75993-75-8Relevant academic research and scientific papers
2,6-Dicyanobarbaralanes Through Phase Trasfer Catalyzed Halogenation/Dehydrohalogenation of Bicyclonona-2,6-diene-2,6-dicarbonitrile
Quast, Helmut,Mayer, Andreas
, p. 515 - 518 (2007/10/02)
Treatment of bicyclonona-2,6-diene-2,6-dicarbonitrile (1) with sodium methoxide in methan-ol or with alkali deuteroxide in deuterium oxide under the conditions of phase transfer catalysis leads to an exchange of the γ-protons for deuterium atoms producing -1.This is converted into the barbaralanedicarbonitrile -3 by known methods.The carbanion generated from 1 by alkali hydroxide under the conditions of phase transfer catalysis is chlorinated by hexachloroethane.Ringforming dehydrochlorination of the intermediate chlorinated dinitriles (presumably 2b and 4b) under the same reaction conditions yields predominantly 3 (76percent) accompanied by small amounts of the 4-chlorobarbaralanedicarbonitrile 5b (11percent), which are separated by chromatography.
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.
