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.

The effect of TPPTS [p(m-C6H4SO3Na)3], RhCl(CO)(TPPTS)2 and olefin on CMC (critical micelle concentration) of the aqueous solution containing cationic surfactant cetyltrimethylammonium bromide (CTAB) was studied by the maximum bubble pressure method. The apparent molar mass of micelle was determined by a light scattering method. The results showed that the addition of TPPTS and RhCl(CO)(TPPTS)2 into aqueous solutions of CTAB caused the decrease of CMC and the increase of the apparent molar mass of micelle. The data supported the suggestions about enrichment of rhodium catalyst in micelle interface layer and about the solubilization of olefin in micelle. This explanation was confirmed by the measurements of rhodium concentration in the interface layer using ICP method. The acceleration mechanism of long chain olefin hydroformylation in a biphasic catalytic system containing a cationic surfactant was provided.

The hydroformylation of 1-dodecene catalyzed by RhCl (CO) (TPPTS) 2-BISBIS [TPPTS: P (m-C6 H4 SO3 Na) 3, BISBIS: sulfonated 1,1-bis (diphenylphosphino methyl)-2, 2-biphenyl] in aqueous/organic two-phase systemwas studied. The addition of cationic surfactant cetyltrimethylamonium bromide (CTAB) greatly accelerated the reaction rate and the high regioselictivity for linear aldehyde using diphosphine as ligand was attained under two-phase conditions. Both high activity (TOF: 740 h−1) and excellent regioselectivity (96.5% of 1-tridecanal) were obtained at 120℃, 2.0 MPa and [BISBIS]/[Rh] ratio of 3 in thepresence of CTAB.

The enantioselective hydrogenation of ethyl pyruvate in the presence of TS-1 supported rhodium nanoclusters and chiral modifier cinchonidine, cinchonine and quinine was investigated. The results showed that cinchonidine was the best modifier and THF was an excellent solvent for the reaction. Cinchonidine and quinine not only induced the enantioselectivity, but also accelerated the reaction. The interaction between the support and rhodium nanoclusters, as well as the adsorption of modifier on the support surface played an important role in promoting the increase of the catalytic activity and enantioselectivity. Under the optimum conditions, 268 K, 7MPa of hydrogen pressure and 4.0×10−3 mol/l of cinchonidine in THF, the mole conversion of ethyl pyruvate and enantiomeric excess of R-ethyl lactate reached up to 100 and 63.1%, respectively.

Hydroformylation of 1-dodecene catalyzed by water-soluble rhodium-phosphine complex, RhCl (CO) (TPPTS)2 (TPPTS: P(m-C6 H4 SO3 Na)), in the presence of various mixed micelles was investigated. When either an anionic surfactant sodium dodecyl sulfate (SDS) or dodecylbenzonesulphonate (DBS), a nonionic surfactant Triton X-100 or Brij 35, or alcohol was added into cationic surfactant cetyl pyrindium bromide (CPB) solution, a mixed micelle formed. The decrease in critical micelle concentration (CMC) and the increase in solubilization of 1-dodecene in the mixed micelle were observed. Hydroformylation of 1-dodecene exhibited higher conversion and higher regioselectivity in the mixed micellar solution than in the single micelle of CPB. The synergistic mechanism of two different surfactants was discussed.