V. I. Namestnikov

Synthesis of Substituted 4,5,8,7-Tetrafluorobenzo[d]-λ5-phospholes

The reactions of diethyl pentafluorophenylphosphonite and ethyl bis(pentafluorophenyl)phosphinite with activated alkynes proceed as two-stage cycloaddition processes and lead to formation of sufficiently stable heterocyclic fused fluorophosphoranes. Hydrolysis of the latter is accompanied by cleavage of the exocyclic P-O bond and formation of substituted 4,5,6,7-tetrafluorobenzo[d]-λ5-phospholes, previously uknown bicyclic phosphorus-containing compounds.

Reaction of Pentafluorophenyl(diphenyl)phosphine with Nitrilimines

Reaction of pentafluorophenyl(diphenyl)phosphine with nitrilimines is a multistep process leading to formation of unstable fused heterocycles with a fluorophosphorane moiety as primary products. Their hydrolysis involves opening of the heteroring and subsequent cleavage of the N-N bond in intermediate phosphorylated hydrazones. The final products are diphenyl(6-arylamino-2,3,4,5-tetrafluorophenyl)phosphine oxides.

Reaction of 2-(4,5-dihydrofur-3-yl)-1,3-diphenyl-1,3-diaza-2-2λ3-phospholidine withC,N-diphenylnitriliminewithC,N-diphenylnitrilimine

The reaction of 2-(4,5-dihydrofur-3-yl)-1,3-diphenyl-1,3-diaza-2λ3-phospholidine withC,N-diphenylnitrilimine is a multistage process, in the course of which the 1,2,4-diazaphosphorine ring is formed and both rings of the initial organophosphorus compound are cleaved. 5-(2-Chloroethyl)-4-(N,N′-diphenylethylenediamino)-1,3-diphenyl-1,4-dihydro-1, 2,4λ5-diazaphosphorine was obtained as the final product.

Synthesis of tricyclic spirophosphoranes via reaction of 2-(4,5-dihydrofuran-3-yl)-N-phenyl-1,3,2-oxazaphospholidine with C,N-diarylnitrile imines

Unique tricyclic compounds with a five-coordinate phosphorus atom shared by three rings, 7-aryl-3′,5-diphenyl-3,5-dihydro-2H-spiro[1,2-oxaphospholo[2,3-d][1,2,4]diazaphosphinine-8,2′-[1,3,2]oxazaphospholidines], have been synthesized for the first time via reaction of 2-(4,5-dihydrofuran-3-yl)-3-phenyl-1,3,2-oxazaphospholidine with C,N-diarylnitrile imines. Presumably, these compounds are formed via a three-step process including generation of P+-C=N-N− dipolar ion, intramolecular N−→C= cyclization with simultaneous opening of the dihydrofuran ring, and closure of oxaphospholane ring.

Reactions of 2-(2-chloro-4,5-dihydro-3-furyl)-1,3-diphenyl-1,3-diaza-2λ3-phospholidine with nitrile imines

The multistep reactions of 2-(2-chloro-4,5-dihydro-3-furyl)-1,3-diphenyl-1,3-diaza-2λ3-phospholidine with nitrile imines afforded phosphorus-containing spiro compounds of a new type, viz., 6,8-disubstituted 9-oxo-10-(2-chloroethyl)-1,4-diphenyl-1,4,7,8-tetraaza-5-phosphaspiro[4.5]-deca-6,10-dienes.

10-(3-Hydroxypropyl)-1,4,6,8-tetraphenyl-1,4,7,8-tetraaza-5-phosphoniaspiro[4.5] deca-6,9-diene chloride: synthesis and molecular structure

The reaction of 2-(3,4-dihydro-2H-pyran-5-yl)-1,3-diphenyl-1,3-diaza-2λ3-phospholidine with C,N-diphenylnitrilimine yields 10-(3-hydroxypropyl)-1,4,6,8-tetraphenyl-1,4,7,8-tetraaza-5-phosphoniaspiro[4.5]deca-6,9-diene chloride. Its structure was determined by X-ray diffraction analysis.