Synthese und Struktur von 2,6-Dicyanbicyclo[3.3.1]nona-2,6-dienen und 2,6-Dicyanbarbaralanen

Zinkiodid-katalysierte Addition von Trimethylsilylcyanid an Bicyclo[3.3.1]nonan-2,6-dion (5) ergibt das sterisch einheitliche O-silylierte Cyanhydrin 9, das mit Trichlorphosphanoxid in Pyridin zum ungesattigten Dinitril 7c umgesetzt wird. Je nach N-Bromsuccinimid-Menge entsteht bei der Bromierung des Dinitrils 7c ein Gemisch aus Monobrom- (10) und Dibromdinitril 7d oder reines Dibromdinitril 7d. Das Monobromdinitril 10 wird durch eine konzertierte Dehydrobromierung mit Natriummethanolat in Methanol in das 2,6-Dicyanbarbaralan (8c) ubergefuhrt. Dieses bildet sich fast quantitativ durch Debromierung des Dibromdinitrils 7d mit Zink/Kupfer, wahrend die Dehydrobromierung von 7d mit Natriummethanolat in Methanol 4-Brom-2,6-dicyanbarbaralan (12) ergibt. Alle Reaktionen verlaufen sehr glatt und mit hohen Ausbeuten. Durch Rontgenstrukturbestimmung der Dinitrile 7c, d und 10 sowie des 4-Brom-2,6-dicyanbarbaralans (12) wurden die exo-Konfiguration der Bromatome von 7d und 10 und erstmal geometrische Parameter von Bicyclo[3.3.1]nona-2,6-dienen und einem Barbaralan ermittelt. Synthesis and Structure of 2,6-Dicyanobicyclo[3.3.1]nona-2,6-dienes and 2,6-Dicyanobarbaralanes The zinc iodide-catalyzed addition of trimethylsilyl cyanide to bicyclo[3.3.1]nonane-2,6-dione (5) yields the sterically defined O-silylated cyanohydrin 9. Trichlorophosphane oxide in pyridine converts the latter to the unsaturated dinitrile 7c. Depending on the amount of N-bromosuccinimide used, the bromination of the dinitrile 7c affords either a mixture of the monobromo- (10) and the dibromodinitrile 7d or pure dibromodinitrile 7d. With sodium methoxide in methanol the monobromodinitrile 10 is converted via concerted dehydrobromination to 2,6-dicyanobarbaralane (8c) The latter is formed almost quantitatively on debromination of the dibromodinitrile 7d with zinc/copper reagent, while sodium methoxide yields the 4-bromo-2,6-dicyanobarbaralane (12). All reactions proceed smoothly in high yields. X-ray structural parameters for bicyclo[3.3.1]nona-2,6-dienes (i. e. 7c, d and 10) and a barbaralane (i. e. 12) have for the first time become available.

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