On the rearrangement in carbonyl oxide intermediates

Sensitized photooxidation of alkylphenyldiazomethanes under oxygen afforded, in addition to alkyl phenyl ketones, alkyl benzoates, which are probably formed by a rearrangement via dioxirane diradical.     

High pressure study on the superconducting transition temperature and Hall coefficient of Ba1−xKxBiO3 up to 8 GPa

The superconducting transition temperature (T_c) of Ba_0.62K_0.38Bio₃ (T_c=30 K) has been measured under high pressure up to 8 GPa. It is observed that T_c increases initially with pressure, as reported by Uwe et al., Shirber et al. and Huang et al., but decreases above 4 GPa. The Hall coefficient of Ba_0.62K_0.38BiO₃ has been measured up to 1.2 GPa. The absolute value of the Hall coefficient decreases with pressure by 10% GPa, the value of which is almost the same as that obtained in most CuO-based high-temperature superconductors.     

Single-electron-capture cross sections for 0.4–5.0 keV He+ ions incident on alkali-vapor targets

Total cross sections for single-electron capture by He⁺ ions in vapor targets of Cs, Rb, K and Na have been determined in the energy range 0.4–5.0 keV. The energy dependence of the cross-section curves is very similar for all the targets. The cross sections for all the targets are maximum at about the same energy, 1.5 keV. Comparison is made with other reported experimental and theoretical results.     

Totalsynthetische untersuchungen an steroiden—VIII Einführung der C-substituenten in die angulare stellung der kondensierten ringsysteme (teil 3). Einwirkung von kaliumcyanid unter zusatz von ammoniumchlorid auf rac. D-homo-18-nor-androstanderivate

Durch Einwirkung von 2 Mol Kaliumcyanid und 1·75 Mol Ammoniumchlorid und nachträgliche Ketalisierung und Acetylierung liess sich rac. -Homo-18-nor-13(17a)-androstan-3β-ol-17-on (I) in die verschiedenen am C₁₃ cyanierten Verbindungen verwandeln. Das Bildungsverhältnis von 13β- zur 13-Cyanverbindung lag bei 5:3. Die räumlichen Strukturen aller hierbei erhaltenen Verbindungen wurden ermittelt. Die angeführten Reaktionsfolgen stellen eine neue Methode zur Einführung der angularen Substituenten dar und lieferten einen Anhaltspunkt zur Totalsynthese der normalen sowie der in 18-Stellung mit einer funktionellen Gruppe versehenen Steroide.     

Synthetic studies on β-lactam antibiotics. VII. Mild removal of the benzyl ester protecting group with aluminum trichloride

The benzyl ester protecting group in β-lactam derivatives can be cleanly removed by treatment with aluminum trichloride under mild conditions, preferably in the presence of anisole, to give the corresponding free acids in high yields.     

18O-tracer study on the rearrangement of carbonyl oxide intermediates to esters

A tracer study for the rearrangement of carbonyl oxides to esters using doubly-labeled oxygen lead to a conclusion that carbonyl oxides do not isomerize directly to dioxyranes and the rearrangement to esters proceeds via a cyclic tetroxide.     

Synthetic studies on β-lactam antibiotics. 15. conversion of 7-epicephems into 1-oxacephems

7-Epi-1-oxacephem was obtained by stereospecific, intramolecular etherification of alcohol prepared from 7-epicephems via aldehyde or formate. Synthesis of the 3-acetoxymethyl analogwas unsuccessful. Biologically active 1-oxacephems were derived from by known processes.     

Synthesis in the diazasteroid group VI. A synthesis of 2,3-dimethoxy-15-methyl-8,15-diazaestra-1,3,5(10)triene

Homoveratrylamine (II) was condensed with 3-(2-carbomethoxyethyl)-1,3-dimethyl-2-pyrrol-idone (Ib) to furnish the corresponding amide (III), which was subjected to the Bischler-Napieralski reaction to afford the corresponding dihydroisoquinoline derivative (IV). Compound V was obtained by the reductive ring closure of Vila which was obtained by the hydrogena-tion of IV. The stereochemistry of V is proposed to have the anti-trans-trans quinolizidine conformation.