The hydroformylation of 1-dodecene under aqueous/organic two-phase reaction conditions with rhodium catalysts derived from BISBIS (sodium salt of sulfonated 2, 2

1-Dodecene hydroformylation catalyzed by water-soluble rhodium complex, RhCl (CO) (TPPTS) [TPPTS: P (m-C6 H4 SO3 Na)3], in the presence of surfactants and alcoholic solvents was studied. The results indicated that the hydroformylation in biphasic catalytic system occurred in the interface of aqueousrorganic phases. The formation of micelle was not only favorable for the reaction acceleration, but also favorable for the increase of linear aldehyde ratio in products. The key factor of the enhancement of reaction rate was the richness of rhodium catalyst in the interlayer with the static electricity attraction between active rhodium anion species and cationic end of surfactant.

The catalytic performance of ruthenium phosphine complexes using (1S, 2S)-DPENDS [(1S, 2S)-1, 2-diphenyl-1, 2-ethylene diamine sulfonate disodium] as a chiral modifier in the asymmetric hydrogenation of aromatic ketones was examined in a series of hydrophilic ionic liquids [RMIM]+[p-CH3 C6 H4 SO3] (R=ethyl, butyl, octyl, dodecyl). The synergistic effect between (1S, 2S)-DPENDS and KOH significantly accelerated the reaction and enhanced the enantioselectivity. An ee value of 84.8% was obtained in the asymmetric hydrogenation of acetophenone under the optimized conditions. The products were conveniently separated with cyclohexane extraction, and both the ruthenium catalyst and (1S, 2S)-DPENDS were kept in the ionic liquid and could be reused.

Alumina supported rhodium catalyst using cinchonidine as a stabilizer exhibited excellent performance in the asymmetric hydrogenation of ethyl pyruvate with the addition of quinine. Quinine as a chiral modifier can not only induce the enantioselectivity, but also greatly accelerate the reaction. Under the optimum conditions: 293 K, 7.0 MPa of hydrogen pressure and 4.6×103 mol/L of quinine concentration in THF, TOF of Rh/2(cinchonidine)-c-Al2O3 as catalyst and ee value of (R)-ethyl lactate can achieve 894 h 1 and 71.6% ee, respectively.

This paper reports the hydroformylation of 1-butene catalyzed by RhCI(CO)(TPPTS)2 (TPPTS: P(m-C6H4SO3Na)3) and BISBIS (sodium salt of sulfonated 2, 2_-bis(diphenylphosphinomethyl)-1, 1_-biphenyl) in aqueous/organic two-phase catalytic system. The effects of reaction parameters on the catalytic activity and regioselectivity were investigated under the optimum eaction conditions: 130. C, 2.5MPa (syngas pressure), [BISBIS]/[Rh]=5, [1-butene]/[H2]/[CO]=1: 1: 1, [1-butene]/[Rh]=10 400, TOF and the regioselectivity for n-valeraldehyde were 2987 h.1 and 98%, respectively. 2003 Elsevier B. V. All rights reserved.