GB2462455A - Hydroformylation process - Google Patents

Hydroformylation process Download PDF

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GB2462455A
GB2462455A GB0814441A GB0814441A GB2462455A GB 2462455 A GB2462455 A GB 2462455A GB 0814441 A GB0814441 A GB 0814441A GB 0814441 A GB0814441 A GB 0814441A GB 2462455 A GB2462455 A GB 2462455A
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acid
group
bis
cyclo
ethylenically unsaturated
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Eite Drent
Willem Wabe Jager
Roelof Van Ginkel
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
    • B01J31/2428—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom
    • B01J31/2433—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • 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
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
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    • 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
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • 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
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum
    • 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
    • B01J2531/847—Nickel

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for hydroformylation of an ethylenically unsaturated compound involves reaction of ethylenically unsaturated compound with carbon monoxide and hydrogen in the presence of a catalyst system. The catalyst system comprises: [a] a source of Group VIII metal cations, such as platinum metal cations; [b] a diphosphine ligand having a general formula (I): X1-R-X2(I), wherein X1and X2each independently is an optionally substituted cyclic group with at least 5 ring atoms, of which one is a phosphorous atom, and R is a bivalent optionally substituted bridging group, connected to each phosphorous atom by a sp2hybridised carbon atom, such as 1,2-bis(cyclo-octylphosphino) cyclopentene, 1,2-bis(cyclo-octylphosphino) benzene and 1,2-bis(cyclo-octylphosphino)-o-xylene; [c] an acid having a pKa< 3, measured in an aqueous solution at 18°C or a salt derived thereof, such as a sulfonic acid selected from methanesulphonic acid, fluoromethanesulphonic acid, trichloro-methanesulphonic acid, trifluoro-methanesulphonic acid, tert-butane-sulphonic acid, p-toluenesulphonic acid and 2,4,6-trimethylbenzene-sulphonic acid; and [d] a phosphonium halide, such as methyltriphenylphosphonium chloride.

Description

PROCESS FOR THE HYDROFORMYLATION OF ETHYLENICALLY
UNSATURATED COMPOUNDS
Field of the Invention
The present invention relates to a process for the hydrofOrmylation of an ethylenicallY unsaturated compound by reaction thereof with carbon monoxide and hydrogen in the presence of a catalyst system.
Background of the Invention
Processes for the hydroformylatiofl of ethylenicallY unsaturated compounds in the presence of carbon monoxide and a source of hydrogen are known in the art. Such io processes can be carried out in the presence of a catalyst system comprising a source of Group VIII metal cations, a diphosphifle ligand and a source of anions.
Processes known in the art include those described in WO 95/05354, EP 0495547 and WO 01/87899.
WO-A-01/87899 relates to the carbonylation of ethylenicallY unsaturated compounds. it describes a specific class of bidentate diphosphines. The phosphorus atoms in these diphosphifles are connected by a bridging group. A wide range of bridging groups is described. In passing, also cyclopentefle is mentioned as a possible bridging group.
WO-A-022669O relates to a process for the carbonylatiOn of conjugated dienes. The examples describe the reaction of 1,3-butadiefle and methanol tomethyl pentenoate in the presence of a catalyst comprising palladium acetate, a bidentate diphosphifle and a carboxylic acid. Several bidentate diphosphifleS are exemplified. The examples show that, for the exemplified reaction with methanol, a catalyst system comprising 1,2-P, pbis(9_phosphabicYc1ononYl) benzene as a bidentate diphosphifle has only a moderate activity (400mol/rflol/hr), much lower than a catalyst system comprising R,S_meso_2,3_P,Pbis(9_ph0spbYcb0n0flyta as a bidentate diphosphine (560 rnol/mol/hr) Although high levels of activity and/or selectivity have been reported in the art for known processes, as with any industrial process, there is still room for improvement. It would, therefore, be desirable to provide a process for the hydroforrflylation of ethylenically unsaturated compounds in which the activity and/or the selectivity of the process was increased.
