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Condensing tartaric acid (R, R) and PCl3, we obtained oligomers 3 and cyclic dimer 4. Oxidizing these compounds by DMSO, we prepared hydroxyphosphoranes 6–9, while reaction of orthoquinones gave six-coordinated compound 10. Compound 4 reacts with triethylamine leading to an equilibrium between phosphoranide 5 and phosphite 5'. The more likely structure of oligomers is a sequence of TBP arranged on a helix, whereas dimers should have an emetic structure with pentacoordinated phosphorus atoms. These results are supported by nmr analysis, molecular weight and elemental analysis. All these compounds have strong optical activity. On the other hand, condensing PCl3 and malic or citric acids, we synthetized new functionalized spirophosphorans 2. En condensant l'acide tartrique (R, R) et PCl3, nous avons obtenu des oligomeres 3 et le dimere cyclique 4. En oxydant ces composes par le DMSO, nous avons prepare les hydroxyphosphoranes 6–9, tandis que la reaction des orthoquinones a donne le compose a phospho...

A phosphorus ozonides series was obtained by reaction of ozone on various phosphites (1a-13a). The oxidative addition of ozone leads to trioxophosphetane ring formation branched on pentacoordinated (1b-9b) or hexacoordinated (10b-13b) phosphorus. The stability and stereochemistry of these compounds were studied.

Ozone reacts quantitatively on tricoordinated and dicoordinated Phosphorus Compounds. The oxidative addition of ozone on phosphites leads to pentacoordinated or hexacoordinated phosphorus adducts. These adducts are unstable in solution. The decomposition gives the corresponding phosphoric ester with singlet oxygen evolution. In the same conditions, ozone reacts on diphosphene and gives after double bond rupture an adduct: the metaphosphonate. The relative stabilities and oxidative properties are discussed.

Ozone reacts very rapidly with alkylidenetriphenylphosphoranes 1a-d. In all cases we observed the cleavage of the P[dbnd]C bond and formation of triphenylphosphine oxide and the corresponding ketone 4a, 4b (R1 [dbnd] Ph) and alkene 4c (R1 [dbnd] H). Ozone also reacts with substituted phosphites 5a-b and gives the ozonides 7a-b.

The ozonization of various halophosphines 1a-j leads with quantitative yields to the corresponding phosphine oxides 2a-j. Ozonization is a convenient method of oxidation, in particular of compounds with bulky ligands (1c, 1d, 1e).