Cobalt catalyzed hydroformylation of higher olefins in the presence of chemically modified cyclodextrins

The cobalt catalyzed hydroformylation of higher olefins in the presence of chemically modified cyclodextrins was investigated in an aqueous biphasic system. The effect of various parameters, such as the nature of the cyclodextrin and olefin, the temperature, the CO/H₂ pressure, the concentration of the cyclodextrin and TPPTS was studied. The results demonstrate that the partially methylated β-cyclodextrin gives good conversion (>92%) and selectivity (>92%) for the hydroformylation of higher olefins without impeding the recovery of the catalytic system.     

碘量法测定三磺化三苯基膦

介绍一种间接碘量法测定三磺化三苯基膦的方法。向样品溶液中加入过量的碘溶液,利用碘的氧化性将三价磷氧化,再用硫代硫酸钠溶液滴定过量的碘,通过反应方程式可计算出样品中三磺化三苯基膦的含量。该方法可操作性强、简便、准确,且采用自动电位滴定仪进行测定,避免了指示剂法的显色观察误差,提高了数据的精密度。     

水溶性配体三-(间磺酸钠基三苯基)膦的合成工艺研究

以硫酸为溶剂，新蒸三氧化硫为磺化剂，研究了三氧化硫浓度对由三苯基膦(TPP)合成三—(间磺酸钠基三苯基)膦(TPPTS)反应的影响；采用IR光谱技术确定磺化反应终点，利用质子保护原理改进了稀释方法，详细分析了后处理过程中TPPTS的损失。其最佳反应条件是：m(SO3)：m(TPP SO3 H2SO4)=1:2，n(SO3)：n(TPP)=12：1，m(H2SO4)：，m(TPP)=3：1，反应温度22℃，反应时间40h。按此工艺合成的TPPTS含两个结晶水，纯度高达95％，收率大于85％。     

The hydrogenation of cinnamaldehyde by supported aqueous phase (SAP) catalyst of RhCl(TPPTS)3: Selectivity, kinetic and mass transfer aspects

The hydrogenation of trans-cinnamaldehyde catalysed by a supported aqueous phase catalyst of RhCl(TPPTS)₃ [TPPTS: trisodium salt of tris(m-sulfophenyl)phosphine] on silica was investigated in terms of the product selectivity, reaction kinetics and mass transfer characteristics. The hydrogenation is selective at the CC bonds in cinnamaldehyde giving hydrocinnamaldehyde as the main product. To achieve high selectivity (99.9%), it is necessary to employ a low initial concentration of cinnamaldehyde (0.076 M). The selectivity also depended on the reaction operating conditions (pressure, temperature, catalyst loading) and the water content property of the SAP catalyst. Optimum water content of the SAP catalyst giving maximum activity was obtained when the pore volume of the supports was completely filled with water. The overall order of reaction was first-order and therefore the conventional three-phase slurry model was applied to the SAP system for the mass transfer analysis. The gas-liquid mass transfer and the reaction resistances were the controlling steps of comparable significance, while liquid-solid mass transfer resistance was negligible in this system. Under similar conditions, the SAP catalyst gave a lower reaction rate than the analogous biphasic catalyst.     

TPPTS柱撑水滑石的制备及表征

制备了水溶性性好的烯烃氢甲酰化反应催化剂的配体－间三苯基膦三磺酸钠盐,采用＾３１ＰＮＭＲ和ＩＲ对其进行了表征。以层柱化合物类水滑石为插层主体,ＴＰＰＴＳ为插层客体,采用离子交换法和一步合成法制备了ＴＰＰＴＳ柱撑水滑石。     

Catalytic Conversions in Aqueous Media. Part 2. A Novel and Highly Efficient Biphasic Hydrogenation of Renewable Methyl Esters of Linseed and Sunflower Oils to High Quality Biodiesel Employing Rh/TPPTS Complexes

An unusual high catalytic activity (TOF = 117,000 h⁻¹) and high catalyst productivity (TON = 9,700) have been achieved in the first example of partial hydrogenation of renewable polyunsaturated crude methyl esters of linseed and sunflower oils catalyzed by water soluble Rh/TPPTS complexes [TPPTS = P(C₆H₄-m-SO₃Na)₃] in aqueous/organic two-phase systems to afford monounsaturated fatty esters which is biodiesel first generation of improved oxidative stability, energy and environmental performance at a low pour point. This exceptionally high catalytic activity contrast with the general perception that industrially applied water soluble Rh/TPPTS catalysts normally exhibit very low rates in the conversions of higher molecular weight starting materials in aqueous/organic two-phase systems. For part 1 of this series see Ref. [14].     

水溶性铑配合物催化环己烯加氢反应的研究

合成了水溶性配体三苯基膦间单磺酸（TPPMS）、三苯基膦间三磺酸（TPPTS）、2，2'-联毗啶-5-磺酸及相应的铑系列水溶性金属有机化合物, 并用相关体系进行了常压环己烯催化加氢反应。结果表明在常压下Rh-EDTA、RH-TPPMS、Rh-TPPTS、RH-联吡啶-5-磺酸等对催化环己烯加氢具有一定的活性, 在水/有机两相反应体系中, 由于催化剂在水中有相当的溶解度, 使反应后催化剂分离简单、快捷, 产物中催化剂残留少。由于烯烃的催化加氢反应可能是在水相中进行, 共溶剂及快速搅拌是必需的。     

Palladium‐Catalyzed Telomerization of Butadiene with Starch

In order to modify the hydrophilic properties of native starch for its incorporation in polymers, the telomerization of butadiene with native starch was investigated. Low to moderate degrees of substitution (DS=0.04–0.52) were obtained depending upon experimental conditions, particularly, reaction time, temperature and solvent. With 0.3‰ water‐soluble palladium catalyst (Pd/TPPTS), the reaction occurred in i‐PrOH/NaOH 0.1 N solvent mixture even at 50 °C and after 3 h reaction the DS reached 0.08, a value suitable for the application.     

Heck reaction using nickel/TPPTS catalyst and inorganic base on supported ethylene glycol phase

The vinylation of butyl acrylate and halobenzene was studied using the Ni/TPPTS (TPPTS: triphenylphosphine trisulfonate, sodium salt) catalyst immobilized on silica. Inorganic base such as potassium acetate was found to be effective. The catalyst stability and recycle ability have been studied in the temperature range of 130–150°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Layered-Double-Hydroxide-Supported Pd(TPPTS)2Cl2: A New Heterogeneous Catalyst for Heck Arylation of Olefins

The Pd(TPPTS)₂Cl₂ (TPPTS: triphenylphosphine trisulfonate, sodium salt) complex is immobilized on layered double hydroxides by the ion-exchange method. This heterogeneous catalyst is successfully used in Heck arylation of olefins. The catalyst can be recycled several times with almost consistent activity.