Summary of the Invention
The present invention provides a process for the hydroforrilYlation of an ethylenicallY unsaturated compound by reaction thereof with carbon monoxide and hydrogen in the presence of a catalyst system comprising: (a) a source of Group VIII metal cations; (b) a diphosphine ligand having the general formula (I) X'-R-X2 (I) wherein X1-and X2 each independently represent an optionally substituted cyclic group with at least 5 ring atoms, of which one is a phosphorus atom, and R represents a bivalent optionally substituted bridging group, connected to each phosphorus atom by a sp2 hybridized carbon atom; -(c) an acid having a pKa < 3, measured in an aqueous solution at 18 00 or a salt derived thereof; and (d) a phosphonium halide.
Detailed Description of the InventiOfl
It has now surprisingly been found that high activity and excellent selectivity to primary alcohols can be achieved in the hydroforrflYlatiOn of ethylenically unsaturated compounds in the presence of carbon monoxide and hydrogen and a catalyst system comprising a source of Group VIII metal cationS, a diphosphifle ligand, an acid having a pKa < 3, measured in an aqueous solution at 18 °C or a salt derived thereof and a phosphonium halide.
In the present invention, the diphosphine ligand is of the general formula (I) X---R--X2 (I) wherein X1 and X2 each independently represent an io optionally substituted cyclic group with at least 5 ring atoms, of which one is a phosphorus atom, and R represents a bivalent optionally substituted bridging group, connected to each phosphorus atom by a sp2 hybridized carbon atom. Both phosphorus atoms can be connected to one and the same sp2 hybridized carbon atom.
Preferably, however, R comprises at least two 5p2 hybridized carbon atoms and each phosphorus atom is connected to a separate sp2 hybridized carbon atom.
preferably R represents a bivalent optionally substituted bridging group comprising 2 or more atoms in the bridge. By "a bridge" is understood to be the shortest connection beiween both phosphorus atoms. More preferably R contains 2 to 6 atoms in the bridge, and most preferably R contains 2 to 4 atoms in the bridge.
EspeciallY preferred are those bridging groups R which contain 2 or 3 atoms in the bridge. Of these bridge atoms, preferably at least 2 are carbon atoms. More preferably all bridge atoms are carbon atoms. Most preferably R represents a bivalent optionally substituted bridging group connecting the phosphorus atoms via a bridge consisting of two sp2 hybridized carbon atoms.
The bridging group R can be any group comprising at least one and preferably two sp2 hybridized carbon atoms.
Examples of such groups include alkene, cycloalkene and aromatic groups, wherein the carbon atom(s) connected to a phosphorus atom are connected via an unsaturated bond to another atom.
Examples of suitable alkene groups include alkene groups having at least 2 carbon atoms, more preferably in the range of from 2 to 10 carbon atoms, and most preferably from 2 to 6 carbon atoms. The alkene group can contain heteroatOmS such as N, o, p or S, either in the carbon chain or attached as a substituent to the carbon chain. The alkene group can contain one or more unsaturated bonds. The group can be a straight chain alkene group or a branched alkene group but is preferably a straight chain alkene group. The alkene group can have substituent groups attached to it containing heteroatomS such as N, o, p or S, alkyl groups or aryl groups.
Preferably such a substituent is an alkyl or aryl group, more preferably an alkyl or aryl group comprising from 1 to 6, more preferably from 1 to 4, carbon atoms, such as for example methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl or tert.-butyl and phenyl. Examples of suitable alkene groups include 1,2-vinylefle (in ItJPAC nomenclature l,2-ethenYlefle) ,2_diphenyl_l,2_V1flylefl 1-methyl- 1, 2-vinylefle 1,2_dimethyl_l,2_vinYlene 1-methyl- 2_ethy1-1,2ViflYleI 1,2_diethyl_1,2_Viflyler 1,3_(l,3_bUtadieflYl) (in IUPAC nomenclature ,_dimethy1eflel,2_ethYle) wherein the two free valencies are connected to the phosphorus atoms.
Examples of suitable cycloalkene groups include cycloalkene groups having more than 3 ring atoms, more preferably in the range of from 4 to 16 ring atoms, and most preferably in the range of from 5 to 10 ring atoms.
