双环戊二烯在水溶性铑膦络合催化体系中的氢甲酰化反应

研究了采用水溶性铑膦络合催化体系对双环戊二烯的氢甲酰化反应，考查了反应温度、相转移剂ＣＴＡＢ、铑催化剂浓度等对反应的影响。氢甲酰化反应的产物经ＧＣ／ＭＳ鉴定是不饱和的三环癸单醛     

Mizellare Zweiphasen-Hydroformylierung von ungesättigten Fettstoffen mit wasserlöslichen Rhodiumcarbonyl/tert. Phosphan-Komplexkatalysatorsystemen

Micellar Two Phase-Hydroformylation of Multiple Unsaturated Fatty Substances with Water Soluble Rhodiumdicarbonyl/tert. Phosphine Catalyst Systems Low- and medium-molecular ω-unsaturated carboxylic acid methyl esters inclusive of the ω-decenoic acid ester can be hydrofomylated successfully according to the two phase method in an aqueous-organic medium using the water soluble rhodium carbonyl/tris(sodium-m-sulfonatophenyl)phosphine complex as catalyst system. Highermolecular unsaturated fatty acid esters, e.g. the triple unsaturated linolenic acid methyl ester or fatty oils like linseed oil can be hydroformylated only according to the micellar two phase technique in course of which surfactant micelles cause a solubilisation of the water insoluble unsaturated fatty substances in the aqueous catalyst phase. The different efficiences of the various types of surfactants for the micellar two phase hydroformylation was investigated and interpreted. Best suitable for the micellar two-phase hydroformylation are cationic surfactants. By means of these surfactants linolenic acid methyl ester could be hydroformylated to the triformyl derivative with a selectivity of 55%. The recovery of the catalyst solution free from losses of rhodium succeeded by simple phase separation in a technically satisfying manner.     

A Study of the Separation of 1-Dodecene and 1-Tetradecene Hydroformylation Products in Aqueous Medium

Abstract

Experimental results of the solubilization of olefins in hydroformylation model systems, comprising 1-dodecene and 1-tridecanal or 1-tetradecene and 1-pentadecanal, water, butanol, sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and/or tri(m-sulfofenyl)phosphine trisodium salt (TPPTS-Na) are presented. The selected systems were used for the hydroformylation of 1-dodecene and 1-tetradecene whereby high yields of aldehydes were obtained. After the reaction, the mixture spontaneously separated into an organic phase with the reaction products and an aqueous phase comprising the catalyst and excess phosphine ligand.     

水溶性铑-膦络合物催化烯烃氢甲酰化反应--阳离子表面活性剂的加速作用

介绍了以水溶性铑-膦络合物RhCl(CO)(TPPTS)₂作为催化剂前体在水/有机两相体系中催化烯烃氢甲酰化反应研究的进展,阐述了阳离子表面活性剂的加速作用和介稳态胶束-离子对协同作用机理关系.通过两相体系中界面分子组装和选择与烯烃分子链长相匹配的表面活性剂, 设计制备了高区域选择性复合催化剂体系.当采用双长链表面活性剂与铑-膦络合物组成的复合催化体系时,在不搅拌的情况下就显示出极高的催化活性.     

Verlustfreie Katalysatorrezirkulation durch ein neuartiges Verfahrensprinzip bei der Hydroformylierung höhermolekularer Olefine

Free-of-loss Catalyst Recycling in the Hydroformylation of Higher Molecular Olefins by a Novel Process Technology In this paper a novel homogenous-heterogeneous procedure for the hydroformylation reaction of higher molecular olefins is presented, at which the reaction itself is homogeneously catalyzed and only after the reaction the catalyst complex is heterogenized only for separation. This procedure is achieved by using the lithium salt of triphenylphosphine monosulfonic acid (Li-TPPMS) as complex ligand for the hydroformylation catalyst and methanol as solubilizer. Li-TPPMS and its complexes with metal carbonyls are highly soluble in water and methanol, but completely insoluble in almost all other organic solvents. After the reaction the methanol is distilled off. The catalyst system becomes insoluble and can be separated from the reaction product by filtration or by extraction with water. The aqueous catalyst solution is evaporated to dryness and the catalyst system dissolved in methanol for a new reaction.     

