1-Octene is consumed as a comonomer in the polyethylene processes and its demand is increasing continuously. Herein, we propose the synthesis method of p-ClC6H4SiR3 using the Grignard reaction. But, sterically encumbered R3SiCl did not react with p-ClC6H4MgCl, necessitating the development of a catalyst for the coupling reaction of the Grignard reagent with such bulky R3SiCl. The reaction occurred with the addition of 3 mol% CuCN catalyst, affording the desired compound p-ClC6H4SiR3. The structure of p-ClC6H4MgCl was elucidated, which existed as an aggregate with MgCl2, indicating that some portion of the Grignard reagents were possibly lost in the coupling reaction due to co-precipitation with the byproduct MgCl2. Without formation of R4Si, R3SiCl could synthesized simply and economically when SiCl4 was reacted with 4 equiv of RMgCl. Using the developed syntheses, iPrN[P(C6H4-p-SiR3)2]2, which are potentially useful compounds for the production of 1-octene, was efficiently prepared with considerable reductions.
