimer due to the ethano bridge.
Synthese von Trispiro[5.2.2.5.2.2.]heneicosa‐1,4,13,16‐tetraen‐3,15‐dion durch doppelte intramolekulare C‐Alkylierung eines Diphenols
Authors: Atkinson R. S. , Dreiding André S.
Published: December 2004

A complex trispiro‐bisdienone has been made available through a relatively simple series of reactions.
Conoflorin
Authors: Dugan J. J. , Hesse M. , Renner U. , Schmid H.
Published: December 2004

A new alkaloid, conoflorine, isolated from Conopharyngia longiflora Stapf., has been assigned the stereostructure 1 by physical and chemical methods, including degradation to (+)‐quebrachamine (7). The mass spectra of conoflorine and its derivatives are discussed briefly.
Die Elektronenzustände von Perimeter‐π‐Systemen. II. Das Elektronenspektrum des trans‐15, 16‐Dimethyl‐dihydropyrens
Authors: Blattmann H.‐R. , Boekelheide V. , Heilbronner E. , Weber J.‐P.
Published: December 2004

The electronic spectrum and the polarisation of the transitions have been determined in the region from 15000 to 50000 cm−1 for the 2‐acetamino derivative of trans‐15, 16‐dimethyl‐dihydropyrene, whose spectrum resembles closely that of the parent compound and its di‐ethyl analogue. It is shown that the sequence of states is 1Lb, 1La, 1Bb, 1Ba, in agreement with theoretical predictions which were deduced from a configuration interaction model for the D2h‐π‐perimeter of these systems. The influence of inductive and hyperconjugative effects on the band positions and the band intensities has been discussed.
«Long‐range»‐Kopplung zwischen Protonen geminaler Methylgruppen in Kernresonanzspektren
Authors: Pascual C. , Simon W.
Published: December 2004

The long‐range coupling between protons in geminal methyl groups is described.
2(3H)‐Oxazolone durch Photoumlagerung von 3‐Hydroxyisoxazolen. Synthese von Muscazon
Authors: Göth H. , Gagneux A. R. , Eugster C. H. , Schmid H.
Published: December 2004

3‐Hydroxyisoxazole, für die ein allgemeines Herstellungsverfahren angegeben wird, lassen sich durch UV.‐Bestrahlung in 2(3H)‐Oxazolone überführen.
Über die Alkaloide von Aspidosperma discolor A. DC.
Authors: Dastoor N. J. , Gorman A. A. , Schmid H.
Published: December 2004

From the stem bark of Aspidosperma discolor A. DC. (–)‐reserpiline, (–)‐isoreserpiline, (+)‐yohimbine, (–)‐10‐methoxy‐geissoschizol and (–)‐10‐methoxy‐dihydrocorynantheol (major alkaloids) and (–)‐isoreserpiline‐ψ‐indoxyl, AD‐V (–)‐β‐yohimbine, (+)‐haplocidine, (+)‐desmethylaspidospermine and (–)‐demethoxy‐aspidospermine (minor alkaloids) have been isolated.
7α‐Methylöstrogene. Über Steroide, 209. Mitteilung
Authors: Kalvoda J. , Krähenbühl Ch. , Desaulles P. A. , Anner G.
Published: December 2004

The synthesis of the 7α‐methyl homologues of estrone, estradiol, 17α‐methyl‐ and 17α‐ethinyl‐estradiol, and of the respective 3‐methyl ethers is described. Their estrogenic activity is compared with that of the corresponding unmethylated compounds.
Der Einfluss unterschiedlicher Trägheitsmomente auf die Thermodiffusion von H35Cl, D35Cl, H37Cl und D37Cl
Authors: Meier Werner
Published: December 2004

The analysis of measurements of the thermal diffusion factor α in the systems H35Cl/H37Cl, D35Cl/D37Cl and H35Cl/D35Cl shows that α may be approximated by the expression
α = C_m \frac{{m_1 − m_2 }}{{m_1 + m_2 }} + C_\theta \frac{{\theta _1 − \theta _2 }}{{\theta _1 + \theta _2 }}.
Über den Einbau von Trichloräthylen in Inhaltsstoffe des Kaffees bei dessen Decoffeinierung
Authors: Brandenberger H. , Bader H.
Published: December 2004

After decaffeination of green coffee beans by extraction with [14C]‐trichloroethylene, the beans were radioactive and did not loose their activity during roasting. On the basis of the radioactivity uptake, it is estimated that during commercial decaffeination 0.25 to 1 g of trichloroethylene is incorporated per kg of beans. The nature of the compound or compounds formed on interaction of trichloroethylene with coffee constituents is still unknown, but attention is directed to the possibility of the formation of highly toxic S‐dichlorovinyl derivatives as is the case in the extraction of soya beans with trichloroethylene.
Reaktivität von Koordinationsverbindungen XVII Die Autoxydation von CuI‐Komplexen mit Ammoniak und Imidazol
Authors: Zuberbühler A.
Published: December 2004

The autoxidation of two cuprous complexes, Cu(NH3)2+ and Cu(imidazole)2+, has been studied by following the oxygen consumption with a coated oxygen sensor, and the formation of CuII by means of a stopped flow technique. The reaction was found to be of third order being proportional to the concentrations of CuI, oxygen, and free ligand. pH variation was without effect in the range studied. The rate constants are kIM = 5,5 ·103 12· Mol−2·s−1 for imidazole, and kNH3 = 1,6·104 12· Mol−2· s−1 for NH3 as ligand, resp. An apparent activation energy of less than 2 Kcal/mole has been found for the autoxidation of the cuprous imidazole complex. This can be explained by the assumption of a rapidly playing equilibrium proceeding the rate determining step.
Der Mechanismus der Umwandlung von γ‐ zu α‐Eisensesquioxid [1]
Authors: Feitknecht W. , Mannweiler U.
Published: December 2004