Thermoregulated phase-transfer cobalt catalyst for production of linear higher alcohols from C11–12 internal olefins in aqueous/organic biphasic system

The thermoregulated phase-transfer cobalt catalyst, composed of a polyethylene glycol tailed phosphine ligand and cobalt carbonyl, has been applied for the conversion of normal C_11–12 internal olefins into linear higher alcohols via hydroformylation and hydrogenation in an aqueous/organic biphasic system. Good catalyst activity (TOF = 2.2 h^− 1) in this biphasic system was obtained which was as high as that in the homogeneous system where a cobalt catalyst was modified by a lipophilic phosphine ligand. Easy catalyst recovery has been done by phase decanting, and the aqueous phase with the cobalt catalyst was used directly in recycling. In 4 times of recycling tests, the yield of alcohols decreased slightly, the leaching of cobalt into the organic phase was less than 2.7% each time and a total catalyst TON of around 150 was obtained.     

Polyether triaryl phosphine oxides for hydroformylation of oleyl alcohol in micellar catalysis

Water-soluble triaryl phosphine oxides bearing polyether moiety proved to be efficient ligand for rhodium catalyzed aqueous/organic two-phase hydroformylation of water-immiscible oleyl alcohol. Under the selected conditions, yield of aldehydes reached 83.3% with 70 h⁻¹ of TOF. The in situ formed catalyst was easily separated from the reaction mixture and could be employed in the successive reaction runs. It was observed that the catalyst exhibited high activity in the isomerization of oleyl alcohol during the hydroformylation. As a result, 19% of hydroformylation product was determined to be 18-formyl-octaldecyl-1-ol.     

Hydroformylierung mit wasser- und methanollöslichen Rhodiumcarbonyl/Phenyl-sulfonatoalkylphosphan-Katalysatorsystemen – Ein neues Konzept für die Hydroformylierung höhermolekularer Olefine

Hydroformylation with Water- and Methanol-soluble Rhodium Carbonyl/phenyl-sulfonatoalkyl-phosphine Catalyst Systems – A New Concept for the Hydroformylation of Higher Molecular Olefins The heterogenization of the homogeneous hydroformylating catalyst system enables the recovery of the catalyst from the reaction products by a simple phase separation but it is unfavourable that many advantages of the homogeneous catalysis are given up by this procedure. To avoid this drawback we used rhodium carbonyl/tert. phosphine catalyst systems soluble as good in methanol as in water for the homogeneously catalyzed hydroformylation of the olefin in methanolic solution. Only after reaction the product mixture is heterogenized by adding water forming an aqueous phase containing the catalyst system. It was shown by the hydroformylation of n-tetradecene-1 with rhodium carbonyl/phenyl-sulfonatoalkyl-phosphine catalyst systems that this new conception is very useful for the oxo reaction of high-molecular olefins.     

Unraveling the Bite Angle Effect: New Ligands for Selective Hydroformylation of Internal Alkenes

Rhodium catalyzed hydroformylation is one of the most important applications of homogeneous catalysis in industry[1]. The addition of CO and H₂ to alkenes is a mild and clean method for the functionalization of hydrocarbons. The atom economy of the reaction can be 100% and the selectivity for the desired aldehyde can be very high. Most of the six million tons of aldehydes produced annually by this process is converted into plasticizers for polymers and detergent alcohols. Since the linear aldehydes are the desired products for these applications, a key issue in industrial hydroformylation is the control of regioselectivity. The generally accepted hydroformylation mechanism is shown in Scheme 1. The active catalyst is the five-coordinated complex A, which usually contains two phosphorus ligands. This catalyst consists of two isomeric structures in which the phosphine ligands coordinate in a diequatorial (e-e) and in an equatorial-apical (e-a) fashion. Bidentate ligands can give rise to either of these two complexes depending on their natural bite angle.     

Water-soluble rhodium/phosphonate–phosphine catalysts for hydroformylation

We have developed new and efficient routes to modify phosphines with phosphonic acid groups. Phosphonate–phosphines showed high solubilities in water and were used to immobilise rhodium catalysts in the aqueous phase of biphasic systems. In the two-phase hydroformylation of propylene, some of the novel catalysts showed activities and regioselectivities similar to those of Rh/TPPTS. Amphiphilic Rh/phosphonate–phosphine catalysts were found widely superior to Rh/TPPTS in the hydroformylation of 1-octene.     

