PHOSPHONIO-SUBSTITUTED TETRAHYDRO-1,3-DIP HOSPHININES AND TETRAHYDRO-1,2,6-AZAPHOSPHININES

The bis(triphenylphosphonio)propenide cation 1 provides two reactive C H sites in 1,3-position and can be condensed with the bis(dichlorophos phanyl)methylene triphenylphosphorane 2 or the bis(dichlorophosphanyl) aniline 3 to form cationic six-membered rings: A tetrahydro-l,3-diphos phinine (4) with three phosphonio or phosphoranediyl substituents in 2 ,4,6-position and a tetrahydro-1,2,6-azadiphosphinine (5) carrying two such substituents in 3,5 position. The bromide of the latter was used for an X-ray structure analysis. The P-III ring members of the cation s 4 and 5 can be oxidized in two steps by elemental sulfur to give the monothioxo and dithioxo derivatives 6, 7 and 8, 9, respectively. A cr ystal of the mixed chloride/bromide of 8 was used for another X-ray st ructure analysis.