Reactions of phenylenedioxytrihalophosphoranes with arylacetylenes: XIII. Reaction of 5- tert-butyl-2,2,2-trihalo-1,3,2λ-benzodioxaphospholes with acetylenes.

Reactions of 5- tert-butyl-2,2,2-trichloro-, 2,2,2-tribromo-5- tert-butyl-, and 2,2-dibromo-5- tert-butyl-2-fluoro-1,3,2λ-benzodioxaphospholes with aryl- and alkylacetylenes lead to quantitative formation of 2-halo-1,2λ-benzoxaphosphinine 2-oxides which may be regarded as phosphorus analogs of natural heterocyclic compounds, coumarin and chromene. The major products (>70%) are 4-aryl-7- tert-butyl-2,6-dichloro-, 4-aryl-2-bromo-7- tert-butyl-, and 4-aryl-7- tert-butyl-2-fluoro-1,2λ-benzoxaphosphinine 2-oxides. Hydrolysis of these compounds and their treatment with amines gives the corresponding 2-hydroxy and 2-amino derivatives, as well as ammonium salts. The structure of some compounds was proved by X-ray analysis. [ABSTRACT FROM AUTHOR]