WO2003066642A1 - Chelates de phosphore - Google Patents

Chelates de phosphore Download PDF

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Publication number
WO2003066642A1
WO2003066642A1 PCT/EP2003/001245 EP0301245W WO03066642A1 WO 2003066642 A1 WO2003066642 A1 WO 2003066642A1 EP 0301245 W EP0301245 W EP 0301245W WO 03066642 A1 WO03066642 A1 WO 03066642A1
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hydrogen
alkyl
aryl
cycloalkyl
group
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PCT/EP2003/001245
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German (de)
English (en)
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Wolfgang Ahlers
Rocco Paciello
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Basf Aktiengesellschaft
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Priority to AU2003210225A priority Critical patent/AU2003210225A1/en
Priority to DE10390373T priority patent/DE10390373D2/de
Publication of WO2003066642A1 publication Critical patent/WO2003066642A1/fr

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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
    • B01J31/16—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
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B01J31/1855—Triamide derivatives thereof
    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
    • 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
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • 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
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
    • 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
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
    • 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
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • 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
    • 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
    • B01J2531/822—Rhodium

Definitions

  • the present invention relates to new phosphorus chelate compounds, catalysts which comprise at least one complex of a metal from subgroup VIII with at least one such phosphorus chelate compound as ligands, and to a process for hydroformylation using these catalysts.
  • Hydroformylation or oxo synthesis is an important large-scale process and is used to produce aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes can optionally be hydrogenated in the same operation with hydrogen to the corresponding oxo alcohols.
  • the reaction itself is highly exothermic and generally takes place under elevated pressure and at elevated temperatures in the presence of catalysts.
  • Co, Rh, Ir, Ru, Pd or Pt compound fertilizers or complexes are used as catalysts, which can be modified with N- or P-containing ligands to influence the activity and / or selectivity.
  • the aim is to optimize the hydroformylation catalysts in order to achieve the highest possible hydroformylation activity with at the same time the lowest possible tendency to form double bonds which are not ⁇ -permanent.
  • hydroformylation catalysts which, starting from internal linear olefins, lead to ⁇ -and in particular n-aldehydes in good yields.
  • the catalyst must allow both the establishment of an equilibrium between internal and terminal double bond isomers and, as selectively as possible, the hydroformylation of the terminal olefins.
  • plasticizer alcohols with about 6 to 12 carbon atoms which are branched to a small degree (so-called semi-linear alcohols) and for corresponding mixtures thereof.
  • semi-linear alcohols include, in particular, 2-propylheptanol and alcohol mixtures containing it.
  • butenes or C-hydrocarbon mixtures containing butenes and butanes can be subjected to hydroformylation and subsequent aldol condensation.
  • hydroformylation can easily lead not only to the formation of n-valeraldehyde, but also to undesired product aldehydes, which means that the entire process is economically disadvantageous.
  • hydroformylation catalyst used must selectively enable the hydroformylation of terminal olefins (1-butene) and / or be capable of shifting internal double bonds to a terminal position. There is also generally great technical interest in the provision of such hydroformylation catalysts.
  • phosphorus-containing ligands are e.g. B. phosphines, phosphinites, phosphonites, phosphites, phosphoramidites, phospholes and phosphabenzenes.
  • the currently most widely used ligands are triarylphosphines, such as. B. triphenylphosphine and sulfonated triphenylphosphine, since these have sufficient stability under the reaction conditions.
  • a disadvantage of these ligands is that generally only very large excesses of ligands yield satisfactory yields, in particular of linear aldehydes.
  • No. 3,816,452 describes the production of differently substituted pyrrolyl monophosphines and their use as flame retardants.
  • AM Trquelak et al. describe in J. Organomet. Chem. 552, pp. 159-164 (1998) unbridged trispyrrolylphosphine-rhodium complexes as catalysts for the hydrogenation of olefins and arenes.
  • AM Trquel et al. describe in J. Chem. Soc, Dalton Trans. 1997, pp. 1831-1837 rhodium complexes with unbridged N-pyrrolylphosphines as ligands and the use of these complexes as hydroformylation catalysts.
  • WO-A-00/56451 on the phosphorus atom relates, inter alia, to cyclic oxaphosphorines substituted with pyrrole derivatives and the use of these as ligands in catalysts for hydroformylation.
  • WO-A-99/52632 relates to a process for hydrocyanation using phosphorus-containing chelate ligands with 1, 1 'bisphenylene or 1, 1' bisnaphthylene backbone, in which the phosphorus atom can be substituted with unsubstituted pyrrole, indole or imidazole groups can, which are bonded to the phosphorus atom via a ring nitrogen atom.
  • No. 5,710,344 describes phosphorus atom-containing ligands with 1, 1'-biphenylene or 1, 1'-binaphthylene backbone, which can be substituted with unsubstituted pyrrole, imidazole or indole groups which are bonded to the phosphorus atom via a ring nitrogen atom.
  • These ligands are suitable for hydroformylation catalysts based on metals from subgroup VIII.
  • DE-A-100 23 471 describes a process for hydroformylation using a hydroformylation catalyst which comprises at least one phosphine ligand which has two triarylphosphine groups, each having an aryl radical of the two triarylphosphine groups via a single bond to a non-aromatic 5- to 8-group -linked carbocyclic or heterocyclic bridging group is bound.
  • the phosphorus atoms may also have hetaryl groups as further substituents.
  • the unpublished German patent application P 100 46 026.7 describes a hydroformylation process in which the catalyst used is a complex based on a phosphorus, arsenic or antimony-containing compound as ligand, this compound in each case two a P-, As- or Sb atom and at least two further heteroatoms having groups bound to a xanthene-like molecular structure.
  • the unpublished international application PCT / EP02 / 09455 describes a hydroformylation process using a catalyst complex which has as ligands at least one pyrrole-phosphorus compound in which a substituted and / or pyrrole group integrated into a fused ring system is covalently linked to the phosphorus atom via its pyrrolic nitrogen atom ,
  • WO 02/83695 describes, inter alia, a process for the hydroformylation of olefins using a hydroformylation catalyst which comprises a complex of a metal from subgroup VIII with at least one pnicogen chelate compound as ligand.
  • ligands have two groups containing pnicogen atoms which are connected to one another via a xanthene-like or triptycene-like molecular structure and where at least one pyrrole group is covalently bound to each pnicogen atom via the nitrogen atom thereof.
  • EP-A-0 754 715 describes a catalyst composition comprising a metal from subgroup VIII and an alkylene-bridged di (proline-phenyl-phosphine) and their use for the preparation of polyketones.
  • WO-A-96/01831 describes chiral diphosphines of biheterocyclic compounds of aromatic, 5-atom heterocycles and their use in chiral catalysts for stereoselective reactions.
