温控相转移膦配体与催化(Ⅺ):OPGPPRh催化的两相高碳烯烃的氢甲酰化反应

一种连由辛基脂肪醇聚氧乙烯基团的邻苯二酚亚磷酸酯新型水溶性膦配体(OPGPP)与铑原位形成的催化剂应用于高碳烯烃的两相氢甲酰化反应。获得了99.3%的烯烃转化率和97.3%醛收率,催化剂表现很高的活性且催化剂可以回收使用。     

烯烃的氢甲酰化串联反应研究

氢甲酰化串联反应是在氢甲酰化反应的基础上,与一个或多个不同类型的反应“一锅法”实现醛类化合物的后续定向转化,得到新的有机分子的合成方法。该反应的产物在日化工业、农业、医药中间体的生产中具有十分重要的用途。本文首先简述了近年来烯烃氢甲酰化串联反应制备高附加值化学品的重要性,随后重点介绍了几种常见的烯烃氢甲酰化串联反应:“异构化-氢甲酰化”串联反应、“氢甲酰化-缩醛化”串联反应、“氢甲酰化-氢化”串联反应和“氢甲酰化-(还原)胺化”串联反应等,以及其在设计新型(多功能)催化剂体系和高效合成目标产物方面的研究进展,最后总结了烯烃氢甲酰化串联反应存在的问题以及对未来发展趋势进行了展望。     

温控相分离催化的高碳烯烃氢甲酰化反应研究

考察了非离子表面活性膦配体P[p-C6H4O(CH2CH2O)nH]3(PETPP,n=6～12,N=3n)在有机溶剂中的溶解度－温度关系，发现其在甲苯中具有临界溶解温度（CST）现象。基于PETPP在甲苯中低温分相、高温互溶的CST特性，提出了温控相分离催化的新概念。并将其应用于癸烯氢甲酰化反应，转化率及醛收率分别达到98.7%和96.0%，催化剂循环使用10次，活性基本保持不变。     

温控相转移纳米铑催化高碳烯烃氢甲酰化反应

 基于温控配体 Ph₂P(CH₂CH₂O)₁₆CH₃ 稳定的 Rh 纳米催化剂在水/1-丁醇两相体系中具有温控相转移功能, 将其用于高碳烯烃氢甲酰化反应中. 在优化的反应条件下, 1-辛烯转化率和醛收率分别达 98% 和 96%, 对其它高碳烯烃氢甲酰化反应也具有较高的催化性能. 催化剂和产物通过简单的相分离即可分开, 连续使用 3 次后, 催化剂性能未见明显降低.     

烯烃氢甲酰化反应研究进展

本文综述了烯烃氢甲酰化反应的催化剂从钴配合物到铑配合物和从均相催化体系到两相催化体系的发展过程。比较了三种催化剂和两个催化体系的特点、应用情况及研究工作进展.     

两相催化体系中烯烃氢甲酰化的高区域选择性

采用水溶性铑膦配合物催化剂在两相(水/有机物)体系中进行长链烯烃氢甲酰化反应合成高碳醛,具有反应条件缓和、催化剂与产物容易分离的优点,而且用水作溶剂既便宜、又安全,有利于环境保护,因此引起国内外化学家重视,进行了大量研究[1,2].     

两相催化体系中长链烯烃氢甲酰化反应研究进展

水溶性有机金属络合物为催化剂的两相催化体系,由于反应条件缓和,产物和催化剂分离简便等特点,已成为发展环境友好的绿色化学的重要方向。本文介绍了近年来两相催化体系中长链烯烃氢甲酰化反应和催化剂研究进展。     

液/液两相催化高碳烯烃氢甲酰化反应

结合作者近年来的研究工作 ,对液/ 液两相催化高碳烯烃氢甲酰化的研究进展作一综述 ,针对经典的水/有机两相体系不能用于高碳烯烃氢甲酰化的问题 ,全面介绍了适用于高碳烯烃水/有机两相氢甲酰化的温控相转移催化等 6种改进方法。同时 ,对 90年代以来发展迅速的氟两相、离子液体两相、超临界流体等非水液/液两相体系中的高碳烯烃氢甲酰化作了系统阐述 ,对它们的应用前景进行了评较。     

两相催化体系中长链烯烃氢甲酰化反应研究——反应初期的界面化学特征

从界面化学的角度研究了水／有机物两相体系中ＲｈＣｌ（ＣＯ）（ＴＰＰＴＳ）２－ＣＴＡＢ催化１－十二碳烯氢甲酰化反应初期的界面特征。结果表明,催化剂及过量配体的加入,使ＣＴＡＢ的ＣＭＣ降低。样品的光散射及显微照片表明,在ＣＴＡＢ浓度为２．７～６ｍｍｏｌ／ｄｍ＾３范围内,体系中存在着ＣＴＡＢ单体／胶束－Ｏ／Ｗ型乳认间的平衡,在较高ＣＴＡＢ浓度下可能形成Ｏ／Ｗ型微乳;胶束及Ｏ／Ｗ型乳状液滴界面呈负电性,证     

