铑催化7-辛烯醛氢甲酰化反应合成1,9-壬二醛
Synthesis of 1,9-Nonanedial via Oct-7-enal in Rhodium-catalyzed Hydroformylation
刘传卓 1李志坚 2汤易天 2李永刚 2董开武3
作者信息
- 1. 上海中化科技有限公司,上海,201315;华东师范大学化学与分子工程学院,上海,200062
- 2. 上海中化科技有限公司,上海,201315
- 3. 华东师范大学化学与分子工程学院,上海,200062
- 折叠
摘要
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、还原酯化、还原胺化等反应获得二酸、二醇、二酯、二胺等各种重要的化学品.我们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49 500.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.
Abstract
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,reductive esterification,reductive amination 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 49 500.Meanwhile,the mechanisms of hydroformylation and side reactions were discussed.
关键词
1,9-壬二醛/7-辛烯醛/氢甲酰化/Xantphos/铑Key words
1,9-nonanedial/oct-7-enal/hydroformylation/Xantphos/Rhodium引用本文复制引用
出版年
2024
NETL
NSTL
万方数据