  • the heterocyclic nuclei are linked by a single bond between two ring carbon atoms.
  • WO-A-99/52915 describes chiral phosphorus atom-containing ligands based on bicyclic compounds of carbocyclic and heterocyclic 5- to 6-atom compounds.
  • the aromatic rings forming the bicyclus are linked to one another via a single bond between two ring carbon atoms.
  • the present invention is based on the object of providing new phosphorus chelate compounds which are suitable as ligands for transition metal complexes of metals of subgroup VIII, in order in this way to provide new catalysts based on these metal complexes.
  • These ligands should preferably be easy to prepare and / or their complexes should be as stable as possible under the reaction conditions of the reactions to be catalyzed and have good catalytic activity.
  • the highest possible proportion of ⁇ -aldehydes or alcohols ( ⁇ -selectivity) should preferably be achieved.
  • catalysts based on these ligands are said to be suitable for the hydroformylation of internal linear olefins with high regioselectivity in favor of terminal product aldehydes.
  • phosphorus chelate compounds of the general formula I are said to be suitable for the hydroformylation of internal linear olefins with high regioselectivity in favor of terminal product aldehydes.
  • B 1 , B 2 , B 3 , B 4 , B 5 and B 6 independently of one another represent a heteroaromatic group which has at least one aromatic ring with a ring nitrogen atom bonded to the phosphorus atom, and
  • Y represents a chemical bond or a divalent bridging group with 1 to 20 bridge atoms in the chain between the flanking bonds.
  • alkyl includes straight-chain and branched alkyl groups. These are preferably straight-chain or branched C 1 -C 2 -alkyl, preferably C 1 -C 2 -alkyl and particularly preferably C 1 -C 4 -alkyl and very particularly preferably C] _- C -alkyl groups.
  • alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3 -Methylbutyl, 1,2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2 -Dimethylbutyl, 1,3-dimethylbutyl, 2, 3-dimethylbutyl, 1, 1-dimethylbutyl, 2, 2-dimethylbutyl, 3, 3-dimethylbutyl, 1, 1, 2-trimethylpropyl, 1,2,2 -Trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, l-e
  • alkyl also includes substituted alkyl groups.
  • Substituted alkyl radicals preferably have 1, 2, 3, 4 or 5, particularly preferably 1, 2 or 3 and in particular 1 substituent, selected from cycloalkyl, aryl, hetaryl, halogen, NE 1 E 2 , (NE 1 E 2 E 3 ) + , Carboxyl, carboxylate, -S0 3 H and sulfonate.
  • alkylene stands for straight-chain and branched alkanediyl groups, preferably with 1 to 4 carbon atoms.
  • cycloalkyl includes unsubstituted and substituted cycloalkyl groups.
  • the cycloalkyl group is preferably a Cs-C 7 -cycloalkyl group, such as cyclopentyl, cyclohexyl or cycloheptyl.
  • cycloalkyl group preferably has 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from alkyl, alkoxy or halogen.
  • heterocycloalkyl for the purposes of the present invention encompasses saturated, cycloaliphatic groups with generally 4 to 7, preferably 5 or 6 ring atoms, in which 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from the elements oxygen, nitrogen and sulfur, and the can optionally be substituted, wherein in the case of a
  • these heterocycloaliphatic groups 1, 2 or 3, preferably 1 or 2, particularly preferably 1 substituent, selected from alkyl, aryl, C00R a , C00 "M + and NE i E 2 , preferably alkyl, can carry.
  • heterocycloalipha - Tical groups are pyrrolidinyl, piperidinyl, 2, 2, 6, 6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, called tetrahydrofuranyl.
  • Aryl comprises unsubstituted and substituted aryl groups and is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular phenyl or naphthyl.
  • Substituted aryl radicals preferably have 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, -S0 3 H, sulfonate, NE 1 E 2 , alkylene NE i E 2 , nitro, cyano or halogen.
  • Hetaryl includes unsubstituted and substituted heteroaromatic groups and is preferably pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl, and the following subgroup of the "pyrrole group".
  • Substituted hetaryl radicals preferably have 1, 2 or 3 substituents selected from alkyl, alkoxy, carboxyl, carboxylate, -S0 3 H, sulfonate, NE i E 2 , alkylene-NE i E 2 , trifluoromethyl or halogen.
  • pyrrole group stands for a series of unsubstituted or substituted, heterocycloaromatic groups which are structurally derived from the pyrrole backbone and contain a pyrrolic nitrogen atom in the heterocycle which is covalent with other atoms, for example a phosphorus atom , can be linked.
  • pyrrole group thus includes the unsubstituted or substituted groups pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl, 1,2, 3-triazolyl, 1, 3,4-triazolyl and carbazolyl, which in the case of a Substitution in general 1, 2 or 3, preferably 1 or 2, particularly preferably 1, selected from the groups alkyl, alkoxy, acyl, carboxyl, carboxylate, -S0 3 H, sulfonate, NE i E 2 , alkylene NE i E 2 , trifluoromethyl or halogen.
  • alkyl, cycloalkyl and aryl radicals apply accordingly to alkoxy, cycloalkyloxy and aryloxy radicals.
  • acyl stands for alkanoyl or aroyl groups with generally 2 to 11, preferably 2 to 8, carbon atoms, for example for the acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, 2-ethyl-hexanoyl, 2-propylheptanoyl, benzoyl or naphthoyl group.
  • the NE i E 2 and NE 4 E 5 radicals are preferably N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-diisopropylamino, N, N-di-n-butylamino, N, N-di-tert. -butylamino, N, N-dicyclohexylamino or N, N-diphenylamino.
  • Halogen represents fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • Carboxylate and sulfonate in the context of this invention preferably represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function.
  • these include e.g. B. the esters with -CC alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.
  • M + stands for a cation equivalent, ie for a monovalent cation or the portion of a multivalent cation corresponding to a positive single charge.
  • M + stands for an alkali metal cation, such as. B. Li + , Na + or K + or for an alkaline earth metal cation, for NH 4 + or a quaternary ammonium compound, as can be obtained by protonation or quaternization of amines is.
  • Alkali metal cations are preferred, in particular sodium or potassium ions.
  • X- stands for an anion equivalent, i.e. H. for a monovalent anion or the proportion of a multivalent anion corresponding to a negative single charge.
  • X- is preferably a carbonate, carboxylate or halide, particularly preferably Cl- and Br ⁇ .
  • the values for x stand for an integer from 1 to 240, preferably for an integer from 3 to 120.
  • Condensed ring systems can be fused aromatic, hydroaromatic and cyclic compounds. Condensed ring systems consist of two, three or more than three rings. Depending on the type of linkage, a distinction is made between condensed ring systems between ortho annulation, i.e. H. each ring has an edge or two atoms in common with each neighboring ring, and a peri-annulation in which one carbon atom belongs to more than two rings. Preferred among the condensed ring systems are ortho-condensed ring systems.
