WO2003018192A2 - Method for the production of 2-propylheptanol and hydroformylating catalysts and the further use thereof for carbonylation, hydrocyanation and hydrogenation - Google Patents

Method for the production of 2-propylheptanol and hydroformylating catalysts and the further use thereof for carbonylation, hydrocyanation and hydrogenation Download PDF

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WO2003018192A2
WO2003018192A2 PCT/EP2002/009455 EP0209455W WO03018192A2 WO 2003018192 A2 WO2003018192 A2 WO 2003018192A2 EP 0209455 W EP0209455 W EP 0209455W WO 03018192 A2 WO03018192 A2 WO 03018192A2
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hydrogen
alkyl
formula
aryl
cycloalkyl
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PCT/EP2002/009455
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German (de)
French (fr)
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WO2003018192A3 (en
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Wolfgang Ahlers
Rocco Paciello
Thomas Mackewitz
Martin Volland
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Basf Aktiengesellschaft
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Priority to AU2002324067A priority Critical patent/AU2002324067A1/en
Publication of WO2003018192A2 publication Critical patent/WO2003018192A2/en
Publication of WO2003018192A3 publication Critical patent/WO2003018192A3/en

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Definitions

  • the present invention relates to a process for the preparation of 2-propylheptanol, comprising the hydroformylation of butene, an aldol condensation of the hydroformylation products thus obtained and their catalytic hydrogenation.
  • the invention further relates to new catalysts for the hydroformylation step and their use.
  • plasticizers are used in large quantities to modify the thermoplastic properties of a large number of products that are important on an industrial scale, such as plastics in particular, but also varnishes, coating agents, sealants, etc.
  • An important class of plasticizers are the ester plasticizers, which include phthalic acid esters, trimellitic acid esters, phosphoric acid esters, etc.
  • the alcohols used to prepare the ester plasticizers are generally referred to as plasticizer alcohols.
  • plasticizer alcohols In order to produce ester plasticizers with good performance properties, there is a need for plasticizer alcohols with about 6 to 12 carbon atoms, which are branched to a small extent (so-called semilinear alcohols), and for corresponding mixtures thereof. These include, in particular, 2-propylheptanol and alcohol mixtures containing it.
  • DE-A-100 03 482 describes an integrated process for the preparation of Cg alcohols and C ⁇ 0 alcohols from butene and butane-containing C 4 -hydrocarbon mixtures, in which, among other things, the hydrocarbon mixture is subjected to hydroformylation and the C 5 - Aldehydes subjected to an aldol condensation and subsequent catalytic hydrogenation to Cio-alcohols.
  • hydroformylation of olefins with more than 2 carbon atoms leads to the formation of mixtures of isomeric aldehydes due to the possible CO addition to each of the two carbon atoms of a double bond.
  • double bond isomerization can occur, ie a shift of internal double bonds to a terminal position and vice versa.
  • 2-propylheptanol or alcohol mixtures With a high proportion of 2-propylheptanol by hydroformylation of butene and subsequent aldol condensation, hydroformylation can therefore easily lead not only to the formation of n-valeraldehyde but also to undesired product aldehydes, which is economically disadvantageous by the entire process.
  • the hydroformylation catalyst used must selectively enable and / or allow the hydroformylation of terminal olefins (1-butene) a shift of internal double bonds to a ter-
  • WO 98/42716 describes a process for the preparation of 35 2,2'-bisphosphino-1,1'-binaphthylene, the phosphorus atoms of which, in addition to a large number of other radicals, can also carry pyrrole groups.
  • No. 3,816,452 describes the production of differently substituted pyrrolyl monophosphines and their use as 40 flame retardants.
  • EP-A-0 754 715 describes a catalyst composition comprising a metal from transition group VIII and an alkylene-bridged di (pyrrolyl-phenyl-phosphine) and their use for the production of polyketones. Catalysts based on phosphorus-containing ligands with substituted or fused pyrrole residues are not described.
  • WO 00/56451 (DE-A-199 13 352) relates to cyclic oxaphosphorines substituted on the phosphorus atom with pyrrole derivatives and the use of these ligands in catalysts for hydroformylation.
  • 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 to one another via 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.
  • 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 with un- substituted pyrrole, indole or imidazole groups which are bonded to the phosphorus atom via a ring nitrogen atom.
  • WO 01/58589 describes compounds of phosphorus, arsenic and antimony based on diaryl-fused bicyclo [2.2.2] basic bodies and catalysts which contain these as ligands.
  • hetaryl radicals can also be bound to the atom of the 5th main group.
  • 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, an aryl radical of the two triarylphosphine groups each having a single bond to a nonaromatic 5- is linked to 8-membered carbocyclic or heterocyclic bridging group.
  • the phosphorus atoms can also have, among other things, hetaryl groups as further substituents.
  • DE-A-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- Has atom and at least two further heteroatoms groups bound to a xanthene-like molecular structure.
  • JP-A-2002 047294 describes phosphorus chelate compounds with backbones of the biphenylene type, in which two nitrogen heterocycles are also bonded to the phosphorus atoms. They are suitable as ligands for hydroformylation catalysts. Both unsubstituted and substituted pyrrole groups integrated in fused ring systems are used as nitrogen heterocycles. This document does not show any preference for substituted pyrrol groups and those which are integrated in a fused ring system and in particular additionally substituted pyrrole groups. The use of ligands of the biphenylene type in which at least one 3-alkylindol-l-yl radical is bonded to the phosphorus atoms is not described in this document.
  • German patent application P 102 05 361.8 describes phosphorus chelate compounds in which three nitrogen atoms are covalently bonded to both phosphorus atoms, which are themselves part of an aromatic ring system.
  • the object of the present invention is to provide an improved process for the preparation of 2-propylheptanol.
  • Another object of the invention is to provide new ligands which, when used in hydroformylation catalysts, are notable for particularly high stability under the hydroformylation conditions and / or for workup.
  • the first object is achieved by a process which comprises the hydroformylation of butene, an aldol condensation of the hydroformylation products thus obtained and their subsequent catalytic hydrogenation, a complex of a metal of subgroup VIII of the periodic table being used as the hydroformylation catalyst at least one pyrrole-phosphorus compound is used as ligand. Accordingly, a process for the preparation of 2-propyl-heptanol was found in which
  • 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 + , WP0 3 (R a ) (R b ), W (P0 3 ) 2 "(M +) 2 , WNE ⁇ -E 2 , W (NE 1 E 2 E 3 ) + X", W0R a , WSR a , (CHRkCH 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, a heteroatom or a divalent bridging group with 1 to 20 bridge atoms
  • R a r E 1 , E 2 , E 3 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
  • Rb represents hydrogen, methyl or ethyl
  • ⁇ ⁇ stands for an anion equivalent and x represents an integer from 1 to 240
  • R 5 and R 6 independently of one another are cycloalkyl, heterocycloalkyl, aryl or hetaryl, it being possible for one of the radicals R 5 or R 6 to also represent a divalent bridging group Y which covalently connects two identical or different ligands or formula I. , and
  • a and b independently of one another denote the number 0 or 1
  • step b) the hydroformylation product obtained in step a) or the n-valeraldehyde enriched in step b)
  • pyrrole-phosphorus compounds in which one or more unsubstituted pyrrole groups are bonded to the phosphorus atom via their nitrogen atom tend to decompose or form undesired reaction products.
  • a noticeable decomposition is already induced by visible light and / or temperatures in the room temperature range and cannot be prevented by using a protective gas.
  • polymeric impurities are noticeably formed.
  • the bridging group Y does not represent a group of the formula
  • R 7 , R 8 'R 9 and R 10 independently of one another for hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, S0 3 H, sulfonate, NEE 5 , alkylene-NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl, Are carboxyl or cyano, in which E 4 and E 5 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
  • a 1 and A 2 independently of one another represent 0, S, SiR 15 R 16 , NR 15 or CR 17 R 18 , where
  • R 17 and R 18 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or the group R 17 together with another group R 17 or the group R 18 together with another group R 18 is an intramolecular bridge group D form,
  • R 19 and R 20 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 bridge,
  • R 21 , R 22 , R 23 and R 24 independently of one another for hydrogen
  • c 0 or 1.
  • alkyl includes straight-chain and branched alkyl groups. These are preferably straight-chain or branched C 1 -C 18 -alkyl, preferably C 1 -C 2 -alkyl and particularly preferably C 1 -C 4 -alkyl and very particularly preferably C 1 -C 4 -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-trimethyl - propyl, 1-ethylbutyl, 2-ethylbutyl, l-ethyl,
  • alkyl also includes substituted alkyl groups.
  • Substituted alkyl radicals preferably have 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from cycloalkyl, aryl, hetaryl, halogen, NE ⁇ 2 , (NE X E 2 E 3 ) + , carboxyl, Carboxylate, -S0 3 H and sulfonate.
  • cycloalkyl includes unsubstituted and substituted cycloalkyl groups.
  • the cycloalkyl group is preferably a C5-C7 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 in the context 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 which may optionally be substituted, where in the case of a substitution these heterocycloaliphatic groups 1, 2 or 3, preferably 1 or 2, particularly preferably 1, selected from alkyl, aryl, C00R a , C00 ⁇ M + and NE ⁇ 2 , preferably alkyl, can wear.
  • heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2, 6, 6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothydhenoluryl, tyridethyridanyl, tyridylanyl, tyridethanyl, tyranethanyl, tyranethanyl called.
  • Aryl preferably represents phenyl, tolyl, xylyl, mesityl, naphthyl, 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, E ⁇ 2 , alkylene-NEiE 2 , Nitro, cyano or halogen.
  • Hetaryl is preferably pyrrolyl, pyrazolyl, imidazolyl, indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.
  • Substituted hetaryl radicals preferably have 1, 2 or 3 substituents selected from alkyl, alkoxy, carboxyl, carboxylate, -S0 3 H, sulfonate, NE X E 2 , alkylene-NE 1 E 2 , trifluoromethyl or halogen.
  • alkyl, cycloalkyl and aryl radicals apply accordingly to alkoxy, cycloalkyloxy and aryloxy radicals.
  • the radicals NE X E 2 and NE 4 E 5 preferably represent N, N-dimethylaamino, 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 + or a quaternary ammonium compound, as can be obtained by protonation or quaternization of amines.
  • Alkali metal cations are preferred, in particular sodium or potassium ions.
  • X- stands for an anion equivalent, ie for a monovalent anion or the portion of a polyvalent 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, ie. 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.
  • Suitable feedstocks for the hydroformylation are both essentially pure 1-butene and mixtures of 1-butene with 2-butene and technically obtainable C-hydrocarbon streams which contain 1-butene and / or 2 butene.
  • C 4 cuts which are available in large quantities from FCC systems and from steak crackers, are preferably suitable. These consist essentially of a mixture of 1,3-butadiene, 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 4 cut from an FCC system or a steam cracker, is used as a particularly preferred feedstock.
  • Hydroformylation catalysts based on the phosphoropyrrole compounds used according to the invention as ligands advantageously have a high n-selectivity, even when using 2-butene and 2-butene-containing hydrocarbon mixtures as starting material.
  • such starting materials can also be used economically in the process according to the invention, since the desired n-valeraldehyde results in good yields.
  • step a) of the process according to the invention preference is given to using a compound of the general formula I in which one or two of the radicals R 1 , R 2 , R 3 and R 4 are one of the abovementioned substituents other than hydrogen and the rest are hydrogen stand.
  • Compounds of the formula I which have a substituent other than hydrogen in the 2-position, 2,5-position or 3,4-position are preferred.
  • the substituents R 1 to R 4 which are different from hydrogen are preferably selected independently of one another from Ci to Cs, preferably Ci to C 4 alkyl, especially methyl, ethyl, isopropyl and tert-butyl, alkoxycarbonyl, such as methoxycarbonyl, ethoxycar- bonyl, isopropyloxycarbonyl and tert-butyloxycarbonyl as well as trifluoromethyl.
  • step a) of the process according to the invention preference is given to using a compound of the general formula I in which 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 attached form 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 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, SO 3 H, sulfonate, NE ⁇ 2 , alkylene-NE ⁇ 2 , trifluoromethyl, nitro, C00R a , alkoxycarbonyl, acyl and cyano.
  • Fused naphthalene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or, in the non-fused ring and / or in the fused ring 2 of the substituents previously mentioned for the fused benzene rings.
  • R 3 and R 4 preferably stand for hydrogen or R 4 stands for hydrogen and R 3 stands for a substituent which is selected from Ci to Cs 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 represents a polar (hydrophilic) group, in which case, as a rule, the complex formation with a Group VIII metal water-soluble complexes result.
  • the polar groups are preferably selected from C00R a , COO-M +, S0 3 R a , S0 3 ⁇ M + , NEiE 2 , alkylene-NE 1 E 2 , NE ⁇ E ⁇ X ", alkylene-NE 1 E 2 E 3 + X-, OR a , SR a , (CHR b CH 2 0) x R a or (CH ⁇ H ⁇ fE 1 )) x R a , where R a , E 1 , E 2 , E 3 , R b , M + , X ⁇ and x have the meanings given above.
  • a hydroformylation catalyst which comprises at least one ligand of the formula I in which the pyrrole group of the formula which is bonded to the phosphorus atom via the pyrrolic nitrogen atom
  • Alk is a -CC 4 alkyl group
  • R9, R h , R 1 and R k independently of one another are hydrogen, C J -C 4 -A1- kyl, C 1 -C 4 alkoxy, acyl, halogen, trifluoromethyl, C 1 -C 4 alkoxycarbonyl or carboxyl.
  • Hydroformylation catalysts based on ligands which have one or more 3-methylindolyl group (s) bonded to the phosphorus atom are distinguished by a particularly high stability and thus particularly long catalyst life.
  • the substituent R 1 together with the substituent R 5 or the substituent R 2 together with the substituent R 5 can represent a divalent group -IW-, in which
  • R ⁇ , R ⁇ , R v , R ⁇ and R ⁇ independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, and
  • W represents cycloalkyl, cycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy.
  • Hydroformylation catalysts which comprise at least one ligand of the formula I are preferably used in the process according to the invention, in which the pyrrole group bonded to the phosphorus atom via the pyrrolic nitrogen atom together with R 5 is a group of the formula
  • I stands for a chemical bond or for O, S, SiR ⁇ Rß, NR ⁇ or optionally substituted C ⁇ -C ⁇ o alkylene, preferably CR ⁇ R ⁇ , wherein R ⁇ , R ⁇ , R ⁇ , R and R ⁇ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
  • R 1 , R 1 ', R 2 , R 2 ', R 3 , R 3 ', R 4 and R 4 ' independently of one another for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCO0R a , WCOO "M + , W (S0 3 ) R a , W (S0 3 ) -M + , WP0 3 (R a ) (R b ) f W (P0 3 ) 2 "(M + ) 2 , WNE i E 2 , W (NE 1 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, halogen, trifluor ormethyl, nitro, acyl or cyano,
  • W represents a single bond, a heteroatom or a divalent bridging group with 1 to 20 bridge atoms
  • R a , E 1 , E 2 , E 3 are each the same or different radicals selected from hydrogen, alkyl, cycloalkyl or
  • R b represents hydrogen, methyl or ethyl
  • x represents an integer from 1 to 240
  • R 1 and R 2 and / or R 1 'and R 2 ' together with the carbon atoms of the pyrrole ring to which they are attached can also represent a condensed ring system with 1, 2 or 3 further rings.
  • I is preferably a chemical bond or a C 1 -C 8 -alkylene group, particularly preferably a methylene group.
  • the compound of general formula I is preferably selected from compounds of general formulas I.1 to 1.4
  • R 1 , R 2 'R 3 ' R 4 'Y, a and b have the meanings given above and
  • R 5 and R 6 independently of one another represent cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • R 1 to R 4 are preferably all hydrogen.
  • R 1 and R 4 are preferably hydrogen and R 2 and R 3 are selected from Ci to Cs alkyl, preferably Ci to C alkyl, such as methyl, ethyl, isopropyl and tert-butyl.
  • R 1 , R 2 , R 3 and R 4 are preferably selected independently of one another from Ci-Cg-alkyl, preferably C ⁇ -C 4 alkyl, such as methyl, ethyl, isopropyl and tert-butyl.
  • the compound of general formula I is preferably selected from compounds of general formulas 1.5 or 1.6
  • R 2 and R 3 have the meanings given above, where at least one of the radicals R 2 or R 3 is not hydrogen,
  • R 5 and R 6 independently of one another represent cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • the radicals R 2 and R 3 are preferably selected from C 1 -C 6 -alkyl, particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, isopropyl and tert-butyl, and C00R a , in which R a for C 1 -C 4 alkyl, such as methyl, ethyl, isopropyl and tert-butyl.
  • the ligands of the formula I are monodentate ligands.
  • the radicals R 5 and R 6 are independently selected from cycloalkyl, heterocycloalkyl, aryl and hetaryl, preferably from aryl and hetaryl.
  • R 5 and R 6 preferably represent optionally substituted phenyl radicals.
  • R 5 furthermore preferably represents an optionally substituted phenyl radical and
  • R 6 represents an optionally substituted hetaryl radical.
  • the hetaryl radicals are preferably selected from radicals of the general formula III
  • R 1 , R 2 , R 3 and R 4 are defined as described above, at least one of the radicals not being hydrogen.
  • the ligands of the general formula I are bidentate ligands.
  • one of the radicals R 5 or R 6 stands for a divalent bridging group Y which covalently connects two identical or different ligands of the formula I.
  • the bridging group Y is preferably selected from groups of the formulas II. A to II.t.
  • R 1 to R XI1 independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, S0 3 H, sulfonate, NEE 5 , alkylene-NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, in which E 4 and E 5 each denote the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
  • Z represents O, S, NR 15 or SiR 15 R 16 , where R 15 and R 16 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or Z represents a C 1 -C 4 -alkylene bridge which can have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent,
  • Z represents a C 2 -C alkylene bridge which is interrupted by O, S or NR 15 or SiR 15 R 16 ,
  • one of the radicals R 1 to R IV can also represent oxo or a ketal thereof.
  • the bridging group Y is preferably selected from groups of the formulas II.1 to II.5
  • R 7 , R 8 'R 9 ' R 10 'R 11 ' R 12 'R 13 and R 14 independently of one another for hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, S0 3 H, sulfonate, NE 4 E 5 , alkylene -NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, in which E 4 and E 5 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
  • Z represents 0, S, NR 15 or SiR 15 R 16 , where R 15 and R 16 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
  • Z represents a Ci to C 3 alkylene bridge which can have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent, or Z represents a C 2 -C alkylene bridge which is interrupted by 0, S or NR 15 or SiR 15 R 16 ,
  • R 7 , R 8 , R 9 and R 10 generally represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl.
  • R 7 and R 9 are preferably hydrogen and R 8 and R 10 are C ⁇ ⁇ to C 4 alkyl, such as. B. methyl, ethyl, n-propyl, n-butyl or tert-butyl. It goes without saying that the positions of the phenyl rings of the bridging group Y which are not occupied by substituents bear a hydrogen atom.
  • the substituents R 7 , R 8 , R 9 and R 10 are preferably hydrogen.
  • R 7 and / or R 9 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 1 E 2 , Trifluoromethyl, nitro, COOR f , 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.
  • Y is preferably a group of the formula II.
  • R 1 and R IV independently of one another are C ⁇ -C alkyl or -CC 4 alkoxy.
  • R 1 and R IV are preferably selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • R 11 and R 111 are preferably hydrogen.
  • Y is preferably a group of the formula II.b, in which R IV and R v independently of one another are C ⁇ -C-alkyl or C ⁇ -C-alkoxy.
  • R IV and R v are preferably selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • R 1 , R 11 , R 1 ", R Vi , R VI m and R v m are preferably hydrogen.
  • Y is furthermore preferably a group of the formula II.b, in which R 1 and R VI11 independently of one another are C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy. R 1 and R VI11 are particularly preferably tert-butyl. In these compounds R ", R 111 , R IV , R v , R VI , R VI1 are particularly preferably hydrogen. Furthermore, in these compounds R 111 and R VI are independently of one another Cein-C 4 -alkyl or C ⁇ -C 4 alkoxy, R 111 and R VI are particularly preferably selected independently of one another from methyl, Ethyl, isopropyl, tert-butyl and methoxy.
  • Y is furthermore preferably a group of the formula II.
  • R 11 and R VI1 are hydrogen.
  • R 1 , R 111 , R IV , R v , R VI and R VI11 are preferably, independently of one another, C ⁇ -C 4 -alkyl or C ⁇ -C-alkoxy.
  • R 1 , R 111 , R IV , R v , R VI and R VI11 are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • Y is furthermore preferably a group of the formula II.c, in which Z represents a C ⁇ -C 4 -alkylene group, in particular methylene.
  • R IV and R v are preferably, independently of one another, C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy.
  • R IV and R v are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • the radicals R 1 , R 11 , R 111 , R VI , R VI1 and R VI11 are preferably hydrogen.
  • Y preferably represents a group of the formula II.c, in which Z represents a C ⁇ -C alkylene bridge which has at least one alkyl, cycloalkyl or aryl radical. Z particularly preferably represents a methylene bridge which has two C ⁇ -C-alkyl radicals, in particular two methyl radicals.
  • the radicals R 1 and R VI11 are preferably independently of one another C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy. R 1 and R VI11 are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • Y is further preferably a group of the formula II.d, in which R 1 and R XI1 independently of one another are C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy.
  • R 1 and R XI1 are independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • the radicals R 11 to R XI are particularly preferably hydrogen.
  • Y preferably represents a group of the formula II.e, in which R 1 and R XI1 independently of one another are C ⁇ -C 4 -alkyl or C ⁇ -C-alkoxy.
  • R 1 and R XI1 are independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • the radicals R 11 to R XI are particularly preferably hydrogen.
  • Y is furthermore preferably a group of the formula II.
  • Z is a C ⁇ -C 4 -alkylene group which has at least one alkyl, cycloalkyl or aryl substituent.
  • Z particularly preferably represents a methylene group which has two C ⁇ -C-alkyl radicals, especially two methyl radicals.
  • the radicals R 1 and R VI11 are particularly preferably independent from each other for C ⁇ -C 4 alkyl or C ⁇ -C-alkoxy.
  • R 1 and R VI11 are selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • the radicals R 11 , R 111 , R IV , R v , R VI and R VI1 are preferably hydrogen.
  • Y is furthermore preferably a group of the formula II.g, in which R 1 , R 11 and R 111 are hydrogen.
  • Y preferably represents a group of the formula II.g, in which the ring carbon atom which carries the R 11 radical does not bear an additional hydrogen atom but an oxo group or a radical thereof and R 1 and R 111 represent hydrogen ,
  • Y is furthermore preferably a group of the formula II.h, in which R 1 , R 11 and R 111 are hydrogen.
  • Y preferably represents a group of the formula II.h, in which the ring carbon atom which carries the R 11 radical does not bear an additional hydrogen atom but an oxo group or a radical thereof and R 1 and R 111 represent hydrogen ,
  • Y is furthermore preferably a group of the formula II.i in which R 1 , R 11 , R 111 and R IV are hydrogen.
  • Y is furthermore preferably a group of the formula II.k, in which R 1 , R 11 , R 111 and R IV stand for hydrogen.
  • Y preferably represents a group of the formula II.1, in which R 1 , R 11 , R 111 and R IV stand for hydrogen.
  • Y preferably represents a group of the formula II.m, in which R 1 , R 11 , R 111 and R IV stand for hydrogen.
  • Y is furthermore preferably a group of the formula II.n, where R 1 , R 11 , R 111 and R IV are hydrogen.
  • Y is furthermore preferably a group of the formula II.n, in which one of the radicals R 1 to R IV is C ⁇ -C 4 -alkyl or C ⁇ -C-alkoxy. At least one of the radicals R 1 to R IV is then particularly preferably methyl, ethyl, isopropyl, tert-butyl or methoxy.
  • Y is furthermore preferably a group of the formula II.o in which R 1 , R 11 , R 111 and R IV are hydrogen.
  • Y further preferably represents a group of the formula II.o, in which one of the radicals R i , R 11 , R i n or R IV represents C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy.
  • R 1 to R IV are methyl, ethyl, tert-butyl or methoxy.
  • Y is furthermore preferably a group of the formula II.p, in which R 1 and R VI independently of one another are C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy. R 1 and R VI are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy. In these compounds, R 11 , R 111 , R IV and R v are particularly preferably hydrogen. In addition, preferably in the compounds II.p R 1 , R 111 , R IV and R VI independently of one another are C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy. R 1 , R 111 , R IV and R VI are then particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • Y is furthermore preferably a group of the formula II.q, where R 1 and R VI independently of one another are C ⁇ -C 4 -alkyl or
  • R 1 and R VI are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • R 11 , R 111 , R IV and R v are particularly preferably hydrogen.
  • R 111 and R IV are independently C ⁇ -C 4 -alkyl or C ⁇ -C-alkoxy.
  • RIII and RIV are then particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
  • Y preferably represents a group of the formula II.r, II.s or Il.t, where Z represents CH 2 , C 2 H 2 or C 2 H.
  • the monodentate phosphoropyrrole compounds of the general formula I used according to the invention can be prepared, for example, according to the following scheme 1:
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the meaning given above.
  • the bidentate phosphoropyrrole compounds of the formula I used according to the invention can be prepared analogously to Scheme 1, starting from compounds L 1 - (0) b -Y- (0) a -L 1 .
  • the preparation of compounds of the formula II.2 can start from compounds of the formula II.2a
  • Butyllithium or the like subsequent reaction with a borane such as B (OCH 3 ) 3 or B (OCH (CH 3 ) 2 ) 3 and oxidation of the diborane compound formed in this way with a peroxide, preferably hydrogen peroxide in the presence of aqueous alkali metal hydroxide, preferably lithium -, sodium or potassium hydroxide can be obtained.
  • a borane such as B (OCH 3 ) 3 or B (OCH (CH 3 ) 2 ) 3
  • a peroxide preferably hydrogen peroxide in the presence of aqueous alkali metal hydroxide, preferably lithium -, sodium or potassium hydroxide
  • the starting compounds of the general formula II.2a are advantageously combined with a halogen compound of the formula HalPX 1 ((0) a R 5 ) and
  • HalPX 1 ((0) b R 6 ) in the presence of a base.
  • Shark is preferably chlorine or bromine.
  • the compounds HalPX ⁇ (0) a R 5 ) and HalPX ⁇ (0) b R 6 ) can, for example, in analogy to the method of Petersen et al, J. Am. Chem. Soc. 117, 7696 (1995) by reacting the substituted and / or fused pyrrole compound in question with the phosphorus trihalide in question, e.g. B. phosphorus trichloride, in the presence of a tertiary amine, e.g. B. triethylamine, are obtained, the stoichiometry of this reaction being observed. In analogy to this procedure, e.g. B.
  • HalPX 1 ((0) a R 5 ) and HalPX 1 ((0) b R 6 ) are obtainable.
  • So z. B. by reacting phenol with phosphorus trichloride in the presence of a tertiary amine, e.g. As triethylamine, the phenoxyphosphorus dichloride are generated, which after reaction with an equivalent of the pyrrole compound in question, for. B. pyrrole, in the presence of a tertiary amine, phenoxy-pyrrolyl-phosphorus chloride.
  • the 2,2'-bisindole starting compounds can be prepared analogously to Tetrahedron 51, 5637 (1995) and Tetrahedron 51, 12801 (1995), and the bis-2, 2'-pyrrolyl-methanes can be prepared in accordance with the information given by J . Org. Chem. 64/1391 (1999) and the preparation of the 2 'pyrrolyl-o-phenoxy-methane according to J. Org. Chem. 16, 5060 (1981).
  • the reaction of these compounds with the compounds HalPX 1 ((0) a R 5 ) and HalPX 1 ((0) b R 6 ) in the presence of a base, preferably a tertiary amine, such as triethylamine, or an alkali metal or alkaline earth metal hydride, for example sodium hydride, potassium hydride or calcium hydride, directly to those according to the invention Picnicogen chelate compounds of the general formula I with a, b 0.
  • catalytically active species of the general formula H g Z d (C0) e G f are formed from the catalysts or catalyst precursors used in each case, in which Z is a metal of subgroup VIII, G is a phosphorus-containing ligand of the formula I and d, e, f, g are integers, depending on the valency and type of the metal and the binding of the ligand G.
  • e and f are independently at least 1, such as. B. 1, 2 or 3.
  • the sum of e and f is preferably from 2 to 5.
  • the complexes of the metal Z with the ligands G according to the invention can, if desired, additionally comprise at least one further non-inventive ligand, for example from the class of triarylphosphines, especially triphenylphosphine, triarylphosphites, triarylphosphinites, triarylphosphonites, phosphabenzenes, trialkylphosphines or phosphametallocenes.
  • Such complexes of the metal Z with ligands according to the invention and not according to the invention are formed, for example, in an equilibrium reaction after adding a ligand not according to the invention to form a complex of the general formula H g Z a (C0) e G f .
  • 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. To prepare the catalysts according to the invention in situ, at least one compound of the general formula I, a compound or a complex of a metal from subgroup VIII, if desired one or more additional ligands not according to the invention and optionally an activating agent in an inert solvent the hydroformylation implement 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) - and 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, ace- tylacetonatobisethylene 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 or complex compounds, such as, for. B. RuHCl (CO) (PPh 3 ) 3 .
  • the 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 , can also be 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 naphthenoate, and the cobalt caprolactamate Complex
  • the carbonyl complexes of cobalt such as dicobalt octacarbonyl, tetrakobalt dodecacarbonyl and hexacobalt hexadecacarbonyl can also be used here.
  • Suitable activating agents are e.g. B. Brönsted acids, Lewis acids, such as. B. BF 3 , A1C1 3 , ZnCl, 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 alkano len, for example ethyl acetate or Texanol ® , ethers such as tert-butyl methyl ether and tetrahydrofuran.
