Reaction of (Phenylenedioxy)trihalophosphoranes with Arylacetylenes:VI.Regiochemistry of the Reaction of 2,2,2-Trihalo-5-methylbenzo[d][l,3,2]dioxaphospholes with Arylacetylenes

摘要

NMR and IR spectroscopy and X-ray diffraction were used to show that the reaction of 2,2,2-tri-chloro- and 2,2,2-tribromo-5-methyibenzo[d|[l,3,2]dioxaphospholes with para-substituted arylacetylenes proceeds with regioselective formation of 4-aryl-2-halo-7-methyl-2- oxobenzo[e][l,2]oxaphosphorines.With the trichlorophosphole,selective chlorination of the phenylene fragment in the para position to the endocyclic oxygen atom occurs.With the tribromophosphole,6-bromo- and unsubstituted benzo[e][l,2]oxaphosphorines are formed as major products.The molecular and supramolecular structure of some of the obtained oxa-phosphorines was studied by X-ray diffraction.