双膦钴配位催化烯烃氢甲酰化的研究

1.前言 叔膦化合物作为配位体在许多均相催化反应,尤其在羰基合成(包括烯烃氢甲酰化、氢羧基化、氢酯基化等)的催化反应中起着重要作用。它们的配位可使许多过渡金属如钴、铑、钯、(钅了)等的羰基络合物催化剂的热稳定性明显增强,无须在高压CO气氛中使用,从而把高压催化反应变成中压催化反应,因之易于实现工业化。近来,双膦配体,如1,2-双(二苯基膦)乙烷(即dppe),对于一些羰化反应已显示出比单膦配体有更大的优越性,它使烯烃氢甲酰化的转化率和产率增加一至二百多倍。因此,对双膦配体进行系统深入     

Cloud Points of Water—soluble Polyether Phosphites and Their Application in the Biphasic Hydroformylation of Higher Olefins

Wate-soluble polyether phosphites alkyl polyethylene glycol ophenylene phosphite(APGPPS)were alcoholysis of phosphorus chloride with plyoxyethylene alkyl ether.With appropriate HLB(hydrophile-lypophile balance),the phosphites possess clear cloud points below 100℃，Addition of some inorganic salts decreases cloud points of the phosphites.When the phosphiites have long polyether chain binding to short-chain alkyl group,their cloud points could be extrapolated from figure of dependece of cloud points on addition of inorganic salts.Utilizing octylpolyglycol-phenylene-phosphite(OPGPP)(APGPP,R:Octyl)/Rh complex formed in situ as catalyst,over 90% conversion of 1-decene was obtained ,avoiding the limitation of water insolubility of substrates.Preliminary results indicated that micellar catalysis and thermoregulated phase-transfer catalysis(TRPTC)coexist in the reaction system.Below cloud point,micellar catalysis induced by plyether phosphites may be existed.When temperature is increased to above cloud point of the phosphies,this reaction works mainly in TRPTC.The catalysts could be easily spearated by simple decantation,but followed by considerable loss in activity after three successive reaction runs.Preliminary results indicated hydrolysis of OPGPP happened during the reaction.which may explain for the bad loss in activity.The catalyst was reused up to seven times with-out clear decrease in activity when OPGPP/Rh ratio was increased to 50.     

Domino Hydroformylation/Aldol Condensation/Hydrogenation Catalysis: Highly Selective Synthesis of Ketones from Olefins

A general and highly chemo‐ and regioselective synthesis of ketones from olefins by domino hydroformylation/aldol condensation/hydrogenation reaction has been developed. A variety of olefins are efficiently converted into various ketones in good to excellent yields and regioselectivities in the presence of a specific rhodium phosphine/base–acid catalyst system.     

Spiroketal‐Based Phosphorus Ligands for Highly Regioselective Hydroformylation of Terminal and Internal Olefins

A new class of bidentate phosphoramidite ligands, based on a spiroketal backbone, has been developed for the rhodium‐catalyzed hydroformylation reactions. A range of short‐ and long‐chain olefins, were found amenable to the protocol, affording high catalytic activity and excellent regioselectivity for the linear aldehydes. Under the optimized reaction conditions, a turnover number (TON) of up to 2.3×10⁴ and linear to branched ratio (l/b) of up to 174.4 were obtained in the Rh^I‐catalyzed hydroformylation of terminal olefins. Remarkably, the catalysts were also found to be efficient in the isomerization–hydroformylation of some internal olefins, to regioselectively afford the linear aldehydes with TON values of up to 2.0×10⁴ and l/b ratios in the range of 23.4–30.6. X‐ray crystallographic analysis revealed the cis coordination of the ligand in the precatalyst [Rh( 3 d )(acac)], whereas NMR and IR studies on the catalytically active hydride complex [HRh(CO)₂( 3 d )] suggested an eq–eq coordination of the ligand in the species.     

Water/Oil Biphasic Hydroformylation of Higher Olefins over a TPPTS-Rh/SiO2 Catalyst

A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous highsurface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.     

Water／Oil Biphasic Hydroformylation of Higher Olefins over a TPPTS-Rh／SiO2 Catalyst

A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of masstransfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performancefor hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of thetraditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersedRh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation ofhigher olefins such as 1-dodecene.     

Water/Oil Diphasic Hydroformylation of Higher Olefins over a TPPTS-Rh/SiO_2 Catalyst

A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.     

Palladium‐Catalyzed Isomerization and Hydroformylation of Olefins

A novel selective palladium catalyst system based on bidentate 2,2′‐heteroarylarylphosphines and p‐TsOH has been developed for hydroformylation reactions (see scheme). By applying optimal conditions good to excellent regioselectivity is obtained for the hydroformylation of aliphatic and aromatic olefins. It is shown that a low acid concentration is crucial for obtaining high degrees of the linear isomer.