Hydroxycarbonylation of 1-octene in supercritical carbon dioxide

Anna M. Masdeu-Bulto 1Clara Tortosa Arantxa Orejón Nuria Ruiz Gabor Laurenczy 2

1. Universitat Rovira i Virgili (URV), Av. Països Catalans, 26, Tarragona 43007, Spain
2. Universite de Lausanne, Institut de Chimie Minerale et Analytique, Batiment de Chimie, Lausanne CH-1015, Switzerland

Hydroxycarbonylation of 1-octene in supercritical carbon dioxide



Clara Tortosa Estoracha, Arantxa Orejón,a Núria Ruiz,a Anna M. Masdeu-Bultóa,* and Gábor Laurenczyb



aDepartament de Quίmica Fίsica i Inorgànica, Universitat Rovira i Virgili, Marcel.li Domingo s/n 43007 Tarragona, Spain. Fax: +34 977 559563; Tel: +34 977 559575; E-mail: annamaria.masdeu@urv.cat

b Laboratory of Medicinal and Organometallic Chemistry, Institut des Sciences et Ingeniérie Chimiques, Ecole Polytéchnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland, E-mail: gabor.laurenczy@epfl.ch




Catalytic hydroxycarbonylation of terminal long chain alkenes is an interesting reaction to transform alkenes into carboxylic acids with CO using a palladium complex as catalyst (1).







The interest of supercritical carbon dioxide (scCO2), as a substitute solvent for catalytic reactions has quickly increased in the last years because of the advantages it presents compared with organic solvents.[1] Unfortunately, ionic and polar reagents generally exhibit low solubility in scCO2, and it has limited application of scCO2 in this catalytic processes.[2] To overcome this limitation modified ligands such as perfluorinated phosphines or/and soluble surfactants, which induces the formation of micelles with high-density fluid phase, have been employed. [3]


In the present work, the hydroxycarbonylation of 1-octene in scCO2 has been studied using palladium catalytic precursors with fluorinated phoshines. Particular attention has been paid in the effect of perfluorinated surfactants (2) in order to generate microemulsions of water.








Although this reaction in organic solvent affords high conversions and selectivities, the chemioselectivity in acids is shown to improve in scCO2. The use of perfluorinated surfactant also enhances the activity and the regioselectivity to the linear acid.


High pressure NMR experiments in toluene-d6 and scCO2 showed the formation of Pd(0) species.

[1] Leitner, W., Acc. Chem. Res., 2002, 35, 746.

[2] Jessop, P. G.; Hsiao, Y.; Ikariya, T.; Noyori, R., J. Am. Chem. Soc, 1996, 118, 344.

[3] Johnston, K. P.; Harrison, K. L.; Clarke, M. J.; Howdle, S. M; Heitz, M. P; Bright, F. V.; Carlier,     C.; Randolph, T. W., Science, 1996, 271, 624.

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Presentation: Poster at COST D30 Final Evaluation Meeting, by Anna M. Masdeu-Bulto
See On-line Journal of COST D30 Final Evaluation Meeting

Submitted: 2007-10-23 18:09
Revised:   2009-06-07 00:44
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