WO2012072594A1 - Ligand, catalyseur et procédé d'hydroformylation - Google Patents

Ligand, catalyseur et procédé d'hydroformylation Download PDF

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Publication number
WO2012072594A1
WO2012072594A1 PCT/EP2011/071206 EP2011071206W WO2012072594A1 WO 2012072594 A1 WO2012072594 A1 WO 2012072594A1 EP 2011071206 W EP2011071206 W EP 2011071206W WO 2012072594 A1 WO2012072594 A1 WO 2012072594A1
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Prior art keywords
group
ligand
hydroformylation
organophosphine ligand
ethylenically unsaturated
Prior art date
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PCT/EP2011/071206
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English (en)
Inventor
Marijke De Boer-Wildschut
Manutsavin Charernsuk
Cornelia Alida Krom
Paul Gerard Pringle
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Shell Internationale Research Maatschappij B.V.
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Publication of WO2012072594A1 publication Critical patent/WO2012072594A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
    • C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1885—Ligands comprising two different formal oxidation states of phosphorus in one at least bidentate ligand, e.g. phosphite/phosphinite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
    • C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Definitions

  • the present invention relates to a ligand and a catalyst suitable for use in the hydroformylation of ethylenically unsaturated compounds. It also relates to a process for the hydroformylation of ethylenically
  • aldehyde and/or alcohol compounds by the reaction of an ethylenically unsaturated compound with carbon monoxide and hydrogen in the presence of a catalyst are known. Typically, these reactions are performed at elevated temperatures and pressures.
  • the aldehyde and alcohol compounds that are produced generally correspond to compounds obtained by the addition of a carbonyl or carbinol group,
  • R 1 R 2 C CR 3 R 4 + CO + H 2 > R 1 R 2 CH-CR 3 RCHO +
  • each group R 1 to R 4 may independently represent an organic radical, for example a hydrocarbyl group, or a suitable atom such as a hydrogen or halogen atom, or a hydroxyl group.
  • the above reaction may also be applied to a cycloaliphatic ring having an olefinic linkage, for example cyclohexene.
  • the catalyst employed in a hydroformylation reaction typically comprises a transition metal, such as cobalt, rhodium or ruthenium, in complex combination with carbon monoxide and ligand(s) such as an organophosphine ligand.
  • a transition metal such as cobalt, rhodium or ruthenium
  • Phosphabicyclohydrocarbyl ligands are known in the art, and their production and use in hydroformylation reactions are for example described in WO200494440,
  • heterohydrocarbyl moiety containing at least one branch at the ⁇ -carbon position. More specifically, said
  • R 6 is a cyclic group.
  • R 6 are tetrahydrofuran, cyclohexane and tetrahydropyran groups .
  • organophosphine ligands and organophosphine-modified metal catalysts provide very good results in the hydroformylation of ethylenically unsaturated compounds
  • the use of such ligands and catalysts is known to lead to the production of paraffins as a by-product.
  • the paraffin by-products have very little commercial value. It would, therefore, be
  • the invention relates to an
  • organophosphine ligand comprising a
  • the invention also relates to a catalytic composition for the hydroformylation of an ethylenically unsaturated compound, said catalytic composition comprising
  • the invention also relates to a process for the hydroformylation of an ethylenically unsaturated compound, said process comprising contacting the
  • the ligand of the present invention is of Formula (I) :
  • the phosphabicyclohydrocarbyl group is selected from the group consisting of 6-phosphabicyclohexyl , 7- phosphabicycloheptyl , 8-phosphabicyclooctyl and 9- phosphabicyclononyl groups, with the proviso that the smallest phosphorus-containing ring in the
  • phosphabicyclohydrocarbyl group contains at least 5 atoms. Any structural isomer of such compounds, e.g. the [3.3.1] and [4.2.1] isomers of a 9-phospha-bicyclononyl group, are suitable in the present invention.
  • Each carbon atom within the phosphabicyclohydrocarbyl group of the ligand of the present invention may
  • Suitable substituents include hydrocarbyl groups,
  • heterohydrocarbyl groups and/or groups comprising hetero- atoms are examples of heterohydrocarbyl groups and/or groups comprising hetero- atoms .