The rate of the isothermal transformation of γ into α Fe2O3 and the increase of the crystallites of α Fe2O3 during the transformation were measured using X‐ray methods.
Eine neuartige Fragmentierung cyclischer α, ß‐ungesättigter Carbonylsysteme; Synthese von Exalton und rac‐Muscon aus Cyclododecanon Vorläufige Mitteilung
Authors: Eschenmoser A. , Felix Dorothee , Ohloff G.
Published: December 2004

The conversion of bicyclo[10.3.0]‐1,12‐epoxy‐13‐pentadecanone into 4‐cyclopenta‐decyne‐1‐one, effected by p‐tolylsulfonylhydrazine under mild conditions and in high yield, provides an example of a new fragmentation reaction.
Synthese und Chiralität des (‐)‐Cannabidiols Vorläufige Mitteilung
Authors: Petrzilka T. , Haefliger W. , Sikemeier C. , Ohloff G. , Eschenmoser A.
Published: December 2004

N, N‐Dimethylformamide‐dineopentylacetal mediates the direct formation of (‐)‐cannabidiol from (+)‐trans‐ or (+)‐cis‐p‐menthadiene‐(2,8)‐ol‐(1) and olivetol. This reaction provides a simple synthetic entry into the series of optically active constituents of haschisch and defines at the same time the chirality of these compounds.
Über die rolle der Aminogruppen der Faser für die Sorption von anionischen farbstoffen: Versuche mit Amino‐ und Hydroxypolypropylen 15. Mitteilung über textilchemische Untersuchungen [1]
Authors: Ferrini B. G. , Zollinger H.
Published: December 2004

(1) Three anionic mono azo dyes (Orange I, Orange II and Orange 8) and a 1:2 metal complex dye (Cibalan Grey BL) are dyed onto aminopolypropylene. With all the dyes, a Langmuir isotherm with a stoichiometric relation between the dye adsorbed and the concentration of amino groups on the substrate is obtained.
Mécanisme de l'hydrolyse acide des carbamates
Authors: Hudson R. F. , Searle R. J. G. , Mancuso A.
Published: December 2004

N, N‐dialkyl carbamates decompose in strongly acidic media to carbon dioxide, olefin, alkyl halide and alcohol, the rate of reaction of the secondary esters closely following the acidity function. This fact, together with the variation in rate of hydrolysis of carbamates of cyclic alcohols with the ring size, shows that, unlike the solvolyses of the corresponding chloroformates which lead to carboxonium ions (\documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R - O -}\mathop {\rm C}\limits^{{\rm (+)}} = {\rm O} $\end{document}), these reactions involve the intermediate formation of carbonium ions.
Die Kristallstruktur von Macrosalhin‐bromid
Authors: Wulf Hannelore , Niggli A.
Published: December 2004

The chemically elucidated structure of Macrosalhine, an alkaloid of Alstonia macrophylla Wall., has been confirmed by X‐ray analysis, the remaining relative stereochemical questions having been at the same time resolved.
Untersuchungen über das Verhalten organischer Mischphasen 5. Mitteilung Dampfdrücke. therodynamische Mischungsfunktionen und Brechungsindices des binären systems Cyclohexan ‐ diäthyläther bei 25°
Authors: Arm H. , Bánkay D. , Strub Kathrin , Wälti M.
Published: December 2004

The total vapor pressures and the heats of mixing of the system cyclohexane‐diethyl ether were measured at 25°C. The index of refraction was used to determine concentrations for the total pressure measurements. The partial pressures, activity coefficients, excess free energies, and entropy functions were calculated.
Propriétés themodynamiques des mélanges binaires. Chaleurs de mélange des n‐alcanes ainsi que de leurs isomères
Authors: Fernández‐García J. G. , Boissonnas Ch. G.
Published: December 2004

The following heats of mixing have been measured: the five isomers of hexane with n‐dodecane at 10°, 20° and 30°C, and with n‐hexadecane at 20°C, as well as the systems dodecane‐hexene‐1 at 20°C, and dodecane‐methyl‐2‐pentene‐1 at 10° 20° and 30°C.
Cyclische, gekreuzt‐konjugierte Bindungssysteme. XIII. NMR.‐untersuchungen am Phenafulven‐system
Authors: Prinzbach H. , Freudenberger V. , Scheidegger U.
Published: December 2004

The HNMR. spectra of phenalene, phenalenone, of some protonated and alkylated derivatives and the spectra of some substituted phenafulvenes are discussed and very qualitatively correlated with the π‐electron distribution in some of these systems.
Recherches sur la formation et la transformation des esters LXXIV [1] etude à l'aide de H2[18O] de la scission de quelques monoesters N‐phénylthiocarbamyl(ou N‐phénylcarbamyl)‐ aminoalcoylphosphoriques et de l'acide dibromo‐2,3‐allyl‐phosphorique
Authors: Cherbuliez Emile , Moll H. , Baehler B. R. , Rabinowitz J.
Published: December 2004

The scission of some N‐phenylthiocarbamoyl(or phenylcarbamoyl)‐aminoalkyl phosphoric monoesters and of 2,3‐dibromoallyl phosphoric monoester is studied in H2[18O], at 100°C and at various pH.
Über eine neuartige Synthese von β‐Ketoallenen durch Reaktion von tertiären Acetylencarbinolen mit Vinyläthern eine ergiebige methode zur darstellung des Pseudojonons und verwandter verbindungen
Authors: Saucy G. , Marbet R.
Published: December 2004

The novel acid‐catalysed reaction of isopropenyl ether with tertiary acetylenic carbinols to give β‐ketoallenes in high yields is described. Upon treatment with bases, these allenes readily undergo isomerization to conjugated dienones. This reaction sequence results in an economic synthesis of pseudo‐ionones and pseudo‐irones from dehydrolinalool and its homologs.
Desaminierung von 6‐Aminopenicillansäure
Authors: Hauser D. , Sigg H. P.
Published: December 2004

The synthesis of 6α‐acyloxy‐penicillanic acids either by deamination of 6‐amino‐penicillanic acid or by rearrangement of N‐nitroso‐penicillins is described.
Über die relative Reaktivität von Nucleophilen. Vorläufige Mitteilung
Authors: Scheffold R.
Published: December 2004