  • the heteroaromatic groups B 1 , B 2 , B 3 , B 4 , B 5 and B 6 are preferably pyrrole groups bonded to the phosphorus atom via a ring nitrogen atom.
  • the meaning of the pyrrole groups corresponds to the definition given at the beginning.
  • B 1 , B 2 , B 3 and B 4 are preferably selected independently of one another from groups of the general formula II
  • R 1 , R 2 , R 3 and R 4 independently of one another for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WC00R a , WC00 _ M + , W (S0 3 ) R a , W (S0 3 ) "M + , WPO ⁇ E 2 , W (P0 3 ) 2 "(M + ) 2 , WNE i E 2 , W (NE X E 2 E 3 ) + X-, W0R a , WSR a , (CHR b CH 2 0) x R a , (CH 2 NE 1 ) x R a , (CH 2 CH 2 NE 1 ) x R a , halogen, trifluoromethyl, nitro, acyl or cyano,
  • W represents a single bond or a divalent bridging group with 1 to 20 bridge atoms
  • R a t E 1 , E 2 , E 3 are each the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
  • R represents hydrogen, methyl or ethyl
  • x represents an integer from 1 to 240
  • the compounds of the formula II are bonded to a phosphorus atom of the phosphorus chelate compounds via the pyrroleic nitrogen atom.
  • one or two of the radicals R 1 , R 2 , R 3 and R 4 are preferably one of the abovementioned substituents other than hydrogen and the rest are hydrogen.
  • Compounds of the formula II are preferred which have a substituent other than hydrogen in the 2-position, 2,5-position or 3,4-position.
  • the substituents R 1 to R 4 which are different from hydrogen are preferably selected independently of one another from C 1 -C 4, preferably C 1 -C 4 alkyl, especially methyl, ethyl, isopropyl and tert-butyl, alkoxycarbonyl, such as methoxycarbonyl, ethoxycarbonyl, isopro - pyloxycarbonyl and tert-butyloxycarbonyl and trifluoromethyl.
  • the radicals R 1 and R 2 and / or R 3 and R 4 together with the carbon atoms of the pyrrole ring to which they are bonded preferably represent a condensed ring system with 1, 2 or 3 further rings. If R 1 and R 2 and / or R 3 and R 4 stand for a fused-on, ie fused-on ring system, it is preferably benzene or naphthalene rings.
  • Fused benzene rings are preferably unsubstituted and have 1, 2 or 3, in particular 1 or 2, substituents which are selected from alkyl, alkoxy, halogen, SOH, sulfonate, NE ⁇ 2 , alkylene-NE ⁇ 2 , trifluoromethyl, nitro, COOR a , AI- koxycarbonyl, acyl and cyano.
  • Fused naphthalene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or 2, of the substituents previously mentioned for the fused benzene rings in the non-fused ring and / or in the fused ring.
  • R 3 and R 4 are preferably hydrogen or R 4 is hydrogen and R 3 is a substituent which is selected from Ci to Cg alkyl, preferably Ci to C-alkyl, especially methyl, ethyl, isopropyl or tert-butyl.
  • At least one of the radicals R 1 , R 2 , R 3 and / or R 4 preferably represents a polar (hydrophilic) group, in which case, as a rule, during the formation of the complex result in water-soluble complexes with a Group VIII metal.
  • the polar groups are preferably selected from C00R a , COO-M + , S0 3 R a , S0 3 "M + , NE i E 2 , alkylene-NE i E 2 , NE 1 E 2 E 3+ X", alkylene NE 1 E 2 E 3+ X ", OR a , SR a , (CHR b CH 2 0) x R a or (CH 2 CH 2 N (E 1 )) x R a , where R a , E 1 , E 2 , E 3 , R b , M + , X- and x have the meanings given above.
  • B 1 , B 2 , B 3 and B 4 are indolyl radicals.
  • the pyrrole ring in the 3-position may have a substituent other than hydrogen, preferably a C 1 -C 4 -alkyl radical.
  • the bridging heteroaromatic groups B 5 and B 6 are preferably selected independently of one another from groups of the general formula III
  • R 5 , R 6 , R 7 and R 8 independently of one another for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WC00R a , WC00 "M + , W (S0 3 ) R a , W (S0 3 ) ⁇ M + , WP0 3 E 1 E 2 , W (P0 3 ) 2 "(M + ) 2 , WNE ⁇ 2 , W (NE 1 E 2 E 3 ) + X", WOR a , WSR a , (CHR b CH 2 0 ) x R a , (CH 2 NE 1 ) x R a , (CH 2 CH 2 NE 1 ) x R a , halogen, trifluoromethyl, nitro, acyl or cyano,
  • W represents a single bond or a divalent bridging group with 1 to 20 bridge atoms
  • R a ( E 1 , E 2 , E 3 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
  • R b represents hydrogen, methyl or ethyl
  • x represents an integer from 1 to 240
  • radicals R 5 , R 6 , R 7 or R 8 stands for a chemical bond to a divalent bridging group Y or together with a group Y stands for a chemical bond which bonds the radicals B 5 and B 6 to one another combines.
  • the compounds of the formula III are bonded to a phosphorus atom of the phosphorochelate compounds via the pyrrolic nitrogen atom.
  • one of the radicals R 5 to R 8 stands for a chemical compound, that is to say the point of attachment of the compound of the formula III to a bridging group Y, or in the case that Y itself is a chemical compound, to a further compound of the formula III , If two compounds of the formula III are directly linked to one another via a chemical bond, the compounds of the formula III can be the same or different, and the compounds of the formula III can be the same or different radicals R 5 to R 8 (ie the same or different positions of the pyrrole ring).
  • one of the radicals in the 2-position of the pyrrole ring ie R 5 or R 8 ) preferably represents a chemical bond, that is to say the point of attachment to the bridging group Y.
  • one, two or three of the radicals R 5 , R 6 , R 7 and R 8 which do not represent a chemical bond are preferably one of the abovementioned of water Substance of various substituents.
  • Preferred compounds of the formula III are those in which the 2-position represents a chemical bond and the 5-position or the 3, 4, 5 position represents a substituent other than hydrogen.
  • the substituents R 5 to R 8 which are different from hydrogen are preferably selected independently of one another from C ⁇ -C 8 -, preferably C; L -C 4 alkyl, especially methyl, ethyl, isopropyl and tert-butyl, alkoxycarbonyl, such as methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl and tert-butyloxycarbonyl and trifluoromethyl.
  • one of the residues in the 2-position of the pyrrole ring (R 5 or R 8 ) preferably represents a chemical bond and one of the residues in the 5-position together with a residue in the 4-position (R 5 and R 6 and / or R 7 and R 8 ) together with the carbon atoms of the pyrrole ring to which they are attached, for a condensed ring system with 1, 2 or 3 further rings.
