Zilin Jin

Thermoregulated phase transfer ligands and catalysis. I. Synthesis of novel polyether-substituted triphyenylphosphines and application of their rhodium complexes in two-phase hydroformylation

A series of novel water-soluble polyether-substituted triphenylphosphines (PETPPs) were prepared by means of the ethoxylation of mono-, di- and tri-p-hydroxytriphenylphosphines. PETPPs manifest inverse temperature-dependent solubility in water that enables them to act as thermoregulated phase transfer ligands. The concept of the thermoregulated phase transfer catalysis is successfully applied to the biphasic hydroformylation of higher olefins, such as 1-dodecene, in the presence of rhodium-PETPP complexes as the catalysts.

Poly(ethylene glycol)-functionalized imidazolium salts–palladium-catalyzed Suzuki reaction in water

Three water-soluble imidazolium salts bearing poly(ethylene glycol) moieties directly attached to an N-atom of imidazole have been synthesized via a simple synthetic method, which could be served as N-heterocyclic carbene precursors for the palladium-catalyzed Suzuki reaction. The catalytic system generated in situ from a source of Pd(OAc)2, a precursor of imidazolium salt, and a base of triethylamine is able to smoothly perform the Suzuki reaction of a variety of substrates in water.

The selective reduction of nitroarenes to N-arylhydroxylamines using Zn in a CO2/H2O system

Nitroarenes are reduced to the corresponding N-arylhydroxylamines with high selectivity using Zn dust in a CO2/H2O system under mild conditions. The yield of N-phenylhydroxylamine from nitrobenzene is 88% when the reaction is carried out at 25 °C for 1.5 hours with a Zn to nitrobenzene molar ratio equal to 3 under 0.1 MPa CO2. Other nitroarenes, which contain reducible functionality other than a nitro group, are also reduced to the corresponding N-arylhydroxylamines with yield from 88% to 99%. The process fully removes the need to use NH4Cl and is environmentally benign.

Thermoregulated phase transfer ligands and catalysis: VII. Cloud point of nonionic surface-active phosphine ligands and their thermoregulated phase transfer property

Abstract A series of nonionic surface-active phosphine ligands with the general formula, Download : Download full-size image , (AEOPP) has been synthesized. Cloud points of the phosphine ligands are measured and effects of changing hydrophilic and lipophilic groups on the cloud point of the phosphine ligand are examined. Experiment shows that AEOPP has distinct cloud point when n is greater than 7, R group larger than butyl and EO/Cj ratio greater than 0.5 (where EO=n×m, Cj represents the total number of carbon atoms of both R and phenyl group). The rhodium complex of AEOPP shows thermoregulated phase transfer property in water/organic two-phase system. The complex exhibits good catalytic activity in the hydroformylation of 1-dodecene in water/organic two-phase medium and the conversion of the 1-dodecene and the yield of the aldehyde are 98% and 96%, respectively.

Thermoregulated Phase Transfer Ligands and Catalysis IX.: Hydroformylation of higher olefins in organic monophase catalytic system based on the concept of critical solution temperature of the nonionic tensioactive phosphine ligand

Abstract Application of the concept of critical solution temperature (CST) of nonionic tensioactive phosphine ligand P[p-C6H4O(CH2CH2O)nH]3 (PETPP) in the hydroformylation of higher olefins in organic monophase system is presented for the first time. The PETPP/Rh complex catalyst is insoluble in organic solvent at room temperature (T CST, the catalyst would be soluble in organic solvent. Thus, the catalytic reaction would have taken place homogeneously at the reaction temperature (T>CST). When the reaction is completed, on cooling to the room temperature (T

Thermoregulated phase transfer ligands and catalysis XIV: Synthesis of N,N-dipolyoxyethylene-substituted-4-(diphenylphosphino) benzenesulfonamide (PEO-DPPSA) and the catalytic activity of its rhodium complex in hydroformylation of 1-decene

Abstract A novel water soluble phosphine, N,N -dipolyoxyethylene-substituted-4-(diphenylphosphino) benzenesulfonamide (PEO-DPPSA), is synthesized by ethoxylation of 4-(diphenylphosphino) benzenesulfonamide Ph 2 P–C 6 H 4 SO 2 NH 2 (DPPSA) obtained from palladium-catalyzed P–C coupling reaction between 4-I–C 6 H 4 SO 2 NH 2 and Ph 2 PH. The PEO-DPPSA possesses the same property of inverse temperature-dependent solubility in water (cloud point, C p ) as nonionic surfactants. Investigation on the behavior of RhCl 3 ·3H 2 O/PEO-DPPSA complex in the aqueous–organic biphasic hydroformylation of 1-decene showed that the complex exhibited high catalytic activity. The conversion of 1-decene and the yield of aldehydes reach as high as 97.8 and 95.6%, respectively, under optimized conditions. The high reactivity of Rh/PEO-DPPSA complex can be attributed to a process termed thermoregulated phase transfer catalysis.

Thermoregulated phase-separable phosphine rhodium complex catalyst for hydroformylation of cyclohexene

Based on the critical solution temperature of nonionic tensioactive phosphine ligand, a novel process termed as thermoregulated phase-separable catalysis has been applied for the first time in the hydroformylation of cyclohexene. The catalyst is formed in situ from P[p-C6H4O(CH2CH2O)nH]3 (PETPP) and RhCl3·3H2O. Under the conditions of T=130 °C, P=5.0 Mpa, the conversion of cyclohexene and yield of aldehyde are 98.4%. The catalyst was reused four times and no loss in activity has been observed.

Rh Nanoparticles Catalyzed Hydroformylation of Olefins in a Thermoregulated Ionic Liquid/Organic Biphasic System

Rh nanoparticles were investigated as a catalyst for hydroformylation of olefins in thermoregulated ionic liquid/organic biphasic systems composed of an ionic liquid, namely [CH3(OCH2CH2)16N+Et3][CH3SO3−] (ILPEG750), and an organic solvent. This enables not only a homogeneous reaction but also easy biphasic separation. Under the optimized reaction conditions, the conversion of 1-octene and yield of aldehyde were 99% and 91%, respectively. The catalyst was easily separated from the product by phase separation and used eight times without evident loss of activity.

Hydroformylation of Higher Olefins by Thermoregulated Phase-Transfer Catalysis with Rhodium Nanoparticles

Thermoregulated ligand Ph2P(CH2CH2O)16CH3-stabilized rhodium nanoparticles were investigated as the catalyst in the hydroformylation of higher olefins by thermoregulated phase-transfer catalysis in an aqueous/1-butanol biphasic system. Under optimized reaction conditions, the conversion of 1-octene and yield of aldehyde were 98% and 96%, respectively. The catalyst can be easily separated from the product by phase separation and was used for three times without evident loss in activity.

Highly efficient and recyclable rhodium nanoparticle catalysts for hydrogenation of quinoline and its derivatives

PEG-stabilized rhodium nanoparticles exhibited high activity, selectivity and recyclability for the hydrogenation of quinoline and its derivatives. The selectivity of 1,2,3,4-tetrahydroquinoline was higher than 99%. The catalysts were recycled ten times with a total turnover number of 10592, which is the highest value ever reported for quinoline.