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

Abstract

Abstract Compound 1 has been prepared by demetallation with PCl3 of bis[3,5-di-tert-butyl-1,2-quinone-1-(2-hydroxy-3,5-di-tert-butylphenyl)imine] zinc complex 14. Compound 1 has been shown to be an excellent precursor in the syntheses of phosphorus heterocycles. The characterization of a new family of compounds such as those derived from 5-aza-2,8-dioxa-1-phosphav-dibenzo-[c,f]bicyclo-[3.3.0]octadiene 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 reported. The phosphorane system 10-P-5 of compounds 1–13 has been characterized by 1H, 13C and 31P 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 atom is a trigonal bipyramid with the oxygen atoms in axial positions. Compounds 9–13 have the diphenolamine ligand in a folded conformation with two oxygen atoms in equatorial and the nitrogen in axial position.