Of these ring atoms at least two are sp2 hybridized carbon atoms. The cycloalkefle group can contain heteroatomS such as N, o, p or S, either in the carbon chain or attached as a substituent to the carbon chain.
preferably, however, the cycloalkene group only contains carbon atoms. The cycloalkene group can contain one or more unsaturated bonds, but preferably only contains one unsaturated bond. The cycloalkene group can have substituent groups attached to it containing heteroatomS such as N, 0, p or S, alkyl groups or aryl groups.
preferably such a substitUent is an alkyl or aryl group, more preferably an alkyl or aryl group comprising in the range of from 1 to 6, more preferably in the range of from 1 to 4, carbon atoms, such as for example methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl or tert.-butyl and phenyl. Most preferably, however, the cycloalkene group does not have substituent groups attached to it. Examples of suitable cycloalkefle groups include 1_cyclopenten_1,2_Yle 1_cyclohexefl_1,2Ylene l_cycloheptefl_l,2Ylene 1_cyclo-octefli,2Y'' 3_methyl_l-cYcl0PentP 2-ylene; 1, 3-cyclopefltefl2, 3-ylene; wherein the two free valencieS areconnected to the phosphorus atoms. Of these 1_cycloPenten_1,2Y1e and 1_cycloheXen_1,2YJe are preferred.
Examples of suitable aromatic groups include monocyclic groups, such as for example a phenyl group, and polycyclic groups, such as for example naphthyl, anthryl or indyl groups. preferably, however, the aromatic group is a monocyclic group. The aromatic group preferably has in the range of from 4 to 20 ring atoms, more preferably in the range of from 5 to 12 ring atoms and most preferably in the range of from 5 to 7 ring atoms. The aromatic group may contain just carbon atoms as ring atoms. Preferably, however, the aromatic ring also contains one or more heteroatoms, such as N, 0, p or S, as a ring atom. Examples of suitable aromatic groups comprising one or more heteroatOmS as a ring atom include for example pyridine, pyrrole, furari, thiophene, oxazole or thiazole groups. preferred aromatic groups include thiophene and benzene. Optionally the aromatic group is substituted. Suitable substitUeflts include groups io containing heteroatOmS such as halides, sulphur, phosphorus oxygen and nitrogen. Examples of such groups include fluoride, chloride, bromide, iodide and groups of the general formula -0-H, -O-X3, -CO-X3, -CO-O-X3, -S-H, -s-x3, -CO-S-X3, -NH2, -NHX3, -NX3X4, -NO2, -ON, -CO-NH2, -CO-NHX3, -CO-NX3X4 and -C13, in which X3 and X4, independently, represent alkyl groups having in the range of from 1 to 4 carbon atoms like methyl, ethyl, r-propyl, isopropyl, n-butyl, iso-butyl and tert.-butYl. If the aromatic group is substituted it is preferably substituted with one or more aryl, alkyl or cycloalkyl groups, preferably having from 1 to 10 carbon atoms.
Suitable groups include, methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, tert.-butyJ-phenyl and cyclohexyl. Most preferably, however, the aromatic group is unsubstituted and only linked to the phosphorus atoms.
Since the electrons of the double bond are delocaliZed in the aromatic ring structure, all aromatic carbon atoms of the ring are sp2 hybridized. Hence, the phosphorus atoms can be connected via each combination of aromatic carbon atoms of the ring. preferably, however, the phosphorus atoms are connected at adjacent positions, for example the 1 and 2 positions, of the aromatic group.
Preferably, X-and X2 represent a substituted or unsubstituted cyclic group with at least 5 ring atoms, of which one is a phosphorus atom, and preferably with in the range of from 6 to 12 ring atoms. The cyclic group can be a monocyclic group, such as for example a substituted or unsubstituted phosphacyclOhexYlr phosphacyclohePtYl or phosphacyclooctYl group, or a polycyclic group. Preferably X1 and/or X2 represent a phosphabicycloalkY]. group with at least 6 ring atoms, such as for example a 7_phosphabicYclOhePtY1 a 8-phosphabicYcloOctYl or a 9-phosphabicycloflonYl group.
