Pressure independence of stereomutation and fragmentation in the bis-spirocyclobutanes, anti- and syn-2,9-dicyanodispiro[5.0.5.2]tetradeca-1,8-dienes.
Pressure dependent rate constants and volumes of activation for stereomutational interconversions of the cyclobutanes, anti- and syn-2,9-dicyanodispiro[5.0.5.2]tetradeca-1,8-dienes (anti-6 and syn-6), and for their fragmentation to 1-cyano-3-methylenecyclohexene (5) have been determined. Although fragmentations might have been expected to have larger and thus more positive volumes of activation than stereomutation, both processes have essentially identical volumes of activation within experimental uncertainties at 50.1 degrees C over the pressure range, 1-3000 bar: DeltaV(not equal) = (+7.4 to +9.9) +/- 2.0 cm3 mol(-1). While these positive values are consistent with the rate of entry into the hypothetical caldera being determined by breaking the weakest bond in the cyclobutanes, the insensitivity of the product-determining exit channels argues against the obligatory second bond-breaking being a significant factor in fragmentation.
Klärner
Frank-Gerrit
FG
Institut für Organische Chemie, Universität Duisburg-Essen, D-45117 Essen, Germany. frank.klaerner@uni-essen.de
Wurche
Frank
F
Doering
William von E
Wv
Yang
Jiade
J