Hydroformylation of 1-octene in supercritical carbon dioxide and organic solvents using trifluoromethyl-substituted triphenylphosphine ligands

A.C.J. Koeken, M.C.A. Vliet, van, L.J.P. Broeke, van den, B.J. Deelman, J.T.F. Keurentjes

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    Abstract

    Two different in situ prepared catalysts generated from Rh(CO)2acac and trifluoromethyl-substituted triphenylphosphine ligands have been evaluated for their activity and selectivity in the hydroformylation of 1-octene. The solvents used were supercritical carbon dioxide, hexane, toluene, and perfluoromethylcyclohexane. The highest value for the turnover frequency, 9820 mol1-octene molRh-1 h-1, has been obtained in supercritical carbon dioxide using ligand I, P[C6H3-3,5-(CF3)2]3. For both supercritical carbon dioxide and hexane employing ligand II, P(C6H4-3-CF3)3, a selectivity towards the linear aldehyde product, nonanal, and an n:iso ratio of 79.3¿% and 4.6–4.8 have been obtained, respectively. These values are significantly higher than those obtained with triphenylphosphine as ligand (nonanal: 74–76¿%, n:iso: 3.1–3.3). An increase in trifluoromethyl substitution on the triphenyl ligand results in an increase in the 1-octene conversion rate, an increase in the n:iso ratio and a decrease in the overall selectivity towards aldehydes. In terms of turn-over frequency and selectivity the three ligands give comparable results in supercritical carbon dioxide and hexane. This leads to the conclusion that the properties of supercritical carbon dioxide as a solvent for hydroformylation can be better compared with those of hexane rather than with those of toluene.
    Original languageEnglish
    Pages (from-to)1553-1559
    Number of pages6
    JournalAdvanced Synthesis & Catalysis
    Volume348
    Issue number12-13
    DOIs
    Publication statusPublished - 2006

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    Hydroformylation
    Carbon Dioxide
    Organic solvents
    Hexanes
    Ligands
    Toluene
    Aldehydes
    1-octene
    triphenylphosphine
    Substitution reactions
    Catalysts

    Cite this

    Koeken, A.C.J. ; Vliet, van, M.C.A. ; Broeke, van den, L.J.P. ; Deelman, B.J. ; Keurentjes, J.T.F. / Hydroformylation of 1-octene in supercritical carbon dioxide and organic solvents using trifluoromethyl-substituted triphenylphosphine ligands. In: Advanced Synthesis & Catalysis. 2006 ; Vol. 348, No. 12-13. pp. 1553-1559.
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    title = "Hydroformylation of 1-octene in supercritical carbon dioxide and organic solvents using trifluoromethyl-substituted triphenylphosphine ligands",
    abstract = "Two different in situ prepared catalysts generated from Rh(CO)2acac and trifluoromethyl-substituted triphenylphosphine ligands have been evaluated for their activity and selectivity in the hydroformylation of 1-octene. The solvents used were supercritical carbon dioxide, hexane, toluene, and perfluoromethylcyclohexane. The highest value for the turnover frequency, 9820 mol1-octene molRh-1 h-1, has been obtained in supercritical carbon dioxide using ligand I, P[C6H3-3,5-(CF3)2]3. For both supercritical carbon dioxide and hexane employing ligand II, P(C6H4-3-CF3)3, a selectivity towards the linear aldehyde product, nonanal, and an n:iso ratio of 79.3¿{\%} and 4.6–4.8 have been obtained, respectively. These values are significantly higher than those obtained with triphenylphosphine as ligand (nonanal: 74–76¿{\%}, n:iso: 3.1–3.3). An increase in trifluoromethyl substitution on the triphenyl ligand results in an increase in the 1-octene conversion rate, an increase in the n:iso ratio and a decrease in the overall selectivity towards aldehydes. In terms of turn-over frequency and selectivity the three ligands give comparable results in supercritical carbon dioxide and hexane. This leads to the conclusion that the properties of supercritical carbon dioxide as a solvent for hydroformylation can be better compared with those of hexane rather than with those of toluene.",
    author = "A.C.J. Koeken and {Vliet, van}, M.C.A. and {Broeke, van den}, L.J.P. and B.J. Deelman and J.T.F. Keurentjes",
    year = "2006",
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    language = "English",
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    Hydroformylation of 1-octene in supercritical carbon dioxide and organic solvents using trifluoromethyl-substituted triphenylphosphine ligands. / Koeken, A.C.J.; Vliet, van, M.C.A.; Broeke, van den, L.J.P.; Deelman, B.J.; Keurentjes, J.T.F.

