Phosphorinane 1-sulphide

The H-nmr spectrum of phosphorinane (1) indicates that the proton on phosphorus is axial and gives no evidence of the presence of an equatorial isomer. Similar conclusions are drawn from the spectrum of phosphorinane 1-sulphide (2), but no conclusions can be reached concerning the proton on the phosphorus of phosphorinane methiodide (3) because of second--order spectral complications (J.B. Lambert and W.L. Oliver, Tetrahedron, 1971, 27, 4245). 

Careful oxidation of phosphorinane in dilute petroleum solution gives 1,T diphosphorinane 1,T dioxide, while oxygen under aqueous conditions gives phosphorinane 1 oxide. The latter compound may also be obtained from the phosphinic acid as indicated in (6.809). Treatment of phosphorinane with sulphur in boiling benzene leads to 1 mercapto phosphorinane 1 sulphide which in turn readily converts into the disulphide. 

Two heterocyclic systems have been investigated - the 1,3,2-dioxaphosphepene (45) and its oxide,13 1,3,2-dioxa-phosphorinanes and their oxides, sulphides and selenides (46).136,137 Three ring vibrations were involved in the conformational study of the amides (46, Y = NR2).137... 

The reaction of 2-methyl-, 2,5-dimethyl-, and 2,2,5--trimethyl-phosphorinan-4-one with hydrogen peroxide or potassium permanganate, or with sulphur or selenium in a suitable solvent on boiling affords the corresponding 1-oxide, -sulphide, or -selenide in good yield (I.N. Azerbaev et at., ibid., 1976, 47). For the preparation, reactions, and... 

The C-nmr spectra of 1-methyl- and 1-ethyl-phosphor-anin-4-one and derivatives and also that of phosphorinane-4,4--diols in water at 30° have been recorded, along with the P-nmr spectra and equilibrium compositions for the hydration of some phosphorinan-4-ones. Also recorded the ir-and uv-spectra for 1-ethylphosphorinan-4-one and its 1-oxide and 1-sulphide (J.J. Breen, S.O. Lee, and L.D. Quin, J. org. Chem., 1975, 0, 2245). P-nmr spectral data of 1-phenyl-phosphorian-4-one (K. Ramarajan, M.D. Herd, and K.D. Berlin, Phosphorus Sulphur, 1981, 11, 199). 

C-nmr spectral data have been used to show that 1-methyl-and 1-phenyl-phosphorinane and their 4-ones, related 1-oxides and 1-sulphides and 1,1-dimethylphosphorinanium salts, possess similar chair conformations to those of the analogous S, O, and N six-membered heterocycles (J.A. Hirsch and K. Banasiak,... 

---