For a number of nucleophiles L an approximate linear correlation between the logarithms of the stability constants of methylmercury‐complexes of L and the nuclear spin‐spin‐coupling constants J of Ch3HgL was found.
Détermination de constantes de stabilité de chélates par résonance magnétique nucléaire du proton
Authors: Merbach A.
Published: December 2004

In a solution containing an excess of two metal ions in regard to a ligand (e.g. NTA) a competitive equilibrium is established. The measure, by proton NMR. spectroscopy, of the individual concentrations of both chelates, and eventually of the free ligand, allows to determine the ratio of the stability constants of the two complexes. As an illustration the ratios of the stability constant of the 1:1 nitrilotriacetate chelates of Pb and Zn, respectively Mo and W, were determined.
Isochinoline. 1. Mitteilung. Über die Umlagerung von α, α‐Dialkylhomophtalimiden zu Derivaten des 1‐Chlor‐3, 4‐dialkyl‐isochinolins
Authors: Marquardt F.‐H. , Nair M. D.
Published: December 2004

On reinvestigation of the reaction of wet phosphorus oxychloride with α,α‐dimethylhomophthalimide, 1‐chloro‐3‐chloromethyl‐4‐methyl‐isoquinoline and 1‐chloro‐4‐chloromethyl‐3‐methyl‐isoquinoline were isolated as the main products (aside from some substances resulting from a redox disproportionation). The production of these two substances can be rationalized by assuming a mechanism in which the rearrangement product is a protonated derivative of 3,4‐dimethylene‐3, 4‐dihydroisoquinoline. With α, α‐diethyl‐homophthalimide the only isolated product was a derivative of 1‐chloro‐3, 4‐diethyl‐isoquinoline, with a chlorine atom in β‐position of one of the ethyl groups, while with α‐methyl‐α‐benzyl‐homophthalimide the isolated product was 1,3‐dichloro‐4‐methyl‐isoquinoline, i.e. elimination had taken place instead of rearrangement. Also these results are in agreement with the proposed mechanism.
Isochinoline. 2. Mitteilung [1]. Die Alkoholyse von 1‐Chlor‐3‐chlormethyl‐4‐methyl‐isochinolin und von 1‐Chlor‐4‐chlormethyl‐3‐methyl‐isochinolin
Authors: Marquardt F.‐H.
Published: December 2004

Methanolysis and ethanolysis of 1‐chloro‐3‐chloromethyl‐4‐methyl‐isoquinoline yield respectively 3‐methoxymethyl‐4‐methyl‐isocarbostyril and 3‐ethoxymethyl‐4‐methyl‐isocarbostyril as main products, together with some 3‐chloromethyl‐4‐methyl‐isocarbostyril. By analogous reactions, 1‐chloro‐4‐chloromethyl‐3‐methyl‐isoquinoline yields 4‐methoxymethyl‐3‐methyl‐isocarbostyril and 4‐ethoxymethyl‐3‐methyl‐isocarbostyril.
Über die Reaktion von Propiolsäure und Propiolsäureester mit Cyclohexanon
Authors: Grob C. A. , Kaiser A.
Published: December 2004

In the presence of potassium t‐butoxide or potassium hydroxide, propiolic acid adds two molecules of cyclohexanone to form the isomeric seq‐cis‐ and seq‐trans‐7, 14‐Dioxa‐dispiro[5.1.5.2]pentadec‐15‐yliden‐acetic acids IIa and IIIa, respectively. Methyl propiolate and cyclohexanone react analogously in the presence of potassium t‐butoxide, yielding the corresponding esters. The structure of these condensation products follows from their physical properties and from degradation reactions to known compounds.
Cyclische gekreuzt‐konjugierte Bindungssysteme. XIV. 5,6‐Dimethyl‐1,2; 3,4‐dibenzo‐ und 5,6‐Dimethyl‐1,2,3,4‐tetraphenyl‐calicen
Authors: Prinzbach H. , Fischer U.
Published: December 2004

The syntheses of 5,6‐dimethyl‐1,2;3,4‐dibenzo‐ and 5,6‐dimethyl‐1,2,3,4‐tetraphenyl‐calicene and some of their physical and chemical properties are reported.
Cyclische gekreuzt‐konjugierte Bindungssysteme. XV. Cycloadditionen mit 5,6‐Dimethyl‐1,2;3,4‐dibenzo‐ und 5,6‐Dimethyl‐1,2,3,4‐tetraphenyl‐calicen
Authors: Prinzbach H. , Fischer U.
Published: December 2004

Cycloaddition reactions of 5,6‐dimethyl‐1,2,3,4‐dibenzo‐ and 5,6‐dimethyl‐1,2,3,4‐tetraphenyl‐calicene with diazo compounds, with dienes, and with dienophilic reagents are described.
Organische Phosphorverbindungen XXX. Herstellung und Eigenschaften aromatisch substituierter Cyclopolyphosphine [1]
Authors: Maier Ludwig , Daly J. J.
Published: December 2004

The interaction of ClC6H4PCl2 or o‐CH3C6H4PCl2 with the corresponding primary phosphines has been studied under a variety of conditions.
Zur Kenntnis des elekrochemischen Verhaltens aufgedampfter Silberschichten. 2. Mitteilung
Authors: Hintermann H. E. , Trümpler G.
Published: December 2004

Der erhöhte Gehalt an freier Enthalpie dünner im Vakuum aufgedampfter Schichten gegenüber demjenigen des Massivkörpers desselben Stoffes kann für Metalle elektrochemisch auf Grund der Negativierung des reversiblen Elektrodenpotentials und der Grösse seines Temperaturkoeffizienten erfasst werden. Am Beispiel des Silbers wird gezeigt, dass diese Abweichung allein verursacht wird durch eine Verminderung der Sublimationsenergie. Der Effekt dieser Verminderung der Sublimationsenergie auf die Bindungsfestigkeit von Atomen auf Oberflächen wird anhand der KOSSEL‐STRANSKI'schen Theorie diskutiert. Es wird auch gezeigt, dass bei Kenntnis des Betrages der Potentialnegativierung und desjenigen des Temperaturkoeffizienten in gewissen Fällen die Korngrösse dünner Schichten abgeschätzt werden kann.
Recherches sur les arômes. 15e communications [1]. Sur l'arôme du cacao II
Authors: Stoll M. , Dietrich P. , Sundt E. , Winter M.
Published: December 2004