  • suitable and preferred condensed ring systems reference is made to the previous statements relating to corresponding radicals R 1 and R 2 and / or R 3 and R 4 in compounds of the formula II.
  • the compound of the formula III then preferably represents an indolyl group.
  • At least one of the radicals R 5 , R 6 , R 7 and / or R 8 preferably represents a polar (hydrophilic) group, as previously for the radicals R 1 to R 4 defines what is referred to here.
  • the bridging group Y stands for a chemical bond, ie in the phosphorus chelate compounds of the general formula I the heteroaromatic groups B 5 and B 6 are directly linked to one another.
  • the bridging group Y is selected from groups of the formulas IV.1 to IV.15
  • R 9 and R 10 independently represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, where R 9 and Rio together with the carbon atom to which they are attached are also a 3- to 8-membered carbocycle or heterocycle which may optionally also be fused once, twice or three times with cycloalkyl, heterocycloalkyl, aryl and / or hetaryl,
  • M represents a zero-valent transition metal, in particular Fe
  • n and n both represent 0 or both represent 1,
  • Z stands for 0, S, NR 19 or SiR 19 R 20 , where
  • R 19 and R 20 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
  • Ci to C 3 alkylene bridge which can have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent,
  • Z represents a C - to C 3 -alkylene bridge which is interrupted by O, S or NR 19 or SiR 19 R 20 ,
  • a 1 and A 2 independently of one another represent 0, S, SiR 19 R 20 , NR 19 or CR 21 R 22 , where
  • R 21 and R 22 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group R 21 together with another group R 2i or the group R 22 together with another group R 22 form an intramolecular bridge group D,
  • R 23 and R 24 independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano or are connected to one another to form a C 1 -C 6 -alkyl bridge,
  • R 25 , R 26 , R 27 and R 28 independently of one another for hydrogen
  • c 0 or 1.
  • Y is preferably a group of the formula IV.1, where R 9 and R 10 are hydrogen and m and n are both 0.
  • Y further preferably represents a group of the formula IV.1, in which R 9 is -C 4 -alkyl, in particular methyl or ethyl, C 1 -C 4 -alkoxy, in particular methoxy, or phenyl and in which R 10 is Hydrogen stands.
  • R 9 is -C 4 -alkyl, in particular methyl or ethyl, C 1 -C 4 -alkoxy, in particular methoxy, or phenyl and in which R 10 is Hydrogen stands.
  • m and n are preferably both 0.
  • Y is furthermore preferably a compound of the formula IV.1, in which R 9 and R 10 are both selected independently of one another from C 1 -C 4 -alkyl radicals. In particular, R 9 and R 10 are both methyl.
  • Y preferably represents a group of the formula IV.1, where R 9 and R 10 together with the carbon atom to which they are attached represent a 3 to 8-membered carbocycle or heterocycle which optionally additionally, once, twice or three times with cycloalkyl, heterocycloalkyl, aryl and / or hetaryl.
  • m and n are preferably either both 0 or both 1.
  • R 9 and R 10 together represent cyclopentyl.
  • Y preferably represents a group of the formula IV.3, in which R 11 and R 12 are selected independently of one another from hydrogen and C 1 -C 4 -alkyl radicals.
  • Y is furthermore preferably a group of the formula IV.5, where R 11 and R i2 are hydrogen.
  • R 11 and R 12 are preferably both hydrogen.
  • Y preferably represents a group of the formula IV.8, in which R 11 , R i2 , R 13 and R 14 stand for hydrogen.
  • Y is furthermore preferably a group of the formula IV.9, where M is Fe and R U , R 12 , R i3 , R 14 , R U ', R 2 ', R 1 'and Rl' are hydrogen.
  • the two cyclopentadienyl rings of the metalocene IV.9 can exist in an ecliptic and staggered conformation.
  • the planes of the cyclopentadienyl rings can be parallel or inclined, for example depending on the central metal.
  • Y is furthermore preferably a group of the formula IV.11, where R n , R 12 , R 13 and R 14 are hydrogen.
  • Y is furthermore preferably a group of the formula IV.15.
  • bridging group Y of the formula IV.15 may groups A l and A 2 in general independently of one another O, S, SiR 9 R 20, NR 19 or CR 21 R 22, the substituents R 19 and R 20 in the general - mean independently of one another the meaning hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, whereas the groups R 21 and R 22 independently represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group R 21 together with another group R 21 or the group R 22 together with another group R 22 can form an intramolecular bridge group D.
  • D is a double-bonded bridge group that is generally selected from the groups
  • R 23 and R 24 independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano or are connected to one another to form a C 3 -C -alkylene group and R 25 , R 26 , R 27 and R 28 independently of one another for hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylate, cyano, alkoxy, S0 3 H, sulfonate, NE 4 E 5 , alkylene-NE 4 E 5 E 6+ X. - Aryl or nitro can stand.
  • the groups R 23 and R 24 are preferably hydrogen, -CC-alkyl or carboxylate and the groups R 25 , R 26 , R 27 and R 28 are hydrogen, -CC-alkyl, halogen, in particular fluorine, chlorine or bromine , Trifluoromethyl, -CC alkoxy, carboxylate, sulfonate or C 6 -c 8 aryl.
  • R 23 , R 24 , R 25 , R 26 , R 27 and R 28 are particularly preferably hydrogen.
  • Particularly preferred bridge groups D are the ethylene group
  • R 21 forms an intramolecular bridge group D with a further group R 2X or R 22 with a further group R 22 , ie the index c in this case is 1, it necessarily results that both A 1 and A 2 are CR 21 R 22 group and the bridging group Y in this case has a triptycene-like carbon skeleton.
  • those bridging groups Y are preferred in which A l is different from A 2 , where A 1 is preferably a CR 21 R 22 group and A 2 is preferably a 0 or S group, particularly preferably an oxa group 0.
  • Particularly preferred bridge groups Y of the formula IV.15 are therefore those which are composed of a triptycene-like or xanthene-like (A 1 : CR 21 R 22 , A 2 : 0) framework.
  • R 11 , R i2 , R 13 and R i4 are preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl.
  • R 11 and R 13 are preferably hydrogen and R i2 and R 14 are -CC 4 alkyl, such as. B. methyl, ethyl, n- Propyl, n-butyl or tert-butyl.
  • the substituents R 11 , I 2 , R 13 and R 14 are preferably all hydrogen.
  • R u and / or R 13 stand for a fused-on, ie fused, ring system, it is preferably benzene or naphthalene rings.