Most advantageously both X1 and X2 represent a substituted or unsubstituted 8_phosphabicYClooctYl group.
One or both of the phosphacyclOalkYlr or more preferably phosphabicYc1oa]kYl rings is suitably substituted with one or more suitable hydrocarbyl groups containing carbon atoms and/or heteroatorns. Suitable substituents include groups containing heteroatoms such as halides, sulphur, phosphorus, oxygen and nitrogen.
Examples of such groups include fluoride, chloride, bromide, iodide and groups of the general formula O, =S, -0-H, -0-X3, -C0-X3, -CO-O-X3, -S-H, -S-X3, -CO-S-X3, -NH2, -NHX3, -NX3X4, -NO2, -ON, -CO-NH2, -CO-NHX3, -CO-NX3X4 and -Cl3, in which X3 and X4, independently, represent alkyl groups having in the range of from 1 to 4 carbon atoms like methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl and tert.-butyl. If a phosphabicyclOoctyl ring is substituted it is preferably substituted with one or more alkyl groups, preferably having in the range of from 1 to 10 carbon atoms, more preferably in the range of 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 phosphabiCYclOOCtY] ring can be mono-or poly-substituted and is preferably di-Preferred bidentate ligands of formula (I) include l,2_bIs(cyclo_octy1phosphino)cyc1opentene 1,2-bis(cyclo-octylphosphiflo)beflzene and l,2_bis(CyclO_0CtYlPh05Ph0) o-xylene.
io Suitable Group VIII metals include the metals rhodium, nickel, palladium and platinum. Of these, palladium and platinum are preferred.
Examples of suitable metal sources are platinum or palladium compounds such as salts of palladium or platinum and nitric acid, sulphuric acid or suiphonic acids, salts of platinum or palladium and carboxylic acids with up to 12 carbon atoms, palladiurn or platinum complexes, e.g. with carbon monoxide or acetylacetonate, or palladium or platinum combined with a solid material such as an ion exchanger. Palladium(II) acetate and platinurn(II) acetylacetoflate are examples of preferred metal sources.
In the catalyst systems of the invention, any acid having a pKa < 3, measured in an aqueous solution at 18 °C or any salt derived thereof can be used.
As used herein, the term pKa is the negative logarithm of the equilibrium constant Ka, i.e. PKa = -logKa, wherein for any acid HA which partially dissociates in solution, the equilibrium HA=H+A is defined by an equilibrium constant Ka, where K = [H][K] a [HA] Suiphonic acids are preferred. Suitable suiphonic acids include suiphonic acids comprising one or more halogen atoms, such as F, Cl, Br and I. Examples of suitable suiphonic acids include therefore methaneSulPhonJc acid, fluoro_methanesUlPhonic acid, trichloromethaneSUlPborc acid, trifluoro methanesuiPhoflic acid, tert_butanesulPhonic acid, p_toluenesulPhonic acid and 2,4,6-trirnethYl benzene-SUlphonic acid.
A source of a phosphonium halide is also required.
This may be selected from phosphonium chloride, bromide or iodide. Preferably, the phosphoniulfl halide is a phosphoflium chloride. The phosphorus atom in the phosphoflium halide may be substituted with alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aromatic, substituted aromatic, heteroaromatic or substituted heteroaromatic groups. Preferably, the phosphorus atom in the phosphorus halide is substituted with alkyl, aromatic groups or mixtures thereof. Alkyl groups are preferably alkyl groups containing at most 6, preferably at most 4 carbon atoms. Particularly preferable alkyl groups are methyl and ethyl groups. A particularly preferred aromatic groups is a phenyl group.
In a particularly preferred embodiment, the phosphorus atom in the phosphonium chloride is substituted with one alkyl group and three aromatic groups. One example of a suitable phosphoriiurn group is MePh3P.