4‐Methyl‐5‐(β‐hydroxyethyl)‐thiazole has been isolated from cocoa. This practically inodorous substance is accompanied by trace amounts of its dehydration product, 4‐methyl‐5‐vinyl‐thiazole, possessing a strong nut‐like odour. The RMN. and MS. spectra of the latter are described.
Über Inhaltsstoffe des Haschisch. 3., vorläufige Mitteilung. Umwandlung von (−)‐Δ6,1‐3,4‐trans‐Tetrahydrocannabinol in (−)‐Δ1,2‐3,4‐trans Tetrahydrocannabinol
Authors: Petrzilka T. , Sikemeier C.
Published: December 2004

Successive treatment of (−)‐Δ6,1‐3,4‐trans‐tetrahydrocannabinol with hydrochloric acid/zinc chloride and potassium‐t‐amylate gives (−)‐Δ1,2‐3,4‐trans‐tetrahydrocannabinol in quantitative yield.
Die Glykoside der Wurzeln von Glossostelma carsoni (N. E. BR.) BULLOCK. Glykoside und Aglykone, 297. Mitteilung
Authors: Reichstein P. , Kaufmann H. , Stöklin W. , Reichstein T.
Published: December 2004

Pentacyclic triterpenes, sterols, cardenolides and pregnane derivatives could be identified in extracts from roots of Glossostelma carsoni (N.E. BR.) Bullock. From the first group, the following substances could be isolated in crystalline form: β‐amyrin, lupeol, their 3‐O‐acetyl derivatives, and 3‐O‐isovaleryl‐β‐amyrin. The sterols were isolated in the form of two mixed but crystalline fractions. The less polar fraction was shown to be a mixture of β‐sitosterol, campesterol, stigmasterol, and cholesterol (stereoisomers are not excluded); the more polar fraction is probably a mixture of monohydroxy derivatives of the four above mentioned sterols.
Die Glykoside der Wurzeln von Kanahia laniflora (FORSSK.) R. BR. 2. Mitteilung: Struktur von Kalanosid‐H und Kalanosid‐K Glykoside und Aglykone, 300. Mitteilung
Authors: Kapur B. M. , Allgeier H. , Reichstein T.
Published: December 2004

The total acidic hydrolysis of kalanoside‐H and kalanoside‐K yielded 12‐O‐acetyl‐17‐isolineolon as well as three sugars: oleandrose, canarose and digitoxose. From partial hydrolysis and UV., IR. and NMR. spectral data, it could be concluded that kalanoside‐H is probably a trisaccharide glycoside having the partial formula 1a or 1b, and similarly that kalanoside‐K has probably the partial formula 2.
IR.‐spektroskopische Untersuchungen in der Chinophtalon‐Reihe
Authors: Kehrer F. , Niklaus P. , Manukian B. K.
Published: December 2004

Es wurden einige bekannte Chinophtalone z. T. auf modifizierte Art hergestellt und IR.‐spektroskopisch mit einer Anzahl neuerer, chinophtalon‐artig gebauter Farbstoffe aus der Reihe der Pyromellitsäure, Naphtalin‐ und Perylen‐tetracarbonsäure verglichen.
Differenzierung sämtlicher raumisomerer 6‐Desoxyhexosen, 3‐O‐Methyl‐6‐desoxyhexosen und 6‐Desoxyhexulosen. Desoxyzucker, 42. Mitt. [1]
Authors: Kaufmann Heinz , Mühlardt P. , Reichstein T.
Published: December 2004

The separation of isomeric sugars with the aid of thin‐layer and paper chromatography, as well as paper electrophoresis, has been reported. Under certain fixed experimental conditions and by a combination of the above mentioned methods, it has been possible to differentiate with certainty between all theoretically possible 6‐deoxyhexoses, 3‐O‐methyl‐6‐deoxyhexoses and 6‐deoxyhexuloses.
Komplexone XLI. Die Komplexe des einwertigen und des dreiwertigen Thalliums mit einigen Polyaminocarboxylaten
Authors: Anderegg G. , Bottari E.
Published: December 2004

The stability constants of the complexes of the monovalent and the trivalent thallium ion with different polyaminocarboxylate ions have been determined using pH and redox measurements.
Ternäre Komplexe in Lösung IV. Einfluss von 2,2′‐Bipyridyl auf Stabilität und Acidität des Cu2+‐Adenosin‐5′‐monophosphat‐N(1)‐oxid‐1:1‐Komplexes
Authors: Sigel Helmut , Prijs Bernhard
Published: December 2004

The ternary Cu2+−2,2′‐bipyridyl‐adenosine‐5′‐monophosphate‐N(1)‐oxide complex was investigated and compared with the binary Cu2+‐adenosine‐5′‐monophosphate‐N(1)‐oxide complex (I) (cf. [2]). In both complexes Cu2+ is bound to the o‐amino‐N‐oxide group of adenosine‐5′‐monophosphate‐N(1)‐oxide (HL). The stabilities of the complexes monoprotonated at the phosphate group are of the same order: log K = 11,20, and log K = 11,19. The acidity constants for the deprolonation of the phosphate group in these complexes are slightly different (pK = 5,55, and pK = 5,88), but as expected both values are lower than the corresponding value pK = 6,12 of the ligand.
Die Strukturen der mittleren Ringverbindungen. XIV. Struktur des Silbernitrat‐trans‐Cyclodecen‐Addukts
Authors: Ganis Paolo , Dunitz J. D.
Published: December 2004