  • ligands are sufficiently hydrophilized, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones such as acetone and methyl ethyl ketone etc. can also be used. So-called “ionic liquids” can also be used as solvents.
  • liquid salts for example N, N'-di-alkylimidazolium 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, tetraalkylphosphonium salts such as the trishexyl (tetra-decyl) phosphonium salts, for example the tetrafluoroborates, acetates, tetrachloroaluminates, hexafluorophosphates, chlorides and tosylates.
  • N, N'-di-alkylimidazolium salts such as the N-butyl-N'-methylimidazolium salts
  • tetraalkylammonium salts such as the tetra-n-buty
  • the reactions are then carried out in the form of a 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 compound I to subgroup VIII metal in the hydroformylation medium is generally in a range from about 1: 1 to 1000: 1, preferably from 1: 1 to 100: 1, in particular from 1: 1 to 50: 1 ,
  • 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 Ullmann's Encyclopedia of Industrial Chemistry, Vol. 1, 3rd ed., 1951, pp. 743 ff.
  • Suitable pressure-resistant reactors are also known to the person skilled in the art and are described, for. B. in Ullmann'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, if desired, with a stirring device and can be provided with an inner lining.
  • composition of the synthesis gas of carbon monoxide and hydrogen used in the process according to the invention can vary in wide ranges.
  • the molar ratio of carbon monoxide and hydrogen is usually about 1:99 to 80:20, preferably about 40:60 to 60:40.
  • a molar ratio of carbon monoxide and 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 according to the invention based on phosphorus-containing compounds allow reaction in a range of low pressures, such as in the range from 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 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 using known separation apparatuses, such as distillation columns, e.g. B. tray columns, which can be equipped with bells, sieve plates, sieve trays, valves etc. if desired, evaporators, such as thin-film evaporators, falling film evaporators, wiper blade evaporators etc. c) aldol condensation
  • Two molecules of C 5 aldehyde can be condensed to form ⁇ , ⁇ -unsaturated C ⁇ 0 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) or after the separation in step b) also has other C 5 aldehydes, such as 2-methylbutanal and, if appropriate, 2,2-dimethylpropanal, these likewise undergo aldol condensation, in which case the condensation products of all possible aldehyde combinations result, for example 2-propyl-4-methyl-2-hexenal.
  • the products of the aldol condensation may by hydrogen catalytically to C ⁇ 0 alcohols, such as especially 2-propylheptanol, be driert hy-.
  • the catalysts of the hydroformylation are generally also suitable at higher temperatures; in general, however, more selective hydrogenation catalysts are 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 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 C ⁇ o-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 10 alcohols. e) separation
  • 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 subgroup VIII of the periodic table and which have at least one pyrrole phosphorus compound of the general formula I with substituted and / or fused pyrrole skeleton as ligands are advantageously suitable for use in a process for the preparation of 2-propylheptanol.
  • the catalysts have a high n-selectivity, so that both when using essentially pure 1-butene and when using l-butene / 2-butene-containing hydrocarbon mixtures, such as C-cuts, a good yield of n- Valeraldehyde is obtained.
  • the catalysts used according to the invention are also suitable for double bond isomerization from an internal 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 used according to the invention based on substituted or fused pyrrole skeletons show essentially no decomposition under the hydroformylation conditions, ie. H. in the presence of aldehydes.
  • the invention furthermore relates to catalysts comprising complexes with a metal of subgroup VIII of the Periodic Table of the Elements, which contain at least one compound of the formula I, as described above, as ligands, with the exception of compounds of the formula
  • R, R d , R e , R f (1-indolyl)
  • R c , R e (1-indolyl)
  • R, R d , R e , R f (1-indolyl)
  • R c , R ⁇ (1-indolyl);
  • R d , Rf ;
  • Phenyl c: R c , Re (i- indolyl);
  • R d , R f (1-pyrrolyl) d:
  • R c , Re (i- indolyl);
  • R, R (O-phenyl);
  • R 1 , R 111 , R IV , R v , R VI and R VI11 represent substituents other than hydrogen and
  • R 1 , R 111 , R VI and R VI11 represent substituents other than hydrogen and
  • R 1 , R 2 , R 3 and R 4 have the meanings given in claim 1.
  • catalysts comprising complexes with a metal of subgroup VIII of the Periodic Table, which have as ligands at least one compound of the formula I, as defined above, in which in at least one of the groups of the formula
  • radicals R 3 and R 4 are selected independently of one another from C ⁇ -C-alkyl radicals, in particular from methyl, ethyl, isopropyl and tert-butyl.
  • These catalysts preferably have 2, 3 or 4 of these groups.
  • Catalysts are particularly preferred, comprising complexes with a metal of subgroup VIII of the periodic table, which have as ligands at least one compound of the formula I, as defined above, in which at least one of the groups of the formula
  • These catalysts preferably have 2, 3 or 4 2,3-dialkylindol-1-yl groups, such as 2,3-dimethylindol-l-yl groups.
  • These catalysts preferably have 2, 3 or 4 3-alkylindol-1-yl groups, such as 3-methylindol-1-yl groups (1-skatolyl groups).
  • Catalysts based on 3-alkylindol-l-yl groups are particularly stable.
  • the metal of subgroup VIII is preferably selected from cobalt, rhodium, ruthenium or iridium.
  • the catalysts of the invention are very generally suitable in processes for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen.
  • catalysts based on ligands which have substituted and / or pyrrole groups integrated in an annulated ring system are notable for greater stability compared to catalysts based on ligands which have unsubstituted pyrrole groups , out.
  • the invention therefore furthermore relates to a process for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst comprising at least one complex of a metal from subgroup VIII with at least one ligand of general formula I as previously defined.
  • a hydroformylation catalyst comprising at least one complex of a metal from subgroup VIII with at least one ligand of general formula I as previously defined.
  • 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. propene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, allyl alcohols etc.
  • Suitable branched, internal olefins are preferably C to C 20 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 also C 5 bis
  • Cg-cycloalkenes such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as. B. whose C ⁇ ⁇ to C 20 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, 3-pentenoic acid methyl ester, 4-pentenoic acid methyl ester, oleic acid methyl ester, acrylic acid methyl ester, methacrylic acid methyl ester, unsaturated nitriles, such as 3-pentenenitrile, 4-pentenenitrile ether, acrylonitrile ether, acrylonitrile ether, acrylonitrile ether Vinyl ethyl ether, vinyl propyl ether etc., C ⁇ ⁇ to C 2 Q-alkenols, -alkenediols and -alkadienols, such as 2,7-octadie
  • Suitable substrates are further 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-heptadiene, 1, 7-0ctadiene, 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 to C 2 o-01efins, such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-0ctene , 4-0cten etc. and mixtures thereof.
  • preference is given to using an industrially accessible olefin mixture which in particular contains 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 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. the predominantly linear ⁇ -olefins obtained in the presence of alkyl aluminum chloride / titanium tetrachloride catalysts and the ⁇ -olefins obtained in the presence of nickel-phosphine complex catalysts according to the Shell Higher Olefin Process (SHOP).
  • SHOP Shell Higher Olefin Process
  • Suitable technically accessible olefin mixtures are still used in the paraffin dehydrogenation of corresponding petroleum fractions, e.g. B. the so-called petroleum or diesel oil fractions obtained.
  • Essentially three processes are used to convert paraffins, primarily n-paraffins to olefins:
  • 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 technical 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® from 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 the hydroformylation conditions to react.
  • 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 catalysts prepared from the compounds of general formula I according to the invention not only have a high activity with regard to the hydroformylation of terminal olefins, but also with respect to the isomerizing hydroformylation of olefins with internal double bonds to give aldehyde products with high linearity.
  • the olefins are hydrogenated only to a very small extent.
  • 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 represents a further area of use for the catalysts according to the invention.
  • the hydrocyanation catalysts according to the invention also comprise complexes of a metal of subgroup VIII, in particular cobalt, nickel, ruthenium, rhodium, palladium, platinum, preferably nickel, palladium and platinum and all particularly preferably nickel.
  • the metal in the metal complex according to the invention is zero-valued.
  • 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 analogous to the process described for the hydroformylation catalysts drive, be made in situ.
  • 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 special embodiment of the method according to the invention relates
  • a hydrocarbon mixture is preferably used which has a 1,3-butadiene content of at least 10% by volume, preferably at least
  • 1,3-butadiene-containing hydrocarbon mixtures are available on an industrial scale. So z. B. when working up oil by steam cracking naphtha as a C-cut
  • hydrocarbon mixture with a high total olefin content, with about 40% being 1,3-butadiene and the rest mono-olefins and polyunsaturated hydrocarbons and alkanes.
  • These streams always contain small amounts of generally up to 5% of alkynes, 1,2-dienes and vinyl
  • Pure 1,3-butadiene can e.g. B. be isolated by extractive distillation from commercially available hydrocarbon mixtures.
  • the catalysts of the invention can advantageously be used for the hydrocyanation of such olefin-containing, in particular 1,3-butadiene-containing, hydrocarbon mixtures, generally also without prior purification of the hydrocarbon 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 specialist
  • 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 the 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.
  • 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 (hydrocar- boxylation). This particularly includes the conversion of ethylene with carbon monoxide and water to propionic acid.
  • Another object of the invention is the use of catalysts comprising a P-containing compound according to the invention, as described above, for hydroformylation, hydrocyanation, carbonylation, hydrogenation, olefin oligomerization and polymerization and for metathesis.
  • Comparative ligand A was according to K.G. Moloy et al., J. Am. Chem. Soc. 117, pp. 7696-7710 (1995). The synthesis leads to
  • Comparative ligand B was produced according to US 5,710,344. The synthesis leads to a clean product with a 31 P-NMR shift of +69 ppm (CeD ß ). After storing the compound under argon for 20-10 days at room temperature, a noticeable darkening was found. A 31 P NMR analysis showed a ligand degradation of 20%.
  • Rh (CO) 2 acac rhodium biscarbonylacetylacetonate
  • Ligand C was analogous to KG Moloy et al., J. Am. Chem. Soc. 117, pp. 7696-7710 (1995). The synthesis leads to a clean product with a 31 P NMR shift of +67 ppm (C ⁇ O). After storing the compound under argon for 3 months at room temperature, no darkening was found. Neither heating nor treatment with water led to a material change.

Abstract

The invention relates to a method for the production of 2-propylheptanol, comprising the hydroformylation of butene, aldol condensation of the hydroformylation product thus obtained and the catalytic hydrogenation thereof. The invention also relates to novel catalysts for the hydroformylation step and to the further use thereof for carbonylation, hydrocyanation and hydrogenation based on a complex of a metal of the VIIIth subgroup with at least one ligand of general formula (1), wherein respectively two adjacent radicals R1,R2,R3 and R4 together with the carbon atoms of the pyrool ring to which they are bound can also represent a condensed ring system with 1,2 or 3 other rings, with the proviso that at least one of the radicals R1,R2,R3 and R4 do not represent hydrogen and R5 and R6 are not joined to each other, R5 and R6 independently from each other represent cylcoalkyl, heterocycloalkyl, aryl or heteroaryl, whereby one of the radicals R5 or R6 can also represent a bivalent bridging group Y binding similar or different ligands of formula (I) to each other in a covalent manner, and a and b independently from each other represent 0 or 1. .

Description

Verfahren zur Herstellung von 2-PropylheptanolProcess for the preparation of 2-propylheptanol
Beschreibungdescription
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von 2-Propylheptanol, umfassend die Hydroformylierung von Buten, eine Aldolkondensation der so erhaltenen Hydroformylierungsprodukte und deren katalytische Hydrierung. Die Erfindung betrifft weiterhin neue Katalysatoren für den Hydroformylierungsschritt und deren Verwendung.The present invention relates to a process for the preparation of 2-propylheptanol, comprising the hydroformylation of butene, an aldol condensation of the hydroformylation products thus obtained and their catalytic hydrogenation. The invention further relates to new catalysts for the hydroformylation step and their use.
Zur Modifizierung der thermoplastischen Eigenschaften einer Vielzahl großtechnisch wichtiger Produkte, wie speziell Kunststoffe, aber auch Lacke, Beschichtungsmittel, Dichtungsmassen etc. werden in großen Mengen so genannte Weichmacher eingesetzt. Eine wichtige Klasse von Weichmachern sind die Ester-Weichmacher, zu denen unter anderem Phthalsäureester, Trimellithsäureester, Phosphorsäureester etc. zählen. Die zur Herstellung der Ester-Weichmacher eingesetzten Alkohole werden allgemein als Weichmacheralkohole bezeichnet. Zur Herstellung von Ester-Weichmachern mit guten anwendungstechnischen Eigenschaften besteht ein Bedarf an Weichmacheralkoholen mit etwa 6 bis 12 Kohlenstoffatomen, die zu einem geringen Grad verzweigt sind (so genannte semilinearer Alkohole), und an entsprechenden Gemischen davon. Dazu zählt insbesondere 2-Propylheptanol und es enthaltende Alkoholgemische.So-called plasticizers are used in large quantities to modify the thermoplastic properties of a large number of products that are important on an industrial scale, such as plastics in particular, but also varnishes, coating agents, sealants, etc. An important class of plasticizers are the ester plasticizers, which include phthalic acid esters, trimellitic acid esters, phosphoric acid esters, etc. The alcohols used to prepare the ester plasticizers are generally referred to as plasticizer alcohols. In order to produce ester plasticizers with good performance properties, there is a need for plasticizer alcohols with about 6 to 12 carbon atoms, which are branched to a small extent (so-called semilinear alcohols), and for corresponding mixtures thereof. These include, in particular, 2-propylheptanol and alcohol mixtures containing it.
Die DE-A-100 03 482 beschreibt ein integriertes Verfahren zur Herstellung von Cg-Alkoholen und Cι0-Alkoholen aus Buten und Butan enthaltenden C4-Kohlenwasserstoffgemischen, bei dem man unter anderem das Kohlenwasserstoffgemisch einer Hydroformylierung unterzieht und die dabei erhaltenen C5-Aldehyde einer Aldolkondensation und anschließenden katalytischen Hydrierung zu Cio-Alkoholen unterzieht.DE-A-100 03 482 describes an integrated process for the preparation of Cg alcohols and Cι 0 alcohols from butene and butane-containing C 4 -hydrocarbon mixtures, in which, among other things, the hydrocarbon mixture is subjected to hydroformylation and the C 5 - Aldehydes subjected to an aldol condensation and subsequent catalytic hydrogenation to Cio-alcohols.
Allgemein kommt es bei der Hydroformylierung von Olefinen mit mehr als 2 C-Atomen aufgrund der möglichen CO-Anlagerung an jedes der beiden C-Atome einer Doppelbindung zur Bildung von Gemischen isomerer Aldehyde. Zusätzlich kann es auch zu einer Doppelbin- dungsisomerisierung kommen, d. h. zu einer Verschiebung interner Doppelbindungen auf eine terminale Position und umgekehrt. Bei der Herstellung von 2-Propylheptanol oder von Alkoholgemischen mit hohem Anteil von 2-Propylheptanol durch Hydroformylierung von Buten und anschließender Aldolkondensation kann es somit bei der Hydroformylierung leicht nicht nur zur Bildung von n-Valeralde- hyd, sondern auch von unerwünschten Produktaldehyden kommen, wo- 5 durch das gesamte Verfahren wirtschaftlich benachteiligt wird.In general, the hydroformylation of olefins with more than 2 carbon atoms leads to the formation of mixtures of isomeric aldehydes due to the possible CO addition to each of the two carbon atoms of a double bond. In addition, double bond isomerization can occur, ie a shift of internal double bonds to a terminal position and vice versa. In the production of 2-propylheptanol or alcohol mixtures With a high proportion of 2-propylheptanol by hydroformylation of butene and subsequent aldol condensation, hydroformylation can therefore easily lead not only to the formation of n-valeraldehyde but also to undesired product aldehydes, which is economically disadvantageous by the entire process.
Werden zur Hydroformylierung technische Gemische, beispielsweise C4-Schnitte eingesetzt, die in großen Mengen sowohl aus FCC-Anlagen als auch aus Steamcrackern zur Verfügung stehen und die imTechnical mixtures, for example C 4 cuts, are used for the hydroformylation, which are available in large quantities both from FCC plants and from steam crackers and which are used in
10 Wesentlichen aus einem Gemisch von 1,3-Butadien, Isobuten, 1-Bu- ten und 2-Buten sowie im Allgemeinen Butan bestehen, so muss der eingesetzte Hydroformylierungskatalysator möglichst selektiv die Hydroformylierung terminaler Olefine (1-Buten) ermöglichen und/ oder zu einer Verschiebung interner Doppelbindungen auf eine ter-If the mixture essentially consists of a mixture of 1,3-butadiene, isobutene, 1-butene and 2-butene and generally butane, the hydroformylation catalyst used must selectively enable and / or allow the hydroformylation of terminal olefins (1-butene) a shift of internal double bonds to a ter-
15 minale Position befähigt sein. An der Bereitstellung solcher Hy- droformylierungskatalysatoren besteht auch allgemein ein großes technisches Interesse. Eine weitere Forderung, die an Hydroformy- lierungskatalysatoren gestellt wird, ist eine gute Stabilität, sowohl unter den Hydroformylierungsbedingungen als auch bei der15 min position. There is also generally great technical interest in the provision of such hydroformylation catalysts. Another requirement that is placed on hydroformylation catalysts is good stability, both under the hydroformylation conditions and under the
20 Aufarbeitung, da Katalysatorverluste sich in besonderem Maße negativ auf die Wirtschaftlichkeit des entsprechenden Verfahrens auswirken.20 Refurbishment because catalyst losses have a particularly negative impact on the economy of the corresponding process.
L. A. van der Veen et al. beschreiben in Organometallics 1999, 25 18, S. 4765-4777 den Einsatz phosphacyclischer Diphosphine mit Rückgraten vom Xanthen-Typ zur Rhodium-katalysierten Hydroformylierung.L.A. van der Veen et al. describe in Organometallics 1999, 25 18, pp. 4765-4777 the use of phosphacyclic diphosphines with backbones of the xanthene type for rhodium-catalyzed hydroformylation.
S. C. van der Slot et al. beschreiben in Organometallics 2000, 30 19, S. 2504-2515 Phosphordiamid-Chelatliganden mit Bisphenoloder Xanthen-Rückgrat, deren Diamid-Einheit durch Biuret-Gruppen gebildet wird.S.C. van der Slot et al. describe in Organometallics 2000, 30 19, pp. 2504-2515 phosphorodiamide chelate ligands with bisphenol or xanthene backbone, the diamide unit of which is formed by biuret groups.
Die WO 98/42716 beschreibt ein Verfahren zur Herstellung von 35 2,2 '-Bisphosphino-1, l'-binaphthylen, deren Phosphoratome neben einer Vielzahl weiterer Reste auch Pyrrolgruppen tragen können.WO 98/42716 describes a process for the preparation of 35 2,2'-bisphosphino-1,1'-binaphthylene, the phosphorus atoms of which, in addition to a large number of other radicals, can also carry pyrrole groups.
Die US 3,816,452 beschreibt die Herstellung unterschiedlich substituierter Pyrrolyl-Monophosphane und deren Verwendung als 40 Flammschutzmittel.No. 3,816,452 describes the production of differently substituted pyrrolyl monophosphines and their use as 40 flame retardants.
K. G. Moloy et al. beschreiben in J. Am. Chem. Soc. 117, S. 7696-7710 (1995) unsubstituierte bzw. nicht anellierte ein- und zweikernige Pyrrolylverbindungen und deren Rh- und Mo-Kom- 45 plexe. D. C. Smith et al. beschreiben in Organometallics 19, S. 1427-1433 (2000) Platinkomplexe des Bis(dipyrrolylphos- phino)ethans. Eine konkrete Anwendung dieser Verbindungen und ihrer Metallkomplexe für katalytische Zwecke wird nicht erwähnt.KG Moloy et al. describe in J. Am. Chem. Soc. 117, pp. 7696-7710 (1995) unsubstituted or non-fused mono- and dinuclear pyrrolyl compounds and their Rh and Mo complexes. DC Smith et al. describe in Platinum complexes of bis (dipyrrolylphosphino) ethane in Organometallics 19, pp. 1427-1433 (2000). A specific application of these compounds and their metal complexes for catalytic purposes is not mentioned.
A. M. Trzeciak et al. beschreiben in J. Organomet. Chem. 552, S.159-164 (1998) Trispyrrolylphosphan-Rhodium-Komplexe als Katalysatoren zur Hydrierung von Olefinen und Arenen. Diese Komplexe basieren auf unsubstituierten bzw. nicht anellierten Pyrrolre- sten.A.M. Trzeciak et al. describe in J. Organomet. Chem. 552, pp. 159-164 (1998) trispyrrolylphosphine-rhodium complexes as catalysts for the hydrogenation of olefins and arenes. These complexes are based on unsubstituted or non-fused pyrrole residues.
A. M. Trzeciak et al. beschreiben in J. Chem. Soc, Dalton Trans. 1997, S. 1831-1837 Rhodiumkomplexe mit N-Pyrrolylphosphinen und deren Einsatz als Liganden für Hydroformylierungskatalysatoren.A.M. Trzeciak et al. describe in J. Chem. Soc, Dalton Trans. 1997, pp. 1831-1837 rhodium complexes with N-pyrrolylphosphines and their use as ligands for hydroformylation catalysts.
A. M. Trzeciak et al. beschreiben in C. R. Acad. Sei., Serie IIc, S. 235-239 (1999) die Hydroformylierung von Vinylsilanen mit Trispyrrolylphosphan-modifizierten Rhodiumkatalysatoren.A.M. Trzeciak et al. describe in C. R. Acad. Sei., Serie IIc, pp. 235-239 (1999) the hydroformylation of vinylsilanes with trispyrrolylphosphine-modified rhodium catalysts.
Die EP-A-0 754 715 beschreibt eine Katalysatorzusammensetzung, umfassend ein Metall der VIII. Nebengruppe und ein Alkylen-ver- brücktes Di(pyrrolyl-phenyl-phosphin) und deren Einsatz zur Herstellung von Polyketonen. Katalysatoren auf Basis von phosphor- haltigen Liganden mit substituierten bzw. anellierten Pyrrolre- sten sind nicht beschrieben.EP-A-0 754 715 describes a catalyst composition comprising a metal from transition group VIII and an alkylene-bridged di (pyrrolyl-phenyl-phosphine) and their use for the production of polyketones. Catalysts based on phosphorus-containing ligands with substituted or fused pyrrole residues are not described.
Die WO 00/56451 (DE-A-199 13 352) betrifft am Phosphoratom mit Pyrrolderivaten substituierte, cyclische Oxaphosphorine und die Verwendung dieser Liganden in Katalysatoren zur Hydroformylie- rung.WO 00/56451 (DE-A-199 13 352) relates to cyclic oxaphosphorines substituted on the phosphorus atom with pyrrole derivatives and the use of these ligands in catalysts for hydroformylation.
Die WO-A-96/01831 beschreibt chirale Diphosphine biheterocycli- scher Verbindungen von aromatischen, 5-atomigen Heterocyclen und deren Verwendung in chiralen Katalysatoren für stereoselektive Reaktionen. Dabei sind die heterocyclischen Kerne über eine Einfachbindung zwischen zwei Ringkohlenstoffatomen miteinander verknüpft .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 to one another via a single bond between two ring carbon atoms.
Die WO-A-99/52915 beschreibt chirale phosphoratomhaltige Liganden auf Basis von bicyclischen Verbindungen von carbocyclischen und heterocyclischen 5- bis 6-atomigen Verbindungen. Dabei sind die den Bicyclus bildenden aromatische Ringe über eine Einfachbindung zwischen zwei Ringkohlenstoffatomen miteinander verknüpft.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.
Die WO-A-99/52632 betrifft ein Verfahren zur Hydrocyanierung unter Einsatz phosphorhaltiger Chelatliganden mit 1, 1 '-Bisphenylen- oder 1, 1 '-Bisnaphthylenrückrat, in denen das Phosphoratom mit un- substituierten Pyrrol-, Indol- oder Imidazolgruppen substituiert sein kann, die über ein Ringstickstoffatom an das Phosphoratom gebunden sind.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 with un- substituted pyrrole, indole or imidazole groups which are bonded to the phosphorus atom via a ring nitrogen atom.
J. Shen et al. beschreiben in Organometallics 1998, 17,J. Shen et al. describe in Organometallics 1998, 17,
S. 3000-3005 kalorimetrische Studien an Diphosphin-Chelatligan- den, wobei unter anderem Hydrazid-verbrückte Diphenylphosphine und Alkylen-verbrückte Dipyrrolphosphine eingesetzt werden.P. 3000-3005 calorimetric studies on diphosphine chelating ligands, using inter alia hydrazide-bridged diphenylphosphines and alkylene-bridged dipyrrole phosphines.
H. Brunner und H. Weber beschreiben in Chem. Ber. 118,H. Brunner and H. Weber describe in Chem. Ber. 118
S. 3380-3395 (1985) optisch aktive Aminophosphane und deren Einsatz in der enantioselektiven Hydrosilylierung. Diese Liganden werden durch Kondensation von 2-Pyrrolcarbaldehyd bzw. 2-Acetyl- pyrrol mit 1-Phenylethylamin und gegebenenfalls weiteren Folge- reaktionen hergestellt und können Pyrrolstickstoff-phosphonierte Gruppen aufweisen.S. 3380-3395 (1985) optically active aminophosphanes and their use in enantioselective hydrosilylation. These ligands are produced by the condensation of 2-pyrrole carbaldehyde or 2-acetylpyrrole with 1-phenylethylamine and, if appropriate, further subsequent reactions and can have pyrrole nitrogen-phosphonated groups.
Die WO 01/58589 beschreibt Verbindungen des Phosphors, Arsens und des Antimons, basierend auf Diaryl-anellierten Bi- cyclo[2.2.2 ]-Grundkörpern und Katalysatoren, die diese als Liganden enthalten. Dabei können an das Atom der 5. Hauptgruppe prinzipiell auch Hetarylreste gebunden sein.WO 01/58589 describes compounds of phosphorus, arsenic and antimony based on diaryl-fused bicyclo [2.2.2] basic bodies and catalysts which contain these as ligands. In principle, hetaryl radicals can also be bound to the atom of the 5th main group.
Die DE-A-100 23 471 beschreibt ein Verfahren zur Hydroformylie- rung unter Einsatz eines Hydroformylierungskatalysators, der wenigstens einen Phosphinliganden umfasst, der zwei Triarylphos- phingruppen aufweist, wobei jeweils ein Arylrest der beiden Tri- arylphosphingruppen über eine Einfachbindung an eine nichtaromatische 5- bis 8-gliedrige carbocyclische oder heterocyclische verbrückende Gruppe gebunden ist. Dabei können die Phosphoratome als weitere Substituenten unter anderem auch Hetarylgruppen aufweisen.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, an aryl radical of the two triarylphosphine groups each having a single bond to a nonaromatic 5- is linked to 8-membered carbocyclic or heterocyclic bridging group. The phosphorus atoms can also have, among other things, hetaryl groups as further substituents.
Die DE-A-100 46 026.7 beschreibt ein Hydroformylierungsverfahren, bei dem man als Katalysator einen Komplex auf Basis einer Phosphor-, Arsen- oder Antimon-haltigen Verbindung als Liganden einsetzt, wobei diese Verbindung jeweils zwei ein P-, As- oder Sb- Atom und wenigstens zwei weitere Heteroatome aufweisende Gruppen gebunden an ein Xanthen-artiges Molekülgerüst aufweist.DE-A-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- Has atom and at least two further heteroatoms groups bound to a xanthene-like molecular structure.
R. Jackstell et al. beschreiben in Eur. J. Org. Chem. 2001, S. 3871-3877 (veröffentlicht am 10.09.2001) die Synthese von Pyrrol-, Indol- und Carbazolphosphanen und deren Einsatz als einzäh- nige Liganden bei der Hydroformylierung von 2-Penten. Die US 5,710,344 beschreibt phosphoratomhaltige Liganden mit 1, 1 '-Biphenylen- oder 1, 1 '-Binaphthylenrückrat, die mit unsubsti- tuierten Pyrrol-, Imidazol- oder Indolgruppen substituiert sein können, die über ein Ringstickstoffatom an das Phosphoratom ge- bunden sind. Diese Liganden eignen sich für Hydroformylierungska- talysatoren auf Basis von Metallen der VIII. Nebengruppe.R. Jackstell et al. describe in Eur. J. Org. Chem. 2001, pp. 3871-3877 (published on September 10, 2001) the synthesis of pyrrole, indole and carbazole phosphines and their use as monodentate ligands in the hydroformylation of 2-pentene. 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.
Die JP-A-2002 047294 beschreibt Phosphorchelatverbindungen mit Rückgraten vom Biphenylen-Typ, bei denen an die Phosphoratome zu- dem jeweils zwei Stickstoff-Heterocyclen gebunden sind. Sie eignen sich als Liganden für Hydroformylierungskatalysatoren. Dabei werden als Stickstoffheterocyclen sowohl unsubstituierte als auch substituierte und in anellierte Ringsysteme integrierte Pyrrol- gruppen eingesetzt. Eine Bevorzugung von substituierten sowie von in ein anelliertes Ringsystem integrierten und insbesondere zusätzlich substituierten Pyrrolgruppen ist diesem Dokument nicht zu entnehmen. Der Einsatz von Liganden vom Biphenylen-Typ, bei denen an die Phosphoratome wenigstens ein 3-Alkylindol-l-ylrest gebunden ist, wird in diesem Dokument nicht beschrieben.JP-A-2002 047294 describes phosphorus chelate compounds with backbones of the biphenylene type, in which two nitrogen heterocycles are also bonded to the phosphorus atoms. They are suitable as ligands for hydroformylation catalysts. Both unsubstituted and substituted pyrrole groups integrated in fused ring systems are used as nitrogen heterocycles. This document does not show any preference for substituted pyrrol groups and those which are integrated in a fused ring system and in particular additionally substituted pyrrole groups. The use of ligands of the biphenylene type in which at least one 3-alkylindol-l-yl radical is bonded to the phosphorus atoms is not described in this document.