In one preferred embodiment of the present invention the catalyst system comprises a source of platinum metal cations, a diphosphifle ligand selected from 1,2- bis (cyclo_octylpllOsPhiflO) cyclopentene, 1, 2-bis (cyclo- -10 -octylphosphino)benzene and 1, 2_biS(Cyc1O_0ctYlPh0sPhr0) o-xylene, a sulfonic acid and a phosphofliUm chloride.
The ethylerliCallY unsaturated compound, used as starting material, is preferably an ethylenica].lY unsaturated compound having from 2 to 40 carbon atoms per molecule, or a mixture thereof. Preferred are compounds having from 2 to 30 carbon atoms, or mixtures thereof.
The ethyleniCallY unsaturated compound can be a straight carbon chain or can be branched. Suitable ethylenicallY io unsaturated compounds hence include substituted compounds. Preferably such 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,flbUtYl, iso-butyl and tert.-butyl. Examples of suitable ethylenicallY unsaturated compounds include ethene, propene, butene, pentene, 1-hexerle, internal hexenes, 1-heptene, internal heptenes, 1-octene, internal octenes, 1-nonene or internal nonenes, 1-decerle or internal decenes, undecenes, methyl-branched undecenes, dodecefles, methyl-branched dodeceneS, methyl-substituted or unsubstitUted 013, 014 or 015-olefins and mixtures of those.
The ethyleniCallY unsaturated compound can further be an ethylenicallY unsaturated compound comprising functional groups or heteroatoms, such as nitrogen, sulphur or oxide. Examples include unsaturated carboxylic acids, esters of such acids or alkene nitriles. Suitable ethyleflicallY unsaturated comprising functional groups or heteroatortis include for example pentene nitriles and methyl_pefltefloates.
preferably, however, the ethyleniCallY unsaturated compound does not comprise any functional groups or -11 -heteroatomS and is an olefin comprising only carbon atoms.
In the process of the invention, the unsaturated starting material and the formed product may act as reaction diluent. Hence, the use of a separate solvent is not necessary. Conveniently, however, the hydro-formylation reaction may be carried out in the additional presence of a solvent. As such, saturated hydrocarbons, e.g. paraffins and isoalkanes are recommended and io furthermore saturated hydrocarbons1 preferably having from 4 to 10 carbon atoms per molecule; ethers such as 2,5,8-trioxanonafle (diglyme), diethylether and anisole, and ketones, such as methylbutylketofle. Solvents, comprising or substantially consisting of suiphones are also preferred. SulphoneS are in particular preferred, for example dialkylsulphOneS such as dimethylsuiphone and diethylsuiPhofle and cyclic suiphoneS, such as sulfolane (tetrahydrothiOPhene2, 2-dioxide), 2-methylSUlfolafle and 2-methyl-4 -ethylsulfolafle.
In a preferred embodiment mixtures of suiphones and alkanols and/or water are used as a solvent. Suitable alkanols that can be used in such a solvent mixture include rnono-alkaflolS and polyalkanols. preferably mono-alkanols having from 1 to 20, more preferably from 4 to 12 carbon atoms are used. The alkanol can be a straight alkanol or it can be branched. Preferably the alkanol is branched and the main carbon chain of the alkanol is substituted with one or more 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. Examples of suitable alkanols include methyl-pentanol, methyl-hexaflOl, ethyl-hexaflOl, methyl-hePtanol, -12 -ethyl-heptaflOl, dimethyiheXaflol, dimethylhePtaflOl and methyl-octanol. Most preferably, however, the alkanol is the alkanol which is obtained when the ethylenically unsaturated compound is hydroformylated and subsequently hydrogenated. A solvent mixture preferably contains in the range from 0.1 to 10, more preferably in the range from 0.5 to 5 ml of alkanol per ml of suiphone; and, if present, in the range from 0.001 to 1, more preferably in the range from 0.01 to 0.5 ml of water per ml of suiphone.
