ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Preparative, Spectroscopic, and Crystallographic Investigations on Phosphinato Complexes of Rhenium with Bidentate Nitrogen LigandsCholestano-cobaloximes and cholestano-rhodoximes, three diastereoisomers of each constitution, were synthesised from cholestane-2,3-dione dioxime (3). The diastereoisomeric complexes were separated and characterised by their spectra. One of the axial ligands was invariably pyridine, the other either chlor (9), methyl (10), 2,2-bis(methoxycarbonyl)propyl (11), 2,2-bis(benzyl-oxycarbonyl)propyl (12), or 2,2-bis(2-naphthylmethoxycarbonyl)propyl (13 and 14). Irradiation of the complexes 11, 12, 13, and 14 in ethanol or 2-propanol afforded, apart from dimethylmalonic diester, other products among which was the corresponding methylsuccinic diester in yields of approx. 1, 20, 23, and 13%, respectively. The methylsuccinic acid bis(2-naphthylmethyl ester) obtained from the irradiation of the diastereoisomeric cholestano-cobaloximes 13a, b and c was found to be practically racemic.
Notes:
Aus Cholestan-2,3-dion-dioxim (3) wurden jeweils drei diastereomere Cholestano-cobaloxime und Cholestano-rhodoxime synthetisiert, die getrennt und spektroskopisch charakterisiert wurden. Pyridin diente durchweg als einer der axialen Liganden, der andere war Chlor (9), Methyl (10), 2,2-Bis(methoxycarbonyl)propyl (11), 2,2-Bis(benzyloxycarbonyl)propyl (12) oder 2,2-Bis(2-naphthylmethoxycarbonyl)propyl (13 und 14). Bestrahlung der Komplexe 11, 12, 13 und 14 in Ethanol oder 2-Propanol gab neben den Dimethylmalonsäureestern und weiteren Produkten auch die entsprechenden Methylbernsteinsäure-diester in Ausbeuten von etwa 1, 20, 23 und 13%. Der aus den diastereomeren Cholestano-cobaloximen 13a, b und c erhaltene Methylbernsteinsäure-bis(2-naphthylmethylester) war praktisch racemisch.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19801130223