  • hydrocarbyl refers to groups
  • Such groups may be saturated or unsaturated, branched or unbranched and may contain aromatic and/or aliphatic moieties.
  • heterohydrocarbyl refers to groups containing hydrogen and carbon atoms as well as
  • Such groups may be saturated or unsaturated, branched or unbranched and may contain aromatic and/or aliphatic moieties.
  • the phosphabicyclohydrocarbyl ring is substituted it is substituted with one or more alkyl groups, preferably having from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms.
  • alkyl groups preferably having from 1 to 10 carbon atoms, more preferably from 1 to 4 carbon atoms.
  • Linear, branched or cyclic alkyl groups can be used. Suitable alkyl groups include, methyl, ethyl, propyl, iso-propyl, butyl and iso-butyl. More suitably methyl groups are used.
  • the substituted phosphabicyclohydrocarbyl ring can be mono- or poly-substituted and is preferably di-substituted. Most preferably, if the phosphabicyclohydrocarbyl ring is substituted, it is substituted with two methyl groups.
  • the phosphabicyclohydrocarbyl group is unsubstituted .
  • the organophosphine ligand of the present invention is of Formula (II) :
  • Rl and R2 are each a hydrocarbyl group. Further, preferably, Rl and R2 are the same hydrocarbyl group. Further, preferably, hydrocarbyl groups for Rl and R2 are selected from the group consisting of alkyl groups and aromatic groups. Suitable alkyl groups for Rl and R2 include alkyl groups containing in the range of from 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 5 to 15 carbon atoms, most preferably 8 to 12 carbon atoms. In particular, Rl and R2 may both be n- hexyl . A suitable aromatic group for Rl and R2 is phenyl. In particular, Rl and R2 may both be phenyl.
  • Substituents on the alkyl and aromatic (including phenyl) groups may include heteroatoms and heterohydrocarbyl moieties.
  • R 4 and R 5 independently represent alkyl groups having from 1 to 4 carbon atoms, such as methyl, ethyl, n- propyl, isopropyl, n-butyl, iso-butyl and t-butyl .
  • the phosphorus atom of the P 0 group together with Rl and R2 form a cyclic heterohydrocarbyl group.
  • Said cyclic heterohydrocarbyl group may contain one ring or more than one ring.
  • the ring or each of the rings may contain 4 to 9, preferably 5 to 7 ring atoms.
  • the cyclic group will be bicyclic, i.e. it will contain two rings.
  • the ring atoms are comprised of phosphorus and carbon and, optionally, one or more of oxygen, nitrogen and sulfur.
  • the organophosphine ligand of the present invention comprises two
  • suitable Group VIII metals are cobalt, rhodium, ruthenium, nickel, palladium and platinum.
  • the Group VIII metal is cobalt. _ g _
  • Cobalt hydroformylation catalysts according to the present invention can be prepared by a diversity of methods well known to those skilled in the art as disclosed in US3369050, US3501515, US3448157, US3420898 and US3440291, which are all herein incorporated by reference.
  • a convenient method is to combine a cobalt salt, organic or inorganic, with the desired phosphine ligand, for example, in liquid phase followed by
  • Suitable cobalt salts comprise, for example, cobalt carboxylates such as acetates, octanoates, etc. as well as cobalt salts of mineral acids such as chlorides, fluoride, sulfates, sulfonates, etc. as well as mixtures of one or more of these cobalt salts.
  • the valence state of the cobalt may be reduced and the cobalt-containing complex formed by heating the solution in an atmosphere of hydrogen and carbon monoxide. The reduction may be performed prior to the use of the organophosphine modified cobalt
  • hydroformylation catalysts or it may be accomplished in- situ with the hydroformylation process in the
  • catalysts can be prepared from a carbon monoxide complex of cobalt.
  • a carbon monoxide complex of cobalt For example, it is possible to start with dicobalt octacarbonyl and, by mixing this substance with a suitable phosphine ligand, the ligand replaces one or more of the carbon monoxide molecules, producing an organophosphine modified cobalt hydroformylation
  • the active catalyst compound is typically formed under process conditions.