Die unveröffentlichte internationale Anmeldung PCT/EP02/03543 beschreibt Pnicogenchelatverbindungen (d. h. Verbindungen des P, As oder Sb) , die eine über das Stickstoffatom an das Pnicogenatom gebundene Pyrrolgruppe aufweisen. Sie eignen sich für den Einsatz in Hydroformylierungskatalysatoren.The unpublished international application PCT / EP02 / 03543 describes pnicogen chelate compounds (i.e. compounds of P, As or Sb) which have a pyrrole group bonded to the pnicogen atom via the nitrogen atom. They are suitable for use in hydroformylation catalysts.
Die unveröffentlichte deutsche Patentanmeldung P 102 05 361.8 beschreibt Phosphorchelatverbindungen, bei denen an beide Phosphoratome jeweils drei Stickstoffatome kovalent gebunden sind, wel- ehe selbst Teil eines aromatischen Ringsystems sind.The unpublished German patent application P 102 05 361.8 describes phosphorus chelate compounds in which three nitrogen atoms are covalently bonded to both phosphorus atoms, which are themselves part of an aromatic ring system.
Der vorliegenden Erfindung liegt die Aufgabe zu Grunde, ein verbessertes Verfahren zur Herstellung von 2-Propylheptanol zur Verfügung zu stellen. Der Erfindung liegt weiterhin die Aufgabe zu Grunde, neue Liganden zur Verfügung zu stellen, die sich bei einem Einsatz in Hydroformylierungskatalysatoren durch eine besonders hohe Stabilität unter den Hydroformylierungsbedingungen und/ oder bei der Aufarbeitung auszeichnen.The object of the present invention is to provide an improved process for the preparation of 2-propylheptanol. Another object of the invention is to provide new ligands which, when used in hydroformylation catalysts, are notable for particularly high stability under the hydroformylation conditions and / or for workup.
Überraschenderweise wurde jetzt gefunden, dass die erste Aufgabe durch ein Verfahren gelöst wird, das die Hydroformylierung von Buten, eine Aldolkondensation der so erhaltenen Hydroformylierungsprodukte und deren anschließende katalytische Hydrierung um- fasst, wobei als Hydroformylierungskatalysator ein Komplex eines Metalls der VIII. Nebengruppe des Periodensystems mit wenigstens einer Pyrrol-Phosphor-Verbindung als Liganden eingesetzt wird. Dementsprechend wurde ein Verfahren zur Herstellung von 2-Propyl- heptanol gefunden, bei dem manSurprisingly, it has now been found that the first object is achieved by a process which comprises the hydroformylation of butene, an aldol condensation of the hydroformylation products thus obtained and their subsequent catalytic hydrogenation, a complex of a metal of subgroup VIII of the periodic table being used as the hydroformylation catalyst at least one pyrrole-phosphorus compound is used as ligand. Accordingly, a process for the preparation of 2-propyl-heptanol was found in which
a) Buten oder ein Buten enthaltendes C4-Kohlenwasserstoffgemisch in Gegenwart eines Hydroformylierungskatalysators mit Kohlen- monoxid und Wasserstoff unter Erhalt eines n-Valeraldehyd enthaltenden Hydroformylierungsprodukts hydroformyliert, wobei der Hydroformylierungskatalysator wenigstens einen Komplex eines Metalls der VIII. Nebengruppe mit wenigstens einem Liganden der allgemeinen Formel Ia) butene or a butene-containing C 4 -hydrocarbon mixture in the presence of a hydroformylation catalyst with carbon monoxide and hydrogen to give a hydroformylation product containing n-valeraldehyde, the hydroformylation catalyst comprising at least one complex of a metal from subgroup VIII with at least one ligand of the general formula I
R5-(0)a^ (O)b-R6 PR 5 - (0) a ^ (O) bR 6 P
Figure imgf000007_0001
Figure imgf000007_0001
umfasst, worinincludes, wherein
R1, R2, R3 und R4 unabhängig voneinander für Wasserstoff, Al- kyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, WC00Ra, WC00-M+, W(S03)Ra, W(S03)"M+, WP03(Ra) (Rb) , W(P03)2"(M+)2, WNE^-E2, W(NE1E2E3)+X", W0Ra, WSRa, (CHRkCH20)xRa, (CH2NE1)xRa, (CH2CH2NE1)xRa, Halogen, Trifluormethyl, Ni- tro, Acyl oder Cyano stehen,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 + , WP0 3 (R a ) (R b ), W (P0 3 ) 2 "(M +) 2 , WNE ^ -E 2 , W (NE 1 E 2 E 3 ) + X", W0R a , WSR a , (CHRkCH 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,
worinwherein
W für eine Einfachbindung, ein Heteroatom oder eine zweiwertige verbrückende Gruppe mit 1 bis 20 Brük- kenatomen steht,W represents a single bond, a heteroatom or a divalent bridging group with 1 to 20 bridge atoms,
Ra r E1, E2, E3 jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl oder Aryl bedeuten,R a r E 1 , E 2 , E 3 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
Rb für Wasserstoff, Methyl oder Ethyl steht,Rb represents hydrogen, methyl or ethyl,
M+ für ein Kationäquivalent steht,M + stands for a cation equivalent,
χ~ für ein Anionäquivalent steht und x für eine ganze Zahl von 1 bis 240 steht,χ ~ stands for an anion equivalent and x represents an integer from 1 to 240,
wobei jeweils zwei benachbarte Reste R1, R2, R3 und R4 zusammen mit den Kohlenstoffatomen des Pyrrolrings, an die sie gebunden sind, auch für ein kondensiertes Ringsystem mit 1, 2 oder 3 weiteren Ringen stehen können,where two adjacent radicals R 1 , R 2 , R 3 and R 4 together with the carbon atoms of the pyrrole ring to which they are bonded can also represent a condensed ring system with 1, 2 or 3 further rings,
mit der Maßgabe, dass wenigstens einer der Reste R1, R2, R3 oder R4 nicht für Wasserstoff steht, und dass R5 und R6 nicht mit einander verknüpft sind,with the proviso that at least one of the radicals R 1 , R 2 , R 3 or R 4 is not hydrogen and that R 5 and R 6 are not linked to one another,
R5 und R6 unabhängig voneinander für Cycloalkyl, Heterocyclo- alkyl, Aryl oder Hetaryl stehen, wobei einer der Reste R5 oder R6 auch für eine zweiwertige verbrückende Gruppe Y stehen kann, die zwei gleiche oder verschiedene Liganden oder Formel I kovalent miteinander verbindet, undR 5 and R 6 independently of one another are cycloalkyl, heterocycloalkyl, aryl or hetaryl, it being possible for one of the radicals R 5 or R 6 to also represent a divalent bridging group Y which covalently connects two identical or different ligands or formula I. , and
a und b unabhängig voneinander die Zahl 0 oder 1 bedeuten,a and b independently of one another denote the number 0 or 1,
b) gegebenenfalls das Hydroformylierungsprodukt einer Auftren- nung unter Erhalt einer an n-Valeraldehyd angereicherten Fraktion unterzieht,b) if appropriate, subjecting the hydroformylation product to a separation to obtain a fraction enriched in n-valeraldehyde,
c) das in Schritt a) erhaltene Hydroformylierungsprodukt oder die in Schritt b) erhaltene an n-Valeraldehyd angereichertec) the hydroformylation product obtained in step a) or the n-valeraldehyde enriched in step b)
Fraktion einer Aldolkondensation unterzieht,Subjecting the fraction to an aldol condensation,
d) die Produkte der Aldolkondensation mit Wasserstoff kataly- tisch zu Alkoholen hydriert, undd) the products of the aldol condensation are hydrogenated catalytically to give alcohols, and
e) gegebenenfalls die Hydrierprodukte einer Auftrennung unter Erhalt einer an 2-Propylheptanol angereicherten Fraktion unterzieht.e) optionally subjecting the hydrogenation products to separation to obtain a fraction enriched in 2-propylheptanol.
Die Erfinder haben weiterhin gefunden, das Pyrrolphosphorverbin- dungen, bei denen eine oder mehrere unsubstituierte Pyrrolgruppen über ihr Stickstoffatom an das Phosphoratom gebunden sind, leicht zur Zersetzung bzw. zur Ausbildung von unerwünschten Umsetzungsprodukten neigen. So wird eine merkliche Zersetzung bereits von sichtbarem Licht und/oder Temperaturen im Bereich der Raumtemperatur induziert und kann durch den Einsatz eines Schutzgases nicht verhindert werden. Speziell in Gegenwart von Aldehyden kommt es zu einer merklichen Bildung von polymeren Verunreinigungen. Beim Einsatz von Pyrrolphosphorverbindungen mit unsubsti- tuierten Pyrrolgruppen als Liganden für Hydroformylierungskataly- satoren kommt es somit zu einem Verlust an Katalysator und Wertprodukt, der sich insbesondere bei mehrstufigen Verfahren, die einen solchen Hydroformylierungsschritt umfassen, negativ auf die Wirtschaftlichkeit auswirkt. Überraschenderweise wurde nun gefunden, dass beim Einsatz von Phosphorverbindungen, bei denen eine substituierte und/oder in ein anelliertes Ringsystem integrierte Pyrrolgruppe über ihr pyrrolisches Stickstoffatom kovalent mit dem Phosphoratom verknüpft ist, die Bildung unerwünschter Produkte im Wesentlichen unterbleibt.The inventors have furthermore found that pyrrole-phosphorus compounds in which one or more unsubstituted pyrrole groups are bonded to the phosphorus atom via their nitrogen atom tend to decompose or form undesired reaction products. A noticeable decomposition is already induced by visible light and / or temperatures in the room temperature range and cannot be prevented by using a protective gas. In the presence of aldehydes in particular, polymeric impurities are noticeably formed. When using pyrrole phosphorus compounds with unsubstituted pyrrole groups as ligands for hydroformylation catalysts, there is therefore a loss of catalyst and product of value, which is particularly the case in multi-stage processes which include such a hydroformylation step, has a negative impact on economy. Surprisingly, it has now been found that the use of phosphorus compounds in which a substituted and / or pyrrole group integrated in a fused ring system is covalently linked to the phosphorus atom via its pyrrolic nitrogen atom essentially prevents the formation of undesired products.
Im Rahmen der vorliegenden Anmeldung steht die verbrückende Gruppe Y nicht für eine Gruppe der FormelIn the context of the present application, the bridging group Y does not represent a group of the formula
Figure imgf000009_0001
Figure imgf000009_0001
worinwherein
R7, R8' R9 und R10 unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Alkoxy, Halogen, S03H, Sulfonat, NEE5, Al- kylen-NE4E5, Trifluormethyl, Nitro, Alkoxycarbonyl, Carboxyl oder Cyano stehen, worin E4 und E5 jeweils gleiche oder ver- schiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl und Aryl bedeuten,R 7 , R 8 'R 9 and R 10 independently of one another for hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, S0 3 H, sulfonate, NEE 5 , alkylene-NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl, Are carboxyl or cyano, in which E 4 and E 5 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
A1 und A2 unabhängig voneinander für 0, S, SiR15R16, NR15 oder CR17R18 stehen, wobeiA 1 and A 2 independently of one another represent 0, S, SiR 15 R 16 , NR 15 or CR 17 R 18 , where
R17 und R18 unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen oder die Gruppe R17 gemeinsam mit einer weiteren Gruppe R17 oder die Gruppe R18 gemeinsam mit einer weiteren Gruppe R18 eine intra- molekulare Brückengruppe D bilden,R 17 and R 18 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or the group R 17 together with another group R 17 or the group R 18 together with another group R 18 is an intramolecular bridge group D form,
D eine zweibindige Brückengruppe, ausgewählt aus den GruppenD a two-gang bridge group selected from the groups
Figure imgf000009_0002
ist, in denen R19 und R20 unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Halogen, Trifluormethyl, Carboxyl, Carboxylat oder Cyano stehen oder miteinander zu einer C3- bis C-Alkylenbrücke verbunden sind,
Figure imgf000009_0002
is where R 19 and R 20 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 bridge,
R21, R22, R23 und R24 unabhängig voneinander für Wasserstoff,R 21 , R 22 , R 23 and R 24 independently of one another for hydrogen,
Alkyl, Cycloalkyl, Aryl, Halogen, Trifluormethyl, COOH,Alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH,
Carboxylat, Cyano, Alkoxy, S03H, Sulfonat, NE4E5, Alky-Carboxylate, cyano, alkoxy, S0 3 H, sulfonate, NE 4 E 5 , alky-
Ien-NE4E5E6+X-, Acyl oder Nitro stehen, wobei X~ für ein Anionäquivalent steht, undIen-NE 4 E 5 E 6+ X-, acyl or nitro, where X ~ stands for an anion equivalent, and
c 0 oder 1 ist.c is 0 or 1.
Derartige Verbindungen sind Gegenstand der internationalen Anmel- düng PCT/EP02/03543.Such connections are the subject of the international application PCT / EP02 / 03543.
Im Rahmen der vorliegenden Erfindung umfasst der Ausdruck Alkyl geradkettige und verzweigte Alkylgruppen. Vorzugsweise handelt es sich dabei um geradkettige oder verzweigte Cι-Co-Alkyl-, bevor- zugterweise Cι-Cι2-Alkyl- und besonders bevorzugt Ci-Cs-Alkyl- und ganz besonders bevorzugt Cι-C4-Alkylgruppen. Beispiele für Alkylgruppen sind insbesondere Methyl, Ethyl, Propyl, Isopropyl, n-Bu- tyl, 2-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, 2-Pentyl, 2-Me- thylbutyl, 3-Methylbutyl, 1,2-Dimethylpropyl, 1, 1-Dimethylpropyl, 2,2-Dimethylpropyl, 1-Ethylpropyl, n-Hexyl, 2-Hexyl, 2-Methylpen- tyl, 3-Methylpentyl, 4-Methylpentyl, 1,2-Dimethylbutyl, 1,3-Dime- thylbutyl, 2,3-Dimethylbutyl, 1, 1-Dimethylbutyl, 2, 2-Dimethylbu- tyl, 3,3-Dimethylbutyl, 1, 1,2-Trimethylpropyl, 1,2,2-Trimethyl- propyl, 1-Ethylbutyl, 2-Ethylbutyl, l-Ethyl-2-methylpropyl, n- Heptyl, 2-Heptyl, 3-Heptyl, 2-Ethylpentyl, 1-Propylbutyl, Octyl, Nonyl , Decyl .In the context of the present invention, the expression alkyl includes straight-chain and branched alkyl groups. These are preferably straight-chain or branched C 1 -C 18 -alkyl, preferably C 1 -C 2 -alkyl and particularly preferably C 1 -C 4 -alkyl and very particularly preferably C 1 -C 4 -alkyl groups. Examples of 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-trimethyl - propyl, 1-ethylbutyl, 2-ethylbutyl, l-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl, nonyl, decyl.
Der Ausdruck Alkyl umfasst auch substituierte Alkylgruppen. Substituierte Alkylreste weisen vorzugsweise 1, 2, 3, 4 oder 5, ins- besondere 1, 2 oder 3 Substituenten, ausgewählt unter Cycloalkyl, Aryl, Hetaryl, Halogen, NE^2, (NEXE2E3)+, Carboxyl, Carboxylat, -S03H und Sulfonat auf.The term alkyl also includes substituted alkyl groups. Substituted alkyl radicals preferably have 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from cycloalkyl, aryl, hetaryl, halogen, NE ^ 2 , (NE X E 2 E 3 ) + , carboxyl, Carboxylate, -S0 3 H and sulfonate.
Der Ausdruck Cycloalkyl umfasst unsubstituierte und substituierte Cycloalkylgruppen. Bei der Cycloalkylgruppe handelt es sich vorzugsweise um eine C5-C7-Cycloalkylgruppe, wie Cyclopentyl, Cyclo- hexyl oder Cycloheptyl.The term cycloalkyl includes unsubstituted and substituted cycloalkyl groups. The cycloalkyl group is preferably a C5-C7 cycloalkyl group such as cyclopentyl, cyclohexyl or cycloheptyl.
Wenn die Cycloalkylgruppe substituiert ist, weist sie vorzugs- weise 1, 2, 3, 4 oder 5, insbesondere 1, 2 oder 3 Substituenten, ausgewählt unter Alkyl, Alkoxy oder Halogen auf. Der Ausdruck Heterocycloalkyl im Sinne der vorliegenden Erfindung umfaßt gesättigte, cycloaliphatische Gruppen mit im Allgemeinen 4 bis 7, vorzugsweise 5 oder 6 Ringatomen, in denen 1 oder 2 der Ringkohlenstoffatome durch Heteroatome, ausgewählt aus den Ele- menten Sauerstoff, Stickstoff und Schwefel, ersetzt sind und die gegebenenfalls substituiert sein können, wobei im Falle einer Substitution, diese heterocycloaliphatischen Gruppen 1, 2 oder 3, vorzugsweise 1 oder 2, besonders bevorzugt 1 Substituenten, ausgewählt aus Alkyl, Aryl, C00Ra, C00~M+ und NE^2, bevorzugt Alkyl, tragen können. Beispielhaft für solche heterocycloaliphatischen Gruppen seien Pyrrolidinyl, Piperidinyl, 2,2, 6, 6-Tetrame- thyl-piperidinyl, Imidazolidinyl, Pyrazolidinyl, Oxazolidinyl, Morpholidinyl, Thiazolidinyl, Isothiazolidinyl, Isoxazolidinyl, Piperazinyl-, Tetrahydrothiophenyl, Tetrahydrofuranyl , Tetra- hydropyranyl, Dioxanyl genannt.If the cycloalkyl group is substituted, it preferably has 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from alkyl, alkoxy or halogen. The term heterocycloalkyl in the context 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 which may optionally be substituted, where in the case of a substitution these heterocycloaliphatic groups 1, 2 or 3, preferably 1 or 2, particularly preferably 1, selected from alkyl, aryl, C00R a , C00 ~ M + and NE ^ 2 , preferably alkyl, can wear. Examples of such heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2, 6, 6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothydhenoluryl, tyridethyridanyl, tyridylanyl, tyridethanyl, tyranethanyl, tyranethanyl called.
Aryl steht vorzugsweise für Phenyl, Tolyl, Xylyl, Mesityl, Naph- thyl, Anthracenyl, Phenanthrenyl, Naphthacenyl und insbesondere für Phenyl oder Naphthyl.Aryl preferably represents phenyl, tolyl, xylyl, mesityl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular phenyl or naphthyl.
Substituierte Arylreste weisen vorzugsweise 1, 2, 3, 4 oder 5, insbesondere 1, 2 oder 3 Substituenten, ausgewählt unter Alkyl, Alkoxy, Carboxyl, Carboxylat, Trifluormethyl, -S03H, Sulfonat, E^2, Alkylen-NEiE2, Nitro, Cyano oder Halogen auf.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, E ^ 2 , alkylene-NEiE 2 , Nitro, cyano or halogen.
Hetaryl steht vorzugsweise für Pyrrolyl, Pyrazolyl, Imidazolyl, Indolyl, Carbazolyl, Pyridyl, Chinolinyl, Acridinyl, Pyridazinyl, Pyrimidinyl oder Pyrazinyl.Hetaryl is preferably pyrrolyl, pyrazolyl, imidazolyl, indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.
Substituierte Hetarylreste weisen vorzugsweise 1, 2 oder 3 Substituenten, ausgewählt unter Alkyl, Alkoxy, Carboxyl, Carboxylat, -S03H, Sulfonat, NEXE2, Alkylen-NE1E2, Trifluormethyl oder Halogen auf.Substituted hetaryl radicals preferably have 1, 2 or 3 substituents selected from alkyl, alkoxy, carboxyl, carboxylate, -S0 3 H, sulfonate, NE X E 2 , alkylene-NE 1 E 2 , trifluoromethyl or halogen.
Die obigen Ausführungen zu Alkyl-, Cycloalkyl- und Arylresten gelten entsprechend für Alkoxy-, Cycloalkyloxy- und Aryloxyreste .The above statements on alkyl, cycloalkyl and aryl radicals apply accordingly to alkoxy, cycloalkyloxy and aryloxy radicals.
Die Reste NEXE2 und NE4E5 stehen vorzugsweise für N,N-Dimethyla- mino, N,N-Diethylamino, N,N-Dipropylamino, N,N-Diisopropylamino, N,N-Di-n-butylamino, N,N-Di-tert.-butylamino, N,N-Dicyclohexyla- mino oder N,N-Diphenylamino.The radicals NE X E 2 and NE 4 E 5 preferably represent N, N-dimethylaamino, 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 steht für Fluor, Chlor, Brom und Iod, bevorzugt für Fluor, Chlor und Brom. Carboxylat und Sulfonat stehen im Rahmen dieser Erfindung vorzugsweise für ein Derivat einer Carbonsäurefunktion bzw. einer Sulfonsäurefunktion, insbesondere für ein Metallcarboxylat oder -sulfonat, eine Carbonsäure- oder Sulfonsäureesterfunktion oder eine Carbonsäure- oder Sulfonsäureamidfunktion. Dazu zählen z. B. die Ester mit Cι-C-Alkanolen, wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, sec.-Butanol und tert.-Butanol.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+ steht für ein Kationäquivalent, d. h. für ein einwertiges Kat- ion oder den einer positiven Einfachladung entsprechenden Anteil eines mehrwertigen Kations. Vorzugsweise steht M+ für ein Alkalimetallkation, wie z. B. Li+, Na+ oder K+ oder für ein Erdalkalimetallkation, für NH+ oder eine quartäre Ammonium-Verbindung, wie sie durch Protonierung oder Quarternierung von Aminen erhältlich ist. Bevorzugt handelt es sich um Alkalimetallkationen, insbesondere um Natrium- oder Kaliumionen.M + stands for a cation equivalent, ie for a monovalent cation or the portion of a multivalent cation corresponding to a positive single charge. Preferably M + stands for an alkali metal cation, such as. B. Li + , Na + or K + or for an alkaline earth metal cation, for NH + or a quaternary ammonium compound, as can be obtained by protonation or quaternization of amines. Alkali metal cations are preferred, in particular sodium or potassium ions.
X- steht für ein Anionäquivalent, d. h. für ein einwertiges Anion oder den einer negativen Einfachladung entsprechenden Anteil ei- nes mehrwertigen Anions. Vorzugsweise steht X- für ein Carbonat, Carboxylat oder Halogenid, besonders bevorzugt für Cl_ und Br_.X- stands for an anion equivalent, ie for a monovalent anion or the portion of a polyvalent anion corresponding to a negative single charge. X- is preferably a carbonate, carboxylate or halide, particularly preferably Cl_ and Br_ .
Die Werte für x stehen für eine ganze Zahl von 1 bis 240, vorzugsweise für eine ganze Zahl von 3 bis 120.The values for x stand for an integer from 1 to 240, preferably for an integer from 3 to 120.
Kondensierte Ringsysteme können durch Anellierung verknüpfte (ankondensierte) aromatische, hydroaromatische und cyclische Verbindungen sein. Kondensierte Ringsysteme bestehen aus zwei, drei oder mehr als drei Ringen. Je nach der Verknüpfungsart unter- scheidet man bei kondensierten Ringsystemen zwischen einer ortho- Anellierung, d. h. jeder Ring hat mit jedem Nachbarring jeweils eine Kante, bzw. zwei Atome gemeinsam, und einer peri-Anellie- rung, bei der ein Kohlenstoffatom mehr als zwei Ringen angehört. Bevorzugt unter den kondensierten Ringsystemen sind ortho-konden- sierte Ringsysteme.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, ie. 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.
a) Hydroformylierunga) Hydroformylation
Als Einsatzmaterial für die Hydroformylierung eignet sich sowohl im Wesentlichen reines 1-Buten als auch Gemische von 1-Buten mit 2-Buten und technisch erhältliche C-Kohlenwasserstoffströme, die 1-Buten und/oder 2 Buten enthalten. Vorzugsweise eignen sich C4-Schnitte, die in großen Mengen aus FCC-Anlagen und aus Stea - crackern zur Verfügung stehen. Diese bestehen im Wesentlichen aus einem Gemisch von 1,3-Butadien, der isomeren Butene und Butan. Als Einsatzmaterial geeignete C -Kohlenwasserstoffströme enthalten z. B. 50 bis 99, vorzugsweise 60 bis 90 Mol-% Butene und 1 bis 50, vorzugsweise 10 bis 40 Mol-% Butane. Vorzugsweise umfasst die Butenfraktion 40 bis 60 Mol-% 1-Buten, 20 bis 30 Mol-% 2-Buten und weniger als 5 Mol-%, insbesondere weniger als 3 Mol-% Isobuten (bezogen auf die Butenfraktion) . Als besonders bevorzugter Einsatzstoff wird das sogenannte Raffinat II verwendet, bei dem es sich um ein Isobuten-abgereicherten C4-Schnitt aus einer FCC- Anlage oder einen Steamcracker handelt.Suitable feedstocks for the hydroformylation are both essentially pure 1-butene and mixtures of 1-butene with 2-butene and technically obtainable C-hydrocarbon streams which contain 1-butene and / or 2 butene. C 4 cuts, which are available in large quantities from FCC systems and from steak crackers, are preferably suitable. These consist essentially of a mixture of 1,3-butadiene, 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 4 cut from an FCC system or a steam cracker, is used as a particularly preferred feedstock.
Hydroformylierungskatalysatoren auf Basis der erfindungsgemäß eingesetzten Phosphorpyrrolverbindungen als Liganden weisen vorteilhafterweise eine hohe n-Selektivität, auch beim Einsatz von 2-Buten und 2-butenhaltigen Kohlenwasserstoffgemischen als Ein- satzmaterial auf. Somit können in dem erfindungsgemäßen Verfahren auch solche Einsatzstoffe wirtschaftlich eingesetzt werden, da der angestrebte n-Valeraldehyd in guten Ausbeuten resultiert.Hydroformylation catalysts based on the phosphoropyrrole compounds used according to the invention as ligands advantageously have a high n-selectivity, even when using 2-butene and 2-butene-containing hydrocarbon mixtures as starting material. Thus, such starting materials can also be used economically in the process according to the invention, since the desired n-valeraldehyde results in good yields.
Bevorzugt wird in Schritt a) des erfindungsgemäßen Verfahrens eine Verbindung der allgemeinen Formel I eingesetzt, worin einer oder zwei der Reste R1, R2, R3 und R4 für einen der zuvor genannten, von Wasserstoff verschiedenen Substituenten stehen und die übrigen für Wasserstoff stehen. Bevorzugt sind Verbindungen der Formel I, die in 2-Position, 2,5-Position oder 3,4-Position einen von Wasserstoff verschiedenen Substituenten tragen.In step a) of the process according to the invention, preference is given to using a compound of the general formula I in which one or two of the radicals R 1 , R 2 , R 3 and R 4 are one of the abovementioned substituents other than hydrogen and the rest are hydrogen stand. Compounds of the formula I which have a substituent other than hydrogen in the 2-position, 2,5-position or 3,4-position are preferred.
Vorzugsweise sind die von Wasserstoff verschiedenen Substituenten R1 bis R4 unabhängig voneinander ausgewählt unter Ci- bis Cs-, vorzugsweise Ci- bis C4-Alkyl, speziell Methyl, Ethyl, Isopropyl und tert.-Butyl, Alkoxycarbonyl, wie Methoxycarbonyl, Ethoxycar- bonyl, Isopropyloxycarbonyl und tert.-Butyloxycarbonyl sowie Tri- fluormethyl .The substituents R 1 to R 4 which are different from hydrogen are preferably selected independently of one another from Ci to Cs, preferably Ci to C 4 alkyl, especially methyl, ethyl, isopropyl and tert-butyl, alkoxycarbonyl, such as methoxycarbonyl, ethoxycar- bonyl, isopropyloxycarbonyl and tert-butyloxycarbonyl as well as trifluoromethyl.
Bevorzugt wird in Schritt a) des erfindungsgemäßen Verfahrens eine Verbindung der allgemeinen Formel I eingesetzt, worin die Reste R1 und R2 und/oder R3 und R4 zusammen mit den Kohlenstoffatomen des Pyrrolrings, an die sie gebunden sind, für ein kondensiertes Ringsystem mit 1, 2 oder 3 weiteren Ringen stehen. Wenn R1 und R2 und/oder R3 und R4 für ein ankondensiertes, also anellier- tes Ringsystem stehen, so handelt es sich bevorzugt um Benzoloder Naphthalinringe. Anellierte Benzolringe sind vorzugsweise unsubstituiert und weisen 1, 2 oder 3, insbesondere 1 oder 2 Substituenten auf, die ausgewählt sind unter Alkyl, Alkoxy, Halogen, S03H, Sulfonat, NE^2, Alkylen-NE^2, Trifluormethyl, Nitro, C00Ra, Alkoxycarbonyl, Acyl und Cyano. Anellierte Naphthalinringe sind vorzugsweise unsubstituiert oder weisen im nichtanellierten Ring und/oder im anellierten Ring je 1, 2 oder 3, insbesondere 1 oder 2 der zuvor bei den anellierten Benzolringen genannten Substituenten auf. Wenn R1 und R2 für ein ankondensiertes Ringsystem stehen, so stehen R3 und R4 vorzugsweise für Wasserstoff oder steht R4 für Wasserstoff und R3 für einen Substituenten, der aus- gewählt ist unter Ci- bis Cs-Alkyl, vorzugsweise Ci- bis C -Alkyl, speziell Methyl, Ethyl, Isopropyl oder tert.-Butyl.In step a) of the process according to the invention, preference is given to using a compound of the general formula I in which 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 attached form 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 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, SO 3 H, sulfonate, NE ^ 2 , alkylene-NE ^ 2 , trifluoromethyl, nitro, C00R a , alkoxycarbonyl, acyl and cyano. Fused naphthalene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or, in the non-fused ring and / or in the fused ring 2 of the substituents previously mentioned for the fused benzene rings. If R 1 and R 2 stand for a fused-on ring system, R 3 and R 4 preferably stand for hydrogen or R 4 stands for hydrogen and R 3 stands for a substituent which is selected from Ci to Cs alkyl, preferably Ci - to C-alkyl, especially methyl, ethyl, isopropyl or tert-butyl.
