Reactions of phosphoryl- and thiophosphorylacetonitriles with poly(bromomethyl)arenes containing closely-spaced bromomethyl groups.New types of phosphorus-substituted fused systems

摘要

Reactions of phosphoryi- and thiophosphorylacetonitriles with poly(bromomethyl)arenes containing closely-spaced bromomethyl groups under conditions of phase-transfer catalysis occur as cycloalkylation to form new types of fused systems,in which aromatic rings are annelated with a five-,six-,or seven-membered ring containing the exocyclic phosphorus-containing and cyano substituents.The reaction pathway is independent of the reagent ratio.Under the same conditions,the reaction with l,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene affords products of monoalkylation at all electrophilic groups of the starting substrate.In the resulting compounds,the alkoxy groups at the phosphorus atom are easily transformed into the hydroxy groups via the corresponding silyl ethers to give the corresponding phosphorus acids,whereas the cyano group is chemically inert.