  • Fused benzene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or 2, substituents which are selected from alkyl, alkoxy, halogen, SO 3 H, sulfonate, NE X E 2 , alkylene NE i E 2 , trifluoro methyl, nitro, C00R a , alkoxycarbonyl, acyl and cyano.
  • Fused naphthalene rings are preferably unsubstituted or have a total of 1, 2 or 3, in particular 1 or 2, of the substituents mentioned above for the fused benzene rings in the non-fused ring and / or in the fused ring.
  • the phosphor chelate compounds of the general formula I according to the invention can be prepared, for example, according to the following scheme: 1 eq Hß, 1 eq HB 2
  • B 1 , B 2 , B 5 , B 6 , R 1 , R 2 , R 3 and R 4 have the aforementioned meaning independently of one another.
  • phosphorus chelate compounds with a bis-indolyl backbone can be produced starting from toluidines according to the following scheme:
  • the invention furthermore relates to a catalyst comprising at least one complex of a metal from subgroup VIII with at least one compound of the formula I according to the invention, as previously defined.
  • the catalysts according to the invention and used according to the invention can have one or more of the compounds of the general formula I as ligands.
  • the metal of subgroup VIII is preferably cobalt, ruthenium, rhodium, palladium, platinum, osmium or iridium and in particular cobalt, rhodium, ruthenium and iridium.
  • catalytically active species of the general formula H x M y (CO) z L q are formed from the catalysts or catalyst precursors used in each case, where M is a metal of subgroup VIII, L is a phosphorus-containing compound of the formula I. and q, x, y, z are integers, depending on the valency and type of the metal and the binding nature of the ligand L.
  • z and q are independently at least 1, such as. B. 1, 2 or 3.
  • the sum of z and q is preferably from 2 to 5.
  • the complexes can, if desired, additionally have at least one of the other ligands described above.
  • the hydroformylation catalysts are prepared in situ in the reactor used for the hydroformylation reaction. If desired, however, the catalysts of the invention can also be prepared separately and isolated by customary processes.
  • z. B at least one compound of general formula I, a compound or a complex of a metal of subgroup VIII, optionally at least one further additional ligand and optionally an activating agent in an inert solvent under the hydroformylation conditions.
  • Suitable rhodium compounds or complexes are e.g. B. rhodium (II) and rhodium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II ) or rhodium (III) carboxylate, rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid, trisammonium hexachlororhodate (III) etc.
  • rhodium (II) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate,
  • rhodium complexes such as rhodium biscarbonylacetylacetonate, acetyl acetonatobisethylene rhodium (I) etc.
  • Rhodium biscarbonylacetylacetonate or rhodium acetate are preferably used.
  • Ruthenium salts or compounds are also suitable. Suitable ruthenium salts are, for example, ruthenium (III) chloride, ruthenium (IV) -, ruthenium (VI) - or ruthenium (VIII) oxide, alkali metal salts of ruthenium oxygen acids such as K 2 Ru0 or KRu0 4 or complex compounds, such as, for. B. RuHCl (CO) (PPh 3 ).
  • Metal carbonyls of ruthenium such as trisruthenium dodecacarbonyl or hexaruthenium octadecacarbonyl, or mixed forms in which CO is partly replaced by ligands of the formula PR 3 , such as Ru (CO) 3 (PPh 3 ) 2 , are used in the process according to the invention.
  • Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) carbonate, cobalt (II) nitrate, their amine or hydrate complexes, cobalt carboxylates, such as cobalt acetate, cobalt ethyl hexanoate, cobalt naphthanoate, and the cobalt caprolactamate -Complex.
  • the carbonyl complexes of cobalt such as dicobalt octacarbonyl, tetracobalt dodecacarbonyl and hexacobalt hexadecacarbonyl can be used.
  • Suitable activating agents are e.g. B. Brönsted acids, Lewis acids, such as. B. BF, AlCl 3 , ZnCl 2 , and Lewis bases.
  • the solvents used are preferably the aldehydes which are formed in the hydroformylation of the respective olefins, and also their higher-boiling secondary reaction products, for. B. the products of aldol condensation.
  • suitable solvents are aromatics, such as toluene and xylenes, hydrocarbons or mixtures of hydrocarbons, also for diluting the above-mentioned aldehydes and the secondary products of the aldehydes.
  • Other solvents are esters of aliphatic carboxylic acids with alkanols, for example ethyl acetate or Texanol TM, ethers such as tert. -Butylmethyl ether and tetrahydrofuran.
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones, such as acetone and methyl ethyl ketone, etc.
  • ketones such as acetone and methyl ethyl ketone, etc.
  • liquid salts for example N, N'-dialkylimidazolium salts such as the N-butyl-N'-methylimidazolium salts, tetraalkylammonium salts such as the tetra-n-butylammonium salts, N-alkylpyridinium salts such as the n-butylpyridinium salts, tetra - Phosphonium salts such as the trishexyl (tetradecyl) phosphonium salts, e.g. B. the tetrafluoroborates, acetates, tetrachloroaluminates, hexafluorophosphates, chlorides and tosylates.
  • N, N'-dialkylimidazolium salts such as the N-butyl-N'-methylimidazolium salts
  • tetraalkylammonium salts such as the tetra-n-butylam
  • aqueous solvent systems which, in addition to water, contain a water-miscible solvent, for example an alcohol such as metha- nol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, a ketone such as acetone and methyl ethyl ketone or another solvent.
  • the reactions then take the form of two-phase catalysis, the catalyst being in the aqueous phase and feedstocks and products forming the organic phase.
  • the implementation in the "Ionic Liquids" can also be designed as a two-phase catalysis.
  • the molar ratio of phosphorus-containing ligand to metal of subgroup VIII is generally in a range from about 1: 1 to 1000: 1.
  • all compounds which contain one or more ethylenically unsaturated double bonds are suitable as substrates for the hydroformylation process according to the invention.
  • These include e.g. B. olefins, such as ⁇ -olefins, internal straight-chain and internal branched olefins.
  • Suitable ⁇ -olefins are e.g. B. ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 1-decene, 1-undecene, 1-dodecene etc.
  • Suitable branched, internal olefins are preferably C -C 2 Q olefins, such as 2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal heptene mixtures, branched, internal Octene mixtures, branched, internal non-mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures etc.
  • Suitable olefins to be hydroformylated are furthermore C 5 -C 8 -cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as, for. B. whose -CC 2 o-alkyl derivatives with 1 to 5 alkyl substituents.
  • Suitable olefins to be hydroformylated are also vinyl aromatics, such as styrene, ⁇ -methylstyrene, 4-isobutylstyrene etc.