Crystals of the AgNO3‐trans‐cyclodecene adduct are orthorhombic, a = 5,47, b = 14,69, c = 26,73 Å, space group Pbcn, with 4 formula units AgNO3·(C10H18)2 in the unit cell. The structure has been solved by the heavy‐atom method and refined by full‐matrix least‐squares analysis of three‐dimensional intensity data. The conformation of the trans‐cyclodecene molecule has features in common with that of the cyclodecane ring, but the trans double bond is twisted about 40° from planarity. This deformation must contribute substantially to the strain‐energy of trans‐cyclodecene. The dependence of the twist‐energy on the twist‐angle is discussed.
Eine Synthese des β‐Sinensals
Authors: Büchi G. , Wüest H.
Published: December 2004

β‐Sinensal, a flavor constituent of the Chinese orange, has been synthesized from myrcene by a four‐step sequence of chemical operations.
Sythese von α und β‐Sinensal
Authors: Bertele E. , Schudel P.
Published: December 2004

β‐Sinensal (2,6‐dimethyl‐10‐methylene‐dodeca‐2,6,11‐trienal) was synthesized from the diene‐aldehyde 5. This was converted into the trans‐ and cis‐triene‐aldehydes 16 and 17, which were condensed with the phosphorane 18 to give the corresponding two geometrical isomers (3 and 19) of β‐sinensal.
Beitrag zur Synthese von Tetracenchinonen
Authors: Winkler R. E.
Published: December 2004

1,4‐Dihydroxyanthraquinones are transformed into the corresponding chlorohydroxy‐ana‐anthraquinone dienophiles, which are subjected to Diels‐Alder addition with 1,3‐dienes. The adducts formed are dehydrogenated to known and to new hydroxynaphthacene quinones.
Stereoselektive Umwandlung von [2.2.2.2.2.2]Metacyclophan in ein all‐trans‐Hexaen
Authors: Burri K. , Jenny W.
Published: December 2004

Starting from [2.2.2.2.2.2]metacyclophane the synthesis of [2.2.2.2.2.2]metacyclophane‐all‐trans‐hexaene via dodecabromo‐[2.2.2.2.2.2]metacyclophane is described. The structure of the new ring system was confirmed by UV.‐, IR.‐, NMR.‐, and mass spectra analyses.
Une fonction d'onde autocohérente (self‐consistent) sans restriction de symétrie pour 1′état X3Π de la molécule BN
Authors: Masse J. L. , Masse‐bärlocher M.
Published: December 2004

We give the self‐consistent wave functions for the BN molecule in the …(5 σ) (1 π+)2 (1 π−), X3 Π state. These wave functions are obtained as linear combinations of SLATER orbitals of the atoms. In this openshell case the π+ and π− orbitals belonging to the same symmetry species but to different subspecies are allowed to vary independently. Their coefficients are found rather different from one another; this seems to mean that the effect of the usual symmetry restriction could be relatively important in such cases.
Recherches sur la formation et la transformation des esters LXXVIII. Sur la réaction de l'isothiocyanate d'o‐méthoxycarbonyl‐phényle avec des diamines et l'hydrazine, et sur la cyclisation de quelques N‐phényl‐N′‐hydroxyalcoyl‐thio‐urées
Authors: Cherbuliez Emile , Willhalm B. , Jaccard S. , Rabinowitz J.
Published: December 2004

1‐Amino‐2‐dimethylamino‐ethane and 1‐amino‐3‐dimethylamino‐propane react with o‐methoxycarbonylphenyl isothiocyanate (I) to yield the corresponding 3‐(ω‐dimethylaminoalkyl)‐2‐thiono‐1,2,3,4‐tetrahydroquinazolin‐4‐ones (V). The tertiary amino group of V is quaternized to the corresponding ammonio derivative VI when treated with methyl iodide in methanol.
Welkstoffe und Antibiotika 37. Mitteilng [1]. Zwischenprodukte zur Synthese von Verbindungen der Lycomarasin‐Reihe aus Glycin und L‐Serin
Authors: Hardegger E. , Szabo F. , Liechti P. , Rostetter Ch. , Zankowska‐Jasinska W.
Published: December 2004

Aus Glycin und L‐Serin, die durch mehrere, offenbar noch unbekannte, einfache Derivate charakterisiert wurden, konnten verschiedene für die Synthese von Verbindungen der Lycomarasmin‐ und der Aspergillomarasmin‐ und der Aspergillomarasmin‐B‐Reihe erfolgversprechende Zwischenprodukte (z. B. IIIc, VII, VIII) hergestellt werden.
BECKMANN‐Umlagerung und Fragmentierung. II. Teil. Versuche zur 7‐Zentren‐Fragmentierung von γ‐Aminoketoximen. Fragmentierungsreaktionen, 19. Mitteilung
Authors: Fischer H. P. , Grob C. A.
Published: December 2004

The occurrence of so‐called synchronous 7‐centre‐fragmentation has been excluded for γ‐amino‐ketoxime derivatives NCCCCNX. Fragmentation may occur, however, by another route.

Reaction rates of the p‐toluenesulfonates of (4‐quinuclidinyl)‐methyl‐ketoxime (10b) and (3β‐tropanyl)‐methyl‐ketoxime (14b) in 80% ethanol and the resulting products have been determined. Whereas the latter γ‐aminoketoxime underwent quantitative BECKMANN rearrangement to 3β‐acetylaminotropane (29), the former yielded 3% fragmentation products besides rearranged 4‐acetylamino‐quinuclidine (13).

A kinetic study reveals that both 10b and 14b react via the rearranged nitrilium ions 12a and 16a, respectively. In the case of the N‐(4‐quinuclidinyl)‐acetonitrilium ion (12a) 5‐centre‐fragmentation competes with hydration to the amide 13.
Über siliciumaromatische Verbindungen I. Trimethylsilylphtalsäuren und davon abgeleitete Farbstoffe
Authors: Hopff H. , Gallegra P.
Published: December 2004

The 3‐ and 4‐trimethylsilyl‐phthalic anhydrides have been prepared by oxidation of the corresponding o‐xylenes and converted into dyestuffs of the type of phthalocyanines, phthaleins and chinophthalones.
Zur Metallion‐Komplexbildung fünfgliedriger α‐Carboxy‐Heterocyclen
Authors: Erlenmeyer H. , Griesser R. , Prijs B. , Sigel H.
Published: December 2004

The stability constants of some 1:1 Me2+‐complexes of the following five‐membered heterocyclic carboxylic acids have been measured in 50 perc. aqueous dioxane (I = 0,1; t = 25°): thiophene‐2‐ (I), 3‐phenylisothiazole‐5‐ (II), tetrahydrothiophene‐2‐ (III), furan‐2‐ (IV), pyrrole‐2‐ (V), and tetrahydrofuran‐2‐carboxylic acid (VI) (table 1 and 2).

