ISSN:
0009-2940
Keywords:
Semibullvalenedicarbonitrile
;
Bicyclo[3.3.0]octanes, derivatives of
;
Cyanohydrins, O-trimethylsilyl
;
Hydrogen fluoride-phosphorus oxychloride-pyridine, elimination by
;
Bromination, N-bromosuccinimide
;
Zinc-copper couple
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
2,6-Dicyanosemibullvalene[1]Bicyclo[3.3.0]octane-2,6-dione (2) adds trimethylsilyl cyanide under catalysis by zinc iodide to afford a mixture of the diastereomeric O-trimethylsilyl cyanohydrins exo,endo- and exo,exo-3 (3:7). Treatment of this mixture with the hydrogen fluoride-pyridine complex in phosphorus oxychloride as solvent and subsequent heating with an excess of pyridine yield 70% of a 1:1 mixture of the unsaturated dinitriles 4 and 5, which is separated by medium-pressure liquid chromatography. Allylic bromination of 4 by N-bromosuccinimide results in the formation of the Y,Y'-dibromodinitrile 6, the configuration of which is elucidated by means of an X-ray diffraction analysis. Reduction of 6 with the zinc-copper couple in tetrahydrofuran under ultrasonic irradiation leads to dilute solutions of the title compound 1 a. Attempts at the isolation of 1 a were frustrated by its tendency to polymerize. The structure of 1 a is based on IR, UV, 1H- and 13C-NMR spectra and a comparison with the known 1,5-dimethylsemibullvalenedicarbonitrile (1 b).
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19921250431
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