  • an ethylenically unsaturated compound having from 2 to 4 0 carbon atoms per molecule, or a mixture thereof.
  • Preferred are compounds having from 2 to 30 carbon atoms, or mixtures thereof.
  • the advantages of the process according to the invention are further especially pronounced for larger ethylenically
  • unsaturated compounds comprising at least 4 carbon atoms, and preferably at least 6 carbon atoms. More preferably such a large ethylenically unsaturated compound comprises 8 or more carbon atoms, preferably from 8 to 25 and more preferably from 8 to 1 8 carbon atoms.
  • the ethylenically unsaturated compound can further be a straight carbon chain or can be branched. Suitable ethylenically
  • substituents are alkyl groups, preferably alkyl groups comprising from 1 to 6 , more preferably from 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl and tert- butyl .
  • ethylenically unsaturated compounds include mono-alkenes , such as ethene, propene, butene, pentene, 1-hexene, internal hexenes, 1-heptene, internal heptenes, 1-octene, internal octenes, 1-nonene or internal nonenes, 1-decene or internal decenes, undecenes, methyl-branched undecenes, dodecenes, methyl- branched dodecenes, methyl-substituted or unsubstituted Ci3, Ci4, Ci5, Ci6, Ci7, Cie , C19 or C 2 o-olefins and mixtures of those.
  • branched such as ethene, propene, butene, pentene, 1-hexene, internal hexenes, 1-heptene, internal heptenes, 1-octene, internal octenes, 1-nonene or internal nonenes,
  • the process is further suitable for the
  • the ethylenically unsaturated compound can further be an ethylenically unsaturated compound comprising
  • Suitable ethylenically unsaturated compounds comprising functional groups or heteroatoms include, for example, pentene nitriles and methyl-pentenoates .
  • the ethylenically unsaturated compound does not comprise any functional groups or heteroatoms and is an olefin comprising only carbon atoms.
  • the unsaturated starting material and the formed product may act as reaction diluent.
  • the hydro- formylation reaction may be carried out in the additional presence of a solvent which is inert, or which does not interfere to any substantial degree with the desired hydroformylation reaction under the conditions employed.
  • Saturated liquid hydrocarbons for example, may be used as solvent in the process, as well as alcohols, ethers, acetonitrile, sulfolane, and the like.
  • a part of an alcoholic reaction product may, if desired, be recycled to the reaction zones to function as solvent and/or diluent and/or suspending medium for the catalyst, the catalyst components, and the like.
  • Admixtures of promoters and/or stabilizers and the like may also be included in the process of the present invention.
  • minor amounts of phenolic stabilizers such as hydroquinone and/or alkaline agents such as hydroxides of alkali metals, for example NaOH and KOH, may be added into the process.
  • the quantity in which the catalyst system is used is not critical and may vary within wide limits. Usually amounts in the range of 1CT 8 to 1CT 1 , preferably in the range of 1CT 7 to 1CT 2 mole atom of Group VIII metal per mole of ethylenically unsaturated compound are used.
  • the amounts of the participants in the catalyst system are conveniently selected such that per mole atom of
  • Group VIII metal from 0.1 to 10, preferably
  • organophosphine from 0.5 to 6, and more preferably from 0.5 to 3 moles of organophosphine are used
  • Carbon monoxide partial pressures in the range of from 1 to 65 bar are preferred.
  • the carbon monoxide can be used in its pure form or diluted with an inert gas such as nitrogen, carbon dioxide or noble gases such as argon.
  • the co-reactant can be molecular hydrogen, or more generally a hydride source.
  • the carbon monoxide and hydrogen are preferably supplied in a molar ratio of hydrogen to carbon monoxide within the range of 10:1 to 1:5, preferably 6:1 to 1:3.
  • the molar ratio of hydrogen to carbon monoxide can influence the type of product prepared.
  • the desired product is an alkanol, an excess of hydrogen is needed to enable the
  • the desired product is an alkanol, preferably a molar ratio of hydrogen to carbon monoxide within the range of 4:1 to 1.3:1 is used.
