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The reaction of phosphorus pentachloride with arylacetylenes followed by hydrolysis of the initially formed phosphonium products is considered as an important method for the synthesis of derivatives of unsaturated phosphonium acids which can be used as initial compounds to prepare various types of new promising biologically active organophosphorus products [1]. The replacement of two chlorine atoms in phosphorus pentachloride by the phenylenedioxy fragment results unexpectedly in 2,6-dichloro-2oxobenzo[ e ]-1,2-oxaphosphorines, which are products of multistep transformations including easy formation of the P‐C bond and the phosphoryl group, ipso -substitution of the oxygen atom, and regioselective chlorination of the aromatic ring in the para -position relative to endocyclic oxygen of the phosphorine heterocycle [2‐ 4]. A similar synthetic outcome can be attained in the phenanthrenequinone‐phosphorus trichloride‐arylacetylene ternary system, in which isolation of the |
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