Ist der Einsatz der Verbindungen der Formel I in einem wässrigen Hydroformylierungsmedium vorgesehen, steht wenigstens einer der Reste R1, R2, R3 und/oder R4 für eine polare (hydrophile) Gruppe, wobei dann in der Regel bei der Komplexbildung mit einem Gruppe VIII Metall wasserlösliche Komplexe resultieren. Bevorzugt sind die polaren Gruppen ausgewählt unter C00Ra, COO-M+, S03Ra, S03~M+, NEiE2, Alkylen-NE1E2, NE^E^X", Alkylen-NE1E2E3+X-, ORa, SRa, (CHRbCH20)xRa oder (CH^H^fE1) )xRa, worin Ra, E1, E2, E3, Rb, M+, X~ und x die zuvor angegebenen Bedeutungen besitzen.If the use of the compounds of the formula I is intended in an aqueous hydroformylation medium, at least one of the radicals R 1 , R 2 , R 3 and / or R 4 represents a polar (hydrophilic) group, in which case, as a rule, the complex formation with a Group VIII metal water-soluble complexes result. The polar groups are preferably selected from C00R a , COO-M +, S0 3 R a , S0 3 ~ M + , NEiE 2 , alkylene-NE 1 E 2 , NE ^ E ^ X ", alkylene-NE 1 E 2 E 3 + X-, OR a , SR a , (CHR b CH 2 0) x R a or (CH ^ H ^ fE 1 )) x R a , where R a , E 1 , E 2 , E 3 , R b , M + , X ~ and x have the meanings given above.
Bevorzugt wird in dem erfindungsgemäßen Verfahren ein Hydroformy- lierungskatalysator eingesetzt, der wenigstens einen Liganden der Formel I umfasst, in dem die über das pyrrolische Stickstoffatom an das Phosphoratom gebundene Pyrrolgruppe der FormelIn the process according to the invention, preference is given to using a hydroformylation catalyst which comprises at least one ligand of the formula I in which the pyrrole group of the formula which is bonded to the phosphorus atom via the pyrrolic nitrogen atom
Figure imgf000014_0001
Figure imgf000014_0001
ausgewählt ist unter Gruppen der Formeln I.a bis I.kis selected from groups of formulas I.a to I.k
Alk. Alk ,N. ^ COOAlkAlk. Alk, N. ^ COOAlk
\\ ft w\\ ft w
(I.a) (I.b)(I.a) (I.b)
AlkOOAlkOO
Figure imgf000014_0002
(I.c) (I.d)
Figure imgf000015_0001
Figure imgf000014_0002
(Ic) (Id)
Figure imgf000015_0001
(I.e) (I.f) (i-g)(I.e) (I.f) (i-g)
worinwherein
Alk eine Cι-C4-Alkylgruppe ist undAlk is a -CC 4 alkyl group and
R9, Rh, R1 und Rk unabhängig voneinander für Wasserstoff, CJ-C4-A1- kyl, Cι-C -Alkoxy, Acyl, Halogen, Trifluormethyl, Cι-C4-Alko- xycarbonyl oder Carboxyl stehen.R9, R h , R 1 and R k independently of one another are hydrogen, C J -C 4 -A1- kyl, C 1 -C 4 alkoxy, acyl, halogen, trifluoromethyl, C 1 -C 4 alkoxycarbonyl or carboxyl.
Zur Veranschaulichung werden im Folgenden einige vorteilhafte Pyrrolgruppen aufgelistet:Some advantageous pyrrole groups are listed below for illustration purposes:
Figure imgf000015_0003
Figure imgf000015_0003
(I.al) (I.a2) (I.bl)(I.al) (I.a2) (I.bl)
Figure imgf000015_0004
Figure imgf000015_0004
(I.b2) (I.cl)
Figure imgf000016_0001
COOCH3 (I.b2) (I.cl)
Figure imgf000016_0001
COOCH 3
(I.C2) (I.dl)(I.C2) (I.dl)
Figure imgf000016_0002
Figure imgf000016_0002
(I.d2) (I.el) (I.e2)(I.d2) (I.el) (I.e2)
Figure imgf000016_0003
Figure imgf000016_0003
H3CH 3 C
(I.f3) (I.gl) (I.hl)(I.f3) (I.gl) (I.hl)
Figure imgf000016_0004
Figure imgf000016_0004
(I.il) (I.kl) (I.k2)(I.il) (I.kl) (I.k2)
Besonders vorteilhaft ist die 3-Methylindolylgruppe (Skatolyl- gruppe) der Formel I.fl. Hydroformylierungskatalysatoren auf Basis von Liganden, die eine oder mehrere 3-Methylindolylgruppe(n) an das Phosphoratom gebunden aufweisen, zeichnen sich durch eine besonders hohe Stabilität und somit besonders lange Katalysatorstandzeiten aus.The 3-methylindolyl group (skatolyl group) of the formula I.fl. Hydroformylation catalysts based on ligands which have one or more 3-methylindolyl group (s) bonded to the phosphorus atom are distinguished by a particularly high stability and thus particularly long catalyst life.
In einer geeigneten Ausführungsform kann der Substituent R1 ge- meinsam mit dem Substituenten R5 oder kann der Substituent R2 gemeinsam mit dem Substituenten R5 für eine zweibindige Gruppe -I-W- stehen, worinIn a suitable embodiment, the substituent R 1 together with the substituent R 5 or the substituent R 2 together with the substituent R 5 can represent a divalent group -IW-, in which
I für eine chemische Bindung oder für O, S, SiRαRß, NRY oder ge- gebenenfalls substituiertes Cχ-Cιo-Alkylen, bevorzugtI for a chemical bond or for O, S, SiR α Rß, NR Y or optionally substituted Cχ-Cιo-alkylene, preferred
CRδRεsteht, worin Rα, R^, Rv, Rδ und Rε unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen, undCR δ R ε , where R α , R ^, R v , R δ and R ε independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, and
W für Cycloalkyl, Cycloalkoxy, Aryl, Aryloxy, Hetaryl oder Hetaryloxy steht.W represents cycloalkyl, cycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy.
Beispielsweise kann die Pyrrolgruppe gemeinsam mit der Gruppe -I-W- fürFor example, the pyrrole group together with the group -I-W- for
Figure imgf000017_0001
Figure imgf000017_0001
Figure imgf000017_0002
stehen.
Figure imgf000017_0002
stand.
Bevorzugt werden in dem erfindungsgemäßen Verfahren Hydroformy- lierungskatalysatoren eingesetzt, die wenigstens einen Liganden der Formel I umfassen, worin die über das pyrrolische Stick- stoffatom an das Phosphoratom gebundene Pyrrolgruppe gemeinsam mit R5 eine Gruppe der Formel
Figure imgf000018_0001
Hydroformylation catalysts which comprise at least one ligand of the formula I are preferably used in the process according to the invention, in which the pyrrole group bonded to the phosphorus atom via the pyrrolic nitrogen atom together with R 5 is a group of the formula
Figure imgf000018_0001
bildet, worinforms what
I für eine chemische Bindung oder für O, S, SiRαRß,NRγ oder gegebenenfalls substituiertes Cι-Cιo-Alkylen, bevorzugt CRδRε, steht, worin Rα , R^, Rγ, R und Rε unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,I stands for a chemical bond or for O, S, SiR α Rß, NR γ or optionally substituted Cι-Cιo alkylene, preferably CR δ R ε , wherein R α , R ^, R γ , R and R ε independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
R1, R1', R2, R2', R3, R3', R4 und R4' unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, WCO0Ra, WCOO"M+, W(S03)Ra, W(S03)-M+, WP03(Ra) (Rb) f W(P03)2"(M+)2, WNEiE2, W(NE1E2E3)+X-, W0Ra, WSRa, (CHRbCH20)xRa, (CH2NEl)xRa, (CH2CH2NE1)xR , Halogen, Triflu- ormethyl, Nitro, Acyl oder Cyano stehen,R 1 , R 1 ', R 2 , R 2 ', R 3 , R 3 ', R 4 and R 4 ' independently of one another for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCO0R a , WCOO "M + , W (S0 3 ) R a , W (S0 3 ) -M + , WP0 3 (R a ) (R b ) f W (P0 3 ) 2 "(M + ) 2 , WNE i E 2 , W (NE 1 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, halogen, trifluor ormethyl, nitro, acyl or cyano,
worinwherein
W für eine Einfachbindung, ein Heteroatom oder eine zweiwertige verbrückende Gruppe mit 1 bis 20 Brük- kenatomen steht,W represents a single bond, a heteroatom or a divalent bridging group with 1 to 20 bridge atoms,
Ra, E1, E2, E3 jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl oderR a , E 1 , E 2 , E 3 are each the same or different radicals selected from hydrogen, alkyl, cycloalkyl or
Aryl bedeuten,Aryl mean
Rb für Wasserstoff, Methyl oder Ethyl steht,R b represents hydrogen, methyl or ethyl,
M+ für ein Kationäquivalent steht,M + stands for a cation equivalent,
X- für ein Anionäquivalent steht undX- stands for an anion equivalent and
x für eine ganze Zahl von 1 bis 240 steht,x represents an integer from 1 to 240,
wobei jeweils zwei benachbarte Reste R1 und R2 und/oder R1' und R2' zusammen mit den Kohlenstoffatomen des Pyrrolrings, an die sie gebunden sind, auch für ein kondensiertes Ringsystem mit 1, 2 oder 3 weiteren Ringen stehen können. Vorzugsweise steht I für eine chemische Bindung oder eine Cι-C -Alkylengruppe, besonders bevorzugt eine Methylengruppe.where two adjacent radicals R 1 and R 2 and / or R 1 'and R 2 ' together with the carbon atoms of the pyrrole ring to which they are attached can also represent a condensed ring system with 1, 2 or 3 further rings. I is preferably a chemical bond or a C 1 -C 8 -alkylene group, particularly preferably a methylene group.
Zur Veranschaulichung werden im Folgenden einige vorteilhafte "Bispyrrolylgruppen" aufgelistet:To illustrate, some advantageous "bispyrrolyl groups" are listed below:
Figure imgf000019_0001
b: Rλ = H
Figure imgf000019_0001
b: R λ = H
Figure imgf000019_0002
Figure imgf000019_0002
Vorzugsweise ist die Verbindung der allgemeinen Formel I ausgewählt unter Verbindungen der allgemeinen Formeln I.l bis 1.4The compound of general formula I is preferably selected from compounds of general formulas I.1 to 1.4
R5-R 5 -
Figure imgf000019_0003
Figure imgf000019_0003
(I.l) (1.2)(I.l) (1.2)
Figure imgf000019_0004
Figure imgf000019_0004
(1.3)
Figure imgf000020_0001
(1.3)
Figure imgf000020_0001
(1.4) worin(1.4) where
R1, R2' R3' R4' Y, a und b die zuvor angegebenen Bedeutungen besitzen undR 1 , R 2 'R 3 ' R 4 'Y, a and b have the meanings given above and
R5 und R6 unabhängig voneinander für Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen.R 5 and R 6 independently of one another represent cycloalkyl, heterocycloalkyl, aryl or hetaryl.
Vorzugsweise stehen in den Formeln I.l und 1.3 die Reste R1 bis R4 (falls vorhanden) alle für Wasserstoff. Des Weiteren vorzugsweise stehen R1 und R4 für Wasserstoff und sind R2 und R3 ausgewählt unter Ci- bis Cs-Alkyl, vorzugsweise Ci- bis C -Alkyl, wie Methyl, Ethyl, Isopropyl und tert.-Butyl. Des Weiteren vorzugsweise sind R1, R2, R3 und R4 unabhängig voneinander ausgewählt unter Ci-Cg-Al- kyl, vorzugsweise Cχ-C4-Alkyl, wie Methyl, Ethyl, Isopropyl und tert.-Butyl.In the formulas II and 1.3, the radicals R 1 to R 4 (if present) are preferably all hydrogen. Furthermore, R 1 and R 4 are preferably hydrogen and R 2 and R 3 are selected from Ci to Cs alkyl, preferably Ci to C alkyl, such as methyl, ethyl, isopropyl and tert-butyl. Furthermore, R 1 , R 2 , R 3 and R 4 are preferably selected independently of one another from Ci-Cg-alkyl, preferably Cχ-C 4 alkyl, such as methyl, ethyl, isopropyl and tert-butyl.
Vorzugsweise ist die Verbindung der allgemeinen Formel I ausgewählt unter Verbindungen der allgemeinen Formeln 1.5 oder 1.6The compound of general formula I is preferably selected from compounds of general formulas 1.5 or 1.6
R5-R 5 -
Figure imgf000020_0002
Figure imgf000021_0001
Figure imgf000020_0002
Figure imgf000021_0001
worinwherein
R2 und R3 die zuvor angegebenen Bedeutungen besitzen, wobei wenigstens einer der Reste R2 oder R3 nicht für Wasserstoff steht,R 2 and R 3 have the meanings given above, where at least one of the radicals R 2 or R 3 is not hydrogen,
R5 und R6 unabhängig voneinander für Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen.R 5 and R 6 independently of one another represent cycloalkyl, heterocycloalkyl, aryl or hetaryl.
Vorzugsweise sind in den Formeln 1.5 und 1.6 die Reste R2 und R3 ausgewählt unter Ci-Cβ-Alkyl, besonders bevorzugt Cι-C-Alkyl, wie Methyl, Ethyl, Isopropyl und tert.-Butyl, sowie C00Ra, worin Ra für Cι-C4-Alkyl, wie Methyl, Ethyl, Isopropyl und tert.-Butyl, steht.In the formulas 1.5 and 1.6, the radicals R 2 and R 3 are preferably selected from C 1 -C 6 -alkyl, particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, isopropyl and tert-butyl, and C00R a , in which R a for C 1 -C 4 alkyl, such as methyl, ethyl, isopropyl and tert-butyl.
Nach einer ersten bevorzugten Ausführungsform handelt es sich bei den Liganden der Formel I um einzähnige Liganden. Dann sind die Reste R5 und R6 unabhängig voneinander ausgewählt unter Cycloal- kyl, Heterocycloalkyl, Aryl und Hetaryl, vorzugsweise unter Aryl und Hetaryl. Bevorzugt stehen R5 und R6 für gegebenenfalls substituierte Phenylreste. Des Weiteren bevorzugt steht R5 für einen gegebenenfalls substituierten Phenylrest und R6 für einen gegebenenfalls substituierten Hetarylrest. Vorzugsweise sind die Hetaryl- reste ausgewählt unter Resten der allgemeinen Formel IIIAccording to a first preferred embodiment, the ligands of the formula I are monodentate ligands. Then the radicals R 5 and R 6 are independently selected from cycloalkyl, heterocycloalkyl, aryl and hetaryl, preferably from aryl and hetaryl. R 5 and R 6 preferably represent optionally substituted phenyl radicals. R 5 furthermore preferably represents an optionally substituted phenyl radical and R 6 represents an optionally substituted hetaryl radical. The hetaryl radicals are preferably selected from radicals of the general formula III
Figure imgf000021_0002
Figure imgf000021_0002
worinwherein
R1, R2, R3 und R4 wie zuvor beschrieben definiert sind, wobei wenigstens einer der Reste nicht für Wasserstoff steht. Lediglich zur Veranschaulichung der erfindungsgemäß eingesetzten einzähnigen Liganden werden im Folgenden einige vorteilhafte Verbindungen aufgelistet:R 1 , R 2 , R 3 and R 4 are defined as described above, at least one of the radicals not being hydrogen. Some advantageous compounds are listed below only to illustrate the monodentate ligands used according to the invention:
Figure imgf000022_0001
Figure imgf000022_0001
II IIIII III
Figure imgf000022_0002
Figure imgf000022_0002
IV V VIIV V VI
Figure imgf000022_0003
Figure imgf000022_0003
VII VIIIVII VIII
Figure imgf000022_0005
nyl
Figure imgf000022_0004
Me = Methyl
Figure imgf000022_0005
nyl
Figure imgf000022_0004
Me = methyl
IX XI Nach einer zweiten bevorzugten Ausführungsform handelt es sich bei den Liganden der allgemeinen Formel I um zweizähnige Liganden. Dann steht einer der Reste R5 oder R6 für eine zweiwertige verbrückende Gruppe Y, die zwei gleiche oder verschiedene Liganden der Formel I kovalent miteinander verbindet. Vorzugsweise ist die verbrückende Gruppe Y ausgewählt unter Gruppen der Formeln II. a bis II.tIX XI According to a second preferred embodiment, the ligands of the general formula I are bidentate ligands. Then one of the radicals R 5 or R 6 stands for a divalent bridging group Y which covalently connects two identical or different ligands of the formula I. The bridging group Y is preferably selected from groups of the formulas II. A to II.t.
Figure imgf000023_0001
Figure imgf000023_0001
(II. a) (II. b)(II. A) (II. B)
Figure imgf000023_0002
Figure imgf000023_0002
(II. e)(II. E)
Figure imgf000023_0003
Figure imgf000023_0003
(II. f) (II. g)
Figure imgf000024_0001
(II.1) (II.m) (II. n)(II. F) (II. G)
Figure imgf000024_0001
(II.1) (II.m) (II. N)
Figure imgf000024_0002
Figure imgf000024_0002
(ii.o) (II.p) (II.q)(ii.o) (II.p) (II.q)
Figure imgf000024_0003
Figure imgf000024_0003
(II. r) (II. s) (II.t)(II. R) (II. S) (II.t)
worinwherein
R1 bis RXI1 unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Alkoxy, Halogen, S03H, Sulfonat, NEE5, Alkylen- NE4E5, Trifluormethyl, Nitro, Alkoxycarbonyl, Carboxyl oder Cyano stehen, worin E4 und E5 jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl und Aryl bedeuten,R 1 to R XI1 independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, S0 3 H, sulfonate, NEE 5 , alkylene-NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, in which E 4 and E 5 each denote the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
Z für O, S, NR15 oder SiR15R16 steht, wobei R15 und R16 unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen, oder Z für eine Ci- bis C4-Alkylenbrücke steht, die eine Doppelbindung und/oder einen Alkyl-, Cycloalkyl-, Heterocycloalkyl-, Aryl- oder Hetaryl-Substituenten aufweisen kann,Z represents O, S, NR 15 or SiR 15 R 16 , where R 15 and R 16 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or Z represents a C 1 -C 4 -alkylene bridge which can have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent,
oder Z für eine C2- bis C-Alkylenbrücke steht, die durch O, S oder NR15 oder SiR15R16 unterbrochen ist,or Z represents a C 2 -C alkylene bridge which is interrupted by O, S or NR 15 or SiR 15 R 16 ,
wobei in den Gruppen der Formeln II. g bis II.m einer der Reste R1 bis RIV auch für Oxo oder ein Ketal davon stehen kann.where in the groups of formulas II. g to II.m one of the radicals R 1 to R IV can also represent oxo or a ketal thereof.
Vorzugsweise ist die verbrückende Gruppe Y ausgewählt unter Gruppen der Formeln II.1 bis II.5The bridging group Y is preferably selected from groups of the formulas II.1 to II.5
Figure imgf000025_0001
Figure imgf000025_0001
(II.4) (II.5)(II.4) (II.5)
worinwherein
R7, R8' R9' R10' R11' R12' R13 und R14 unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Alkoxy, Halogen, S03H, Sulfonat, NE4E5, Alkylen-NE4E5, Trifluormethyl, Nitro, Alkoxycarbonyl, Carboxyl oder Cyano stehen, worin E4 und E5 jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl und Aryl bedeuten,R 7 , R 8 'R 9 ' R 10 'R 11 ' R 12 'R 13 and R 14 independently of one another for hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, S0 3 H, sulfonate, NE 4 E 5 , alkylene -NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, in which E 4 and E 5 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
Z für 0, S, NR15 oder SiR15R16 steht, wobei R15 und R16 unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,Z represents 0, S, NR 15 or SiR 15 R 16 , where R 15 and R 16 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
oder Z für eine Ci- bis C3-Alkylenbrücke steht, die eine Doppelbindung und/oder einen Alkyl-, Cycloalkyl-, Heterocycloalkyl-, Aryl- oder Hetaryl-Substituenten aufweisen kann, oder Z für eine C2- bis C -Alkylenbrücke steht, die durch 0, S oder NR15 oder SiR15R16 unterbrochen ist,or Z represents a Ci to C 3 alkylene bridge which can have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent, or Z represents a C 2 -C alkylene bridge which is interrupted by 0, S or NR 15 or SiR 15 R 16 ,
Die Substituenten R7, R8, R9 und R10 stehen im Allgemeinen für Was- serstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl und Hetaryl. Bevorzugt stehen R7 und R9 für Wasserstoff und R8 und R10 für Cχ~ bis C4-Alkyl, wie z. B. Methyl, Ethyl, n-Propyl, n-Butyl oder tert.-Butyl. Es versteht sich von selbst, dass die nicht mit Substituenten besetzten Positionen der Phenylringe der Brücken- gruppe Y ein Wasserstoffatom tragen.The substituents R 7 , R 8 , R 9 and R 10 generally represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl. R 7 and R 9 are preferably hydrogen and R 8 and R 10 are Cχ ~ to C 4 alkyl, such as. B. methyl, ethyl, n-propyl, n-butyl or tert-butyl. It goes without saying that the positions of the phenyl rings of the bridging group Y which are not occupied by substituents bear a hydrogen atom.
Die Substituenten R7, R8, R9 und R10 stehen bevorzugt für Wasserstoff.The substituents R 7 , R 8 , R 9 and R 10 are preferably hydrogen.
Wenn R7 und/oder R9 für ein ankondensiertes, also anelliertes, Ringsystem stehen, so handelt es sich bevorzugt um Benzol- oder Naphthalinringe. Anellierte Benzolringe sind vorzugsweise unsubstituiert oder weisen 1, 2 oder 3, insbesondere 1 oder 2 Substituenten auf, die ausgewählt sind unter Alkyl, Alkoxy, Halo- gen, S03H, Sulfonat, NEXE2, Alkylen-NE1E2, Trifluormethyl, Nitro, COORf, Alkoxycarbonyl, Acyl und Cyano. Anellierte Naphthalinringe sind vorzugsweise unsubstituiert oder weisen im nicht anellierten Ring und/oder im anellierten Ring insgesamt 1, 2 oder 3, insbesondere 1 oder 2 der zuvor bei den anellierten Benzolringen ge- nannten Substituenten auf.If R 7 and / or R 9 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 1 E 2 , Trifluoromethyl, nitro, COOR f , 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.
Bevorzugt steht Y für eine Gruppe der Formel II. a, worin R1 und RIV unabhängig voneinander für Cχ-C -Alkyl oder Cι-C4-Alkoxy stehen. Vorzugsweise sind R1 und RIV ausgewählt unter Methyl, Ethyl, Isopropyl, tert.-Butyl und Methoxy. Bevorzugt stehen in diesen Verbindungen R11 und R111 für Wasserstoff.Y is preferably a group of the formula II. A, in which R 1 and R IV independently of one another are Cχ-C alkyl or -CC 4 alkoxy. R 1 and R IV are preferably selected from methyl, ethyl, isopropyl, tert-butyl and methoxy. In these compounds, R 11 and R 111 are preferably hydrogen.
Bevorzugt steht Y für eine Gruppe der Formel II.b, worin RIV und Rv unabhängig voneinander für Cχ-C -Alkyl oder Cχ-C -Alkoxy ste- hen. Vorzugsweise sind RIV und Rv ausgewählt unter Methyl, Ethyl, Isopropyl, tert.-Butyl und Methoxy. Bevorzugt stehen in diesen Verbindungen R1, R11, R1", RVi, RVI∑ und Rvm für Wasserstoff.Y is preferably a group of the formula II.b, in which R IV and R v independently of one another are Cχ-C-alkyl or Cχ-C-alkoxy. R IV and R v are preferably selected from methyl, ethyl, isopropyl, tert-butyl and methoxy. In these compounds, R 1 , R 11 , R 1 ", R Vi , R VI m and R v m are preferably hydrogen.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.b, worin R1 und RVI11 unabhängig voneinander für Cχ-C4-Alkyl oder Cχ-C4-Alkoxy stehen. Besonders bevorzugt stehen R1 und RVI11 für tert.-Butyl. Besonders bevorzugt stehen in diesen Verbindungen R", R111, RIV, Rv, RVI, RVI1 für Wasserstoff. Des Weiteren bevorzugt stehen in diesen Verbindungen R111 und RVI unabhängig vonein- ander für Cχ-C4-Alkyl oder Cχ-C4-Alkoxy. Besonders bevorzugt sind R111 und RVI unabhängig voneinander ausgewählt unter Methyl, Ethyl, Isopropyl, tert.-Butyl und Methoxy.Y is furthermore preferably a group of the formula II.b, in which R 1 and R VI11 independently of one another are Cχ-C 4 -alkyl or Cχ-C 4 -alkoxy. R 1 and R VI11 are particularly preferably tert-butyl. In these compounds R ", R 111 , R IV , R v , R VI , R VI1 are particularly preferably hydrogen. Furthermore, in these compounds R 111 and R VI are independently of one another Cein-C 4 -alkyl or Cχ-C 4 alkoxy, R 111 and R VI are particularly preferably selected independently of one another from methyl, Ethyl, isopropyl, tert-butyl and methoxy.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II. , worin R11 und RVI1 für Wasserstoff stehen. Bevorzugt stehen in diesen Verbindungen R1, R111, RIV, Rv, RVI und RVI11 unabhängig voneinander für Cχ-C4-Alkyl oder Cχ-C -Alkoxy. Besonders bevorzugt sind R1, R111, RIV, Rv, RVI und RVI11 unabhängig voneinander ausgewählt unter Methyl, Ethyl, Isopropyl, tert.-Butyl und Methoxy.Y is furthermore preferably a group of the formula II. In which R 11 and R VI1 are hydrogen. In these compounds, R 1 , R 111 , R IV , R v , R VI and R VI11 are preferably, independently of one another, Cχ-C 4 -alkyl or Cχ-C-alkoxy. R 1 , R 111 , R IV , R v , R VI and R VI11 are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
Weiterhin bevorzugt steht Y für eine Gruppe der Formel II.c, worin Z für eine Cχ-C4-Alkylengruppe, insbesondere Methylen, steht. Bevorzugt stehen in diesen Verbindungen RIV und Rv unabhängig voneinander für Cχ-C4-Alkyl oder Cχ-C4-Alkoxy. Besonders bevorzugt sind RIV und Rv unabhängig voneinander ausgewählt unter Methyl, Ethyl, Isopropyl, tert.-Butyl und Methoxy. Die Reste R1, R11, R111, RVI, RVI1 und RVI11 stehen vorzugsweise für Wasserstoff.Y is furthermore preferably a group of the formula II.c, in which Z represents a Cχ-C 4 -alkylene group, in particular methylene. In these compounds, R IV and R v are preferably, independently of one another, Cχ-C 4 -alkyl or Cχ-C 4 -alkoxy. R IV and R v are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy. The radicals R 1 , R 11 , R 111 , R VI , R VI1 and R VI11 are preferably hydrogen.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.c, worin Z für eine Cχ-C -Alkylenbrücke steht, die wenigstens einen Alkyl-, Cycloalkyl- oder Arylrest aufweist. Besonders bevorzugt steht Z für eine Methylenbrücke, die zwei Cχ-C-Alkylreste, insbesondere zwei Methylreste, aufweist. Vorzugsweise stehen in diesen Verbindungen die Reste R1 und RVI11 unabhängig voneinander für Cχ-C4-Alkyl oder Cχ-C4-Alkoxy. Besonders bevorzugt sind R1 und RVI11 unabhängig voneinander ausgewählt unter Methyl, Ethyl, Isopropyl, tert.-Butyl und Methoxy.Furthermore, Y preferably represents a group of the formula II.c, in which Z represents a Cχ-C alkylene bridge which has at least one alkyl, cycloalkyl or aryl radical. Z particularly preferably represents a methylene bridge which has two Cχ-C-alkyl radicals, in particular two methyl radicals. In these compounds, the radicals R 1 and R VI11 are preferably independently of one another Cχ-C 4 -alkyl or Cχ-C 4 -alkoxy. R 1 and R VI11 are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
Weiterhin bevorzugt steht Y für eine Gruppe der Formel II.d, worin R1 und RXI1 unabhängig voneinander für Cχ-C4-Alkyl oder Cχ-C4-Alkoxy stehen. Insbesondere sind R1 und RXI1 unabhängig voneinander ausgewählt unter Methyl, Ethyl, Isopropyl, tert.-Butyl und Methoxy. Besonders bevorzugt stehen in diesen Verbindungen die Reste R11 bis RXI für Wasserstoff.Y is further preferably a group of the formula II.d, in which R 1 and R XI1 independently of one another are Cχ-C 4 -alkyl or Cχ-C 4 -alkoxy. In particular, R 1 and R XI1 are independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy. In these compounds, the radicals R 11 to R XI are particularly preferably hydrogen.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.e, worin R1 und RXI1 unabhängig voneinander für Cχ-C4-Alkyl oder Cχ-C -Alkoxy stehen. Insbesondere sind R1 und RXI1 unabhängig voneinander ausgewählt unter Methyl, Ethyl, Isopropyl, tert.-Butyl und Methoxy. Besonders bevorzugt stehen in diesen Verbindungen die Reste R11 bis RXI für Wasserstoff.Furthermore, Y preferably represents a group of the formula II.e, in which R 1 and R XI1 independently of one another are Cχ-C 4 -alkyl or Cχ-C-alkoxy. In particular, R 1 and R XI1 are independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy. In these compounds, the radicals R 11 to R XI are particularly preferably hydrogen.
