Vier- und fünfgliedrige Phosphorheterocyclen, XXXVIII [1] Azaphospholo-benzoxazaphosphole - Synthese, Prototropie und Struktur / Four- and Five - membered Phosphorus Heterocycles, XXXVIII [1] Azaphospholo-benzoaxazaphospholes - Preparation, Proton Shift and Structure

Abstract

Abstract The o-hydroxyanile of cinnamic aldehyde reacts with methyl, phenyl, oxy-, and aminochlorophosphanes in a combined substitution and oxidative addition to give phosphoranes with the above mentioned bicyclic structure containing phosphorus as bridgehead. For the aminosubstituted species the reaction is followed by a 1.3 proton shift in the C 3 moiety from the cinnamic aldehyde. Whether the bicyclic system occupies meridional of facial positions of the phosphorus trigonal bipyramid is shown to depend on the nature of the phosphorus substituents. An X - ray structure determination of a tricyclic derivative with axial annelation shows the deviation from the ideal trigonal bipyramidal geometry to lie on the Berry pseudorotion pathway