trans-Ylidation was carried out between resonance-stabilized ethoxycarbonylmethylene-, cyanomethylene-, benzoylmethylene-, furoylmethylene-, and p-nitrobenzylidene-triphenylphosphorane and benzene-, p-toluene-, p-chlorobenzene-, p-bromobenzene-, o-nitrobenzene-, and p-nitrobenzenesulfenyl cholride These reactions were effected almost quantitatively and 21 kinds of novel phosphoranes were obtained in which o-or p-substituted phenylthio group was introduced into the carbon atom in α-position of the phosphorus atom in the starting phosphoranes.