Weiterhin bevorzugt steht Y für eine Gruppe der Formel II. f, worin Z für eine Cχ-C4-Alkylengruppe steht, die wenigstens einen Alkyl-, Cycloalkyl- oder Arylsubstituenten aufweist. Besonders be- vorzugt steht Z für eine Methylengruppe, die zwei Cχ-C-Alkylre- ste, speziell zwei Methylreste, aufweist. Besonders bevorzugt stehen in diesen Verbindungen die Reste R1 und RVI11 unabhängig voneinander für Cχ-C4-Alkyl oder Cχ-C-Alkoxy. Insbesondere sind R1 und RVI11 unabhängig voneinander ausgewählt unter Methyl, Ethyl, Isopropyl, tert.-Butyl und Methoxy. Die Reste R11, R111, RIV, Rv, RVI und RVI1 stehen vorzugsweise für Wasserstoff.Y is furthermore preferably a group of the formula II. F, where Z is a Cχ-C 4 -alkylene group which has at least one alkyl, cycloalkyl or aryl substituent. Z particularly preferably represents a methylene group which has two Cχ-C-alkyl radicals, especially two methyl radicals. In these compounds, the radicals R 1 and R VI11 are particularly preferably independent from each other for Cχ-C 4 alkyl or Cχ-C-alkoxy. In particular, R 1 and R VI11 are selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy. The radicals R 11 , R 111 , R IV , R v , R VI and R VI1 are preferably hydrogen.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.g, worin R1, R11 und R111 für Wasserstoff stehen.Y is furthermore preferably a group of the formula II.g, in which R 1 , R 11 and R 111 are hydrogen.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.g, worin das Ringkohlenstoffatom, das den Rest R11 trägt, kein zusätzliches Wasserstoffatom, sondern eine Oxo-Gruppe oder ein Ke- tal davon trägt und R1 und R111 für Wasserstoff stehen.Furthermore, Y preferably represents a group of the formula II.g, in which the ring carbon atom which carries the R 11 radical does not bear an additional hydrogen atom but an oxo group or a radical thereof and R 1 and R 111 represent hydrogen ,
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.h, worin R1, R11 und R111 für Wasserstoff stehen.Y is furthermore preferably a group of the formula II.h, in which R 1 , R 11 and R 111 are hydrogen.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.h, worin das Ringkohlenstoffatom, das den Rest R11 trägt, kein zusätzliches Wasserstoffatom, sondern eine Oxo-Gruppe oder ein Ke- tal davon trägt und R1 und R111 für Wasserstoff stehen.Furthermore, Y preferably represents a group of the formula II.h, in which the ring carbon atom which carries the R 11 radical does not bear an additional hydrogen atom but an oxo group or a radical thereof and R 1 and R 111 represent hydrogen ,
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.i, worin R1, R11, R111 und RIV für Wasserstoff stehen.Y is furthermore preferably a group of the formula II.i in which R 1 , R 11 , R 111 and R IV are hydrogen.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.k, worin R1, R11, R111 und RIV für Wasserstoff stehen.Y is furthermore preferably a group of the formula II.k, in which R 1 , R 11 , R 111 and R IV stand for hydrogen.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.1, worin R1, R11, R111 und RIV für Wasserstoff stehen.Furthermore, Y preferably represents a group of the formula II.1, in which R 1 , R 11 , R 111 and R IV stand for hydrogen.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.m, worin R1, R11, R111 und RIV für Wasserstoff stehen.Furthermore, Y preferably represents a group of the formula II.m, in which R 1 , R 11 , R 111 and R IV stand for hydrogen.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.n, worin R1, R11, R111 und RIV für Wasserstoff stehen.Y is furthermore preferably a group of the formula II.n, where R 1 , R 11 , R 111 and R IV are hydrogen.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.n, worin einer der Reste R1 bis RIV für Cχ-C4-Alkyl oder Cχ-C -Alkoxy steht. Besonders bevorzugt steht dann wenigstens einer der Reste R1 bis RIV für Methyl, Ethyl, Isopropyl, tert.-Butyl oder Methoxy.Y is furthermore preferably a group of the formula II.n, in which one of the radicals R 1 to R IV is Cχ-C 4 -alkyl or Cχ-C-alkoxy. At least one of the radicals R 1 to R IV is then particularly preferably methyl, ethyl, isopropyl, tert-butyl or methoxy.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.o, worin R1, R11, R111 und RIV für Wasserstoff stehen.Y is furthermore preferably a group of the formula II.o in which R 1 , R 11 , R 111 and R IV are hydrogen.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.o, worin einer der Reste Ri, R11, Rin oder RIV für für Cχ-C4-Alkyl oder Cχ-C4-Alkoxy steht. Besonders bevorzugt steht dann einer der Reste R1 bis RIV für Methyl, Ethyl, tert.-Butyl oder Methoxy.Y further preferably represents a group of the formula II.o, in which one of the radicals R i , R 11 , R i n or R IV represents Cχ-C 4 -alkyl or Cχ-C 4 -alkoxy. One of the R 1 to R IV are methyl, ethyl, tert-butyl or methoxy.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.p, worin R1 und RVI unabhängig voneinander für Cχ-C4-Alkyl oder Cχ-C4-Alkoxy stehen. Besonders bevorzugt sind R1 und RVI unabhängig voneinander ausgewählt unter Methyl, Ethyl, Isopropyl, tert.- Butyl und Methoxy. Besonders bevorzugt stehen in diesen Verbindungen R11, R111, RIV und Rv für Wasserstoff. Des Weiteren bevorzugt stehen in den Verbindungen II.p R1, R111, RIV und RVI unabhän- gig voneinander für Cχ-C4-Alkyl oder Cχ-C4-Alkoxy. Besonders bevorzugt sind R1, R111, RIV und RVI dann unabhängig voneinander ausgewählt unter Methyl, Ethyl, Isopropyl, tert.-Butyl und Methoxy.Y is furthermore preferably a group of the formula II.p, in which R 1 and R VI independently of one another are Cχ-C 4 -alkyl or Cχ-C 4 -alkoxy. R 1 and R VI are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy. In these compounds, R 11 , R 111 , R IV and R v are particularly preferably hydrogen. In addition, preferably in the compounds II.p R 1 , R 111 , R IV and R VI independently of one another are Cχ-C 4 -alkyl or Cχ-C 4 -alkoxy. R 1 , R 111 , R IV and R VI are then particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.q, worin R1 und RVI unabhängig voneinander für Cχ-C4-Alkyl oderY is furthermore preferably a group of the formula II.q, where R 1 and R VI independently of one another are Cχ-C 4 -alkyl or
Cχ-C4-Alkoxy stehen. Besonders bevorzugt sind R1 und RVI unabhängig voneinander ausgewählt unter Methyl, Ethyl, Isopropyl, tert.- Butyl und Methoxy. Besonders bevorzugt stehen in diesen Verbindungen R11, R111, RIV und Rv für Wasserstoff. Des Weiteren bevor- zugt stehen in diesen Verbindungen R111 und RIV unabhängig voneinander für Cχ-C4-Alkyl oder Cχ-C -Alkoxy. Besonders bevorzugt sind RIII und RIV dann unabhängig voneinander ausgewählt unter Methyl, Ethyl, Isopropyl, tert.-Butyl und Methoxy.Cχ-C 4 alkoxy. R 1 and R VI are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy. In these compounds, R 11 , R 111 , R IV and R v are particularly preferably hydrogen. Furthermore, in these compounds, R 111 and R IV are independently Cχ-C 4 -alkyl or Cχ-C-alkoxy. RIII and RIV are then particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
Des Weiteren bevorzugt steht Y für eine Gruppe der Formel II.r, II.s oder Il.t, worin Z für CH2, C2H2 oder C2H steht.Furthermore, Y preferably represents a group of the formula II.r, II.s or Il.t, where Z represents CH 2 , C 2 H 2 or C 2 H.
Lediglich zur Veranschaulichung der erfindungsgemäß eingesetzten zweizähnigen Verbindungen werden im Folgenden einige aufgelistet:A few are listed below only to illustrate the bidentate compounds used according to the invention:
Figure imgf000029_0001
Figure imgf000029_0001
XI XII
Figure imgf000030_0001
XI XII
Figure imgf000030_0001
XIIIXIII
Figure imgf000030_0002
Figure imgf000030_0002
XIVXIV
Figure imgf000030_0003
Figure imgf000030_0003
XV
Figure imgf000031_0001
XV
Figure imgf000031_0001
XVI XVIIXVI XVII
Figure imgf000031_0002
Figure imgf000031_0002
XVIIIXVIII
Figure imgf000031_0003
Figure imgf000031_0003
XIX XIX
Figure imgf000032_0001
Figure imgf000032_0001
Figure imgf000032_0002
Figure imgf000032_0002
XXIIXXII
Figure imgf000032_0003
Figure imgf000032_0003
XXIII
Figure imgf000033_0001
XXIII
Figure imgf000033_0001
XXIV XXVXXIV XXV
Figure imgf000033_0002
Figure imgf000033_0002
XXVIXXVI
Figure imgf000033_0003
Figure imgf000033_0003
XXVII
Figure imgf000034_0001
XXVII
Figure imgf000034_0001
XXVIII XXIXXXVIII XXIX
Figure imgf000034_0002
Figure imgf000034_0002
XXXXXX
Figure imgf000034_0003
Figure imgf000034_0003
XXXI XXXI
Figure imgf000035_0001
Figure imgf000035_0001
XXXII XXXIIIXXXII XXXIII
Figure imgf000035_0002
Figure imgf000035_0002
XXXIVXXXIV
Figure imgf000035_0003
Figure imgf000035_0003
XXXV XXXV
Figure imgf000036_0001
Figure imgf000036_0001
XXXVI XXXVIIXXXVI XXXVII
Figure imgf000036_0002
Figure imgf000036_0002
XXXVIIIXXXVIII
Figure imgf000036_0003
Figure imgf000036_0003
XXXIX
Figure imgf000037_0001
XXXIX
Figure imgf000037_0001
XLIXLI
Figure imgf000037_0002
Figure imgf000038_0001
Figure imgf000037_0002
Figure imgf000038_0001
XLIIIXLIII
Figure imgf000038_0002
Figure imgf000038_0002
XLIV XLVXLIV XLV
Figure imgf000038_0003
Figure imgf000038_0003
XLVIXLVI
Figure imgf000038_0004
Figure imgf000038_0004
XLVII XLVII
Figure imgf000039_0001
Figure imgf000039_0001
Figure imgf000039_0002
Figure imgf000039_0002
LILI
Figure imgf000039_0003
Figure imgf000039_0003
Figure imgf000040_0001
Figure imgf000040_0001
LIVLIV
Figure imgf000040_0002
Figure imgf000040_0002
25 LV25 LV
Figure imgf000040_0003
Figure imgf000040_0003
45 LVI 45 LVI
Figure imgf000041_0001
Figure imgf000041_0001
LVIIILVIII
Figure imgf000041_0002
Figure imgf000041_0002
4545
LIX LIX
Figure imgf000042_0001
Figure imgf000042_0001
1515
Figure imgf000042_0002
Figure imgf000042_0002
LXILXI
3030
Figure imgf000042_0003
Figure imgf000042_0003
45
Figure imgf000043_0001
45
Figure imgf000043_0001
LXIIILXIII
Figure imgf000043_0002
Figure imgf000043_0002
LXIVLXIV
Figure imgf000043_0003
Figure imgf000043_0003
LXV LXV
Figure imgf000044_0001
Figure imgf000044_0001
LXVILXVI
Figure imgf000044_0002
Figure imgf000044_0002
LXVIILXVII
Figure imgf000044_0003
Figure imgf000044_0003
LXVI II LXIX LXVI II LXIX
Figure imgf000045_0001
Figure imgf000045_0001
LXXLXX
Figure imgf000045_0002
LXXI
Figure imgf000045_0002
LXXI
Figure imgf000045_0003
Figure imgf000045_0003
LXXII
Figure imgf000046_0001
LXXII
Figure imgf000046_0001
LXXIIILXXIII
Figure imgf000046_0002
Figure imgf000046_0002
LXXIV
Figure imgf000046_0003
LXXIV
Figure imgf000046_0003
Figure imgf000046_0004
Figure imgf000046_0004
LXXVI
Figure imgf000047_0001
LXXVI
Figure imgf000047_0001
LXXVIILXXVII
Figure imgf000047_0002
Figure imgf000047_0002
LX VI II LXXIXLX VI II LXXIX
Figure imgf000047_0003
Figure imgf000047_0003
LXXX
Figure imgf000048_0001
LXXXILXXX
Figure imgf000048_0001
LXXXI
Figure imgf000048_0002
Figure imgf000048_0002
LXXXII LXXXIIILXXXII LXXXIII
Figure imgf000048_0003
Figure imgf000048_0003
LXXXIV
Figure imgf000049_0001
LXXXIV
Figure imgf000049_0001
LXXXVLXXXV
Figure imgf000049_0002
Figure imgf000049_0002
LXXVILXXVI
LXXXVIILXXXVII
Figure imgf000049_0003
Figure imgf000049_0003
LXXXVIII
Figure imgf000050_0001
LXXXVIII
Figure imgf000050_0001
LXXXIXLXXXIX
Figure imgf000050_0002
LXXXX
Figure imgf000050_0002
Lxxxx
Figure imgf000050_0003
LXXXXI
Figure imgf000051_0001
LXXXXII
Figure imgf000050_0003
LXXXXI
Figure imgf000051_0001
LXXXXII
Figure imgf000051_0002
Figure imgf000051_0002
LXXXXIIILXXXXIII
Figure imgf000051_0003
Figure imgf000051_0003
LXXXXIV LXXXXV
Figure imgf000052_0001
LXXXXIV LXXXXV
Figure imgf000052_0001
LXXXXVILXXXXVI
Me = Methyl Et = Ethyl R3 = H, Carboxylat Rh = H, CarboxylatMe = methyl Et = ethyl R3 = H, carboxylate R h = H, carboxylate
Die Herstellung der erfindungsgemäß eingesetzten einzähnigen Phosphorpyrrolverbindungen der allgemeinen Formel I kann bei- spielsweise gemäß folgendem Schema 1 erfolgen: The monodentate phosphoropyrrole compounds of the general formula I used according to the invention can be prepared, for example, according to the following scheme 1:
Schema 1Scheme 1
1 äq. HX1 1 eq. HX 1
P(Hal)3 X1P(Hal)2 -HHalP (Hal) 3 X 1 P (Hal) 2 -HHal
2 äq. HX1 2 eq. HX 1
X12PHal -2 HHalX 1 2PHal -2 HHal
aq. R5-(0)aLl äq. R6-(0)bL2 χl P(Hal)2 χlp((0)aR5)((0)bR6)aq. R 5 - (0) a L l eq. R 6 - (0) b L 2 χl P (Hal) 2 χ l p ((0) a R5) ((0) b R6)
(Xi)2PHal 1 äq. R5-(0) aLl., χl)2P((0)aR5) (X i ) 2 PHal 1 eq. R5 - ( 0 ) a L l ., Χ l ) 2 P ((0) a R5)
Hai = CI, BrHai = CI, Br
Figure imgf000053_0001
Figure imgf000053_0001
LX,L2 = AbgangsgruppenL X , L 2 = leaving groups
Darin haben R1, R2, R3, R4, R5 und R6 die zuvor genannte Bedeutung. L1 und L2 stehen für eine Abgangsgruppe, die falls a bzw. b für die Zahl 0 steht, beispielsweise ausgewählt ist unter Halogen, insbesondere Fluor, Chlor, Brom, S03M mit M = Wasserstoff oder Alkalimetall, insbesondere Li, Na oder K, oder falls a bzw. b für die Zahl 1 stehen, beispielsweise für Wasserstoff, C(0)CF3, S02CH3, S02-Tolyl oder S02CF3 stehen kann.R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the meaning given above. L 1 and L 2 stand for a leaving group which, if a or b stands for the number 0, is selected, for example, from halogen, in particular fluorine, chlorine, bromine, S0 3 M with M = hydrogen or alkali metal, in particular Li, Na or K, or if a or b are the number 1, for example hydrogen, C (0) CF 3 , S0 2 CH 3 , S0 2 -tolyl or S0 2 CF 3 can be.
Die Herstellung der erfindungsgemäß eingesetzten zweizähnigen Phosphorpyrrolverbindungen der Formel I kann analog zu Schema 1 ausgehend von Verbindungen L1-(0)b-Y-(0)a-L1 erfolgen.The bidentate phosphoropyrrole compounds of the formula I used according to the invention can be prepared analogously to Scheme 1, starting from compounds L 1 - (0) b -Y- (0) a -L 1 .
So kann die Herstellung von Verbindungen der Formel II.2 beispielsweise ausgehend von Verbindungen der Formel II.2a
Figure imgf000054_0001
For example, the preparation of compounds of the formula II.2 can start from compounds of the formula II.2a
Figure imgf000054_0001
erfolgen, in denen R7, R8, R9, R10, a und b die genannte Bedeutung haben und L für eine Abgangsgruppe steht, die falls a und b für die Zahl 0 stehen, beispielsweise für Wasserstoff, Halogen, insbesondere Fluor, Chlor, Brom, S03M mit M = Wasserstoff oder Alkalimetall, insbesondere Li, Na oder K, stehen kann, oder falls a und b für die Zahl 1 stehen, beispielsweise für Wasserstoff, C(0)CF3, S02CH3, S02-Tolyl oder S02CF3 stehen kann.take place in which R 7 , R 8 , R 9 , R 10 , a and b have the meaning given and L represents a leaving group which if a and b represent the number 0, for example hydrogen, halogen, in particular fluorine, Chlorine, bromine, S0 3 M with M = hydrogen or alkali metal, in particular Li, Na or K, or if a and b are 1, for example hydrogen, C (0) CF 3 , S0 2 CH 3 , S0 2 -Tolyl or S0 2 CF 3 can stand.
Die Ausgangsverbindungen der allgemeinen Formel II.2a mit a, b = 0 können gemäß den von van Leuwen et al., Organometallics 14, 3081 (1995) angegebenen Methoden hergestellt werden.The starting compounds of the general formula II.2a with a, b = 0 can be prepared according to the methods given by van Leuwen et al., Organometallics 14, 3081 (1995).
Die Ausgangsverbindungen der allgemeinen Formel II.2a mit a, b = 1 und L = H, können z. B. aus den entsprechenden 2,2'-Dibrom- verbindungen der allgemeinen Formel II (a, b = 0; L = Br) z. B. durch Metallierung mit Alkalimetallorganylen, wie n-Butyllithium, tert. Butyllithium oder dergleichen, anschließende Umsetzung mit einem Boran, wie B(OCH3)3 oder B(OCH(CH3)2)3 und Oxidation der dabei gebildeten Diboranverbindung mit einem Peroxid, vorzugsweise Wasserstoffperoxid in Gegenwart von wässrigem Alkalimetall- hydroxid, vorzugsweise Lithium-, Natrium- oder Kaliumhydroxid, erhalten werden.The starting compounds of general formula II.2a with a, b = 1 and L = H, z. B. from the corresponding 2,2'-dibromo compounds of the general formula II (a, b = 0; L = Br) z. B. by metalation with alkali metal organyls, such as n-butyllithium, tert. Butyllithium or the like, subsequent reaction with a borane such as B (OCH 3 ) 3 or B (OCH (CH 3 ) 2 ) 3 and oxidation of the diborane compound formed in this way with a peroxide, preferably hydrogen peroxide in the presence of aqueous alkali metal hydroxide, preferably lithium -, sodium or potassium hydroxide can be obtained.
Zur Anknüpfung der Gruppen PX^fO^R5) und PX1((0)bR6) werden die Ausgangsverbindungen der allgemeinen Formel II.2a vorteilhaft mit einer Halogenverbindung der Formel HalPX1( (0)aR5) undTo link the groups PX ^ fO ^ R 5 ) and PX 1 ((0) b R 6 ), the starting compounds of the general formula II.2a are advantageously combined with a halogen compound of the formula HalPX 1 ((0) a R 5 ) and
HalPX1( (0)bR6) in Gegenwart einer Base umgesetzt. Hai steht hierbei vorzugsweise für Chlor oder Brom.HalPX 1 ((0) b R 6 ) in the presence of a base. Shark is preferably chlorine or bromine.
Die Verbindungen HalPX^ (0)aR5) und HalPX^ (0)bR6) können beispielsweise in Analogie zur Methode von Petersen et al, J. Am. Chem. Soc. 117, 7696 (1995) durch Umsetzung der betreffenden substituierten und/oder anellierten Pyrrolverbindung mit dem betreffenden Phosphortrihalogenid, z. B. Phosphortrichlorid, in Gegenwart eines tertiären Amins, z. B. Triethylamin, erhalten werden, wobei die Stöchiometrie dieser Umsetzung zu beachten ist. In Analogie zu dieser Vorgehensweise können z. B. aus den betreffenden Hydroxyaryl-pyrrolyl-Verbindungen durch Umsetzung mit dem Phosphortrihalogenid in Gegenwart eines tertiären Amins die entsprechenden Ausgangsverbindungen HalPX1 ( (0)aR5) und HalPX1( (0)bR6) erhalten werden.The compounds HalPX ^ (0) a R 5 ) and HalPX ^ (0) b R 6 ) can, for example, in analogy to the method of Petersen et al, J. Am. Chem. Soc. 117, 7696 (1995) by reacting the substituted and / or fused pyrrole compound in question with the phosphorus trihalide in question, e.g. B. phosphorus trichloride, in the presence of a tertiary amine, e.g. B. triethylamine, are obtained, the stoichiometry of this reaction being observed. In analogy to this procedure, e.g. B. from the relevant hydroxyaryl-pyrrolyl compounds by reaction with the phosphorus trihalide in the presence of a tertiary amine, the corresponding starting compounds HalPX 1 ((0) a R 5 ) and HalPX 1 ((0) b R 6 ) can be obtained.
Durch stufenweise Synthese sind weitere Ausgangsverbindungen HalPX1( (0)aR5) und HalPX1( (0)bR6) erhältlich. So kann z. B. durch Umsetzung von Phenol mit Phosphortrichlorid in Gegenwart eines tertiären Amins, z. B. Triethylamin, das Phenoxyphosphordichlorid erzeugt werden, das nach Umsetzung mit einem Äquivalent der betreffenden PyrrolVerbindung, z. B. Pyrrol, in Gegenwart eines tertiären Amins, Phenoxy-pyrrolyl-phosphorchlorid ergibt.By stepwise synthesis, further starting compounds HalPX 1 ((0) a R 5 ) and HalPX 1 ((0) b R 6 ) are obtainable. So z. B. by reacting phenol with phosphorus trichloride in the presence of a tertiary amine, e.g. As triethylamine, the phenoxyphosphorus dichloride are generated, which after reaction with an equivalent of the pyrrole compound in question, for. B. pyrrole, in the presence of a tertiary amine, phenoxy-pyrrolyl-phosphorus chloride.
Die Herstellung der 2,2 '-Bisindol-Ausgangsverbindungen kann in Analogie zu Tetrahedron 51, 5637 (1995) und Tetrahedron 51, 12801 (1995) erfolgen, die Herstellung der Bis-2, 2 '-pyrrolyl-methane entsprechend den Angaben von J. Org. Chem. 64/ 1391 (1999) und die Herstellung der 2 '-Pyrrolyl-o-phenoxy-methane nach J. Org. Chem. 16, 5060 (1981).The 2,2'-bisindole starting compounds can be prepared analogously to Tetrahedron 51, 5637 (1995) and Tetrahedron 51, 12801 (1995), and the bis-2, 2'-pyrrolyl-methanes can be prepared in accordance with the information given by J . Org. Chem. 64/1391 (1999) and the preparation of the 2 'pyrrolyl-o-phenoxy-methane according to J. Org. Chem. 16, 5060 (1981).
Zur Herstellung der Phosphorchelatverbindungen der allgemeinen Formel II.6 aus den Verbindungen der allgemeinen Formel II.2a durch deren Umsetzung mit den Verbindungen HalPX1 ( (O)aR5) und HalPX1 ( (0)bR6) müssen die Verbindungen der allgemeinen Formel II.2a zunächst aktiviert werden.To prepare the phosphorus chelate compounds of the general formula II.6 from the compounds of the general formula II.2a by reacting them with the compounds HalPX 1 ((O) a R 5 ) and HalPX 1 ((0) b R 6 ), the compounds of general formula II.2a are activated first.
Für Verbindungen der allgemeinen Formel II.2a mit a, b = 0 gelingt dies vorteilhaft durch Metallierung mittels einer Alkalime- tallorganyl-Verbindung, vorzugsweise mit einer Alkyllithiumver- bindung, wie n-Butyllithium, tert .-Butyllithium oder Methyllithium, wobei die Abgangsgruppe L in separater Umsetzung durch das betreffende Alkalimetallatom, vorzugsweise Lithium, ersetzt wird.For compounds of the general formula II.2a with a, b = 0, this is advantageously achieved by metalation using an alkali metal organyl compound, preferably with an alkyl lithium compound, such as n-butyllithium, tert-butyllithium or methyl lithium, the leaving group L is replaced in a separate reaction by the alkali metal atom in question, preferably lithium.
Nach Zugabe von HalPX1 ( (0)aR5) und HalPX1 ( (0)bR6) zu dieser metallierten Verbindung bilden sich die entsprechenden Phosphorchelatverbindungen der allgemeinen Formel I mit a, b = 0.After adding HalPX 1 ((0) a R 5 ) and HalPX 1 ((0) b R 6 ) to this metalated compound, the corresponding phosphorus chelate compounds of the general formula I are formed with a, b = 0.
Für die Aktivierung der Verbindungen der allgemeinen Formel II.2a mit a, b = 1 ist in der Regel keine separate Aktivierung mit Al- kalimetallorganyl-Verbindungen erforderlich. Im Allgemeinen führt die Umsetzung dieser Verbindungen mit den Verbindungen HalPX1 ( (0)aR5) und HalPX1( (0)bR6) in Gegenwart einer Base, vorzugs- weise einem tertiären Amin, wie Triethylamin, oder einem Alkalimetall- oder Erdalkalimetallhydrid, beispielsweise Natriumhydrid, Kaliumhydrid oder Calciumhydrid, direkt zu den erfindungsgemäßen Pnicogenchelatverbindungen der allgemeinen Formel I mit a, b = 0.A separate activation with alkali metal organyl compounds is generally not necessary for the activation of the compounds of the general formula II.2a with a, b = 1. In general, the reaction of these compounds with the compounds HalPX 1 ((0) a R 5 ) and HalPX 1 ((0) b R 6 ) in the presence of a base, preferably a tertiary amine, such as triethylamine, or an alkali metal or alkaline earth metal hydride, for example sodium hydride, potassium hydride or calcium hydride, directly to those according to the invention Picnicogen chelate compounds of the general formula I with a, b = 0.
Anstelle von Verbindungen der Formel II.2a (mit a, b = 0) mit L = Halogen oder S03Me können auch solche Verbindungen mit L = Wasser- Stoff lithiiert werden, in denen in der meta-Position von A2 (A2 = 0 oder S) sich jeweils Wasserstoff, eine Alkoxygruppe oder Alkoxycarbonylgruppe befindet. Derartige Reaktionen sind unter dem Begriff "ortho-Lithiierung" in der Literatur beschrieben (siehe z. B. D. W. Slocum, J. Org. Chem., 41, 3652-3654 (1976); J. M. Mallan, R. L. Bebb, Chem. Rev. , 1969, 693ff; V. Snieckus, Chem. Rev., 1980, 6, 879-933). Die dabei erhaltenen Organolithi- umverbindungen können dann mit den Phosphorhalogenverbindungen in der oben angegebenen Weise zu den Chelatverbindungen der Formel I umgesetzt werden.Instead of compounds of the formula II.2a (with a, b = 0) with L = halogen or S0 3 Me, it is also possible to lithiate compounds with L = hydrogen in which the meta position of A 2 (A 2 = 0 or S) is in each case hydrogen, an alkoxy group or alkoxycarbonyl group. Such reactions are described in the literature under the term “ortho-lithiation” (see, for example, BDW Slocum, J. Org. Chem., 41, 3652-3654 (1976); JM Mallan, RL Bebb, Chem. Rev., 1969 , 693ff; V. Snieckus, Chem. Rev., 1980, 6, 879-933). The organolithium compounds obtained in this way can then be reacted with the phosphorus halogen compounds in the manner given above to give the chelate compounds of the formula I.
