Hydroformylation of 1-hexene catalyzed with rhodium fluorinated phosphine complexes in supercritical carbon dioxide and in conventional organic solvents: effects of ligands and pressures

Rhodium-catalyzed hydroformylation of 1-hexene was investigated in compressed CO2 and organic solvents using different fluorinated phosphine compounds as ligands at a temperature of 333 K. The reaction runs were conducted under conditions where the reaction mixtures were homogeneous in order to examine the activity of the rhodium complexes in different media. The effects of phosphine ligand, CO2 pressure, syngas (H2/CO) pressure and solvent on the hydroformylation activity were studied, along with FTIR examination of reaction mixtures. Such phosphine compounds as diphenyl(pentafluorophenyl)phosphine (II), bis(pentafluorophenyl)phenylphosphine (III), and tris(p-trifluoromethylphenyl)phosphine (VI) are effective ligands in scCO2. Compound II is better since with it the undesirable isomerization side reaction is avoided. The n/iso ratio (heptanal/2-methylhexanal) does not change so much with the phosphine ligand used. It is interesting that the aldehyde yield goes through a minimum at about 9 MPa with increasing CO2 pressure, and it tends to increase with an increase in the syngas pressure. The catalytic activities in scCO2 are comparable with those in toluene and it is suggested that scCO2 has some positive effects in promoting the hydroformylation.

[1]  M. Arai,et al.  Palladium-catalyzed Heck coupling reactions using different fluorinated phosphine ligands in compressed carbon dioxide and conventional organic solvents , 2002 .

[2]  A. Akgerman,et al.  Synthesis and characterization of {((COD)Rh(bis-(2R,3R)-2,5-diethylphospholanobenzene)) + BARF − } for use in homogeneous catalysis in supercritical carbon dioxide , 2001 .

[3]  M. Arai,et al.  CATALYST PRODUCT SEPARATION TECHNIQUES IN HECK REACTION , 2001 .

[4]  M. Abraham,et al.  Evaluation of catalyst support effects during rhodium-catalyzed hydroformylation in supercritical CO2 , 2001 .

[5]  M. Shirai,et al.  Heck reactions in supercritical carbon dioxide using organometallic complex catalysts , 2001 .

[6]  W. Leitner,et al.  Highly efficient enantioselective catalysis in supercritical carbon dioxide using the perfluoroalkyl-substituted ligand (R,S)-3-H2F6-BINAPHOS , 2001 .

[7]  C. Erkey,et al.  Hydroformylation of Higher Olefins in Supercritical Carbon Dioxide with HRh(CO)[P(3,5-(CF3)2−C6H3)3]3 , 2000 .

[8]  E. Dinjus,et al.  Solubility of triphenylphosphine, tris(p-fluorophenyl)phosphine, tris(pentafluorophenyl)phosphine, and tris(p-trifluoromethylphenyl)phosphine in liquid and supercritical carbon dioxide , 2000 .

[9]  C. Erkey,et al.  Effect of Ligand Modification on Rhodium-Catalyzed Homogeneous Hydroformylation in Supercritical Carbon Dioxide , 2000 .

[10]  C. Erkey,et al.  Kinetics of the homogeneous catalytic hydroformylation of 1-octene in supercritical carbon dioxide with HRh(CO)[P(p-CF3C6H4)3]3 , 1999 .

[11]  Daniel Koch,et al.  Rhodium-Catalyzed Hydroformylation in Supercritical Carbon Dioxide , 1998 .

[12]  C. Erkey,et al.  Homogeneous Catalytic Hydroformylation of 1-Octene in Supercritical Carbon Dioxide Using a Novel Rhodium Catalyst with Fluorinated Arylphosphine Ligands , 1998 .

[13]  M. Okano,et al.  Selective Conversion of Carbon Dioxide to Dimethyl Carbonate by Molecular Catalysis. , 1998, The Journal of organic chemistry.

[14]  Gabor Kiss,et al.  Molecular Engineering in Homogeneous Catalysis: One-Phase Catalysis Coupled with Biphase Catalyst Separation. The Fluorous-Soluble HRh(CO){P[CH2CH2(CF2)5CF3]3}3 Hydroformylation System , 1998 .

[15]  A. Akgerman,et al.  Hydroformylation of propylene in supercritical carbon dioxide , 1997 .

[16]  W. Leitner,et al.  Perfluoroalkyl‐Substituted Arylphosphanes as Ligands for Homogenous Catalysis in Supercritical Carbon Dioxide , 1997 .

[17]  W. Herrmann,et al.  Organometallic Homogeneous Catalysis—Quo vadis? , 1997 .

[18]  R. V. Chaudhari,et al.  Kinetics of hydroformylation of l-dodecene using homogeneous HRh(CO) (PPh3)3 catalyst , 1997 .

[19]  M. Arai,et al.  Promotion of Lipase-Catalyzed Esterification of N-Valeric Acid and Citronellol in Supercritical Carbon Dioxide in the Near-Critical Region , 1996 .

[20]  P. Jessop,et al.  Homogeneous catalysis in supercritical fluids. , 1999, Science.

[21]  C. Martino,et al.  Reactions at supercritical conditions: Applications and fundamentals , 1995 .

[22]  M. Arai,et al.  Activation of a Lipase Triggered by Interactions with Supercritical Carbon Dioxide in the Near-Critical Region , 1995 .

[23]  J. Brennecke,et al.  Effect of Local Composition Enhancements on the Esterification of Phthalic Anhydride with Methanol in Supercritical Carbon Dioxide , 1994 .

[24]  C. Eckert,et al.  Molecular charisma in supercritical fluids , 1993 .

[25]  P. Debenedetti,et al.  Molecular dynamics study of solute-solute microstructure in attractive and repulsive supercritical mixtures , 1992 .

[26]  R. J. Klingler,et al.  Propylene hydroformylation in supercritical carbon dioxide , 1991 .

[27]  C. Eckert,et al.  Fluorescence spectroscopy studies of dilute supercritical solutions , 1990 .

[28]  J. Prausnitz,et al.  Enzymatic Oxidation of Cholesterol Aggregates in Supercritical Carbon Dioxide , 1988, Science.

[29]  K. Johnston,et al.  Molecular interactions in dilute supercritical fluid solutions , 1987 .