A comparison of the stability constants of the Cu2+‐complexes of acetic acid (VII), benzoic acid (VIII), m‐chlorobenzoic acid (IX), p‐nitrobenzoic acid (X), and chloroacetic acid (VI) shows that the heterocyclic S and O atoms coordinate with Cu2+, i.e. Cu2+ chelates (structure XII) are formed (Figure 1).

NMR. spectra (Fig. 2) give evidence for the coordination of the «aromatic» S atom in the Cu2+ complexes of thiophene‐2‐carboxylic acid (I), i.e. at least a part of the complexes are chelates. The NMR. spectra of furan‐2‐carboxylic acid (IV) gave no unequivocal results; in the case of pyrrole‐2‐carboxylic acid (V) the interaction between Cu2+ and the NH‐group is very small (Fig. 4), i.e. a simple carboxylic acid complex is formed.
ESR.‐Spektrum des Radikal‐Anions des [18]Annulen‐1,4;7,10;13,16‐trisulfids
Authors: Gerson F. , Heinzer J.
Published: December 2004

The ESR spectrum of the radical‐anion of [18]annulene‐1,4;7,10;13,16‐trisulfide (ATS) has been recorded. Its analysis yields six coupling constants for pair of equivalent protons indicating the lack of a threefold symmetry axis. A provisional assignment has been attempted which is based on calculated spinpopulations. Conformations of ATS and ATS⊖ are shortly discussed.
Die NO‐katalysierte Isomerisierung von 2,6‐Dimethyl‐1, trans‐3,6‐heptatrien in der Gasphase
Authors: Egger Kurt W.
Published: December 2004

The nitric oxide catalyzed isomerization of 2,6‐dimethyl‐1, trans‐3,6‐heptatriene has been measured for temperatures ranging between 209.1 and 311.4°C. The reaction follows second order kinetics and appears to be truly homogeneous. The main products are 1.5.5‐trimethyl‐1.3‐cyclohexadiene (1,5,5‐TCHD), 2.6.6‐trimethyl‐1.3‐cyclohexadiene (2,6,6‐TCHD) and 2.6‐dimethyl‐1, trans‐3.5‐heptatriene. Only traces of the cisoid structures of the linear trienes are detected, in equilibrium with the trans‐isomers, which is attributed primarily to a loss of conjugation energy in the cis‐isomer. The least squares regression analysis yields for the overall rate constants the ARRHENIUS equation log k (1/mole‐s) = (7.78 ± 0.14) − (25340 ± 350) /2.303 RT (°K). The analysis of the rate data shows that the reaction proceeds via a NO catalyzed geometrical isomerization followed by a thermal intramolecular 1,5‐hydrogen transfer and subsequent cyclization of the 1, cis‐3. 5‐triene structure. No competition with abstraction of the «triallylic» hydrogen by NO is observed.
Farbstoffe aus Naphtazarin‐1,3‐Dien‐Addukten
Authors: Winkler R. E.
Published: December 2004

The amination and oxidation of naphthazarin‐diene adducts leads to known and to new anthraquinone and tricyclic naphthazarin dyestuffs and their intermediates. The new products allow extension of the hitherto known (especially green) color range of dyes. The mechanism of the reaction is discussed.
Über Pterinchemie. 25. Mitteilung [1]. Synthesen von Pterinen und Lumazinen aus α‐Oxo‐β‐hydroxy‐Derivaten und den entsprechenden Pyrimidinen
Authors: Viscontini M. , Leidner H.
Published: December 2004

Die Synthesen von 6,7‐Diphenyl‐5,6‐dihydro‐, 6,7‐Diphenyl‐7,8‐dihydro‐ und 6,7‐Diphenyl‐5,6,7,8‐tetrahydro‐lumazin werden beschrieben. Alle Produkte sind jenen der entsprechenden Pterinreihe sehr ähnlich. Eine allgemeine Theorie der Pterin‐ und Lumazin‐Synthesen, ausgehend von Aminopyrimidinen und α‐Oxo‐β‐hydroxy‐Derivaten, die schon von WEYGAND postuliert wurde, wird bestätigt und erweitert.
Zur Theorie grosser Molekeln. I. Revision der Grundlagen der Quantenchemie
Authors: Primas H.
Published: December 2004

The present day quantum chemistry is mathematically based on von NEUMANN'S formulation of quantum mechanics and therefore not able to deal correctly with anomal quantum states. A general theory of large molecules and large molecular systems has to be founded on quantum field theory allowing for inequivalent irreducible representations. It is proposed to formulate quantum chemistry in the framework of the B*‐algebra of the observables. The paradox of molecular systems having an infinite number of degrees of freedom is discussed, and the possible significance of anomal molecular quantum states for molecular biology is pointed out.
Partialsynthese von 6‐Methyl‐9‐ergolen‐8β‐essigsäure und einiger ihrer Derivate. 68. Mitt. über Mutterkornalkaloide [1]
Authors: Troxler F. , Stadler P. A.
Published: December 2004

The transformation of lysergic acid and 1‐methyllysergic acid into their homologous acids, i.e. 6‐methyl‐9‐ergolen‐8β‐acetic acid and 1,6‐dimethyl‐9‐ergolen‐8β‐acetic acid, and the synthesis of some of their derivatives are described.
BECKMANN‐Umlagerung und Fragmentierung; V. Teil Mechanismus der 7‐Zentren‐Fragmentierung von 1‐Oxo‐5‐oximino‐9‐methyl‐trans‐decalin. Fragmentierungsreaktionen, 22. Mitteilung
Authors: Grob C. A. , von Tschammer H.
Published: December 2004

The reaction rates of heterolytic fragmentation of 5‐(p, ‐toluenesulfonyloxyimino)‐1‐oxo‐9‐methyl‐trans‐decalin (1), induced by sodium hydroxide in 80% ethanol and by sodium ethoxide in 100% ethanol, has been determined. The reaction of the oxime tosylate 1 with sodium ethoxide is first order with respect to both reactants. A similar base‐dependence is observed in the reaction of the oxime tosylate 1 with sodium hydroxide.