ROTACAT: A Rotating Device Containing a Designed Catalyst for Highly Selective Hydroformylation

A novel concept is presented for the immobilization of a homogeneous catalyst. A hydroformylation catalyst was covalently anchored to monoliths that were constructed as the blades of a mechanical stirrer and used in a batch process. The catalyst was effective in the hydroformylation of both higher and lower alkenes and showed a high regioselectivity for the linear aldehyde. The concept was proven to be useful in a liquid organic and aqueous phase as well as in the gas phase and the catalyst could be used numerous times without catalyst deterioration. No catalyst deactivation was observed in a period over half a year.     

Amphiphilic phosphines for catalysis in the aqueous phase

Two new phosphines, Tris[p-(10-phenyldecyl)phenyl]phosphine and 2,2′-Bis{di[p-(10-phenyldecyl)phenylphosphinomethyl}-1,1′-biphenyl were successfully synthesized and sulfonated in concentrated H₂SO₄. The resulting water soluble surface active phosphines were applied to the rhodium catalyzed hydroformylation of higher olefins. It is found that these two ligands are not only excellent for octene hydroformylation, but catalyze tetradecene hydroformylation under two phase conditions as well. Rates and selectivities are superior to TPPTS modified rhodium catalysts under the same reaction conditions.     

Hydroformylation of C8 olefins catalyzed by rhodium–inorganic ammonium salt systems

The effect of inorganic ammonium salts which contain group VIB metals of the periodic table (ammonium chromate, ammonium dichromate, ammonium molybdate and ammonium tungstate) as additives on the catalytic performance of Rh catalysts for the hydroformylation of C₈-olefins and 1-dodecylene has been investigated. Modification of rhodium with ammonium salts could increase the yield of aldehydes in the hydroformylation of the olefins without phosphine oxide or phosphine ligands and also decrease Rh loss in the distillation process for the separation of the products from the catalyst.     

均相铑膦催化体系下1-癸烯氢甲酰化反应研究

氢甲酰化反应是目前生产醛醇化合物最重要的反应之一,高碳烯烃氢甲酰化工艺改进是研究的难点和热点之一。探索了一种C10烯烃氢甲酰化反应的工艺,以三苯基膦（Ph₃P）和亚磷酸三（2-叔丁基-4-甲氧基苯基）酯（L_A）混合物为配体,与乙酰丙酮二羰基铑原位合成的催化体系催化1-癸烯氢甲酰化反应。系统考察了反应温度、反应压力、铑浓度、膦铑比、无机盐添加剂对反应的影响。结果表明,在n（Ph₃P）/n（L_A）=10、铑质量分数为280 mg/kg,1-癸烯用量（相对于甲苯）为0.3 g/mL,n（膦）/n（铑）=45、反应温度为90 ℃、反应压力为2.0 MPa、n（一氧化碳）/n（氢气）=1条件下反应4 h,1-癸烯转化率为98.1%、醛收率为93.2%、正异比为7.5。研究还发现,在减压蒸馏产物与催化剂分离时,加入无机盐添加剂能够提高催化剂的稳定性,减少铑损失。     

Hydroformylation of high olefin in biphasic catalytic system: effect of electronic and steric factor of phosphine ligands

Water-soluble ligands, tri[4-methoxyl-3-(sodium sulfonato)phenyl]phosphine (4-MOTPPTS) and tri[2-methoxyl-3-(sodium sulfonato)phenyl]phosphine (2-MOTPPTS) were synthesized and their application as ligand in Rh-catalyzed hydroformylation of higher olefin was investigated in aqueous biphasic catalytic system. The electron-donating methoxyl group of aromatic ring in phosphine ligand induced the decrease of the activity and selectivity for aldehyde of Rh catalyst than TPPTS used as ligand. The Rh catalyst with more crowded and basic 2-MOTPPTS showed lower activity than 4-MOTPPTS.     