Im Allgemeinen werden unter Hydroformylierungsbedingungen aus den jeweils eingesetzten Katalysatoren oder Katalysatorvorstufen ka- talytisch aktive Spezies der allgemeinen Formel HgZd(C0)eGf gebildet, worin Z für ein Metall der VIII. Nebengruppe, G für einen phosphorhaltigen Liganden der Formel I und d, e, f, g für ganze Zahlen, abhängig von der Wertigkeit und Art des Metalls sowie der Bindigkeit des Liganden G, stehen. Vorzugsweise stehen e und f unabhängig voneinander mindestens für einen Wert von 1, wie z. B. 1 , 2 oder 3. Die Summe aus e und f steht bevorzugt für einen Wert von 2 bis 5. Dabei können die Komplexe des Metalls Z mit den erfindungsgemäßen Liganden G gewünschtenfalls zusätzlich noch mindestens einen weiteren, nicht-erfindungsgemäßen Liganden, z.B. aus der Klasse der Triarylphosphine, insbesondere Triphenyl- phosphin, Triarylphosphite, Triarylphosphinite, Triarylphospho- nite, Phosphabenzole, Trialkylphosphine oder Phosphametallocene enthalten. Derlei Komplexe des Metalls Z mit erfindungsgemäßen und nicht-erfindungsgemäßen Liganden bilden sich z.B. in einer Gleichgewichtsreaktion nach Zusatz eines nicht-erfindungsgemäßen Liganden zu einem Komplex der allgemeinen Formel HgZa(C0)eGf.In general, under hydroformylation conditions, catalytically active species of the general formula H g Z d (C0) e G f are formed from the catalysts or catalyst precursors used in each case, in which Z is a metal of subgroup VIII, G is a phosphorus-containing ligand of the formula I and d, e, f, g are integers, depending on the valency and type of the metal and the binding of the ligand G. Preferably, e and f are independently at least 1, such as. B. 1, 2 or 3. The sum of e and f is preferably from 2 to 5. The complexes of the metal Z with the ligands G according to the invention can, if desired, additionally comprise at least one further non-inventive ligand, for example from the class of triarylphosphines, especially triphenylphosphine, triarylphosphites, triarylphosphinites, triarylphosphonites, phosphabenzenes, trialkylphosphines or phosphametallocenes. Such complexes of the metal Z with ligands according to the invention and not according to the invention are formed, for example, in an equilibrium reaction after adding a ligand not according to the invention to form a complex of the general formula H g Z a (C0) e G f .
Nach einer bevorzugten Ausführungsform werden die Hydroformylie- rungskatalysatoren in situ, in dem für die Hydroformylierungs- reaktion eingesetzten Reaktor, hergestellt. Gewünschtenfalls können die erfindungsgemäßen Katalysatoren jedoch auch separat her- gestellt und nach üblichen Verfahren isoliert werden. Zur in situ-Herstellung der erfindungsgemäßen Katalysatoren kann man wenigstens eine Verbindung der allgemeinen Formel I, eine Verbindung oder einen Komplex eines Metalls der VIII. Nebengruppe, gewünschtenfalls einen oder mehrere weitere zusätzliche, nicht- erfindungsgemäße Liganden und gegebenenfalls ein Aktivierungsmittel in einem inerten Lösungsmittel unter den Hydroformylierungs- bedingungen umsetzen.According to a preferred embodiment, 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. To prepare the catalysts according to the invention in situ, at least one compound of the general formula I, a compound or a complex of a metal from subgroup VIII, if desired one or more additional ligands not according to the invention and optionally an activating agent in an inert solvent the hydroformylation implement conditions.
Geeignete Rhodiumverbindungen oder -komplexe sind z. B. Rhodium(II)- und Rhodium( III) -salze, wie Rhodium( III)-chlorid, Rhodium(III)-nitrat, Rhodium(III)-sulfat, Kalium-Rhodiumsulfat, Rhodium(II)- bzw. Rhodium( III) -carboxylat, Rhodium(II)- und Rhodium(III)-acetat, Rhodium(III)-oxid, Salze der Rhodium(III)- säure, Trisammoniumhexachlororhodat(III) etc. Weiterhin eignen sich Rhodiumkomplexe, wie Rhodiumbiscarbonylacetylacetonat, Ace- tylacetonatobisethylenrhodium(I) etc. Vorzugsweise werden Rhodi- umbiscarbonylacetylacetonat oder Rhodiumacetat eingesetzt.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) - and rhodium ( III) carboxylate, rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid, trisammonium hexachlororhodate (III) etc. Furthermore, rhodium complexes, such as rhodium biscarbonylacetylacetonate, ace- tylacetonatobisethylene rhodium (I) etc. Rhodium biscarbonylacetylacetonate or rhodium acetate are preferably used.
Ebenfalls geeignet sind Rutheniumsalze oder -Verbindungen. Geeignete Rutheniumsalze sind beispielsweise Ruthenium( III)chlo- rid, Ruthenium(IV)-, Ruthenium(VI)- oder Ruthenium(VIII)oxid, Alkalisalze der Rutheniumsauerstoffsäuren wie K2Ru0 oder KRu0 oder Komplexverbindungen, wie z. B. RuHCl(CO) (PPh3)3. Auch können die Metallcarbonyle des Rutheniums wie Trisrutheniumdodecacarbo- nyl oder Hexarutheniumoctadecacarbonyl, oder Mischformen, in denen CO teilweise durch Liganden der Formel PR3 ersetzt sind, wie Ru(CO)3(PPh3)2, im erfindungsgemäßen Verfahren verwendet werden.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 or complex compounds, such as, for. B. RuHCl (CO) (PPh 3 ) 3 . The 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 , can also be used in the process according to the invention.
Geeignete Kobaltverbindungen sind beispielsweise Kobalt(II)Chlorid, Kobalt(II) sulfat, Kobalt( II Jcarbonat, Kobalt( II )nitrat, deren Amin- oder Hydratkomplexe, Kobaltcarboxylate, wie Kobalt- acetat, Kobaltethylhexanoat, Kobaltnaphthenoat, sowie der Kobalt- Caprolactamat-Komplex. Auch hier können die Carbonylkomplexe des Kobalts wie Dikobaltoctacarbonyl, Tetrakobaltdodecacarbonyl und Hexakobalthexadecacarbonyl eingesetzt werden.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 naphthenoate, and the cobalt caprolactamate Complex The carbonyl complexes of cobalt such as dicobalt octacarbonyl, tetrakobalt dodecacarbonyl and hexacobalt hexadecacarbonyl can also be used here.
Die genannten und weitere geeignete Verbindungen des Kobalts, Rhodiums, Rutheniums und Iridiums sind bekannt, kommerziell erhältlich oder ihre Herstellung ist in der Literatur hinreichend beschrieben oder sie können vom Fachmann analog zu den bereits bekannten Verbindungen hergestellt werden.The above-mentioned and other suitable compounds of cobalt, rhodium, ruthenium and iridium are known, commercially available, or their preparation is adequately described in the literature, or they can be prepared by a person skilled in the art analogously to the compounds which are already known.
Geeignete Aktivierungsmittel sind z. B. Brönsted-Säuren, Lewis- Säuren, wie z. B. BF3, A1C13, ZnCl , und Lewis-Basen.Suitable activating agents are e.g. B. Brönsted acids, Lewis acids, such as. B. BF 3 , A1C1 3 , ZnCl, and Lewis bases.
Als Lösungsmittel werden vorzugsweise die Aldehyde eingesetzt, die bei der Hydroformylierung der jeweiligen Olefine entstehen, sowie deren höher siedende Folgereaktionsprodukte, z. B. die Produkte der Aldolkondensation. Ebenfalls geeignete Lösungsmittel sind Aromaten, wie Toluol und Xylole, Kohlenwasserstoffe oder Gemische von Kohlenwasserstoffen, auch zum Verdünnen der oben genannten Aldehyde und der Folgeprodukte der Aldehyde. Weitere Lösungsmittel sind Ester aliphatischer Carbonsäuren mit Alkano- len, beispielsweise Essigester oder Texanol®, Ether wie tert.-Bu- tylmethylether und Tetrahydrofuran. Bei ausreichend hydrophili- sierten Liganden können auch Alkohole, wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, Ketone, wie Ace- ton und Methylethylketon etc., eingesetzt werden. Ferner können als Lösungsmittel auch sogenannte "Ionische Flüssigkeiten" verwendet werden. Hierbei handelt es sich um flüssige Salze, beispielsweise um N,N'-Di-alkylimidazoliumsalze wie die N-Butyl-N'- methylimidazoliumsalze, Tetraalkylammoniumsalze wie die Tetra- n-butylammoniumsalze, N-Alkylpyridiniumsalze wie die N-Butylpyri- diniumsalze, Tetraalkylphosphoniumsalze wie die Trishexyl(tetra- decyl)phosphoniumsalze, z.B. die Tetrafluoroborate, Acetate, Tetrachloroaluminate, Hexafluorophosphate, Chloride und Tosylate.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. Likewise 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 alkano len, for example ethyl acetate or Texanol ® , ethers such as tert-butyl methyl ether and tetrahydrofuran. If the ligands are sufficiently hydrophilized, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones such as acetone and methyl ethyl ketone etc. can also be used. So-called "ionic liquids" can also be used as solvents. These are liquid salts, for example N, N'-di-alkylimidazolium 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, tetraalkylphosphonium salts such as the trishexyl (tetra-decyl) phosphonium salts, for example the tetrafluoroborates, acetates, tetrachloroaluminates, hexafluorophosphates, chlorides and tosylates.
Weiterhin ist es möglich die Umsetzungen auch in Wasser oder wässrigen Lösungsmittelsystemen, die neben Wasser ein mit Wasser mischbares Lösungsmittel, beispielsweise einen Alkohol wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, ein Keton wie Aceton und Methylethylketon oder ein anderes Lösungs- mittel enthalten. Zu diesem Zweck setzt man Liganden der Formel I ein, die mit polaren Gruppen, beispielsweise ionischen Gruppen wie S03M, C02M mit M = Na, K oder NH oder wie N(CH3) + modifiziert sind. Die Umsetzungen erfolgen dann im Sinne einer Zweiphasenkatalyse, wobei der Katalysator sich in der wässrigen Phase befin- det und Einsatzstoffe und Produkte die organische Phase bilden. Auch die Umsetzung in den "Ionischen Flüssigkeiten" kann als Zweiphasenkatalyse ausgestaltet sein.It is also possible to carry out the reactions in water or aqueous solvent systems which, in addition to water, contain a water-miscible solvent, for example an alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, a ketone such as acetone and methyl ethyl ketone or a contain another solvent. For this purpose, ligands of formula I are used which are modified with polar groups, for example ionic groups such as S0 3 M, C0 2 M with M = Na, K or NH or like N (CH 3 ) + . The reactions are then carried out in the form of a 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.
Das Molmengenverhältnis von Verbindung I zum Metall der VIII. Ne- bengruppe im Hydroformylierungsmedium liegt im Allgemeinen in einem Bereich von etwa 1:1 bis 1000:1, vorzugsweise von 1:1 bis 100:1, insbesondere von 1:1 bis 50:1.The molar ratio of compound I to subgroup VIII metal in the hydroformylation medium is generally in a range from about 1: 1 to 1000: 1, preferably from 1: 1 to 100: 1, in particular from 1: 1 to 50: 1 ,
Die Hydroformylierungsreaktion kann kontinuierlich, semikonti- nuierlich oder diskontinuierlich erfolgen.The hydroformylation reaction can be carried out continuously, semi-continuously or batchwise.
Geeignete Reaktoren für die kontinuierliche Umsetzung sind dem Fachmann bekannt und werden z. B. in Ullmanns Enzyklopädie der technischen Chemie, Bd. 1, 3. Aufl., 1951, S. 743 ff. beschrie- ben.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, Vol. 1, 3rd ed., 1951, pp. 743 ff.
Geeignete druckfeste Reaktoren sind dem Fachmann ebenfalls bekannt und werden z. B. in Ullmanns Encyklopädie der technischen Chemie, Bd. 1, 3. Auflage, 1951, S. 769 ff. beschrieben. Im All- gemeinen wird für das erfindungsgemäße Verfahren ein Autoklav verwendet, der gewünschtenfalls mit einer Rührvorrichtung und einer Innenauskleidung versehen sein kann.Suitable pressure-resistant reactors are also known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 1, 3rd Edition, 1951, pp. 769 ff. In general, an autoclave is used for the method according to the invention, which, if desired, with a stirring device and can be provided with an inner lining.
Die Zusammensetzung des im erfindungsgemäßen Verfahren eingesetzten Synthesegases aus Kohlenmonoxid und Wasserstoff kann in wei- ten Bereichen variieren. Das molare Verhältnis von Kohlenmonoxid und Wasserstoff beträgt in der Regel etwa 1:99 bis 80:20, bevorzugt etwa 40:60 bis 60:40. Insbesondere bevorzugt wird ein molares Verhältnis von Kohlenmonoxid und Wasserstoff im Bereich von etwa 1:1 eingesetzt.The composition of the synthesis gas of carbon monoxide and hydrogen used in the process according to the invention can vary in wide ranges. The molar ratio of carbon monoxide and hydrogen is usually about 1:99 to 80:20, preferably about 40:60 to 60:40. A molar ratio of carbon monoxide and hydrogen in the range of approximately 1: 1 is particularly preferably used.
Die Temperatur bei der Hydroformylierungsreaktion liegt im Allgemeinen in einem Bereich von etwa 20 bis 180 °C, bevorzugt etwa 50 bis 150°C. Die Reaktion wird in der Regel bei dem Partialdruck des Reaktionsgases bei der gewählten Reaktionstemperatur durchge- führt. Im Allgemeinen liegt der Druck in einem Bereich von etwa 1 bis 700 bar, bevorzugt 1 bis 600 bar, insbesondere 1 bis 300 bar. Der Reaktionsdruck kann in Abhängigkeit von der Aktivität des eingesetzten erfindungsgemäßen Hydroformylierungskatalysators variiert werden. Im Allgemeinen erlauben die erfindungsgemäßen Ka- talysatoren auf Basis von phosphorhaltigen Verbindungen eine Umsetzung in einem Bereich niedriger Drücke, wie etwa im Bereich von 1 bis 100 bar.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. In general, 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. In general, the catalysts according to the invention based on phosphorus-containing compounds allow reaction in a range of low pressures, such as in the range from 1 to 100 bar.
Die erfindungsgemäß eingesetzten und die erfindungsgemäßen Hydro- formylierungskatalysatoren lassen sich nach üblichen, dem Fachmann bekannten Verfahren vom Austrag der Hydroformylierungsreaktion abtrennen und können im Allgemeinen erneut für die Hydroformylierung eingesetzt werden.The 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.
b) Auftrennungb) separation
Nach einer geeigneten Verfahrensvariante wird die in Schritt a) nach Abtrennung des Katalysatorsystems erhaltene produktangereicherte Fraktion einer weiteren Auftrennung zum Erhalt einer an n- Valeraldehyd angereicherten Fraktion unterzogen. Die Auftrennung des Hydroformylierungsprodukts in eine n-Valeraldehyd angereicherte Fraktion und eine n-Valeraldehyd abgereicherte Fraktion erfolgt nach üblichen, dem Fachmann bekannten Verfahren. Bevorzugt ist die Destillation unter Einsatz bekannter Trennapparatu- ren, wie Destillationskolonnen, z. B. Bodenkolonnen, die gewünschtenfalls mit Glocken, Siebplatten, Siebböden, Ventilen etc. ausgerüstet sein können, Verdampfer, wie Dünnschichtverdampfer, Fallfilmverdampfer, Wischblattverdampfer etc. c) AldolkondensationAccording to a suitable process variant, 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 using known separation apparatuses, such as distillation columns, e.g. B. tray columns, which can be equipped with bells, sieve plates, sieve trays, valves etc. if desired, evaporators, such as thin-film evaporators, falling film evaporators, wiper blade evaporators etc. c) aldol condensation
Zwei Moleküle C5-Aldehyd können zu α,ß-ungesättigten Cχ0-Aldehyden kondensiert werden. Die Aldolkondensation erfolgt auf an sich be- kannte Weise z. B. durch Einwirkung einer wässrigen Base, wie Natronlauge oder Kalilauge. Alternativ kann auch ein heterogener basischer Katalysator, wie Magnesium- und/oder Aluminiumoxid, verwendet werden (vgl. z. B. die EP-A 792 862). Dabei resultiert bei der Kondensation von zwei Molekülen n-Valeraldehyd 2-Pro- pyl-2-heptenal. Sofern das in Schritt a) bzw. nach der Auftren- nung in Schritt b) erhaltene Hydroformylierungsprodukt noch weitere C5-Aldehyde, wie 2-Methylbutanal und gegebenenfalls 2,2-Dime- thylpropanal aufweist, so untergehen diese ebenfalls eine Aldolkondensation, wobei dann die Kondensationsprodukte aller mögli- chen Aldehydkombinationen resultieren, beispielsweise 2-Pro- pyl-4-methyl-2-hexenal. Ein Anteil dieser Kondensationsprodukte, z. B. von bis zu 30 Gew.-%, steht einer vorteilhaften Weiterverarbeitung zu als Weichmacheralkoholen geeigneten 2-Propylhepta- nol-haltigen Cχo-Alkoholgemischen nicht entgegen.Two molecules of C 5 aldehyde can be condensed to form α, β-unsaturated Cχ 0 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. Alternatively, 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. If the hydroformylation product obtained in step a) or after the separation in step b) also has other C 5 aldehydes, such as 2-methylbutanal and, if appropriate, 2,2-dimethylpropanal, these likewise undergo aldol condensation, in which case the condensation products of all possible aldehyde combinations result, for example 2-propyl-4-methyl-2-hexenal. A portion of these condensation products, e.g. B. of up to 30 wt .-%, an advantageous further processing to 2-propylheptanol-containing Cχo alcohol mixtures suitable as plasticizer alcohols does not conflict.
d) Hydrierungd) hydrogenation
Die Produkte der Aldolkondensation können mit Wasserstoff kataly- tisch zu Cχ0-Alkoholen, wie insbesondere 2-Propylheptanol, hy- driert werden.The products of the aldol condensation may by hydrogen catalytically to Cχ 0 alcohols, such as especially 2-propylheptanol, be driert hy-.
Für die Hydrierung der Cχo-Aldehyde zu den Cχo-Alkoholen sind prinzipiell auch die Katalysatoren der Hydroformylierung zumeist bei höherer Temperatur geeignet; im Allgemeinen werden jedoch se- lektivere Hydrierkatalysatoren vorgezogen, die in einer separaten Hydrierstufe eingesetzt werden. Geeignete Hydrierkatalysatoren sind im Allgemeinen Übergangsmetalle, wie z. B. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru usw. oder deren Mischungen, die zur Erhöhung der Aktivität und Stabilität auf Trägern, wie z. B. Aktiv- kohle, Aluminiumoxid, Kieselgur usw. aufgebracht werden können. Zur Erhöhung der katalytischen Aktivität können Fe, Co und bevorzugt Ni, auch in Form der Raney-Katalysatoren, als Metallschwamm mit einer sehr großen Oberfläche verwendet werden. Die Hydrierung der Cχo-Aldehyde erfolgt in Abhängigkeit von der Aktivität des Ka- talysators, vorzugsweise bei erhöhten Temperaturen und erhöhtem Druck. Vorzugsweise liegt die Hydriertemperatur bei etwa 80 bis 250 °C, bevorzugt liegt der Druck bei etwa 50 bis 350 bar.For the hydrogenation of the Cχo-aldehydes to the Cχo-alcohols, the catalysts of the hydroformylation are generally also suitable at higher temperatures; in general, however, more selective hydrogenation catalysts are 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 increase the activity and stability on supports such. B. activated carbon, aluminum oxide, diatomaceous earth, etc. can be applied. To increase the catalytic activity, 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 Cχo-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.
Das rohe Hydrierungsprodukt kann nach üblichen Verfahren, z. B. durch Destillation, zu den C10-Alkoholen aufgearbeitet werden. e) AuftrennungThe crude hydrogenation product can by conventional methods, e.g. B. by distillation to the C 10 alcohols. e) separation
Gewünschtenfalls können die Hydrierprodukte einer weiteren Auftrennung unter Erhalt einer an 2-Propylheptanol angereicherten Fraktion und einer an 2-Propylheptanol abgereicherten Fraktion unterzogen werden. Diese Auftrennung kann nach üblichen, dem Fachmann bekannten Verfahren, wie z. B. durch Destillation, erfolgen.If desired, 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.
Hydroformylierungskatalysatoren, die einen Komplex wenigstens eines Metalls der VIII. Nebengruppe des Periodensystems aufweisen, der als Liganden mindestens eine Pyrrolphosphorverbindung der allgemeinen Formel I mit substituiertem und/oder anelliertem Pyr- rolgerüst aufweist, eignen sich in vorteilhafter Weise für den Einsatz in einem Verfahren zur Herstellung von 2-Propylheptanol . Dabei weisen die Katalysatoren eine hohe n-Selektivität auf, so dass sowohl beim Einsatz von im Wesentlichen reinem 1-Buten als auch beim Einsatz von l-Buten/2-Buten-haltigen Kohlenwasserstoffgemischen, wie beispielsweise C-Schnitten eine gute Ausbeute an n-Valeraldehyd erhalten wird. Des Weiteren eignen sich die erfindungsgemäß eingesetzten Katalysatoren auch zur Doppelbindungsiso- merisierung von einer innenständigen auf eine endständige Position, so dass auch beim Einsatz von 2-Buten und höhere Konzentrationen an 2-Buten-haltigen Kohlenwasserstoffgemischen n-Valeral- dehyd in guten Ausbeuten erhalten wird. Vorteilhafterweise zeigen die erfindungsgemäß eingesetzten Katalysatoren auf Basis von substituierten bzw. anellierten Pyrrolgerüsten im Wesentlichen keine Zersetzung unter den Hydroformylierungsbedingungen, d. h. in Anwesenheit von Aldehyden. Vorteilhafterweise werden auch in Gegen- wart von Luftsauerstoff und/oder Licht und/oder Säuren und/oder bei Raumtemperatur und erhöhten Temperaturen, wie bis zu etwa 150 °C, im Wesentlichen keine Zersetzungsprodukte gebildet, so dass auf den Einsatz aufwendiger Maßnahmen zur Stabilisierung des eingesetzten Hydroformylierungskatalysators, insbesondere bei der Aufarbeitung, verzichtet werden kann.Hydroformylation catalysts which have a complex of at least one metal from subgroup VIII of the periodic table and which have at least one pyrrole phosphorus compound of the general formula I with substituted and / or fused pyrrole skeleton as ligands are advantageously suitable for use in a process for the preparation of 2-propylheptanol. The catalysts have a high n-selectivity, so that both when using essentially pure 1-butene and when using l-butene / 2-butene-containing hydrocarbon mixtures, such as C-cuts, a good yield of n- Valeraldehyde is obtained. Furthermore, the catalysts used according to the invention are also suitable for double bond isomerization from an internal 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 , Advantageously, the catalysts used according to the invention based on substituted or fused pyrrole skeletons show essentially no decomposition under the hydroformylation conditions, ie. H. in the presence of aldehydes. Advantageously, even in the presence of atmospheric oxygen and / or light and / or acids and / or at room temperature and elevated temperatures, such as up to about 150 ° C., essentially no decomposition products are formed, so that complex measures to stabilize the Hydroformylation catalyst used, especially in the workup, can be omitted.
Ein weiterer Gegenstand der Erfindung sind Katalysatoren, umfassend Komplexe mit einem Metall der VIII. Nebengruppe des Periodensystems der Elemente, die als Liganden mindestens eine Verbin- düng der Formel I, wie zuvor beschrieben, enthalten, ausgenommen Verbindungen der Formel
Figure imgf000062_0001
The invention furthermore relates to catalysts comprising complexes with a metal of subgroup VIII of the Periodic Table of the Elements, which contain at least one compound of the formula I, as described above, as ligands, with the exception of compounds of the formula
Figure imgf000062_0001
a: R , Rd, Re, Rf = (1-Indolyl) b: Rc, Re = (1-Indolyl); Rd, Rf = (O-Phenyl) c: Rc, Rd, Re, Rf = (1-Carbazolyl) d: Rc, Rd, Re, Rf = ( 3,4 , 5, 6-Tetrahydrocarbazol-l-yl ) e: Rc, Rd, Re, Rf = (Isoindol-1-yl);a: R, R d , R e , R f = (1-indolyl) b: R c , R e = (1-indolyl); R d , Rf = (O-phenyl) c: R c , R d , R e , R f = (1-carbazolyl) d: R c , R d , R e , R f = (3,4, 5, 6-tetrahydrocarbazol-l-yl) e: R c , R d , R e , R f = (isoindol-1-yl);
Figure imgf000062_0002
Figure imgf000062_0002
a: R , Rd, Re, Rf = (1-Indolyl) b: Rc, Rβ = (1 -Indolyl) ; Rd, Rf = ; Phenyl c: Rc, Re = (i- -Indolyl) ; Rd, Rf = ( 1-Pyrrolyl) d: Rc, Re = (i- -Indolyl) ; Rd, Rf = (0-(2-Isopropyl- -5-methyl phenyl) ) e: Rc, Re = (i- -Indolyl) ; Rd, Rf = (O-Phenyl) f: Rc, Re = (1-Carbazolyl) ; R , R = (O-Phenyl);a: R, R d , R e , R f = (1-indolyl) b: R c , R β = (1-indolyl); R d , Rf = ; Phenyl c: R c , Re = (i- indolyl); R d , R f = (1-pyrrolyl) d: R c , Re = (i- indolyl); R d , R f = (0- (2-isopropyl--5-methylphenyl)) e: R c , Re = (i- indolyl); R d , R f = (O-phenyl) f: R c , R e = (1-carbazolyl); R, R = (O-phenyl);
Figure imgf000062_0003
Figure imgf000063_0001
worin
Figure imgf000062_0003
Figure imgf000063_0001
wherein
R1 , R111 , RIV, Rv, RVI und RVI11 für von Wasserstoff verschiedene Substituenten stehen undR 1 , R 111 , R IV , R v , R VI and R VI11 represent substituents other than hydrogen and
Rc , Rd, Re und R£ für Gruppen der FormelR c , R d , R e and R £ for groups of the formula
Figure imgf000063_0002
Figure imgf000063_0002
stehen, worin R1, R2, R3 und R4 die in Anspruch 1 angegebenen Be- deutungen besitzen;stand in which R 1 , R 2 , R 3 and R 4 have the meanings given in claim 1;
Figure imgf000063_0003
Figure imgf000063_0003
worinwherein
R1, R111, RVI und RVI11 für von Wasserstoff verschiedene Substituenten stehen undR 1 , R 111 , R VI and R VI11 represent substituents other than hydrogen and
Rc, Rd, Re und Rf für Gruppen der Formel
Figure imgf000064_0001
R c , R d , R e and R f for groups of the formula
Figure imgf000064_0001
stehen, worin R1, R2, R3 und R4 die in Anspruch 1 angegebenen Bedeutungen besitzen.stand in which R 1 , R 2 , R 3 and R 4 have the meanings given in claim 1.
Bezüglich geeigneter und bevorzugter Liganden der Formel I wird auf die diesbezüglichen Ausführungen unter Verfahrensschritt a) in vollem Umfang Bezug genommen.With regard to suitable and preferred ligands of the formula I, reference is made in full to the statements relating to this under process step a).
Bevorzugt sind Katalysatoren, umfassend Komplexe mit einem Metall der VIII. Nebengruppe des Periodensystems, die als Liganden mindestens eine Verbindung der Formel I, wie zuvor definiert, aufweisen, in denen in wenigstens einer der Gruppen der FormelPreference is given to catalysts comprising complexes with a metal of subgroup VIII of the Periodic Table, which have as ligands at least one compound of the formula I, as defined above, in which in at least one of the groups of the formula
Figure imgf000064_0002
Figure imgf000064_0002
die Reste R3 und R4 unabhängig voneinander ausgewählt sind unter Cχ-C-Alkylresten, insbesondere unter Methyl, Ethyl, Isopropyl und tert.-Butyl .the radicals R 3 and R 4 are selected independently of one another from Cχ-C-alkyl radicals, in particular from methyl, ethyl, isopropyl and tert-butyl.
Vorzugsweise weisen diese Katalysatoren 2, 3 oder 4 dieser Gruppen auf.These catalysts preferably have 2, 3 or 4 of these groups.
Besonders bevorzugt sind Katalysatoren, umfassend Komplexe mit einem Metall der VIII. Nebengruppe des Periodensystems, die als Liganden mindestens eine Verbindung der Formel I, wie zuvor definiert, aufweisen, in denen wenigstens eine der Gruppen der FormelCatalysts are particularly preferred, comprising complexes with a metal of subgroup VIII of the periodic table, which have as ligands at least one compound of the formula I, as defined above, in which at least one of the groups of the formula
Figure imgf000064_0003
für 3-Alkylindol-l-yl, insbesondere für 3-Methylindol-l-yl, steht.
Figure imgf000064_0003
stands for 3-alkylindol-l-yl, in particular for 3-methylindol-l-yl.
Vorzugsweise weisen diese Katalysatoren 2, 3 oder 4 2,3-Dial- kylindol-1-ylgruppen, wie 2,3-Dimethylindol-l-ylgruppen auf.These catalysts preferably have 2, 3 or 4 2,3-dialkylindol-1-yl groups, such as 2,3-dimethylindol-l-yl groups.
Vorzugsweise weisen diese Katalysatoren 2, 3 oder 4 3-Alkylin- dol-1-ylgruppen, wie 3-Methylindol-l-ylgruppen ( 1-Skatolylgrup- pen), auf.These catalysts preferably have 2, 3 or 4 3-alkylindol-1-yl groups, such as 3-methylindol-1-yl groups (1-skatolyl groups).
Katalysatoren auf Basis von 3-Alkylindol-l-ylgruppen zeichnen sich durch eine besondere Stabilität aus.Catalysts based on 3-alkylindol-l-yl groups are particularly stable.
Vorzugsweise ist das Metall der VIII. Nebengruppe ausgewählt un- ter Kobalt, Rhodium, Ruthenium oder Iridium.The metal of subgroup VIII is preferably selected from cobalt, rhodium, ruthenium or iridium.
Die erfindungsgemäßen Katalysatoren eignen sich ganz allgemein in Verfahren zur Hydroformylierung von Verbindungen, die wenigstens eine ethylenisch ungesättigte Doppelbindung enthalten, durch Um- setzung mit Kohlenmonoxid und Wasserstoff.The catalysts of the invention are very generally suitable in processes for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen.