These results are explained in terms of an addition‐fragmentation mechanism. This involves reversible addition of NaOH or NaOC2H5 to the carbonyl group of the oxime tosylate 1 and concerted fragmentation of the addition compounds 5a and 5b, yielding 9‐cyano‐6‐methyl‐trans‐non‐5‐enoic acid (4a) and the corresponding ethyl ester 4b, respectively.

These reaction appear to be the first cases of concerted and stereospecific 7‐centre fragmentation.
Fluorénacènes et fluorénaphènes Synthèses dans la série des indéno‐fluorènes XII [1]. Méthyl‐11‐dihydro‐10, 12‐indéno [2, 1‐b] fluorène
Authors: Chardonnens Louis , Maritz Fritz , Stauner Thomas
Published: December 2004

La bis‐cyclohexylation du m‐xylène selon Friedel‐Crafts se fait, pour une bonne part, dans les positions 4 et 6; l'aromatisation du produit obtenu donne en effet le diphényl‐4, 6‐xylène‐1, 3 connu. La bis‐cyclohexylation de l'hémimellitène se fait de même, du moins en partie, en 4 et 6; une série de transformations (aromatisation, oxydation, cyclisation et réduction) conduit au méthyl‐11‐dihydro‐10, 12‐indéno [2, 1‐b] fluorène ou isophatalacène d'Errera.
Über die Synthese des Pronuciferins und einiger weiterer Proaporphin‐Alkaloide. 6. Mitteilung über natürliche und synthetische Isochinolinderivate
Authors: Bernauer Karl
Published: December 2004

Total syntheses of the proaporphine alkaloids pronuciferine (6), stepharine (19), amuronine (7), amuroline (24) and of some derivatives thereof, all as racemates, are described.
Étude des spectres infrarouges de divers dialcoyl‐diméthoxy‐stannanes
Authors: Maire Jean‐Claude , Ouaki Raymonde
Published: December 2004

The infrared absorption spectra of some dialkyldimethoxystannanes have been investigated in the 400–1500 cm−1 region. The bands associated with vs(SnC2) and vs(SnO2) vibrations have been found at 510–521 cm−1 and 466–475 cm−1. The group of bands between 560 and 620 cm−1 is assigned jointly to va(SnC2) and va(SnO2) vibrations. v(CO) of the methoxy groups linked to tin appears at 1064–1068 cm−1.
Die Fraktionierung von Serumproteinen mit flüssigen Phasenpaaren. 4. Mitteilung [1]. Die Gegenstromfraktionierung von γ‐Globulinen
Authors: Tavel P. V.
Published: December 2004

γ‐Globuline sind mit fast‐kritischen flüssigen Phasenpaaren aus Diäthylenglykol‐diäthyläther, Wasser, Magnesiumsulfat und Dinatriumglycerophosphat bei + 1° C mittels multiplikativer Gegenstromverteilung fraktioniert worden. Der mittlere Verteilungskoeffizient des γ‐Globulingemischs ist vom pH und vom Mengenverhältnis Magnesiumsulfat/Dinatrium‐glycerophosphat abhängig. Er lässt sich auf einen für die multiplikative Verteilung günstigen Wert einstellen. Diese wurde in einer Verteilzentrifuge vorgenommen, mit welcher die Phasen nach jeder Gleichgewichtseinstellung rasch getrennt werden können. Mit 40 Gefässen wurden über 200 Verteilungsschritte ausgeführt. Das γ‐Globulin konnte reproduzierbar in eine Reihe von Fraktionen zerlegt werden, deren Verteilungskoeffizienten stetig bis über das 10fache ansteigen. Die Verteilungskoeffizienten entsprechen den für die Prozesse berechneten Werten. Die wegen ihrer Verteilungskoeffizienten eindeutig verschiedenen Fraktionen unterscheiden sich aber weder in der Ultrazentrifuge noch immuno‐elektrophoretisch; d.h. ihre elektrophoretische Beweglichkeit und ihr Verteilungskoeffizient stellen im gegebenen Phasenpaar zwei unabhängige Parameter dar. Die Gegenstromverteilung zerlegt das Gemisch nach anderen Eigenschaftskriterien als die Elektrophorese und die Ionenaustausch‐Chromatographie. Die Fraktionen eines bovinen Antisalmonellen‐Colostrum‐γ‐Globulins zeigten ausser einer Randfraktion keinen Unterschied in ihren Antikörper‐Titern.
Über die Chiralität der enantiomeren Spiro[4.4]nonan‐1,6‐dione
Authors: Gerlach H.
Published: December 2004

Spiro [4.4] nonane‐1, 6‐dione (III) has been synthesized in optically active form, and the chirality of the enantiomers determined by chemical correlation.
Hochauflösungs‐Protonenresonanz‐Spektren von Nitroäthylen, 1‐Nitropropen‐(1) und 1‐Nitropropen‐(2)
Authors: Fröhlin H. J. , Loos K. R. , Günthard Hs. H.
Published: December 2004

The proton resonance spectra of nitroethylene, 1‐nitropropene‐(1), and 1‐nitropropene‐(2) have been measured in solution with high resolving power at 60 and 100 MHz. A full set of chemical shift and coupling constants, obtained from analysis of the spectra in terms of ABC, ABX3 and ABCD2 systems, respectively, is given.
Zur Kenntnis des Kohlenstoffringes. 81. Mitteilung [1]. Acetolyse des 3,3,8,8‐Tetramethyl‐cyclodecyl‐p‐toluolsulfonates
Authors: Prelog V. , Troxler E. , Westen H. H.
Published: December 2004

