Die Umsetzung des Phosphinchlorids (II) mit H2S führt abhängig von den Reaktionsbedingungen zu dem Diastereomerengemisch des Diphosphinmonosulfids (Ia)/(Ib) und dem Phosphinsulfid (Ic) oder nur zu (Ic).
237ChemInform Abstract The menthyl-substituted chlorophosphines (I) are prepared by reaction of PRCl2 (R: Ph, Me, Et) with Mg(L-men)Cl or P(L-men)Cl2 with MgRCl (R: iPr, tBu) and are converted into the epimeric thiophosphoryl chlorides (II) and (III). These series are subjected to 1H, 13C, and 31P NMR studies at ambient temperature. Chemical shifts of C-4, C-8, H-8, CH3-7, CH3-9, and CH3-10 and the coupling constants 2JPC-2, 2JPC-4, 3JPC-1, and 3JPC-8 are stereospecific indicators for the configurations of phosphorus in P-epimeric forms (II) and (III). Influences from substituents R on chemical shifts and coupling constants are discussed. Variable-temp. 31P NMR studies using line broadening and selective inversion-recovery techniques on chlorophosphines (I) (R: Ph, Et) reveal halogen-exchange processes which arelikely to have cationic phosphorus intermediates.
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