Über eine neue Ringschlussreaktion mit 3-Dimethylaminopropyl-carbinolen zu Oxolanen. Mitteilung über Grignard-Reaktionen mit Halogenalkylaminen [1]

A new ring-closure reaction is described, consisting in the treatment of basic carbinols of types 2 , 8 , 13 , 16 , with sodamide or sodium hydride, and adding to the sodium salts formed an alkyl halide. Oxolanes of types 5 , 9 , 14 , 17 , 20 , are formed.     

Über eine Ringerweiterungsreaktion an einem Barbitursäure-Derivat. 10. Mitteilung über Umamidierungsreaktionen

A Ring Enlargement Reaction with a Barbiturate The (6-membered) barbituric acid derivative 3 was synthesized and treated with KF/DMF/18-crown-6 to form the ring-enlarged 14-membered compound 8 in good yield.     

Über eine neue Synthese von Desmethylambraoxid

A new synthesis of the title compound starting from abietic acid is described. Regioselective osmylation of the ^{13, 14}-double bond of abietic acid methyl ester (6) and subsequent hydrogenation furnishes dihydrodihydroxyabietic acid methyl ester (12) with anall-trans-connection of the three rings. Periodate cleavage of12 leads to13 which can be transformed into the triester14 byBaeyer-Villiger oxidation. The configuration of the aldehyde group in13 as well of the formyloxy group in14 has been ensured to be equatorial.LAH-reduction of14 leads to the triol16 which after cyclisation and reductive dehydroxylation furnishes the fragrance compound4.

Auszugsweise vorgetragen auf der 5. wissenschaftlichen Tagung der Österreichischen Pharmazeutischen Gesellschaft am 16. April 1985 in Graz.     

Über eine neue Chi-Phase im System Kobalt-Chrom-Wolfram-Kohlenstoff

Zusammenfassung Im System Co–Cr–W–C wird eine Verbindung der Zusammensetzung Co₂₅Cr₂₅W₈C₂ beobachtet. Diese Phase kristallisiert mit -Mangan-Struktur mit dem Gitterparametera=8,892Å. An Hand von röntgenographischen Intensitätsmessungen wird die wahrscheinliche Verteilung der Atome der Elementarzelle ermittelt.

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A new chi-phase in the system cobalt-chromium-tungsten-carbon

In the system Co–Cr–W–C a compound of composition Co₂₅Cr₂₅W₈C₂ has been observed. This phase has an -manganese type structure and a lattice constanta=8.892 Å. By means of intensity measurements of X-ray diffraction lines the probable distribution of atoms on the lattice sites has been evaluated.

     

Über eine neue Modifikation des Na2C2

On a New Modification of Na₂C₂ On heating NaC₂H to temperatures between 80 °C and 150 °C in vacuum two coexisting modifications of Na₂C₂ are observed, as was shown by temperature dependent X‐ray powder diffraction. The known modification I (I4₁/acd, Z = 8) and a previously unknown modification II could be identified, which is isotypic to Li₂C₂ (Rb₂O₂ structure type, Immm, Z = 2). Modification II is also stable on cooling to room temperature, but a complete conversion of NaC₂H to Na₂C₂‐II could not be achieved up to now. Heating to temperatures above 150 °C leads to a complete conversion of Na₂C₂‐II to Na₂C₂‐I. According to MAPLE calculations Na₂C₂‐I represents the thermodynamically stable modification at room temperature.     

Synthese von (±)-Muscopyridin über eine C-ZIP-Ringerweiterungsreaktion

Synthesis of (±)-Muscopyridine via C-ZIP Ring Enlargement Treatment of 4-(1-nitro-2-oxocyclododec-1-yl)butanal ( 1 ) and of its methyl derivative 5 with pentylamine in EtOH at room temperature gave the ring-enlarged aminomethylidene derivatives 6 and 7 , respectively (Scheme 1). After hydrolysis of the aminomethylidene group in 6 and 7 and deformylation followed by a reductive Nef-type reaction, the macrocyclic diketones 10 and 11 , respectively, were obtained. They were transformed by a modified Hantzsch procedure to the title compound (±)-muscopyridine ( 13 ) and normuscopyridine ( 12 ), respectively.     

Über eine neue Diels—Alder-Reaktion am Thebain

Zusammenfassung 6,14-endo-Ätheno-tetrahydrothebain-7-carbonsäureamide (2) werden durchDiels—Alder-Reaktion von Thebain mit Acrylsäureamiden synthetisiert und mit den Produkten verglichen, die bei der Umsetzung des 6,14-endo-Ätheno-tetrahydro-thebain-7-carbonsäurechlorid-hydrochlorids (3) mit Aminen entstehen.

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6,14-endo-Etheno-tetrahydrothebaine-7-carboxamides (2) are synthesized byDiels—Alder reaction of thebaine with acrylamides and compared with the products which are obtained by reaction of 6,14-endo-etheno-tetrahydrothebaine-7-carbonyl chloride hydrochloride (3) with amines.

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