Acetolysis of 3,3,8,8‐tetramethyl‐cyclodecyl p‐toluenesulfonate yields 3,3,8,8‐tetramethyl‐trans‐cyclodecene‐(1) (6), 4,4,9,9‐tetramethyl‐cis‐cyclodecene‐(1) (4), and 4,4,9,9‐tetramethyl‐trans‐cyclodecene‐(1) (5). In each case 12 to 13 per cent of the product involves transannular hydride shifts. The rate constant k25 = 4,35 · 10−5 s−1 is approximately the same as for cyclodecyl p‐toluenesulfonate. The reaction is discussed in terms of conformational analysis.
Synthese des (±)‐VerrucarinsäUrelactons. Verrucarine und Roridine, 16. Mitteilung [1]
Authors: Achini R. , Meyer U. , Tamm Ch.
Published: December 2004

The synthesis of (±)‐verrucarinolactone (threo‐α‐hydroxy‐β‐methyl‐Δ‐valerolactone) is described.
Elektronen‐Donator‐Acceptor‐Komplexe bei Polypeptiden III. Optische Aktivität von intra‐und intermolekularen Charge Transfer‐Absorptionbanden
Authors: Moser P.
Published: December 2004

Optical activity, i. e. circular dichroism (CD) and optical rotatory dispersion (ORD) associated with charge‐transfer (CT) absorption bands were found for intra‐ and intermolecular electron‐donor‐acceptor (EDA)‐complexes containing centers of configurational asymmetry.
Zur Deutung der thermodynamischen Daten von Komplexbildungsreaktionen I
Authors: Anderegg G.
Published: December 2004

The free enthalpy of complex formation, corrected for the involved change of the number of particles, is described as a sum: δGta + δGtu (= δG ‐ δGm), which permits the separation of the temperature dependent terms. Following Gurney, it is supposed that the temperature dependent free enthalpy δGta varies in the same way as the reciprocal of the dielectric constant of the solvent. This model furnishes some relations which permit a correct description of the complex formation in terms of an electrovalent and of a nonelectrovalent interaction.
Spektroskopische Untersuchung einiger α,β‐ungesättigter cyclischer Ketone
Authors: Marsh Grace , Kearns D. R. , Schaffner K.
Published: December 2004

The results of the spectroscopic investigation of the steroidal enones 1–6 can be summarized as follows:

Direct absorption and phosphorescence excitation techniques have been used to locate the 3(n,π*) states, and in each case it has been found to be the second triplet state.

The lowest excited state in each case is assigned as 3(π,π*) state.

The diffuseness in the phosphorescence emission from the 3(π,π*) states is attributed to a large change in the molecular geometry upon excitation (probably to a non‐planar configuration).

The diffuseness in the S→ Tn,π* absorption is correspondingly attributed to interaction between the 3(n,π*) and 3(π,π*) states. A summary of the energy levels for these compounds is given in Fig. 4.
Synthese von substituierten 1, 2‐Malonyl‐1,2‐dihydrocinnolinen (1,3‐Dioxo‐2, 3‐dihydro‐1H‐pyrazolo [1, 2‐a] cinnolinen) mit antiinflammatorischen Eigenschaften
Authors: Schatz F. , Wagner‐Jauregg Th.
Published: December 2004

A new class of antiphlogistic substances is described. They are 4‐phenyl‐1, 2‐dihydrocinnolins diacylated in 1, 2‐position by alkylmalonic acids. The compound which pharmacologically has been investigated most thoroughly is cinnopentazone (II). Its synthesis and behaviour towards hydrolytic and oxidative agents are described. Some relations between the chemical structure of these series of substances and their antiinflammatory activity as well as their classification as antiphlogistics according to some model reactions are discussed.
Synthese von A‐Homo‐19‐norsteroiden. Über Steroide, 214. Mitteilung
Authors: Wieland P. , Anner G.
Published: December 2004

3‐Oxo‐19‐mesyloxy‐Δ1; 4‐steroids and their 19‐chloro analogues are converted into 4‐oxo‐Δ1; 5(10)‐A‐homo‐19‐norsteroids by treatment with lithium and biphenyl in tetrahydrofuran solution.
Synthèses dans la série des bis‐indéno‐fluorènes IV [1] Hydroxy‐8‐dihydro‐9, 15‐7H‐bis‐indéno[2, 1‐b;2′, 1′‐g]fluorène
Authors: Chardonnens Louis , Hammer Wolfgang
Published: December 2004

8‐Hydroxy‐9, 15‐dihydro‐7H‐diindeno [2, 1‐b;2′, 1′‐g] fluorene, a derivative of a new mono‐angular diindenofluorene system, has been synthesised in 6 steps (overall yield 42%) starting from 9‐oxo‐fluorene‐1‐carbaldehyde and acetophenone. The corresponding hydrocarbon could not be obtained by reductive scission of the hydroxyl group.
Eine neue, einfache Methode zur Synthese von Cystinpeptiden
Authors: Kamber B. , Rittel W.
Published: December 2004

A report is given on the conversion of S‐trityl‐cysteine‐containing protected peptides to cystine peptides by a reaction with iodine in methanol. The new method permits the synthesis of symmetrical, open‐chain unsymmetrical, and especially cyclic cystine peptides.
Herstellung und Umsetzungen von β‐Lactamen
Authors: Haug Th. , Lohse F. , Metzger K. , Batzer H.
Published: December 2004

The cycloaddition of N‐chlorosulfonyl‐isocyanate with isoprene, butadiene and a polyolefin as well as the reaction of ketenes with some bis‐azomethines were investigated. Suitably substituted bis‐azomethines could be separated in the rac. and the meso‐form. The reactivity of the azetidinones towards hydrolysis and hydrogenation was tested. Attempts to polymerise 4‐vinyl‐azetidin‐2‐one, polyazetidinone and N‐substituted bis‐azetidinones to give cross‐linked poly‐β‐amides were not successful.