[(4-(N,N-二甲氨基)苯基]二叔丁基磷的合成工艺

Synthesis of [(4-Dimethylaminophenyl)]di(tert-butyl)phosphine

摘要:

以 N,N-二甲基苯胺为原料，经与三氯化磷和吡啶反应生成[(4-(N,N-二甲氨基)苯基]二氯化磷 (I)，然后在碘化亚铜和溴化锂的催化作用下与叔丁基氯化镁反应得到[(4-(N,N-二甲氨基)苯基]二叔丁基磷 (Ⅱ) ，采用31PNMR、1HNMR和HRMS 对目标化合物进行结构表征，通过考察各步的反应条件，得出最佳的工艺条件：n (N,N-二甲基苯胺) : n (三氯化磷) : n (吡啶) = 1 : 3 : 3，110 ℃反应 24 h，[(4-(N,N-二甲氨基)苯基]二氯化磷的收率为85.3%；n（化合物Ⅰ）: n (碘化亚铜) : n (溴化锂) : n (叔丁基氯化镁) = 1 : 0.1 : 0.2 : 3，40 ℃反应 12 h，[(4-(N,N-二甲氨基)苯基]二叔丁基磷收率可达83.4%。

Abstract:

[(4-Dimethylaminophenyl)]di(tert-butyl)phosphine was prepared in two steps. Dichloro-4-(N,N-dimethylamino)phenylphosphane was firstly synthesized from N,N-dimethylaniline and PCl3 as starting materials. And the title compound was funished by coupling reaction of dichloro-4-(N,N-dimethylamino)phenylphosphane and tert-butylmagnesium chloride. Structure characterization of the intermediates was conducted by methods of 31PNMR、1HNMR and HRMS. The optimum reaction conditions were determined as follows: n (N,N-dimethylaniline) : n (PCl3) : n (pyridine) = 1 : 3 : 3，the reaction temperature and time was 110 ℃ and 24 h, the yield of Ⅰ was 85.3%. In the coupling step, n（Ⅰ）: n (CuI) : n (LiBr) : n (t-BuMgCl) = 1 : 0.1 : 0.2 : 3，[(4-dimethylaminophenyl)]di(tert-butyl)phosphine was got in yield of 83.4% at 40 ℃ for 12 h．