SYNTHESES, CHARACTERIZATION AND REACTIVITY OF DIBENZOBICYCLIC PHOSPHORANES 10-P-5

Compound 1 has been prepared by demetallation with PCl3 of uinone-1-(2 -hydroxy-3,5-di-tert-butylphenyl)imine] zinc complex 14. Compound 1 ha s been shown to be an excellent precursor in the syntheses of phosphor us heterocycles. The characterization of a new family of compounds suc h as these derived from 1-phospha(V)-dibenzo-[c,f]bicyclo-[3.3.0]octad iene in which the phosphorus substituents are X = chlorine 1, methyl 2 , methoxy 3, isopropylamine 4, n-butylamine 5, sec-butylamine 6, tert- butylamine 7, 2-aminopyrimidine 8, glycol 9, catechol 10, 3,5-di-tert- butylcatechol 11, o-aminophenol 12, and phenylenediamine 13 is reporte d. The phosphorane system 10-P-5 of compounds 1-13 has been characteri zed by H-1, C-13 and P-31 NMR, IR, and mass spectra. The structure of compound 4 was determined by X-ray diffraction. Phosphoranes 1-8 have an aromatic, planar tetracyclic structure, in which the phosphorus ato m is a trigonal bipyramid with the oxygen atoms in axial positions. Co mpounds 9-13 have the diphenolamine ligand in a folded conformation wi th two oxygen atoms in equatorial and the nitrogen in axial position.