Reactions of phenylenedioxytrihalophosphoranes with arylacetylenes. 5. Regiochemistry of the reaction of 2,2,2-trichloro-5-chlorocarbonylbenzo[d]-1,3,2-dioxaphosphole with phenylacetylene. Synthesis and three-dimensional structures of 6-alkylaminocarbonyl-2-oxo-4-phenylbenzo[e]-1,2-oxaphosphorinine derivatives

Alkenylation of Arenes and Heteroarenes with Alkynes

“…In a series of reports, − addition of phosphorus-based electrophiles to alkynes was studied by Mironov et al Thus, phenylene dioxatrihalogen phosphoranes 577 react with terminal alkyl and aryl acetylenes with formation of benzo­[ e ]-1,2-oxaphosphorin-3-enones 578 (Scheme ). In the course of this reaction, under mild conditions, the ipso -substitution of the oxygen atom, formation of P–C and PO bonds, as well as the regioselective halogenations of the phenylene fragment para to the endocyclic oxygen atom of the oxaphosphorinine heterocycle take place.…”

“…While the mechanism of the reaction is rather complicated, the authors were able to determine its main features. − In cases where a halide is present in the benzo fragment of the initial phosphorole, a second halide is incorporated ortho to the first halide and para to the oxygen atom of the resulting annulated O,P -heterocycle. If positions 5 and 6 in the benzophosphole are occupied by bromide, the introduction of a third halogen atom does not occur.…”

Reaction of 2,2,2-trichlorobenzo[d]-1,3,2-dioxaphosphole-5-carbonylchloride with phenylacetylene: predominant formation of 2-(2-chloro-2-phenylethenyl)-2,2-dichlorobenzo[d]-1,3,2-dioxaphosphole-5-carbonylchloride

“…8 Since the percentage of product 2 was no higher than 20%, it was not isolated in pure form. 1,2 Recently, we have demon strated 3,4 that the closest stable analog of phosphorus pentachloride, viz., 2,2,2 trichlorobenzo[d] 1,3,2 dioxa phosphole, reacts with arylacetylenes to form phospho rus containing analogs of coumarins and α chromenes, viz., benzo[e] 1,2 oxaphosphorinines.…”