铑催化7-辛烯醛氢甲酰化反应合成1,9-壬二醛

脂肪族二醛是一类重要的工业化学品中间体，可以经过氧化、还原、氢酯化、氢胺化等反应获得二酸、二醇、二酯、二胺等各种重要的化学品。本文报道了一种以丁二烯下游中间体——7-辛烯醛为原料的铑催化氢甲酰化反应合成1,9-壬二醛的方法，考察了不同膦配体对催化剂性能的影响，对反应工艺条件进行了研究和优化。使用Rh(I)/Xantphos催化剂，较优工艺条件下，7-辛烯醛转化率＞99%，直链壬二醛收率86%，醛产物正异比27，TON可达49500。最后，对7-辛烯醛的氢甲酰化主反应和副反应机理进行了探讨。

Synthesis of 1,9-nonanedial via Oct-7-enal in Rhodium-catalyzed Hydroformylation

As important chemical intermediates, aliphatic dialdehyde are synthesized by hydroformylation, normally, and can be further transformed to diacid, diol, diester, diamine and other important chemicals through oxidation, reduction, hydroesterification, hydroamination and other processes. Herein, we report the rhodium-catalyzed hydroformylation of oct-7-enal to prepare 1,9-nonanedial. The effects of the phosphine ligands and the reaction conditions on the catalytic performance in the hydroformylation were investigated in detailed. Under the Rh(I)/Xantphos catalytic system and the optimal reaction conditions, the oct-7-enal was almost completely conversed and 1,9-nonanedial in 86% yield was produced. Notably, the ratio of linear/branched aldehyde reached 27 and the TON reached 49500. Meanwhile, the mechanisms of hydroformylation and side reactions were discussed.