The quantity in which the catalyst system is used, is not critical and may vary within wide limits. Usually amounts in the range of 10-8 to i01, preferably in the range of l0 to 10-2 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 from 0.5 to 6, and more preferably from 1 to 3 moles of bidentate diphoshine are used; from 0.1 to 15, preferably from 0.5 to 10, and more preferably from 1 to 6 moles of anion *source or a complex anion source; and from 0.05 to 0.5, preferably from 0.1 to 0.4 and more preferably from 0.15 to 0.3 moles of phosphonium chloride are used.
Carbon monoxide partial pressures in the range of 1-65 bar are preferred. In the process according to the present invention, 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.
For hydroformylation 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 -13 -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. When the desired product is an alkanol, an excess of hydrogen is needed to enable the hydrogenation of the originally formed aldehyde or ketone. Therefore, if the desired product is an alkanol, preferably a molar ratio of hydrogen to carbon monoxide within the range of 4:1 to 1.5:1 is used.
The hydroformylatiOn can be suitably carried out at moderate reaction conditions. Hence temperatures in the range of 50 to 200 °C are recommended, preferred temperatures being in the range of 70 to 160 °C. Reaction pressures in the range of 5 to 150 bar are preferred, lower or higher pressures may be selected, but are not considered particularly advantageous. Moreover, higher pressures require special equipment provisions.
In one embodiment of the present invention, after hydroformYlatiOn the resultant alcohol may be subjected to dehydration in order to yield their corresponding olefinic compound isomers. Any suitable dehydration process may be used to convert the alcohol to the olefinic compound. Representative methods are described in US 2006/0173223.
The invention will be illustrated by the following non-limiting examples.
Example 1 -8
Examples 1 to 8 were carried out in a 150 ml magnetically stirred autoclave. The autoclave was charged with the materials indicated in Table 1 and 100 mg of Pt(acac)2. After being flushed with nitrogen, the auto-clave was pressurized with carbon monoxide to a partial pressure of 20 bar and hydrogen to a partial pressure of 40 bar. Subsequently, the reactor was sealed and the -14 -contents were heated to 115 °C and maintained at that temperature for 10 hours. After cooling, a sample was taken from the contents of the reactor and analysed by Gas Liquid Chromatography. The percentage 1-alkanol product, based on the total amount of alkariol product, is indicated in Table 1. The experiments in Table I indicate that the catalyst according to the invention is more selective towards a primary alcohol hydrofOrmylatiofl
product than prior art catalysts.
-15 -Solvent Feed Ligand Promoter Acid End 1-alcohol Total liq. Total gas Olefin Gas (ml) (ml) (mg,pmol) (mg,pmol) (mg,pmol) pressure /(1-alcohol volume volume (mol) consumption "-2-alcohol) (ml) (ml) (mol) Methoxy-1-butene 1(110, MePh3PCI Me3-benzene 31 0.94 50 100 0.10 0.12 benzene (40) (10) 0.3) (15, 0.05) sulfonic acid (71, 0.3) ________ _______ ______ __________ 2 Methoxy-1-butene 2(110, MePh3PCI Me3-benzene 34 0.94 50 100 0.10 0.11 benzene (40) (10) 0.3) (15, 0.05) sulfonic acid (71,0.3) ________ _______ ______ ______ _________ 3 Sulfolane(40) 1-butene 1 (110, MePh3PCI Me3-benzene 48 0.87 50 100 0.10 0.05 Methoxy-(10) 0.3) (15, 0.05) sulfonic acid benzene (40) (71, 0.3) _________ folane (10) Titene 1(110, MePh3PCI Me3-benzene 36 0.96 60 90 0.10 0.09 (10) 0.3) (15, 0.05) sulfonic acid (71, 0.3) ________ ________ ______ ___________ ______ p ____ Methoxy-1-butene 1(110, MePh3PCI tert-butyl 29 0.95 60 90 0.10 0.11 benzene (50) (10) 0.3) (15, 0.05) sulfonic acid (52, 0.3) _________ ________ ______ ___________ 6 Toluene (40) 1-butene 1(110, MePh3PCI Me3-benzene 30 0.95 50 100 0.10 0.12 (10) 0.3) (15, 0.05) sulfonic acid L ((710.3) -16 - 1-pentene MePh3PC Me3-benzefle 7 Methoxy (15 0 05) sulfonic acid benzene (50) 8 Methoxy 1-butene 3(100, MePh3PCI MethyuIfonic benzene(50) (10) 0 3) (15 0 05) acid (15, 005) Ligand 1 = l,2_bIS(CYC0_0CtYPh0sPhmfb)db0n1t1e Ligand 2 = l,2_bis(CyC1o_octYphosPfo)' Ligand 3 = l,2_bis(CYC1O_0CtY1Ph0sPfb)_0-l

Claims (7)

  1. -17 -CL A I M S1. A process for the hydroforrflYlation of an ethylenicallY unsaturated compound by reaction thereof with carbon monoxide and hydrogen in the presence of a catalyst system comprising: (a) a source of Group VIII metal cations; (b) a diphosphine ligand having the general formula (I) X1-R-X2 (I) wherein X-and X2 each independently represent an optionally substituted cyclic group with at least 5 ring atoms, of which one is a phosphorus atom, and R represents a bivalent optionally substituted bridging group, connected to each phosphorus atom by a sp2 hybridized carbon atom; (c) an acid having a PKa < 3, measured in an aqueous solution at 18 00 or a salt derived thereof; and (d) a phosphonium halide.
