75993-76-9Relevant academic research and scientific papers
Synthesis and Structure of 2,6-Dicyanobicyclonona-2,6-dienes and 2,6-Dicyanobarbaralanes
Quast, Helmut,Goerlach, Yvonne,Stawitz, Josef,Peters, Eva-Maria,Peters, Karl,Schnering, Hans Georg von
, p. 2745 - 2760 (2007/10/02)
The zinc iodide-catalyzed addition of trimethylsilyl cyanide to bicyclononane-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 a 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 analyses reveal the exo-configuration of the bromine atoms in 7d and 10.X-ray structural parameters for bicyclonona-2,6-dienes (i.e. 7c, d and 10) and a barbaralane (i.e. 12) have for the first time become available.