Vorteilhafterweise wird bei einem Einsatz von Phosphorverbindungen, bei denen substituierte und/oder in ein anelliertes Ringsystem integrierte Pyrrolgruppen über ihr pyrrolisches Stickstoffa- tom kovalent mit dem Phosphoratom verknüpft sind, als Liganden in Hydroformylierungskatalysatoren eine Zersetzung bzw. die Bildung unerwünschter Nebenprodukte vermieden. Dies betrifft insbesondere die bei Katalysatoren auf Basis von unsubstituierten Pyrrolgruppen zum Teil beobachtete Zersetzung an Licht bzw. bei Temperatu- ren im Bereich der Raumtemperatur. Auch unter den Hydroformylie- rungsbedingungen und bei der Aufarbeitung der Reaktionsprodukte zeichnen sich Katalysatoren auf Basis von Liganden, die substituierte und/oder in ein anelliertes Ringsystem integrierte Pyrrolgruppen aufweisen, durch eine höhere Stabilität gegenüber Ka- talysatoren auf Basis von Liganden, die unsubstituierte Pyrrolgruppen aufweisen, aus.When using phosphorus compounds in which substituted and / or pyrrole groups integrated in a fused ring system are covalently linked to the phosphorus atom via their pyrrolic nitrogen atom, decomposition or the formation of undesired by-products is advantageously avoided as ligands in hydroformylation catalysts. This applies in particular to the decomposition of light sometimes observed in the case of catalysts based on unsubstituted pyrrole groups or at temperatures in the region of room temperature. Even under the hydroformylation conditions and in the workup of the reaction products, catalysts based on ligands which have substituted and / or pyrrole groups integrated in an annulated ring system are notable for greater stability compared to catalysts based on ligands which have unsubstituted pyrrole groups , out.
Ein weiterer Gegenstand der Erfindung ist daher ein Verfahren zur Hydroformylierung von Verbindungen, die wenigstens eine ethyle- nisch ungesättigte Doppelbindung enthalten durch Umsetzung mit Kohlenmonoxid und Wasserstoff in Gegenwart eines Hydroformylie- rungskatalysators, umfassend wenigstens einen Komplex eines Metalls der VIII. Nebengruppe mit wenigstens einem Liganden der allgemeinen Formel I, wie zuvor definiert. Bezüglich geeigneter und bevorzugter Bedingungen der Hydroformylierung und speziell der eingesetzten Liganden der Formel I wird auf das zuvor zu Schritt a) Gesagte Bezug genommen.The invention therefore furthermore relates to a process for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst comprising at least one complex of a metal from subgroup VIII with at least one ligand of general formula I as previously defined. With regard to suitable and preferred conditions of the hydroformylation and especially the ligands of the formula I used, reference is made to what was said above in relation to step a).
Als Substrate für das erfindungsgemäße Hydroformylierungsverfah- ren kommen prinzipiell alle Verbindungen in Betracht, welche eine oder mehrere ethylenisch ungesättigte Doppelbindungen enthalten. Dazu zählen z. B. Olefine, wie α-Olefine, interne geradkettige und interne verzweigte Olefine. Geeignete α-Olefine sind z. B. Propen, 1-Buten, Isobuten, 1-Penten, 1-Hexen, 1-Hepten, 1-Octen, 1-Nonen, 1-Decen, 1-Undecen, 1-Dodecen, Allylalkohole etc.In principle, 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 α-olefins, internal straight-chain and internal branched olefins. Suitable α-olefins are e.g. B. propene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, allyl alcohols etc.
Geeignete verzweigte, interne Olefine sind vorzugsweise C- bis C20-Olefine, wie 2-Methyl-2-Buten, 2-Methyl-2-Penten, 3-Methyl- 2-Penten, verzweigte, interne Hepten-Gemische, verzweigte, interne Octen-Gemische, verzweigte, interne Nonen-Gemische, verzweigte, interne Decen-Gemische, verzweigte, interne Undecen- Gemische, verzweigte, interne Dodecen-Gemische etc.Suitable branched, internal olefins are preferably C to C 20 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.
Geeignete zu hydroformylierende Olefine sind weiterhin C5- bisSuitable olefins to be hydroformylated are also C 5 bis
Cg-Cycloalkene, wie Cyclopenten, Cyclohexen, Cyclohepten, Cyclooc- ten und deren Derivate, wie z. B. deren Cχ~ bis C20-Alkylderivate mit 1 bis 5 Alkylsubstituenten. Geeignete zu hydroformylierende Olefine sind weiterhin Vinylaromaten, wie Styrol, α-Methylstyrol, 4-Isobutylstyrol etc. Geeignete zu hydroformylierende Olefine sind weiterhin α,ß-ethylenisch ungesättigte Mono- und/oder Dicar- bonsäuren, deren Ester, Halbester und Amide, wie Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Crotonsäure, Itacon- säure, 3-Pentensäuremethylester, 4-Pentensäuremethylester, Ölsäu- remethylester, Acrylsäuremethylester, Methacrylsäuremethylester, ungesättigte Nitrile, wie 3-Pentennitril, 4-Pentennitril, Acryl- nitril, Vinylether, wie Vinylmethylether, Vinylethylether, Vinyl- propylether etc., Cχ~ bis C2Q-Alkenole, -Alkendiole und -Alkadie- nole, wie 2,7-Octadienol-l. Geeignete Substrate sind weiterhin Di- oder Polyene mit isolierten oder konjugierten Doppelbindungen. Dazu zählen z. B. 1,3-Butadien, 1,4-Pentadien, 1,5-Hexadien, 1,6-Heptadien, 1, 7-0ctadien, Vinylcyclohexen, Dicyclopentadien, 1,5,9-Cyclooctatrien sowie Butadienhomo- und -copolymere.Cg-cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as. B. whose Cχ ~ to C 20 alkyl derivatives with 1 to 5 alkyl substituents. Suitable olefins to be hydroformylated are also vinyl aromatics, such as styrene, α-methylstyrene, 4-isobutylstyrene etc. Suitable olefins to be hydroformylated are furthermore α, β-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, 3-pentenoic acid methyl ester, 4-pentenoic acid methyl ester, oleic acid methyl ester, acrylic acid methyl ester, methacrylic acid methyl ester, unsaturated nitriles, such as 3-pentenenitrile, 4-pentenenitrile ether, acrylonitrile ether, acrylonitrile ether, acrylonitrile ether Vinyl ethyl ether, vinyl propyl ether etc., Cχ ~ to C 2 Q-alkenols, -alkenediols and -alkadienols, such as 2,7-octadienol-l. Suitable substrates are further 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-heptadiene, 1, 7-0ctadiene, vinylcyclohexene, dicyclopentadiene, 1,5,9-cyclooctatriene and butadiene homo- and copolymers.
Bevorzugt ist die zur Hydroformylierung eingesetzte ungesättigte Verbindung ausgewählt unter internen linearen Olefinen und Ole- fingemischen, die wenigstens ein internes lineares Olefin enthalten. Geeignete lineare (geradkettige) interne Olefine sind vorzugsweise C- bis C2o-01efine, wie 2-Buten, 2-Penten, 2-Hexen, 3-Hexen, 2-Hepten, 3-Hepten, 2-Octen, 3-0cten, 4-0cten etc. und Mischungen davon. Vorzugsweise wird in dem erfindungsgemäßen Hydroformylierungsver- fahren ein großtechnisch zugängliches Olefingemisch eingesetzt, das insbesondere wenigstens ein internes lineares Olefin enthält. Dazu zählen z. B. die durch gezielte Ethen-Oligomerisierung in Gegenwart von Alkylaluminiumkatalysatoren erhaltenen Ziegler-Ole- fine. Dabei handelt es sich im Wesentlichen um unverzweigte Olefine mit endständiger Doppelbindung und gerader Kohlenstoffatomanzahl. Dazu zählen weiterhin die durch Ethen-Oligomerisierung in Gegenwart verschiedener Katalysatorsysteme erhaltenen Olefine, z. B. die in Gegenwart von Alkylaluminiumchlorid/Titantetrachlo- rid-Katalysatoren erhaltenen, überwiegend linearen α-Olefine und die in Gegenwart von Nickel-Phosphinkomplex-Katalysatoren nach dem Shell Higher Olefin Process (SHOP) erhaltenen α-Olefine. Geeignete technisch zugängige Olefingemische werden weiterhin bei der Paraffin-Dehydrierung entsprechender Erdölfraktionen, z. B. der sog. Petroleum- oder Dieselölfraktionen, erhalten. Zur Überführung von Paraffinen, vorwiegend von n-Paraffinen in Olefine, werden im Wesentlichen drei Verfahren eingesetzt: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 to C 2 o-01efins, such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-0ctene , 4-0cten etc. and mixtures thereof. In the hydroformylation process according to the invention, preference is given to using an industrially accessible olefin mixture which in particular contains 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. the predominantly linear α-olefins obtained in the presence of alkyl aluminum chloride / titanium tetrachloride catalysts and the α-olefins obtained in the presence of nickel-phosphine complex catalysts according to the Shell Higher Olefin Process (SHOP). Suitable technically accessible olefin mixtures are still used in the paraffin dehydrogenation of corresponding petroleum fractions, e.g. B. the so-called petroleum or diesel oil fractions obtained. Essentially three processes are used to convert paraffins, primarily n-paraffins to olefins:
- thermisches Cracken (Steamcracken) , katalytisches Dehydrieren und chemisches Dehydrieren durch Chlorieren und Dehydrochlorie- ren.- Thermal cracking (steam cracking), catalytic dehydration and chemical dehydration by chlorination and dehydrochlorination.
Dabei führt das thermische Cracken überwiegend zu α-Olefinen, während die anderen Varianten Olefingemische ergeben, die im Allgemeinen auch größere Anteile an Olefinen mit innenständiger Doppelbindung aufweisen. Geeignete Olefingemische sind weiterhin die bei Metathese- bzw. Telomerisationsreaktionen erhaltenen Olefine. Dazu zählen z. B. die Olefine aus dem Phillips-Triolefin-Prozess, einem modifizierten SHOP-Prozess aus Ethylen-Oligomerisierung, Doppelbindungs-Isomerisierung und anschließender Metathese (Ethe- nolyse) .Thermal cracking leads predominantly to α-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).
Geeignete in dem erfindungsgemäßen Hydroformylierungsverfahren einsetzbare technische Olefingemische sind weiterhin ausgewählt unter Dibutenen, Tributenen, Tetrabutenen, Dipropenen, Triprope- nen, Tetrapropenen, Mischungen von Butenisomeren, insbesondere Raffinat II, Dihexenen, Dimeren und Oligomeren aus dem Dimersol®-Prozess von IFP, Octolprozess® von Hüls, Polygas®-pro- zess etc.Suitable technical 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® from Hüls, Polygas® process etc.
Bevorzugt ist ein Verfahren, das dadurch gekennzeichnet ist, dass der Hydroformylierungskatalysator in situ hergestellt wird, wobei man mindestens eine Verbindung der Formel I, eine Verbindung oder einen Komplex eines Metalls der VIII. Nebengruppe und gegebenenfalls ein Aktivierungsmittel in einem inerten Lösungsmittel unter den Hydroformylierungsbedingungen zur Reaktion bringt.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 the hydroformylation conditions to react.
Die zuvor beschriebenen, erfindungsgemäßen Katalysatoren, die chirale Verbindungen der allgemeinen Formel I umfassen, eignen sich zur enantioselektiven Hydroformylierung.The catalysts according to the invention described above, which comprise chiral compounds of the general formula I, are suitable for enantioselective hydroformylation.
Die zuvor beschriebenen Katalysatoren können auch in geeigneter Weise, z. B. durch Anbindung über als Ankergruppen geeignete funktionelle Gruppen, Adsorption, Pfropfung, etc. an einen geei- gneten Träger, z. B. aus Glas, Kieselgel, Kunstharzen etc., immobilisiert werden. Sie eignen sich dann auch für einen Einsatz als Festphasenkatalysatoren .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.
Überraschenderweise haben die aus den erfindungsgemäßen Verbin- düngen der allgemeinen Formel I hergestellten Katalysatoren nicht nur eine hohe Aktivität bezüglich der Hydroformylierung endständiger Olefine, sondern ebenfalls bezüglich der isomerisierenden Hydroformylierung von Olefinen mit internen Doppelbindungen zu Aldehydprodukten mit hoher Linearität. Vorteilhafterweise findet unter den Bedingungen der Hydroformylierung mit den erfindungsgemäßen Katalysatoren eine Hydrierung der Olefine nur in sehr geringem Ausmaß statt.Surprisingly, the catalysts prepared from the compounds of general formula I according to the invention not only have a high activity with regard to the hydroformylation of terminal olefins, but also with respect to the isomerizing hydroformylation of olefins with internal double bonds to give aldehyde products with high linearity. Advantageously, under the conditions of hydroformylation with the catalysts according to the invention, the olefins are hydrogenated only to a very small extent.
Ein weiterer Gegenstand der Erfindung ist die Verwendung von Ka- talysatoren, umfassend wenigstens einen Komplex eines Metalls der VIII. Nebengruppe mit wenigstens einer Verbindung der allgemeinen Formel I, wie zuvor beschrieben, zur Hydroformylierung, Hydrocya- nierung, Carbonylierung und zur Hydrierung.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.
Wie erwähnt stellt die Hydrocyanierung von Olefinen ein weiteres Einsatzgebiet für die erfindungsgemäßen Katalysatoren dar. Auch die erfindungsgemäßen Hydrocyanierungskatalysatoren umfassen Komplexe eines Metalls der VIII. Nebengruppe, insbesondere Cobalt, Nickel, Ruthenium, Rhodium, Palladium, Platin, bevorzugt Nickel, Palladium und Platin und ganz besonders bevorzugt Nickel. In der Regel liegt das Metall im erfindungsgemäßen Metallkomplex null- wertig vor. Die Herstellung der Metallkomplexe kann, wie bereits für den Einsatz als Hydroformylierungskatalysatoren zuvor beschrieben, erfolgen. Gleiches gilt für die in situ-Herstellung der erfindungsgemäßen Hydrocyanierungskatalysatoren.As mentioned, the hydrocyanation of olefins represents a further area of use for the catalysts according to the invention. The hydrocyanation catalysts according to the invention also comprise complexes of a metal of subgroup VIII, in particular cobalt, nickel, ruthenium, rhodium, palladium, platinum, preferably nickel, palladium and platinum and all particularly preferably nickel. As a rule, the metal in the metal complex according to the invention is zero-valued. 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.
Ein zur Herstellung eines Hydrocyanierungskatalysators geeigneter Nickelkomplex ist z. B. Bis( l,5-cyclooctadien)nickel(0) .A suitable nickel complex for the preparation of a hydrocyanation catalyst is e.g. B. Bis (1,5-cyclooctadiene) nickel (0).
Gegebenenfalls können die Hydrocyanierungskatalysatoren, analog zu dem bei den Hydroformylierungskatalysatoren beschriebenen Ver- fahren, in situ hergestellt werden.Optionally, the hydrocyanation catalysts, analogous to the process described for the hydroformylation catalysts drive, be made in situ.
Ein weiterer Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von Nitrilen durch katalytische Hydrocyanierung, in 5 dem die Hydrocyanierung in Gegenwart mindestens eines der zuvor beschriebenen erfindungsgemäßen Katalysatoren erfolgt. Geeignete Olefine für die Hydrocyanierung sind allgemein die zuvor als Einsatzstoffe für die Hydroformylierung genannten Olefine. Eine spezielle Ausführungsform des erfindungsgemäßen Verfahrens betrifftThe 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 special embodiment of the method according to the invention relates
10 die Herstellung von Gemischen monoolefinischer Cs-Mononitrile mit nichtkonjugierter C =C- und C≡N-Bindung durch katalytische Hydrocyanierung von 1,3-Butadien oder 1,3-Butadien-haltigen Kohlenwas- serstoffgemischen und die Isomerisierung/Weiterreaktion zu gesättigten C-Dinitrilen, vorzugsweise Adipodinitril in Gegenwart min-10 the preparation of mixtures of monoolefinic Cs-mononitriles with a non-conjugated C = C and C≡N bond by catalytic hydrocyanation of 1,3-butadiene or 1,3-butadiene-containing hydrocarbon mixtures and the isomerization / further reaction to give saturated C- Dinitriles, preferably adiponitrile in the presence of min.
15 destens eines erfindungsgemäßen Katalysators. Bei der Verwendung von Kohlenwasserstoffgemischen zur Herstellung von monoolefinischer C5-Mononitrilen nach dem erfindungsgemäßen Verfahren wird vorzugsweise ein Kohlenwasserstoffgemisch eingesetzt, das einen 1,3-Butadiengehalt von mindestens 10 Vol.-%, bevorzugt mindestens15 least of a catalyst according to the invention. When using hydrocarbon mixtures for the production of monoolefinic C 5 -mononitriles by the process according to the invention, a hydrocarbon mixture is preferably used which has a 1,3-butadiene content of at least 10% by volume, preferably at least
20 25 Vol.-%, insbesondere mindestens 40 Vol.-%, aufweist.20 25% by volume, in particular at least 40% by volume.
1,3-Butadien-haltige Kohlenwasserstoffge ische sind in großtechnischem Maßstab erhältlich. So fällt z. B. bei der Aufarbeitung von Erdöl durch Steamcracken von Naphtha ein als C-Schnitt be-1,3-butadiene-containing hydrocarbon mixtures are available on an industrial scale. So z. B. when working up oil by steam cracking naphtha as a C-cut
25 zeichnetes Kohlenwasserstoffgemisch mit einem hohen Gesamtolefin- anteil an, wobei etwa 40 % auf 1,3-Butadien und der Rest auf Mo- noolefine und mehrfach ungesättigte Kohlenwasserstoffe sowie Al- kane entfällt. Diese Ströme enthalten immer auch geringe Anteile von im Allgemeinen bis zu 5 % an Alkinen, 1,2-Dienen und Vinyl-25 marked hydrocarbon mixture with a high total olefin content, with about 40% being 1,3-butadiene and the rest mono-olefins and polyunsaturated hydrocarbons and alkanes. These streams always contain small amounts of generally up to 5% of alkynes, 1,2-dienes and vinyl
30 acetylen.30 acetylene.
Reines 1,3-Butadien kann z. B. durch extraktive Destillation aus technisch erhältlichen Kohlenwasserstoffgemischen isoliert werden.Pure 1,3-butadiene can e.g. B. be isolated by extractive distillation from commercially available hydrocarbon mixtures.
3535
Die erfindungsgemäßen Katalysatoren lassen sich vorteilhaft zur Hydrocyanierung solcher olefinhaltiger, insbesondere 1,3-Buta- dien-haltiger KohlenwasserStoffgemische einsetzen, in der Regel auch ohne vorherige destillative Aufreinigung des Kohlenwasser-The catalysts of the invention can advantageously be used for the hydrocyanation of such olefin-containing, in particular 1,3-butadiene-containing, hydrocarbon mixtures, generally also without prior purification of the hydrocarbon by distillation.
40 stoffgemischs. Möglicherweise enthaltene, die Effektivität der Katalysatoren beeinträchtigende Olefine, wie z. B. Alkine oder Cumulene, können gegebenenfalls vor der Hydrocyanierung durch selektive Hydrierung aus dem Kohlenwasserstoffgemisch entfernt werden. Geeignete Verfahren zur selektiven Hydrierung sind dem Fach-40 mixed fabrics. Possible contained, 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 specialist
45 mann bekannt. Die erfindungsgemäße Hydrocyanierung kann kontinuierlich, semikontinuierlich oder diskontinuierlich erfolgen. Geeignete Reaktoren für die kontinuierliche Umsetzung sind dem Fachmann bekannt und werden z. B. in Ullmanns Enzyklopädie der technischen Chemie, Band 1, 3. Auflage, 1951, S. 743 ff. beschrieben. Vorzugsweise wird für die kontinuierliche Variante des erfindungsgemäßen Verfahrens eine Rührkesselkaskade oder ein Rohrreaktor verwendet. Geeignete, gegebenenfalls druckfeste Reaktoren für die semikontinuierliche oder kontinuierliche Ausführung sind dem Fachmann be- kannt und werden z. B. in Ullmanns Enzyklopädie der technischen Chemie, Band 1, 3. Auflage, 1951, S. 769 ff. beschrieben. Im Allgemeinen wird für das erfindungsgemäße Verfahren ein Autoklav verwendet, der gewünschtenfalls mit einer Rührvorrichtung und einer Innenauskleidung versehen sein kann.45 men known. 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 the 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. In general, 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.
Die erfindungsgemäßen Hydrocyanierungskatalysatoren lassen sich nach üblichen, dem Fachmann bekannten Verfahren vom Austrag der Hydrocyanierungsreaktion abtrennen und können im Allgemeinen erneut für die Hydrocyanierung eingesetzt werden.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.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Car- bonylierung von Verbindungen, die wenigstens eine ethylenisch ungesättigte Doppelbindung enthalten, durch Umsetzung mit Kohlenmonoxid und wenigstens einer Verbindung mit einer nucleophilen Gruppe in Gegenwart eines Carbonylierungskatalysators, in dem man als Carbonylierungskatalysator einen Katalysator auf Basis eines Liganden der allgemeinen Formel I einsetzt.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.
Auch die erfindungsgemäßen Carbonylierungskatalysatoren umfassen Komplexe eines Metalls der VIII. Nebengruppe, bevorzugt Nickel, Cobalt, Eisen, Ruthenium, Rhodium und Palladium, insbesondere Palladium. Die Herstellung der Metallkomplexe kann wie bereits zuvor bei den Hydroformylierungskatalysatoren und Hydrocyanierungskatalysatoren beschrieben erfolgen. Gleiches gilt für die in situ-Herstellung der erfindungsgemäßen Carbonylierungskatalysatoren.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.
Geeignete Olefine für die Carbonylierung sind die allgemein zuvor als Einsatzstoffe für die Hydroformylierung und Hydrocyanierung genannten Olefine.Suitable olefins for carbonylation are the olefins which have generally been mentioned above as starting materials for hydroformylation and hydrocyanation.
Vorzugsweise sind die Verbindungen mit einer nucleophilen Gruppe, ausgewählt unter Wasser, Alkoholen, Thiolen, Carbonsäureestern, primären und sekundären Aminen.The compounds having a nucleophilic group are preferably selected from water, alcohols, thiols, carboxylic acid esters, primary and secondary amines.
Eine bevorzugte Carbonylierungsreaktion ist die Überführung von Olefinen mit Kohlenmonoxid und Wasser zu Carbonsäuren (Hydrocar- boxylierung) . Dazu zählt insbesondere die Umsetzung von Ethylen mit Kohlenmonoxid und Wasser zu Propionsäure.A preferred carbonylation reaction is the conversion of olefins with carbon monoxide and water to carboxylic acids (hydrocar- boxylation). This particularly includes the conversion of ethylene with carbon monoxide and water to propionic acid.
Ein weiterer Gegenstand der Erfindung ist die Verwendung von Ka- 5 talysatoren, umfassend eine erfindungsgemäße P-haltige Verbindung, wie zuvor beschrieben, zur Hydroformylierung, Hydrocyanierung, Carbonylierung, Hydrierung, Olefinoligomerisierung und -po- lymerisierung und zur Metathese.Another object of the invention is the use of catalysts comprising a P-containing compound according to the invention, as described above, for hydroformylation, hydrocyanation, carbonylation, hydrogenation, olefin oligomerization and polymerization and for metathesis.
10 Die Erfindung wird anhand der folgenden, nicht einschränkenden Beispiele näher erläutert.10 The invention is illustrated by the following, non-limiting examples.
Es wurden die folgenden Liganden eingesetzt:The following ligands were used:
15 Vergleichsbeispiel 115 Comparative Example 1
Lagerung von Vergleichsligand A bei RaumtemperaturStorage of comparative ligand A at room temperature
Figure imgf000071_0001
Figure imgf000071_0001
Vergleichsligand AComparative Ligand A
^•3^ • 3
Vergleichsligand A wurde gemäß K.G. Moloy et al., J. Am. Chem. Soc. 117, S. 7696-7710 (1995) hergestellt. Die Synthese führt zuComparative ligand A was according to K.G. Moloy et al., J. Am. Chem. Soc. 117, pp. 7696-7710 (1995). The synthesis leads to
30 sauberem Produkt mit einer 31P-NMR-Verschiebung von +79 ppm30 clean product with a 31 P NMR shift of +79 ppm
(C6D6). Nach Lagerung der Verbindung unter Argon für 5 Tage bei Raumtemperatur konnte eine merkliche Dunkelfärbung festgestellt werden. Nach acht Wochen bildete sich eine teerartige Verbindung, die in der Katalyse nicht mehr eingesetzt werden konnte.(C 6 D 6 ). After storing the compound under argon for 5 days at room temperature, a noticeable darkening was observed. After eight weeks, a tar-like compound formed that could no longer be used in catalysis.
3535
Hydroformylierung von 2-Octen mit Vergleichsligand AHydroformylation of 2-octene with comparative ligand A
0,9 mg Rh(C0)2acac und 8 mg Vergleichsligand A (60 ppm Rh, Ligand/ Rhodium = 10/1) wurden separat eingewogen, in je 1,5 g Xylol ge-0.9 mg Rh (C0) 2 acac and 8 mg reference ligand A (60 ppm Rh, ligand / rhodium = 10/1) were weighed in separately, each in 1.5 g xylene
40 löst, vermischt und bei 100 °C mit 10 bar Synthesegas (C0:H2 = 1:1) begast. Nach 30 min wurde entspannt, dann wurden 3,0 g 2-Octen zugegeben und 4 h bei 100 °C und 10 bar hydroformyliert . Die Umsatz betrug 74 %, die Aldehydselektivität 44 % und die Li- nearität 51 %. Der α-Anteil (n-Nonanal + iso-Nonanal) betrug40 dissolves, mixed and gassed at 100 ° C with 10 bar synthesis gas (C0: H 2 = 1: 1). After 30 minutes, the pressure was released, then 3.0 g of 2-octene were added and hydroformylated for 4 hours at 100 ° C. and 10 bar. The conversion was 74%, the aldehyde selectivity 44% and the linearity 51%. The proportion of α (n-nonanal + iso-nonanal) was
45 85 %. Vergleichsbeispiel 245 85%. Comparative Example 2
Lagerung von Vergleichsligand B bei RaumtemperaturStorage of comparative ligand B at room temperature
Figure imgf000072_0001
Figure imgf000072_0001
Vergleichsligand BComparative ligand B
1515
Vergleichsligand B wurde gemäß US 5,710,344 hergestellt. Die Synthese führt zu sauberem Produkt mit einer 31P-NMR-Verschiebung von +69 ppm (CeDß). Nach Lagerung der Verbindung unter Argon für 20 10 Tage bei Raumtemperatur konnte eine merkliche Dunkelfärbung festgestellt werden. Eine 31P-NMR-Untersuchung zeigte einen Li- gandabbau von 20 %.Comparative ligand B was produced according to US 5,710,344. The synthesis leads to a clean product with a 31 P-NMR shift of +69 ppm (CeD ß ). After storing the compound under argon for 20-10 days at room temperature, a noticeable darkening was found. A 31 P NMR analysis showed a ligand degradation of 20%.
Hydroformylierung von 1-Octen vor Lagerung bei RaumtemperaturHydroformylation of 1-octene before storage at room temperature
2525
1,6 mg Rh(CO)2acac (Rhodiumbiscarbonylacetylacetonat) und 36,9 mg Vergleichsligand B (106 ppm Rh, Verhältnis Ligand : Metall = 10:1) wurden separat eingewogen, in je 1,5 g Palatinol-AH® (Phthalsäureester von 2-Ethylhexanol der BASF Aktienges.) gelöst,1.6 mg Rh (CO) 2 acac (rhodium biscarbonylacetylacetonate) and 36.9 mg comparative ligand B (106 ppm Rh, ratio ligand: metal = 10: 1) were weighed out separately, in 1.5 g each of Palatinol-AH® (phthalic acid ester dissolved by 2-ethylhexanol from BASF Aktienges.),
30 vermischt und in einem 100 ml-Autoklaven bei 100 °C mit 10 bar Synthesegas (C0:H2 = 1:1) begast. Nach 30 min. wurde entspannt, dann wurden 3 g 1-Octen zugegeben und 4 h bei 100 °C und 10 bar hydroformyliert. Der Umsatz betrug 98 %, die Aldehydselektivität 59 % und die Linearität 99 %. Die Selektivität zu internen Octe-30 mixed and gassed in a 100 ml autoclave at 100 ° C with 10 bar synthesis gas (C0: H 2 = 1: 1). After 30 min. was relaxed, then 3 g of 1-octene were added and hydroformylated at 100 ° C. and 10 bar for 4 h. The conversion was 98%, the aldehyde selectivity 59% and the linearity 99%. The selectivity to internal Octe-
35 nen betrug 41 %.35% was 41%.
