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A new phosphine-isocyanide 1 was synthesized to react with Lithium to give the azaphospholide 2,which is a valuble synthetic precursor Quenching 2 with water led to 1H-2-phenyl-1,3-benzazaphosphole 3(Scheme 1) And the reaction of 2 with RX and sulfur resulted in desired 4 and 5 respectively.