USES OF ADSORBED REAGENTS IN THE SYNTHESIS OF REACTIVE MOLECULES VIA ELIMINATION REACTIONS

Article abstract of DOI:10.1016/S0040-4020(01)87573-6

The synthesis of reactive molecules (in vacuo) using reagents adsorbed on inert surfaces to effect elimination reactions has been investigated.Potassium t-butoxide adsorbed on Chromosorb W can be used to generate methylenecyclopropene from 2-chloromethylenecyclopropane and 1-vinylcyclopropene from either 1,4-dichlorospiropentane or 1-chloro-2-vinylcyclopropane.Both compounds can be characterized at low temperature using NMR and IR spectroscopy.Methyllithium on glass helices has been used in the reductive elimination of halogen from vicinal cyclopropyl dihalides to yield cyclopropenes. β-Halocyclopropylsilanes can be converted in high yield to the corresponding cyclopropene using tetra-n-buthylammonium fluoride deposited on glass helices.The fluoride route has been used to generate bicyclo<4.1.0>hept-(1,6)-ene and bicyclo<4.1.0>hept-(1,7)-ene in the gas phase under conditions wich allow either spectroscopic characterization or trapping as Diels-Alder adducts.