  • Suitable olefins to be hydroformylated are furthermore ⁇ , ⁇ -ethylenically unsaturated mono- and / or dicarboxylic acids, their esters, half-esters and amides, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, methyl 3-pentenoate, methyl 4-pentenoate, methyl oleic acid, methyl acrylate, methyl methacrylate, unsaturated nitriles, such as 3-pentenenitrile, 4-pentenenitrile, and acrylate Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether etc., -C-C 2 o-alkenols, alkene diols and alkadienols, such as 2, 7-0ctadienol-l.
  • Suitable substrates are also di- or polyenes with isolated or conjugated double bonds. These include e.g. B. 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-hepta- diene, 1, 7-octadiene, vinylcyclohexene, dicyclopentadiene, 1,5,9-cyclooctatriene and butadiene homo- and copolymers.
  • the unsaturated compound used for the hydroformylation is preferably selected from internal linear olefins and olefin mixtures which contain at least one internal linear olefin.
  • Suitable linear (straight-chain) internal olefins are preferably C 4 -C 2 o-olefins, such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-0ctene, 3-octene , 4-0cten etc. and mixtures thereof.
  • an industrially accessible olefin mixture is used in the hydroformylation process according to the invention, which contains in particular at least one internal linear olefin.
  • these include e.g. B. the Ziegler olefins obtained by targeted ethene oligomerization in the presence of alkyl aluminum catalysts. These are essentially unbranched olefins with a terminal double bond and an even number of carbon atoms. These also include the olefins obtained by ethene oligomerization in the presence of various catalyst systems, e.g. B.
  • thermal cracking steam cracking
  • catalytic dehydration catalytic dehydration
  • chemical dehydration by chlorination and dehydrochlorination.
  • Thermal cracking leads predominantly to ⁇ -olefins, while the other variants result in olefin mixtures which generally also have relatively large proportions of olefins with an internal double bond.
  • Suitable olefin mixtures are furthermore the olefins obtained in metathesis or telomerization reactions. These include e.g. B. the olefins from the Phillips-triolefin process, a modified SHOP process from ethylene oligomerization, double bond isomerization and subsequent metathesis (ethanolysis).
  • Suitable industrial olefin mixtures which can be used in the hydroformylation process according to the invention are furthermore selected from dibutenes, tributenes, tetrabutenes, dipropenes, tripropenes, tetrapropenes, mixtures of butene isomers, in particular raffinate II, dihexenes, dimers and oligomers from the Dimersol® process from IFP, Octolprocess® of Hüls, polygas process etc.
  • a process is preferred which is characterized in that the hydroformylation catalyst is prepared in situ, using at least one compound of the formula I, a compound or a complex of a metal from subgroup VIII and optionally an activating agent in an inert solvent under the hydroformylation conditions Brings reaction.
  • the hydroformylation reaction can be carried out continuously, semi-continuously or batchwise.
  • Suitable reactors for the continuous reaction are known to the person skilled in the art and are described, for. B. in Ulimann's Encyclopedia of Industrial Chemistry, Vol. 1, 3rd Edition, 1951, p. 743 ff.
  • Suitable pressure-resistant reactors are also known to the person skilled in the art and are described, for. B. in Ulimann's Encyclopedia of Industrial Chemistry, Vol. 1, 3rd Edition, 1951, pp. 769 ff.
  • an autoclave is used for the method according to the invention, which can, if desired, be provided with a stirring device and an inner lining.
  • composition of the synthesis gas of carbon monoxide and hydrogen used in the process according to the invention can vary within wide ranges.
  • the molar ratio of carbon monoxide and hydrogen is usually about 5:95 to 70:30, preferably about 40:60 to 60:40.
  • a molar ratio of carbon monoxide to hydrogen in the range of approximately 1: 1 is particularly preferably used.
  • the temperature in the hydroformylation reaction is generally in the range from about 20 to 180 ° C., preferably about 50 to 150 ° C.
  • the reaction is usually carried out at the partial pressure of the reaction gas at the selected reaction temperature.
  • the pressure is in a range from about 1 to 700 bar, preferably 1 to 600 bar, in particular 1 to 300 bar.
  • the reaction pressure can be varied depending on the activity of the hydroformylation catalyst according to the invention used.
  • the catalysts based on phosphorus-containing compounds according to the invention permit setting in a range of low pressures, such as in the range of 1 to 100 bar.
  • hydroformylation catalysts used according to the invention and the hydroformylation catalysts according to the invention can be separated from the discharge of the hydroformylation reaction by customary processes known to the person skilled in the art and can generally be used again for the hydroformylation.
  • the catalysts according to the invention described above which comprise chiral compounds of the general formula I, are suitable for enantioselective hydroformylation.
  • the catalysts described above can also be suitably, e.g. B. by connection via functional groups suitable as anchor groups, adsorption, grafting, etc. to a suitable carrier, for. B. made of glass, silica gel, synthetic resins etc., immobilized. They are then also suitable for use as solid-phase catalysts.
  • the hydroformylation activity of catalysts based on ligands of the formula I is surprisingly generally higher than the isomerization activity with regard to the formation of central double bonds.
  • the catalysts according to the invention and those used according to the invention advantageously show a high selectivity in favor of the ⁇ -aldehydes or alcohols in the hydroformylation of ⁇ -olefins.
  • good yields of ⁇ -aldehydes or alcohols and in particular also of n-aldehydes or alcohols are also generally obtained in the hydroformylation of internal linear olefins (isomerizing hydroformylation).
  • these catalysts generally have a high stability under the hydroformylation conditions, so that they generally achieve a longer catalyst service life than with catalysts known from the prior art based on conventional chelate ligands.
  • the catalysts according to the invention and those used according to the invention advantageously also have a high activity, so that the corresponding aldehydes or alcohols are generally obtained in good yields.
  • they also show a very low selectivity for the hydrogenation product of the olefin used.
  • Another object of the invention is a process for the preparation of 2-propylheptanol, in which a) butene or a butene-containing C -hydrocarbon mixture is hydroformylated in the presence of a catalyst, as previously defined, with carbon monoxide and hydrogen to give a hydroformylation product containing n-valeraldehyde,
  • step c) subjecting the hydroformylation product obtained in step a) or the fraction enriched in n-valeraldehyde obtained in step b) to an aldol condensation
  • Suitable starting materials for the hydroformylation are both essentially pure 1-butene and mixtures of 1-butene with 2-butene and technically available C 4 hydrocarbon streams which contain 1-butene and / or 2 butene.
  • C 4 cuts which are available in large quantities from FCC systems and from steam crackers, are preferably suitable. These consist essentially of a mixture of the isomeric butenes and butane.
  • Suitable C -carbon streams as feed contain z. B. 50 to 99, preferably 60 to 90 mol% of butenes and 1 to 50, preferably 10 to 40 mol% of butanes.
  • the butene fraction preferably comprises 40 to 60 mol% of 1-butene, 20 to 30 mol% of 2-butene and less than 5 mol%, in particular less than 3 mol%, of isobutene (based on the butene fraction).
