Under the following reaction conditions: temperature 50-70℃, pressure 1.0-2.MPa, solvent C~6D~6, initiator AIBN, the reactions of 1,5-cyclooctadiene, dicyclopentadiene, 1, 3-cyclohexadiene, 1, 4- cyclohexadiene and 1, 5, 9-cyclododecatriene with PH~3 were studied by using the pressurized in-situ NMR technique. Experimental results indicated that the bicyclophosphanonane was formed by the addition of PH~3 to 1, 5-cyclooctadiene. On the other hand, the heterocyclic compounds containing phosphorus could not be obtained in the reaction of PH~3 with other three cyclic olefins, primary phosphines being the only products observed. The results also indicated that the reaction of PH~3 with cyclic olefins proceeded with a sequential mechanism.

Key words: PHOSPHOROUS HYDRIDE, AZOBISISOBUTYRONITRILE (AIBN), CYCLOALKENE