  2. 2. The process as claimed in claim 1, wherein the Group VIII metal is platinum.
  3. 3. The process as claimed in claim 1 or claim 2, wherein X-and X2 represent a substituted or unsubstituted cyclic group with at least 5 ring atoms, of which one is a phosphorus atom.
  4. 4. The process as claimed in any one of claims 1 to 3, wherein the diphosphine ligand is selected from the group consisting of l,2_bis(cyClO_OCtY1Ph05Pn0) cyclopentefle, l,2_bis(cyclo_OctY1Ph0SPhmfb)bze and 1,2-bis(cyC10 octylphosphJ-fl0) -o--xylene.
  5. 5. The process as claimed in any one of claims 1 to 4, wherein the acid is a sulfonic acid selected from the group consisting of methaneSuiphonic acid, fluoro- -18 -methanesuiphOflic acid, trich1oro_methafleSUlPh0c acid, trif1uoro_methafle5UlPh00 acid, tert_butaneSUlPhOniC acid, p-toluenesulphOflic acid and 2,4,6-trimethyl-benzene-SUlphOflic acid.
  6. 6. The process as claimed in any one of claims 1 to 5, wherein the phosphonium halide is methyltriphèflYlPh0SPh011m chloride.
  7. 7. The process as claimed in any one of claims 1 to 6, wherein the ethylenicallY unsaturated compound is an alkene comprising at least 3 carbon atoms.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995005354A1 (en) * 1993-08-19 1995-02-23 Shell Internationale Research Maatschappij B.V. Hydroformylation process
EP0900776A1 (en) * 1997-08-27 1999-03-10 Shell Internationale Researchmaatschappij B.V. Hydroformylation process
EP0903333A1 (en) * 1997-09-18 1999-03-24 Shell Internationale Researchmaatschappij B.V. Hydroformylation process
EP0943597A2 (en) * 1998-03-16 1999-09-22 Shell Internationale Researchmaatschappij B.V. Hydroformylation of olefin feeds containing dienes
US6156936A (en) * 1998-03-16 2000-12-05 Shell Oil Company Hydroformylation of olefin feeds containing dienes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995005354A1 (en) * 1993-08-19 1995-02-23 Shell Internationale Research Maatschappij B.V. Hydroformylation process
EP0900776A1 (en) * 1997-08-27 1999-03-10 Shell Internationale Researchmaatschappij B.V. Hydroformylation process
EP0903333A1 (en) * 1997-09-18 1999-03-24 Shell Internationale Researchmaatschappij B.V. Hydroformylation process
EP0943597A2 (en) * 1998-03-16 1999-09-22 Shell Internationale Researchmaatschappij B.V. Hydroformylation of olefin feeds containing dienes
US6156936A (en) * 1998-03-16 2000-12-05 Shell Oil Company Hydroformylation of olefin feeds containing dienes

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