  • the so-called raffinate II which is an isobutene-depleted C-section from an FCC system or a steam cracker, is used as a particularly preferred feedstock.
  • Hydroformylation catalysts based on the phosphorus chelate compounds used as ligands advantageously have a high n-selectivity, even when using 2-butene and 2-butene-containing hydrocarbon mixtures as feedstock.
  • feedstocks can also be used economically, since the desired n-valeraldehyde results in good yields.
  • the product-enriched fraction obtained in step a) after separation of the catalyst system is subjected to a further separation in order to obtain a fraction enriched in n-valeraldehyde.
  • the hydroformylation product is separated into an n-valeraldehyde-enriched fraction and an n-valeraldehyde-depleted fraction by conventional methods known to those skilled in the art. Distillation is preferred using known separation apparatuses, such as distillation columns, e.g. B. tray columns, which can optionally be equipped with bells, sieve plates, sieve trays, valves etc., evaporators, such as thin-film evaporators, falling film evaporators, wiper blade evaporators etc.
  • Cio-aldehydes Two molecules of Cs-aldehyde can be condensed to ⁇ , ⁇ -unsaturated Cio-aldehydes.
  • the aldol condensation takes place in a manner known per se, for. B. by the action of an aqueous base such as sodium hydroxide solution or potassium hydroxide solution.
  • a heterogeneous basic catalyst such as magnesium and / or aluminum oxide, can also be used (see, for example, EP-A 792 862).
  • the condensation of two molecules of n-valeraldehyde results in 2-propyl-2-heptenal.
  • step a) If the hydroformylation product obtained in step a) or after the separation in step b) has further Cs aldehydes, such as 2-methylbutanal and, if appropriate, 2,2-dimethylpropanal, these also undergo aldol condensation, where then the condensation products of all possible aldehyde combinations result, for example 2-propyl-4-methyl-2-hexenal.
  • aldehydes such as 2-methylbutanal and, if appropriate, 2,2-dimethylpropanal
  • a portion of these condensation products e.g. B. of up to 30 wt .-%, an advantageous further processing to 2-propylheptanol-containing Cio-alcohol mixtures suitable as plasticizer alcohols does not stand in the way.
  • the products of the aldol condensation can be hydrogenated catalytically with hydrogen to CIO alcohols, such as, in particular, 2-propylheptanol.
  • the hydroformylation catalysts are also generally suitable for the hydrogenation of the cio-aldehydes to the cio-alcohols at a higher temperature; in general, however, more selective hydrogenation catalysts preferred, which are used in a separate hydrogenation stage.
  • Suitable hydrogenation catalysts are generally transition metals, such as. B. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru etc. or mixtures thereof, which to increase the activity and stability on supports such. B. activated carbon, aluminum oxide, diatomaceous earth, etc. can be applied.
  • Fe, Co and preferably Ni also in the form of the Raney catalysts, can be used as a metal sponge with a very large surface area.
  • the hydrogenation of the cio-aldehydes takes place depending on the activity of the catalyst, preferably at elevated temperatures and elevated pressure.
  • the hydrogenation temperature is preferably about 80 to 250 ° C., the pressure is preferably about 50 to 350 bar.
  • the crude hydrogenation product can by conventional methods, e.g. B. by distillation to the C ⁇ o alcohols.
  • the hydrogenation products can be subjected to a further separation to obtain a fraction enriched in 2-propylheptanol and a fraction depleted in 2-propylheptanol.
  • This separation can be carried out by customary methods known to those skilled in the art, such as, for. B. by distillation.
  • Hydroformylation catalysts which have a complex of at least one metal from transition group VIII of the Periodic Table, which has at least one chelate phosphorus compound of the general formula I as ligands, are advantageously suitable for use in a process for the preparation of 2-propyl-heptanol.
  • the catalysts have a high n-selectivity, so that both when using essentially pure 1-butene and when using 1-butene / 2-butene-containing hydrocarbon mixtures, such as C-cuts, for example, a good one Yield of n-valeraldehyde is obtained.
  • the catalysts used according to the invention are also suitable for double bond isomerization from an internal position to a terminal position, so that n-valeraldehyde is obtained in good yields even when using 2-butene and higher concentrations of hydrocarbon mixtures containing 2-butene.
  • the catalysts based on heteroaromatics used according to the invention show essentially no decomposition under the hydroformylation conditions, ie in the presence of aldehydes.
  • Another object of the invention is the use of catalysts comprising at least one complex of a metal of subgroup VIII with at least one compound of the general formula I, as described above, for hydroformylation, hydrocyanation, carbonylation and for hydrogenation.
  • the hydrocyanation of olefins is a further area of application for the catalysts according to the invention.
  • the hydrocyanation catalysts according to the invention also comprise complexes of a metal from subgroup VIII, in particular cobalt, nickel, ruthenium, rhodium, palladium, platinum, preferably nickel, palladium and platinum and very particularly preferably nickel.
  • the metal is zero-valued in the metal complex according to the invention.
  • the metal complexes can be prepared as previously described for use as hydroformylation catalysts. The same applies to the in situ production of the hydrocyanation catalysts according to the invention.
  • a suitable nickel complex for the preparation of a hydrocyanation catalyst is e.g. B. Bis (1,5-cyclooctadiene) nickel (0).
  • hydrocyanation catalysts can be prepared in situ, analogously to the process described for the hydroformylation catalysts.
  • the invention therefore furthermore relates to a process for the preparation of nitriles by catalytic hydrocyanation, in which the hydrocyanation takes place in the presence of at least one of the catalysts according to the invention described above.
  • Suitable olefins for hydrocyanation are generally the olefins previously mentioned as starting materials for hydroformylation.
  • a hydrocarbon mixture is preferably used which has a 1,3-butadiene content of at least 10% by volume, preferably at least 25 vol .-%, in particular at least 40 vol .-%, has.
  • Hydrocarbon mixtures containing 1,3-butadiene are available on an industrial scale. So z. B. in the processing of petroleum by steam cracking of naphtha a C -cut hydrocarbon mixture with a high total olefin content, with about 40% on 1,3-butadiene and the rest on mono-olefins and polyunsaturated hydrocarbons and Al- kane is dropped. These streams always contain small amounts of generally up to 5% of alkynes, 1,2-dienes and vinyl acetylene.
  • Pure 1,3-butadiene can e.g. B. be isolated by extractive distillation from commercially available hydrocarbon mixtures.
  • the catalysts according to the invention can advantageously be used for the hydrocyanation of such olefin-containing, in particular 1,3-butadiene-containing, hydrocarbon mixtures, as a rule also without prior purification of the hydrocarbon mixture by distillation.