  • the process of the present invention may be carried out over a wide range of temperatures. Suitable
  • temperatures for the reaction environment are in the range of from 130 to 220 °C, preferably in the range of from 140 to 210 °C, more preferably in the range of from 150 to 205 °C.
  • the process of the present invention may be carried out at various pressures. Consequently, hydroformylation in accordance with the process of the present invention may typically be carried out at pressures below 8 x 10 6 Pa, to as low as 1 x 10 5 Pa.
  • the process of the present invention is, however, not limited in its applicability to the lower pressures. Pressures in the broad range of from 1 x 10 5 Pa up to about 2 x 10 7 Pa, and in some cases up to about 2 x 10 8 Pa or higher, may be employed.
  • the specific pressure used will be governed to some extent by the specific charge and catalyst employed. In general, pressures in the range of from about 2 x 10 6
  • the invention is further illustrated by the following Examples .
  • reaction mixture was stirred for 16 h and the temperature was slowly raised to room temperature over 16 h.
  • the solvent was removed under reduced pressure to give a brown oil and then redissolved in acetonitrile (400 cm 3 ) . After 48 h, the solvent was removed under reduced
  • Comparative Examples 1, 2 and 3 and Example 4 were carried out as follows.
  • the mixture was heated to 190°C and a pressure of 50 bars syngas (at a 3 ⁇ 4 : CO ratio of 1.8:1) was applied.
  • the cobalt concentration in the reaction mixture was 0.11 wt . % .
  • the reaction was followed for 6 hours and samples were taken at regular intervals. The results obtained are shown in Table 1.
  • solvent 2-ethylhexanol
  • the cobalt concentration in the reaction mixture was 0.11 wt . % .
  • the reaction was followed for 6 hours and samples were taken at regular intervals. The results obtained are shown in Table 1.
  • Example 6 was carried out in the same way as Example
  • the ligands used in Examples 4, 5 and 6 are in accordance with the present invention.
  • the ligands used in Comparative Examples 1, 2 and 3 comprised Compounds 1, 2 and 3, respectively, as shown below, which compounds are also disclosed in above-mentioned US20100036171.
  • Examples 4, 5 and 6 perform surprisingly far better in that the amount of paraffin by-products formed in the hydroformylation process is reduced significantly, and at the same time the activity or reaction rate of the hydroformylation reaction is considerably improved.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un ligand organophosphine comprenant un groupement phosphabicyclohydrocarbyle dans lequel l'atome de phosphore du groupement phosphabicyclohydrocarbyle est substitué plus avant par un groupement hétérohydrocarbyle comportant au moins un groupement oxyde de phosphore [P=O] ou oxyde de soufre [S=O]. La présente invention concerne également une composition catalytique pour l'hydroformylation d'un composé à insaturations éthyléniques, comprenant une source de cations d'un métal du Groupe VIII et ledit ligand organophosphine. En outre, la présente invention concerne également un procédé d'hydroformylation d'un composé à insaturations éthyléniques comprenant la mise en contact dudit composé avec du monoxyde de carbone et de l'hydrogène en présence de ladite composition catalytique.