Palladium catalyzed P–C coupling – a powerful tool for the syntheses of hydrophilic phosphines

A new synthetic procedure for the preparation of hydrophilic phosphines based on the palladium catalyzed P–C coupling of mono and multiply functionalized aromatic bromides and iodides with primary and secondary phosphines has been developed. In addition to multiply functionalized anionic phosphines and those bearing electron rich substituents like OH, NH₂ cationic guanidinium type phosphine ligands are accessible by this method in high yields. The novel guanidinium phosphines are readily soluble in water showing a remarkable stability in a wide pH range. They turned out to be quite effective catalyst ligands in Rh catalyzed hydroformylation reactions and Pd catalyzed C–C coupling in two-phase systems and aqueous solutions.     

Heptakis(2,3‐di‐O‐methyl‐6‐O‐sulfopropyl)‐β‐cyclodextrin: A Genuine Supramolecular Carrier for Aqueous Organometallic Catalysis

The behavior of heptakis(2,3‐di‐O‐methyl‐6‐O‐sulfopropyl)‐β‐cyclodextrin as inverse phase transfer catalyst in biphasic Tsuji–Trost and hydroformylation reactions has been investigated. In terms of activity, this methylated sulfopropyl ether β‐cyclodextrin is much more efficient than the randomly methylated β‐cyclodextrin, which was the most active cyclodextrin known to date. From a selectivity point of view, the intrinsic properties of the catalytic system are fully preserved in the presence of this cyclodextrin as the chemo‐ or regioselectivity was found to be identical to that observed without a mass transfer promoter in the hydroformylation reaction. The efficiency of this cyclodextrin was attributed to its high surface activity and to the absence of interactions with the catalytically active species and the water‐soluble phosphane used to dissolve the organometallic catalyst in the aqueous phase.     

Core-Functionalized Dendrimeric Mono- and Diphosphine Rhodium Complexes; Application in Hydroformylation and Hydrogenation

Three novel series of core-functionalized dendrimeric phosphine ligands were synthesized and their rhodium complexes were studied as catalysts in both hydroformylation and hydrogenation of alkenes. Generally similar activities were obtained for the dendrimeric systems and the parent compounds except in the hydroformylation of a bulky substrate, 4,4,4-triphenylbut-1-ene, which gave a significant decrease in activity when the larger dendrimers were used. The rhodium complexes of the dppf-type dendrimeric ligands were studied in the hydrogenation of dimethyl itaconate in a continuous-flow membrane reactor showing a reasonable constant formation of the product compared to the non-dendrimeric catalyst.     

Kinetics and mass transfer in hydroformylation—bulk or film reaction?

The kinetics of a gas–liquid reaction, alkene hydroformylation was studied in the presence of a homogeneous catalyst in a pressurised laboratory‐scale semibatch reactor. Hydroformylation of propene to isobutyraldehyde and n‐butyraldehyde was carried out at 70–115°C and 1–15 bar pressure in 2,2,4‐trimethyl‐1,3‐pentanediol monoisobutyrate solvent with rhodium catalyst using the ligands cyclohexyl diphenylphosphine. In order to evaluate the influence of mass transfer, experiments were made using varied stirring rate from 100 to 1000 rpm at 100°C and 10 MPa syngas pressure. Only at higher stirrings rates, the reaction took place in the kinetic regime. A reactor model was developed comprising both complex kinetics and liquid‐phase mass transfer. The model was based on the theory of reactive films. The model is able to predict under which circumstances the hydroformylation process is affected by liquid‐phase diffusion of the reactants. Experimental data and model simulations are presented for the hydroformylation of propene in the presence of a homogeneous rhodium catalyst.     

Mass transfer effects on hydroformylation catalyzed by a water soluble complex

The rate of hydroformylation of 1-octene catalyzed by a water soluble catalyst is measured in mechanically agitated batch reactor at various stirrer speeds and organic phase holdups. The data have been analyzed by coupling reaction kinetics to a pseudo-homogeneous gas–liquid–liquid model based on Higbie's penetration theory which takes into account the presence of the dispersed organic phase. A rapid liquid–liquid mass transfer of the reactants is assumed leading to an equilibrium between the continuous and the dispersed phases. The predicted values of the rate are in good agreement with the experimental one. The depletion of the organic substrate in the continuous phase is found negligible.