N,N-双(二苯膦甲基)哌嗪和钯配合物的合成及苄基氯的催化羰基化反应

Synthesis of N,N-Bis(diphenylphosphinomethyl) piperazine and Its Palladium Complexes and Catalytic Carbonylation of Benzyl Chloride

以季盐 [Ph2 P(CH2 OH) 2 ]+ Cl- 与胺的曼尼希反应在温和的反应条件下 ,高产率合成了含Ph2 PCH2 N配位络合基团的两亲膦配体 N ,N -双 (二苯膦甲基 )哌嗪 ,用 NMR、MS、IR、UV等对其结构进行了表征 .正丁醇中 N2 气保护下制备了 n(Ph2 P) :n(Pd)为 4∶ 1和 2∶ 1的钯配合物 .XPS测定表明 ,PPh2中的磷原子与过渡金属钯之间形成了配位键 .钯配合物催化苄基氯的常压羰基化反应有很高的催化活性 ,苯乙酸的产率可达 91 % ,可重复使用 。

A novel amphiphilic phosphine ligand N,N bis(diphenylphosphinomethyl)piperazine was synthesized by reaction of piperazine with [Ph 2P(CH 2OH) 2] +Cl - in the medium with pH ranged in 9~10 at 65~70 ℃ for 2 5 h in 97% yield, and characterized by elemental analysis, NMR, MS, IR and UV. Its palladium complexes with different molar ratio of Ph 2P to Pd were prepared in n butanol. XPS data revealed that the coordination bonds were formed between phosphorous and palladium atoms in the palladium complexes 1a, 1b. High catalytic activities of the complexes 1a, 1b were observed in carbonylation of benzyl chloride with CO. The catalyst could be reused repeatedly in five times.