PCT/EP2011/071206 2010-11-30 2011-11-28 Ligand, catalyseur et procédé d'hydroformylation WO2012072594A1 (fr)

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EP10193072.5 2010-11-30

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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3369050A (en) 1961-10-06 1968-02-13 Shell Oil Co Separation, recovery and recycle of the catalyst complex in the oxo process
US3420898A (en) 1965-03-29 1969-01-07 Shell Oil Co Single stage hydroformylation of olefins to alcohols
US3448157A (en) 1965-09-27 1969-06-03 Shell Oil Co Hydroformylation of olefins
US3448158A (en) 1966-01-28 1969-06-03 Shell Oil Co Hydroformylation of olefins
US3501515A (en) 1965-03-29 1970-03-17 Shell Oil Co Bicyclic heterocyclic tertiary phosphine-cobalt-carbonyl complexes
GB2323359A (en) * 1997-03-18 1998-09-23 Shell Int Research Preparation of homogenous cationic transition metal catalysts from tertiary phosphonium salts containing a weakly coordinating anion
WO2000052017A1 (fr) 1999-03-03 2000-09-08 Cytec Technology Corp. Preparation de 9-hydrocarbyle-9-phosphabicyclononanes
WO2003068786A1 (fr) 2002-02-13 2003-08-21 Cytec Technology Corp Composes de phosphine
WO2003082779A1 (fr) 2002-03-29 2003-10-09 Exxonmobil Chemical Patents, Inc. Procede de preparation d'un melange d'hydrocarbures olefiniques
WO2004054946A1 (fr) 2002-12-17 2004-07-01 Shell Internationale Research Maatschappij B.V. Processus d'hydroformylation pour la conversion d'un compose insature sur le plan ethylenique en un alcool
WO2004056732A1 (fr) 2002-12-19 2004-07-08 Shell Internationale Research Maatschappij B.V. Procede d’hydroformylation en presence d’un additif contenant du soufre
WO2004094440A2 (fr) 2003-03-31 2004-11-04 Cytec Canada Inc. Phosphines tertiaires et leurs procedes de preparation
US7012162B2 (en) 2000-06-26 2006-03-14 Basf Aktiengesellschaft Phosphacyclohexanes and the use thereof in the hydroformylation of olefins
WO2007003589A1 (fr) 2005-06-30 2007-01-11 Shell Internationale Research Maatschappij B.V. Processus d'hydroformylation
US20100036171A1 (en) 2008-08-11 2010-02-11 Marijke De Boer-Wildschut Ligand, catalyst and process for hydroformylation

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3369050A (en) 1961-10-06 1968-02-13 Shell Oil Co Separation, recovery and recycle of the catalyst complex in the oxo process
US3420898A (en) 1965-03-29 1969-01-07 Shell Oil Co Single stage hydroformylation of olefins to alcohols
US3440291A (en) 1965-03-29 1969-04-22 Shell Oil Co Single-stage hydroformylation of olefins to alcohols
US3501515A (en) 1965-03-29 1970-03-17 Shell Oil Co Bicyclic heterocyclic tertiary phosphine-cobalt-carbonyl complexes
US3448157A (en) 1965-09-27 1969-06-03 Shell Oil Co Hydroformylation of olefins
US3448158A (en) 1966-01-28 1969-06-03 Shell Oil Co Hydroformylation of olefins
GB2323359A (en) * 1997-03-18 1998-09-23 Shell Int Research Preparation of homogenous cationic transition metal catalysts from tertiary phosphonium salts containing a weakly coordinating anion
WO2000052017A1 (fr) 1999-03-03 2000-09-08 Cytec Technology Corp. Preparation de 9-hydrocarbyle-9-phosphabicyclononanes
US7012162B2 (en) 2000-06-26 2006-03-14 Basf Aktiengesellschaft Phosphacyclohexanes and the use thereof in the hydroformylation of olefins
WO2003068786A1 (fr) 2002-02-13 2003-08-21 Cytec Technology Corp Composes de phosphine
WO2003068719A2 (fr) 2002-02-13 2003-08-21 Sasol Technology (Proprietary) Limited Production de produits oxygenes
WO2003082779A1 (fr) 2002-03-29 2003-10-09 Exxonmobil Chemical Patents, Inc. Procede de preparation d'un melange d'hydrocarbures olefiniques
WO2004054946A1 (fr) 2002-12-17 2004-07-01 Shell Internationale Research Maatschappij B.V. Processus d'hydroformylation pour la conversion d'un compose insature sur le plan ethylenique en un alcool
WO2004056732A1 (fr) 2002-12-19 2004-07-08 Shell Internationale Research Maatschappij B.V. Procede d’hydroformylation en presence d’un additif contenant du soufre
WO2004094440A2 (fr) 2003-03-31 2004-11-04 Cytec Canada Inc. Phosphines tertiaires et leurs procedes de preparation
WO2007003589A1 (fr) 2005-06-30 2007-01-11 Shell Internationale Research Maatschappij B.V. Processus d'hydroformylation
US20100036171A1 (en) 2008-08-11 2010-02-11 Marijke De Boer-Wildschut Ligand, catalyst and process for hydroformylation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Handbook of Chemistry and Physics", CRC PRESS

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