    In: Advanced Synthesis & Catalysis, Vol. 348, No. 12-13, 2006, p. 1553-1559.

    Research output: Contribution to journalArticleAcademicpeer-review

    TY - JOUR

    T1 - Hydroformylation of 1-octene in supercritical carbon dioxide and organic solvents using trifluoromethyl-substituted triphenylphosphine ligands

    AU - Koeken, A.C.J.

    AU - Vliet, van, M.C.A.

    AU - Broeke, van den, L.J.P.

    AU - Deelman, B.J.

    AU - Keurentjes, J.T.F.

    PY - 2006

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    N2 - Two different in situ prepared catalysts generated from Rh(CO)2acac and trifluoromethyl-substituted triphenylphosphine ligands have been evaluated for their activity and selectivity in the hydroformylation of 1-octene. The solvents used were supercritical carbon dioxide, hexane, toluene, and perfluoromethylcyclohexane. The highest value for the turnover frequency, 9820 mol1-octene molRh-1 h-1, has been obtained in supercritical carbon dioxide using ligand I, P[C6H3-3,5-(CF3)2]3. For both supercritical carbon dioxide and hexane employing ligand II, P(C6H4-3-CF3)3, a selectivity towards the linear aldehyde product, nonanal, and an n:iso ratio of 79.3¿% and 4.6–4.8 have been obtained, respectively. These values are significantly higher than those obtained with triphenylphosphine as ligand (nonanal: 74–76¿%, n:iso: 3.1–3.3). An increase in trifluoromethyl substitution on the triphenyl ligand results in an increase in the 1-octene conversion rate, an increase in the n:iso ratio and a decrease in the overall selectivity towards aldehydes. In terms of turn-over frequency and selectivity the three ligands give comparable results in supercritical carbon dioxide and hexane. This leads to the conclusion that the properties of supercritical carbon dioxide as a solvent for hydroformylation can be better compared with those of hexane rather than with those of toluene.

    AB - Two different in situ prepared catalysts generated from Rh(CO)2acac and trifluoromethyl-substituted triphenylphosphine ligands have been evaluated for their activity and selectivity in the hydroformylation of 1-octene. The solvents used were supercritical carbon dioxide, hexane, toluene, and perfluoromethylcyclohexane. The highest value for the turnover frequency, 9820 mol1-octene molRh-1 h-1, has been obtained in supercritical carbon dioxide using ligand I, P[C6H3-3,5-(CF3)2]3. For both supercritical carbon dioxide and hexane employing ligand II, P(C6H4-3-CF3)3, a selectivity towards the linear aldehyde product, nonanal, and an n:iso ratio of 79.3¿% and 4.6–4.8 have been obtained, respectively. These values are significantly higher than those obtained with triphenylphosphine as ligand (nonanal: 74–76¿%, n:iso: 3.1–3.3). An increase in trifluoromethyl substitution on the triphenyl ligand results in an increase in the 1-octene conversion rate, an increase in the n:iso ratio and a decrease in the overall selectivity towards aldehydes. In terms of turn-over frequency and selectivity the three ligands give comparable results in supercritical carbon dioxide and hexane. This leads to the conclusion that the properties of supercritical carbon dioxide as a solvent for hydroformylation can be better compared with those of hexane rather than with those of toluene.

    U2 - 10.1002/adsc.200606150

    DO - 10.1002/adsc.200606150

    M3 - Article

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    SP - 1553

    EP - 1559

    JO - Advanced Synthesis & Catalysis

    JF - Advanced Synthesis & Catalysis

    SN - 1615-4150

    IS - 12-13

    ER -