  • the effectiveness of the catalysts impairing olefins, such as. B. alkynes or cumulenes can optionally be removed from the hydrocarbon mixture by selective hydrogenation before the hydrocyanation. Suitable processes for selective hydrogenation are known to the person skilled in the art.
  • the hydrocyanation according to the invention can be carried out continuously, semi-continuously or batchwise.
  • Suitable reactors for the continuous reaction are known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Volume 1, 3rd edition, 1951, p. 743 ff.
  • a stirred tank cascade or a tubular reactor is preferably used for the continuous variant of the process according to the invention.
  • Suitable, optionally pressure-resistant reactors for semi-continuous or continuous execution are known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Volume 1, 3rd Edition, 1951, pp 769 ff.
  • an autoclave is used for the method according to the invention, which can, if desired, be provided with a stirring device and an inner lining.
  • the hydrocyanation catalysts according to the invention can be separated from the discharge of the hydrocyanation reaction by customary processes known to the person skilled in the art and can generally be used again for the hydrocyanation.
  • the invention further relates to a process for carbonylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and at least one compound having a nucleophilic group in the presence of a carbonylation catalyst, in which a catalyst based on a carbonylation catalyst is used Ligands of the general formula I used.
  • the carbonylation catalysts according to the invention also comprise complexes of a metal from subgroup VIII, preferably nickel, cobalt, iron, ruthenium, rhodium and palladium, in particular palladium.
  • the metal complexes can be prepared as previously described for the hydroformylation catalysts and hydrocyanation catalysts. The same applies to the in situ production of the carbonylation catalysts according to the invention.
  • Suitable olefins for carbonylation are the olefins which have generally been mentioned above as starting materials for hydroformylation and hydrocyanation.
  • the compounds having a nucleophilic group are preferably selected from water, alcohols, thiols, carboxylic acid esters, primary and secondary amines.
  • a preferred carbonylation reaction is the conversion of olefins with carbon monoxide and water to carboxylic acids (hydrocarbylation). This particularly includes the conversion of ethylene with carbon monoxide and water to propionic acid.
  • Example 2 Hydroformylation of a butene / butane mixture with 5 ligand I.

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Abstract

L'invention concerne de nouveaux chélates de phosphore ainsi que des catalyseurs contenant au moins un complexe constitué d'un métal du sous-groupe VIII et d'au moins un tel chélate de phosphore servant de ligand. L'invention concerne également un procédé d'hydroformylation au moyen desdits catalyseurs.
PCT/EP2003/001245 2002-02-08 2003-02-07 Chelates de phosphore WO2003066642A1 (fr)

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AU2003210225A AU2003210225A1 (en) 2002-02-08 2003-02-07 Phosphorus chelate compounds
DE10390373T DE10390373D2 (de) 2002-02-08 2003-02-07 Phosphorchelatverbindungen

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WO2004026803A1 (fr) * 2002-09-13 2004-04-01 Basf Aktiengesellschaft Procede de production de dialdehydes et/ou de monoaldehydes ethyleniquement insatures par hydroformylation de composes ethyleniquement insatures
US7173138B2 (en) 2001-03-29 2007-02-06 Basf Aktiengesellschaft Ligands for pnicogen chelate complexes with a metal of subgroup VIII and use of the complexes as catalysts for hydroformylation, carbonylation, hydrocyanation or hydrogenation
WO2011054781A1 (fr) 2009-11-03 2011-05-12 Basf Se Compositions thermoplastiques avec fluidité améliorée
EP2377844A2 (fr) 2004-06-21 2011-10-19 Basf Se Moyen d'aide contenant des dérivés d'acide cyclohexane-polycarboxylique
WO2011151301A1 (fr) 2010-06-01 2011-12-08 Basf Se Procédé de production de compositions expansibles à base de polymère de styrène
EP2716623A1 (fr) 2012-10-05 2014-04-09 Basf Se Procédé de fabrication de dérivés d'acide de polycarbonate cyclohexane avec part étroite de produits annexes
WO2017150337A1 (fr) 2016-03-01 2017-09-08 株式会社クラレ Procédé de production de composé dialdéhyde
WO2020173818A1 (fr) 2019-02-25 2020-09-03 Basf Se Procédé pour le retraitement d'esters d'acide benzènepolycarboxylique et leur utilisation pour la production d'esters d'acide cyclohexanepolycarboxylique

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WO1999052632A1 (fr) * 1998-04-16 1999-10-21 E.I. Du Pont De Nemours And Company Cyanhydratation d'olefines et isomerisation de 2-alkyl-3-monoalcenitriles non conjugues
WO2003018192A2 (fr) * 2001-08-24 2003-03-06 Basf Aktiengesellschaft Procede de preparation de 2-propylheptanol

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WO1999052632A1 (fr) * 1998-04-16 1999-10-21 E.I. Du Pont De Nemours And Company Cyanhydratation d'olefines et isomerisation de 2-alkyl-3-monoalcenitriles non conjugues
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7173138B2 (en) 2001-03-29 2007-02-06 Basf Aktiengesellschaft Ligands for pnicogen chelate complexes with a metal of subgroup VIII and use of the complexes as catalysts for hydroformylation, carbonylation, hydrocyanation or hydrogenation
WO2004026803A1 (fr) * 2002-09-13 2004-04-01 Basf Aktiengesellschaft Procede de production de dialdehydes et/ou de monoaldehydes ethyleniquement insatures par hydroformylation de composes ethyleniquement insatures
US7145042B2 (en) 2002-09-13 2006-12-05 Basf Aktiengesellschaft Method for producing dialdehydes and or ethylenically unsaturated monoaldehydes by hydroformylating ethylenically unsaturated compounds
EP2377844A2 (fr) 2004-06-21 2011-10-19 Basf Se Moyen d'aide contenant des dérivés d'acide cyclohexane-polycarboxylique
WO2011054781A1 (fr) 2009-11-03 2011-05-12 Basf Se Compositions thermoplastiques avec fluidité améliorée
WO2011151301A1 (fr) 2010-06-01 2011-12-08 Basf Se Procédé de production de compositions expansibles à base de polymère de styrène
EP2716623A1 (fr) 2012-10-05 2014-04-09 Basf Se Procédé de fabrication de dérivés d'acide de polycarbonate cyclohexane avec part étroite de produits annexes
WO2014053618A1 (fr) 2012-10-05 2014-04-10 Basf Se Procédé de préparation de dérivés d'acide polycarboxyique de cyclohexane avec une teneur faible en sous-produits
WO2017150337A1 (fr) 2016-03-01 2017-09-08 株式会社クラレ Procédé de production de composé dialdéhyde
WO2020173818A1 (fr) 2019-02-25 2020-09-03 Basf Se Procédé pour le retraitement d'esters d'acide benzènepolycarboxylique et leur utilisation pour la production d'esters d'acide cyclohexanepolycarboxylique

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