Development of Multi-Functional Metal-Complex Catalysts for Liquid/Liquid Biphasic Reactions and Their Application to Hydroformylation

液/液双相反应多功能金属配合物催化剂的开发及其在加氢甲酰化中的应用

• 批准号: 13650907
• 负责人: SHIMIZU Shoichi
• 金额: $ 2.24万
• 依托单位: Nihon University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650907/
• 关键词: Hydrofromylation; Biphasic reaction; Metal complex catalysts; Water-soluble catalysts; Water as a reaction medium; 液液ニ相系反応; 超分子触媒作用; ホストゲスト; グリーンケミストリー

Biphasic catalysis is a well-established method for effective catalyst separation and recycling. The Ruhrchemie/Rhone-Poulenc process for the hydroformylation of propene catalyzed by a water-soluble rhodium complex with triphenylphosphane trisulfonate (TPPTS) as a ligand has been repeatedly discussed in the literature, because it allows the exclusive use of water as the reaction medium. However, its application is limited to olefins which have appreciable water solubility. Furthermore, the key issue in this process, where linear aldehydes are the most desired products, is the control of regioselectivity. In this research project, our attention was focused on the design and preparation of novel water-soluble diphosphine ligands for metal-complex catalysts which function inverse phase-transfer catalysts and induce high regioselectivity.First of all, we have designed sulfonated derivative of 4,5-diphosphino-9,9-dimethylxanthene possessing one p-(p-alkyloxyphenyl) phenylalkyl group on each … More two phosphorus atoms, such as 4,5-bis{[p-(p-methoxyphenyl)-phenylethyl]-phenylphosphino}-9,9-dimethylxanthene and 4,5-bis{tert-butyl[p-(p-methoxyphenyl)phenylethyl]-phosphino}-9,9-dimethylxanthene. The sulfonated derivatives would be expected not to form aggregates in water, while syntheses of *eir precursors are generally difficult owing to P-chirogenic bisphosphines with tree different substituent groups on the two phosphorus atoms.As one of intermediates, we have prepared 4,5-bis(boranato-terf-butylphosphino)-9,9-dimethylxanthene as a mixture of (rac)-diphosphine and (meso)-one, and separated it to two diastereomers. However, it was unsuitable as a intermediate, because the treatment with BuLi afforded no lithio derivative. Also, removal of the boranato group was difficult by treatment with amines or acids such as tetrafluoroboric acid. Then, to obtained precursors of the target compounds, one-pot reaction starting from dichlorophenylphosphine was conducted with (p-methoxyphenyl)phenylethylmagnesium chloride, where 4,5-bis(chlorophenylphosphino)-9,9-dimethylxanthene would be formed selectively as an intermediate. Finally, the precursor, 4,5-bis{[p-(p-methoxyphenyl)phenylethyl]-phenylphosphino}-9,9-dimethylxanthene, was obtained as a mixture of (rac)-diphosphine and (meso)-one, and separated to two diastereomers. After sulfonation of the precursor, we will conduct hydroformylation of higher olefins in aqueous biphasic system using Rh-complexes with the sulfonated ligands to realize high regioselectivity. Less

两相催化是一种行之有效的催化剂分离和回收方法。文献中反复讨论了以三苯基膦三磺酸盐（TPPTS）为配体的水溶性铑络合物催化丙烯加氢的Ruhrchemie/Rhone-Poulenc方法，因为它允许仅使用水作为反应介质。然而，其应用限于具有可观水溶性的烯烃。此外，该方法中的关键问题是区域选择性的控制，其中直链醛是最期望的产物。本论文的主要工作是设计和制备新型的水溶性双膦配体，用于金属配合物催化剂的反相转移催化和高区域选择性催化，首先设计了一个带有一个对烷氧基苯基苯基烷基的4，5-二膦基-9，9-二甲基氧杂蒽的磺化衍生物 ...更多信息 两个磷原子，例如4，5-双{[对-（对-甲氧基苯基）-苯乙基]-苯基膦基}-9，9-二甲基氧杂蒽和4，5-双{叔丁基[对-（对-甲氧基苯基）-苯乙基]-膦基}-9，9-二甲基氧杂蒽。磺化衍生物在水中不会形成聚集体，而它们的前体合成一般都很困难，这是由于P-手性双膦在两个磷原子上有三个不同的取代基，作为中间体之一，我们合成了（外消旋）-双膦和（内消旋）-酮的混合物4，5-双（硼化-叔丁基膦基）-9，9-二甲基氧杂蒽，并将其分离成两种非对映体。然而，它不适合作为中间体，因为用BuLi处理没有得到锂代衍生物。此外，通过用胺或酸（例如四氟硼酸）处理来去除硼烷基也很困难。然后，以二氯苯膦为原料，与（对甲氧基苯基）苯乙基氯化镁进行一锅法反应，选择性地生成中间体4，5-双（氯苯膦基）-9，9-二甲基氧杂蒽。最后，得到作为（外消旋）-二膦和（内消旋）-酮的混合物的前体4，5-双{[对-（对-甲氧基苯基）苯乙基]-苯基膦基}-9，9-二甲基咕吨，并分离成两种非对映异构体。将前体磺化后，在双水相体系中利用铑与磺化配体的配合物进行高碳烯烃的加氢反应，实现高区域选择性。少

项目成果

S.Shirakawa, S.Shimizu, Y.Sasaki: "Rhodium-catalyzed biphasic hydroformylation of 4-octene using water-soluble calix[4]arene-phoshine ligands"New Journal of Chemistry. 25. 777-779 (2001)

S.Shirakawa、S.Shimizu、Y.Sasaki：“使用水溶性杯[4]芳烃-膦配体进行铑催化的 4-辛烯双相加氢甲酰化”《化学新杂志》。

S.Shirakawa, S.Shimizu, Y.Sasaki: "Rhodium-catalyzed biphasic hydroformylation of 4-octene using water-soluble calix[4]arene-phoshine ligands"New Journal of Chemistry. 25・6. 777-779 (2001)

S. Shirakawa、S. Shimizu、Y. Sasaki：“使用水溶性杯[4]芳烃-膦配体的铑催化双相加氢甲酰化”新化学杂志 25・6（2001）。

S. Shirakawa, S. Shimizu, Y. Sasaki: "Rhodium-catalyzed biphasic hydroformylation of 4-octene using water-soluble calix[4]arene-phoshine ligands"New Journal of Chemistry. 25. 777-779 (2001)

S. Shirakawa、S. Shimizu、Y. Sasaki：“使用水溶性杯[4]芳烃-膦配体进行铑催化的 4-辛烯双相加氢甲酰化”《新化学杂志》。