Hydroformylierung von 1-Octen nach Lagerung bei RaumtemperaturHydroformylation of 1-octene after storage at room temperature
1,6 mg Rh(CO)2acac und 36,9 mg Vergleichsligand B (106 ppm Rh, 40 Verhältnis Ligand : Metall = 10:1) wurden separat eingewogen, in je 1,5 g Palatinol-AH® gelöst, vermischt und bei 100 °C mit 10 bar Synthesegas (C0:H2 = 1:1) begast. Nach 30 min. wurde entspannt, dann wurden 3 g 1-Octen mit der Spritze zugegeben und 4 h bei 100 °C und 10 bar hydroformyliert. Der Umsatz betrug 20 %, die 45 Aldehydselektivität 5 % und die Linearität 71 %. Die Selektivität zu internen Octenen betrug 95 %. Beispiel 11.6 mg Rh (CO) 2 acac and 36.9 mg comparison ligand B (106 ppm Rh, 40 ratio ligand: metal = 10: 1) were weighed in separately, dissolved in 1.5 g Palatinol-AH®, mixed and gassed at 100 ° C with 10 bar synthesis gas (C0: H 2 = 1: 1). After 30 min. was relaxed, then 3 g of 1-octene were added with the syringe and hydroformylated for 4 h at 100 ° C. and 10 bar. The conversion was 20%, the 45 aldehyde selectivity 5% and the linearity 71%. The selectivity to internal octenes was 95%. example 1
Lagerung von Ligand C bei RaumtemperaturStorage of ligand C at room temperature
Figure imgf000073_0001
Figure imgf000073_0001
Ligand C wurde analog K.G. Moloy et al., J. Am. Chem. Soc. 117, S. 7696-7710 (1995) hergestellt. Die Synthese führt zu sauberem Produkt mit einer 31P-NMR-Verschiebung von +67 ppm (C^O ) . Nach Lagerung der Verbindung unter Argon für 3 Monate bei Raumtempera- tur konnte keine Dunkelfärbung festgestellt werden. Weder Erhitzen noch Behandlung mit Wasser führte zu einer stofflichen Veränderung.Ligand C was analogous to KG Moloy et al., J. Am. Chem. Soc. 117, pp. 7696-7710 (1995). The synthesis leads to a clean product with a 31 P NMR shift of +67 ppm (C ^ O). After storing the compound under argon for 3 months at room temperature, no darkening was found. Neither heating nor treatment with water led to a material change.
Beispiel 2 Synthese von Ligand DExample 2 Synthesis of Ligand D
Figure imgf000073_0002
Figure imgf000073_0002
Ligand DLigand D
8,2 g (60 mmol) PC13 wurden bei -70 °C unter Argon in Tetrahydro- furan vorgelegt. Anschließend wurden unter Rühren 11,7 g (120 mmol) 2-Ethylpyrrol langsam zugegeben und danach 18,2 g (180 mmol) Triethylamin ebenfalls langsam zugetropft. Dann wurde die Reaktionsmischung langsam auf Raumtemperatur gebracht und weitere 16 h bei Raumtemperatur gerührt. Danach wurden 6 g (21 mmol) 2 ,2 '-Dihydroxy-1, 1 ' -binaphthyl gelöst in 50 ml Tetrahy- drofuran langsam zugetropft, wobei die Temperatur bis auf 35 °C anstieg. Nach vollendeter Zugabe wurde 16 h bei Raumtemperatur gerührt, ein farbloser Feststoff (Et3N*HCl) abgesaugt und das Fil- trat bis zur Trockene eingeengt. Der Rückstand wird mit Methanol gewaschen, wobei ein Feststoff zurückbleibt, der im Vakuum getrocknet wird. 31P-NMR (CDC13): δ = 133.8.2 g (60 mmol) of PC1 3 were placed at -70 ° C under argon in tetrahydrofuran. Then 11.7 g (120 mmol) of 2-ethylpyrrole were slowly added with stirring and then 18.2 g (180 mmol) of triethylamine were also slowly added dropwise. The reaction mixture was then slowly brought to room temperature and stirred at room temperature for a further 16 h. 6 g (21 mmol) of 2,2'-dihydroxy-1,1'-binaphthyl were then dissolved in 50 ml of tetrahy- drofuran was slowly added dropwise, the temperature rising to 35 ° C. After the addition was complete, the mixture was stirred at room temperature for 16 h, a colorless solid (Et 3 N * HCl) was filtered off with suction and the filtrate was evaporated to dryness. The residue is washed with methanol, leaving a solid which is dried in vacuo. 31 P NMR (CDC1 3 ): δ = 133.
Hydroformylierung von 1-OctenHydroformylation of 1-octene
1,6 mg Rh(C0)2acac und 44,8 mg Ligand D wurden separat eingewogen, in je 1,5 g Palatinol AH® gelöst, vermischt und bei 100 °C mit 10 bar Synthesegas (CO:H2 = 1:1) begast. Nach 30 min. wurde entspannt, dann wurden 3 g 1-Octen zugegeben und 4 h bei 100 °C mit 10 bar Synthesegas (CO:H2 = 1:1) hydroformyliert. Der Umsatz be- trug 91 %, die Aldehydselektivität 63 % und die Linearität 91 %. Die Selektivität zu internen Olefinen betrug 37 %.1.6 mg Rh (C0) 2 acac and 44.8 mg Ligand D were weighed in separately, dissolved in 1.5 g Palatinol AH®, mixed and mixed at 100 ° C with 10 bar synthesis gas (CO: H 2 = 1: 1) fumigated. After 30 min. was depressurized, then 3 g of 1-octene were added and hydroformylated for 4 h at 100 ° C. with 10 bar synthesis gas (CO: H 2 = 1: 1). The conversion was 91%, the aldehyde selectivity 63% and the linearity 91%. The selectivity to internal olefins was 37%.
Hydroformylierung von 1-Octen nach Lagerung des Liganden bei RaumtemperaturHydroformylation of 1-octene after storing the ligand at room temperature
Nach Lagerung des Liganden bei Raumtemperatur unter Argon für 10 Tage wurde nur eine leichte Farbvertiefung beobachtet.After storing the ligand at room temperature under argon for 10 days, only a slight color deepening was observed.
1,6 mg Rh(CO)2acac und 44,8 mg Ligand D (nach 10-tägiger Lagerung unter Argon bei Raumtemperatur) wurden separat eingewogen, in je 1,5 g Palatinol AH® gelöst, vermischt und bei 100 °C mit 10 bar Synthesegas (C0:H2 = 1:1) begast. Nach 30 min. wurde entspannt, dann wurden 3 g 1-Octen zugegeben und 4 h bei 100 °C mit 10 bar Synthesegas (CO:H2 = 1:1) hydroformyliert. Der Umsatz betrug 92 %, die Aldehydselektivität 60 % und die Linearität 89 %. Die Selektivität zu internen Olefinen betrug 40 %.1.6 mg Rh (CO) 2 acac and 44.8 mg Ligand D (after 10 days storage under argon at room temperature) were weighed in separately, dissolved in 1.5 g Palatinol AH®, mixed and mixed at 100 ° C with 10 bar synthesis gas (C0: H 2 = 1: 1) gassed. After 30 min. was depressurized, then 3 g of 1-octene were added and hydroformylated for 4 h at 100 ° C. with 10 bar synthesis gas (CO: H 2 = 1: 1). The conversion was 92%, the aldehyde selectivity 60% and the linearity 89%. The selectivity to internal olefins was 40%.
Die erfindungsgemäßen Beispiele belegen, dass durch geeignete Substituenten am Pyrrolring eine erhebliche Erhöhung der Ligand- Stabilität erzielt werden kann. The examples according to the invention demonstrate that a significant increase in ligand stability can be achieved by suitable substituents on the pyrrole ring.

Claims

Patentansprücheclaims
1. Verfahren zur Herstellung von 2-Propylheptanol, bei dem man1. A process for the preparation of 2-propylheptanol, in which
a) Buten oder ein Buten enthaltendes C-Kohlenwasserstoffgemisch in Gegenwart eines Hydroformylierungskatalysators mit Kohlenmonoxid und Wasserstoff unter Erhalt eines n-Valeraldehyd enthaltenden Hydroformylierungsprodukts hydroformyliert, wobei der Hydroformylierungskatalysator wenigstens einen Komplex eines Metalls der VIII. Nebengruppe mit wenigstens einem Liganden der allgemeinen Formel Ia) butene or a butene-containing C-hydrocarbon mixture in the presence of a hydroformylation catalyst with carbon monoxide and hydrogen to give an n-valeraldehyde-containing hydroformylation product, the hydroformylation catalyst comprising at least one complex of a metal from subgroup VIII with at least one ligand of the general formula I
R5-(0)( (O)b-R6 R 5 - (0) ( (O) bR 6
\ /\ /
Figure imgf000075_0001
Figure imgf000075_0001
umfasst, worinincludes, wherein
R1, R2, R3 und R4 unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, WC00Ra, WC00-M+, W(S03)Ra, W(S03)~M+, WP03(Ra) (Rb) , W(P03)2"(M+)2, WNE^2, W(NE1E2E3)+X~, W0Ra, WSRa, (CHRbCH20)xRa, (CH^E^xR3, (CH2CH2NE1 )xRa, Halogen, Trifluormethyl, Nitro, Acyl oder Cyano stehen,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 + , WP0 3 (R a ) (R b ), W (P0 3 ) 2 "(M + ) 2 , WNE ^ 2 , W (NE 1 E 2 E 3 ) + X ~, W0R a , WSR a , (CHR b CH 2 0) x R a , (CH ^ E ^ x R 3 , (CH 2 CH 2 NE 1 ) x R a , halogen, trifluoromethyl, nitro, acyl or cyano,
worinwherein
W für eine Einfachbindung, ein Heteroatom oder eine zweiwertige verbrückende Gruppe mit 1 bis 20 Brückenatomen steht,W represents a single bond, a hetero atom or a divalent bridging group with 1 to 20 bridge atoms,
Ra, E1, E2, E3 jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl oder Aryl bedeuten, Rb für Wasserstoff, Methyl oder Ethyl steht,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,
M+ für ein Kationäquivalent steht,M + stands for a cation equivalent,
X- für ein Anionäquivalent steht undX- stands for an anion equivalent and
x für eine ganze Zahl von 1 bis 240 steht,x represents an integer from 1 to 240,
wobei jeweils zwei benachbarte Reste R1, R2, R3 und R4 zu- sa men mit den Kohlenstoffatomen des Pyrrolrings, an die sie gebunden sind, auch für ein kondensiertes Ringsystem mit 1, 2 oder 3 weiteren Ringen stehen können,where two adjacent radicals R 1 , R 2 , R 3 and R 4 together with the carbon atoms of the pyrrole ring to which they are bonded can also represent a condensed ring system with 1, 2 or 3 further rings,
mit der Maßgabe, dass wenigstens einer der Reste R1, R2, R3 oder R4 nicht für Wasserstoff steht, und dass R5 und R6 nicht mit einander verknüpft sind,with the proviso that at least one of the radicals R 1 , R 2 , R 3 or R 4 is not hydrogen and that R 5 and R 6 are not linked to one another,
R5 und R6 unabhängig voneinander für Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen, wobei einer der Reste R5 oder R6 auch für eine zweiwertige verbrückende Gruppe Y stehen kann, die zwei gleiche oder verschiedene Liganden oder Formel I kovalent miteinander verbindet, undR 5 and R 6 independently of one another represent cycloalkyl, heterocycloalkyl, aryl or hetaryl, it being possible for one of the radicals R 5 or R 6 also to represent a divalent bridging group Y which covalently connects two identical or different ligands or formula I to one another, and
a und b unabhängig voneinander die Zahl 0 oder 1 bedeuten,a and b independently of one another denote the number 0 or 1,
b) gegebenenfalls das Hydroformylierungsprodukt einer Auf- trennung unter Erhalt einer an n-Valeraldehyd angerei- cherten Fraktion unterzieht,b) optionally subjecting the hydroformylation product to a separation to obtain a fraction enriched in n-valeraldehyde,
c) das in Schritt a) erhaltene Hydroformylierungsprodukt oder die in Schritt b) erhaltene an n-Valeraldehyd angereicherte Fraktion einer Aldolkondensation unterzieht,c) subjecting the hydroformylation product obtained in step a) or the fraction enriched in n-valeraldehyde obtained in step b) to an aldol condensation,
d) die Produkte der Aldolkondensation mit Wasserstoff kata- lytisch zu Alkoholen hydriert, undd) the products of the aldol condensation are hydrogenated catalytically to give alcohols, and
e) gegebenenfalls die Hydrierprodukte einer Auftrennung un- ter Erhalt einer an 2-Propylheptanol angereicherten Fraktion unterzieht.e) optionally subjecting the hydrogenation products to separation to obtain a fraction enriched in 2-propylheptanol.
2. Verfahren nach Anspruch 1, bei dem man wenigstens einen Liganden der Formel I einsetzt, in dem die über das pyrrolische Stickstoffatom an das Phosphoratom gebundene Pyrrolgruppe ausgewählt ist unter Gruppen der Formeln I.a bis I.k COOAlk
Figure imgf000077_0001
2. The method according to claim 1, in which at least one ligand of the formula I is used, in which the pyrrole group bonded to the phosphorus atom via the pyrrolic nitrogen atom is selected from groups of the formulas Ia to Ik COOAlk
Figure imgf000077_0001
(I.a) (I.b)(I.a) (I.b)
Figure imgf000077_0002
Figure imgf000077_0002
(I.d)(I.d)
Figure imgf000077_0003
Figure imgf000077_0003
(I.e) (I.f) (i.g)(I.e) (I.f) (i.g)
Figure imgf000077_0004
Figure imgf000077_0004
(I.h) (I.i) (I.k)(I.h) (I.i) (I.k)
worinwherein
Alk eine Cχ-C -Alkylgruppe ist undAlk is a Cχ-C alkyl group and
R9, Rh, R1 und Rk unabhängig voneinander für Wasserstoff, Cχ-C -Alkyl, Cχ-C -Alkoxy, Acyl, Halogen, Trifluormethyl, Cχ-C -Alkoxycarbonyl oder Carboxyl stehen.R9, R h , R 1 and R k independently of one another are hydrogen, Cχ-C-alkyl, Cχ-C alkoxy, acyl, halogen, trifluoromethyl, Cχ-C alkoxycarbonyl or carboxyl.
3. Verfahren nach Anspruch 2, bei dem man wenigstens einen Liganden der Formel I einsetzt, in dem die über das pyrrolische Stickstoffatom an das Phosphoratom gebundene Pyrrolgruppe für eine 3-Alkylindolylgruppe, bevorzugt eine 3-Methylindolyl- gruppe, steht.3. The method according to claim 2, in which at least one ligand of the formula I is used in which the pyrrole group bonded to the phosphorus atom via the pyrrolic nitrogen atom for a 3-alkylindolyl group, preferably a 3-methylindolyl group.
4. Verfahren nach Anspruch 1, bei dem man wenigstens einen Li- ganden der Formel I einsetzt, worin die über das pyrrolische Stickstoffatom an das Phosphoratom gebundene Pyrrolgruppe gemeinsam mit R5 eine Gruppe der Formel4. The method according to claim 1, in which at least one ligand of the formula I is used, wherein the pyrrole group bonded to the phosphorus atom via the pyrrolic nitrogen atom together with R 5 is a group of the formula
Figure imgf000078_0001
Figure imgf000078_0001
bildet, worinforms what
I für eine chemische Bindung oder für 0, S, SiRαRß,NRγ oder gegebenenfalls substituiertes Cχ-Cχo-Alkylen, bevorzugt CRδRε, steht, worin Rα , R^, Rγ, Rδ und Rε unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,I stands for a chemical bond or for 0, S, SiR α Rß, NR γ or optionally substituted Cχ-Cχo-alkylene, preferably CR δ R ε , wherein R α , R ^, R γ , R δ and R ε independently are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
R1, R1', R2, R2', R3, R3', R4 und R4 ' unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl,R 1 , R 1 ', R 2 , R 2 ', R 3 , R 3 ', R 4 and R 4 ' independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl,
Aryl, Hetaryl, WC00Ra, WC00"M+, W(S03)Ra, W(S03)~M+, WP03(Ra) (Rb), W(P03)2"(M+)2, WNEiE2, WfNE^E3 )+X", WOR- a, WSRa, (CHRbCH20)xRa, (CH2NE1)xRa, (O^C^NE1 )xRa, Halogen, Trifluormethyl, Nitro, Acyl oder Cyano stehen,Aryl, hetaryl, WC00R a , WC00 "M + , W (S0 3 ) R a , W (S0 3 ) ~ M + , WP0 3 (R a ) (R b ), W (P0 3 ) 2 " (M + ) 2 , WNE i E 2 , WfNE ^ E 3 ) + X ", WOR- a , WSR a , (CHR b CH 2 0) x R a , (CH 2 NE 1 ) x R a , (O ^ C ^ NE 1 ) x R a , halogen, trifluoromethyl, nitro, acyl or cyano,
worinwherein
W für eine Einfachbindung, ein Heteroatom oder eine zweiwertige verbrückende Gruppe mit 1 bis 20 Brückenatomen steht,W represents a single bond, a hetero atom or a divalent bridging group with 1 to 20 bridge atoms,
Ra, E1, E2, E3 jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl oder Aryl bedeuten,R a , E 1 , E 2 , E 3 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
R für Wasserstoff, Methyl oder Ethyl steht,R represents hydrogen, methyl or ethyl,
M+ für ein Kationäquivalent steht r M + stands for a cation equivalent r
X- für ein Anionäquivalent steht und x für eine ganze Zahl von 1 bis 240 steht,X- stands for an anion equivalent and x represents an integer from 1 to 240,
wobei jeweils zwei benachbarte Reste R1 und R2 und/oder R1' und R2' zusammen mit den Kohlenstoffatomen des Pyrrol- rings, an die sie gebunden sind, auch für ein kondensiertes Ringsystem mit 1, 2 oder 3 weiteren Ringen stehen können.where two adjacent radicals R 1 and R 2 and / or R 1 'and R 2 ' together with the carbon atoms of the pyrrole ring to which they are attached can also represent a condensed ring system with 1, 2 or 3 further rings ,
5. Verfahren nach Anspruch 1, wobei die Verbindung der Formel I ausgewählt ist unter Verbindungen der allgemeinen Formeln I .1 bis 1.45. The method according to claim 1, wherein the compound of formula I is selected from compounds of general formulas I .1 to 1.4
R5-R 5 -
Figure imgf000079_0001
Figure imgf000079_0001
Figure imgf000079_0002
Figure imgf000079_0002
( 1 . 3 )(1. 3)
Figure imgf000079_0003
Figure imgf000079_0003
( 1 . 4 ) worin(1. 4) wherein
R1, R2' R3' R4' Y, a und b die in Anspruch 1 angegebenen Bedeutungen besitzen undR 1 , R 2 'R 3 ' R 4 'Y, a and b have the meanings given in claim 1 and
R5 und R6 unabhängig voneinander für Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen.R 5 and R 6 independently of one another represent cycloalkyl, heterocycloalkyl, aryl or hetaryl.
6. Verfahren nach Anspruch 1, wobei die Verbindung der allgemei- nen Formel I ausgewählt ist unter Verbindungen der allgemeinen Formeln I .5 und I .66. The method according to claim 1, wherein the compound of the general formula I is selected from compounds of the general formulas I .5 and I .6
R5-(0) 0)b-R6 R 5 - (0) 0) b -R 6
Figure imgf000080_0001
(1.5)
Figure imgf000080_0001
(1.5)
Figure imgf000080_0002
Figure imgf000080_0002
(1.6)(1.6)
worinwherein
R2 und R3 die in Anspruch 1 angegebenen Bedeutungen besitzen, wobei wenigstens einer der Reste R2 oder R3 nicht für Wasserstoff steht,R 2 and R 3 have the meanings given in claim 1, where at least one of the radicals R 2 or R 3 is not hydrogen,
R5 und R6 unabhängig voneinander für Cycloalkyl, Heterocyclo- alkyl, Aryl oder Hetaryl stehen.R 5 and R 6 independently of one another are cycloalkyl, heterocycloalkyl, aryl or hetaryl.
7. Verfahren nach einem der vorhergehenden Ansprüche, wobei in der Formel I die verbrückende Gruppe Y ausgewählt ist unter Gruppen der Formeln Il.a bis Il.t
Figure imgf000081_0001
7. The method according to any one of the preceding claims, wherein in the formula I, the bridging group Y is selected from groups of the formulas Il.a to Il.t
Figure imgf000081_0001
(II. a) (II. b)(II. A) (II. B)
Figure imgf000081_0002
Figure imgf000081_0002
(II. e)(II. E)
Figure imgf000081_0003
Figure imgf000081_0003
(II. f) (II. g)(II. F) (II. G)
Figure imgf000081_0004
Figure imgf000081_0004
(li. h) (II. i) (II. k)
Figure imgf000082_0001
(left h) (II. i) (II. k)
Figure imgf000082_0001
(II.1) (II.m) (II. n)(II.1) (II.m) (II. N)
Figure imgf000082_0002
Figure imgf000082_0002
Figure imgf000082_0003
Figure imgf000082_0003
(II. r) (II. s) (II.t)(II. R) (II. S) (II.t)
worinwherein
R bis RXI1 unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Alkoxy, Halogen, S03H, Sulfonat, NE4E5, Alkylen-NE4E5, Trifluormethyl, Nitro, Alkoxycarbonyl, Carboxyl oder Cyano stehen, worin E4 und E5 jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl und Aryl bedeuten,R to R XI1 independently of one another are hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, S0 3 H, sulfonate, NE 4 E 5 , alkylene-NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, in which E 4 and E 5 each denote the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
Z für O, S, NR15 oder SiR15R16 steht, wobeiZ represents O, S, NR 15 or SiR 15 R 16 , where
R15 und R16 unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,R 15 and R 16 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
oder Z für eine Cχ~ bis C -Alkylenbrücke steht, die eine Doppelbindung und/oder einen Alkyl-, Cycloalkyl-, Heterocycloalkyl-, Aryl- oder Hetaryl-Substituenten aufweisen kann,or Z represents a Cχ ~ to C alkylene bridge which may have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent,
oder Z für eine C2- bis C -Alkylenbrücke steht, die durch 0, S oder NR15 oder SiR15R16 unterbrochen ist, wobei in den Gruppen der Formeln II. g bis II.m einer der Reste R1 bis RIV auch für Oxo oder ein Ketal davon stehen kann,or Z represents a C 2 -C alkylene bridge which is interrupted by 0, S or NR 15 or SiR 15 R 16 , in the groups of the formulas II. g to II.m one of the radicals R 1 to R IV can also represent oxo or a ketal thereof,
8. Verfahren nach einem der vorhergehenden Ansprüche, wobei in der Formel I die verbrückende Gruppe Y ausgewählt ist unter Gruppen der Formeln II.1 bis II.58. The method according to any one of the preceding claims, wherein in the formula I, the bridging group Y is selected from groups of formulas II.1 to II.5
Figure imgf000083_0001
Figure imgf000083_0001
(II.1) (II.2) (II.3)(II.1) (II.2) (II.3)
Figure imgf000083_0002
Figure imgf000083_0002
(II.4) (II.5)(II.4) (II.5)
worinwherein
R7, R8' R9' R10' R11' R12' R13 und R14 unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Aryl, Alkoxy, Halogen, S03H, Sulfonat, NE4E5, Alkylen-NE4E5, Trifluormethyl, Ni- tro, Alkoxycarbonyl, Carboxyl oder Cyano stehen, worin E4 und E5 jeweils gleiche oder verschiedene Reste, ausgewählt unter Wasserstoff, Alkyl, Cycloalkyl und Aryl bedeuten,R 7 , R 8 'R 9 ' R 10 'R 11 ' R 12 'R 13 and R 14 independently of one another for hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, S0 3 H, sulfonate, NE 4 E 5 , alkylene -NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, in which E 4 and E 5 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
für 0, S, NR15 oder SiR15R16 steht, wobeirepresents 0, S, NR 15 or SiR 15 R 16 , where
R15 und R16 unabhängig voneinander für Wasserstoff, Alkyl,R 15 and R 16 independently of one another for hydrogen, alkyl,
Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,Cycloalkyl, heterocycloalkyl, aryl or hetaryl,
oder Z für eine Cχ~ bis C3-Alkylenbrücke steht, die eine Doppelbindung und/oder einen Alkyl-, Cycloalkyl-, Heterocycloalkyl-, Aryl- oder Hetaryl-Substituenten aufweisen kann,or Z represents a Cχ ~ to C 3 alkylene bridge which can have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent,
oder Z für eine C2- bis C3-Alkylenbrücke steht, die durch 0, S oder NR15 oder SiR15R16 unterbrochen ist. Katalysatoren, umfassend Komplexe mit einem Metall der VIII. Nebengruppe des Periodensystems der Elemente, die als Liganden mindestens eine Verbindung der Formel I gemäß Anspruch 1 enthalten, ausgenommen Verbindungen der Formelnor Z stands for a C 2 - to C 3 -alkylene bridge which is interrupted by 0, S or NR 15 or SiR 15 R 16 . Catalysts comprising complexes with a metal of subgroup VIII of the Periodic Table of the Elements which contain as ligands at least one compound of the formula I according to claim 1, with the exception of compounds of the formulas
Figure imgf000084_0001
Figure imgf000084_0001
a: Rc, Rd, Re, Rf = (1-Indolyl) b: Rc, Re = (1-Indolyl); Rd, Rf = (O-Phenyl) c: Rc, Rd, Re, Rf = ( 1-Carbazolyl) d: Rc, Rd, Re, Rf = (3, 4 , 5, 6-Tetrahydrocarbazol-l-yl) e: Rc, Rd, Re, Rf = (Isoindol-1-yl) ;a: R c , R d , R e , R f = (1-indolyl) b: R c , R e = (1-indolyl); R d , R f = (O-phenyl) c: R c , R d , R e , R f = (1-carbazolyl) d: R c , R d , R e , R f = (3, 4, 5 , 6-tetrahydrocarbazol-l-yl) e: R c , R d , R e , R f = (isoindol-1-yl);
Figure imgf000084_0002
Figure imgf000084_0002
a: Rc, Rd, Re, Rf = (1-Indolyl) b: Rc, Re = (1-Indolyl); Rd, Rf = Phenyl c: Rc, Re = (1-Indolyl); Rd, Rf = (1-Pyrrolyl) d: Rc, Re = (l-lndolyl); Rd, Rf = (0-(2-Isopropyl-5-methyl- phenyl) ) e: Rc, Re = (1-Indolyl); Rd, Rf = (O-Phenyl) f: Rc, Re = (1-Carbazolyl) ; Rd, R£ = (O-Phenyl);a: R c , R d , R e , R f = (1-indolyl) b: R c , R e = (1-indolyl); R d , R f = phenyl c: R c , R e = (1-indolyl); R d , R f = (1-pyrrolyl) d: R c , R e = (l-indolyl); R d , R f = (0- (2-isopropyl-5-methylphenyl)) e: R c , R e = (1-indolyl); R d , R f = (O-phenyl) f: R c , R e = (1-carbazolyl); R d , R £ = (O-phenyl);
Figure imgf000084_0003
Figure imgf000085_0001
worin
Figure imgf000084_0003
Figure imgf000085_0001
wherein
R , Rüi, RIV, RV, RVI und Rvιπ für von Wasserstoff verschiedene Substituenten stehen undR, Rü i , R IV , R V , R VI and R vιπ stand for substituents other than hydrogen and
Rc, Rd, Re und Rf für Gruppen der FormelR c , R d , R e and R f for groups of the formula
Figure imgf000085_0002
Figure imgf000085_0002
stehen, worin R1, R2, R3 und R4 die in Anspruch 1 angegebenen Bedeutungen besitzen;stand in which R 1 , R 2 , R 3 and R 4 have the meanings given in claim 1;
Figure imgf000085_0003
worin
Figure imgf000085_0003
wherein
Ri, Ri11, RVI und Rm für von Wasserstoff verschiedene Substituenten stehen undR i , R i11 , R VI and Rm represent substituents other than hydrogen and
Rc, Rd, Re und Rf für Gruppen der FormelR c , R d , R e and R f for groups of the formula
Figure imgf000085_0004
stehen, worin R1, R2, R3 und R4 die in Anspruch 1 angegebenen Bedeutungen besitzen.
Figure imgf000085_0004
stand in which R 1 , R 2 , R 3 and R 4 have the meanings given in claim 1.
10. Katalysatoren, umfassend Komplexe mit einem Metall der VIII. 5 Nebengruppe des Periodensystems, die als Liganden mindestens eine Verbindung der Formel I, wie in einem der Ansprüche 1 bis 8 definiert, aufweisen, in denen wenigstens eine der Gruppen der Formel10. Catalysts comprising complexes with a metal of VIII. 5 subgroup of the periodic table, which have as ligands at least one compound of the formula I, as defined in one of claims 1 to 8, in which at least one of the groups of the formula
Figure imgf000086_0001
Figure imgf000086_0001
für 3-Alkylindol-l-yl, insbesondere für 3-Methylindol-l-yl, steht .stands for 3-alkylindol-l-yl, in particular for 3-methylindol-l-yl.
20 11. Katalysatoren nach einem der Ansprüche 9 oder 10, in denen das Metall ausgewählt ist aus Kobalt, Rhodium, Ruthenium oder Iridium.11. Catalysts according to one of claims 9 or 10, in which the metal is selected from cobalt, rhodium, ruthenium or iridium.
12. Verfahren zur Hydroformylierung von Verbindungen, die wenig- 25 stens eine ethylenisch ungesättigte Doppelbindung enthalten durch Umsetzung mit Kohlenmonoxid und Wasserstoff in Gegenwart eines Hydroformylierungskatalysators, umfassend wenigstens einen Komplex eines Metalls der VIII. Nebengruppe mit wenigstens einem Liganden der allgemeinen Formel I, wie in 30 einem der Ansprüche 1 bis 8 definiert.12. A process for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst comprising at least one complex of a metal from subgroup VIII with at least one ligand of the general formula I, as in 30 one of claims 1 to 8 defined.
13. Verfahren zur Hydroformylierung von Verbindungen, die wenigstens eine ethylenisch ungesättigte Doppelbindung enthalten durch Umsetzung mit Kohlenmonoxid und Wasserstoff in Gegen-13. Process for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in counter
35 wart eines Katalysators, wie in einem der Ansprüche 9 bis 11 definiert.35 were a catalyst as defined in any one of claims 9 to 11.
14. Verwendung eines Katalysators, wie in einem der Ansprüche 9 bis 11 definiert, zur Hydroformylierung, Carbonylierung, Hy-14. Use of a catalyst as defined in any one of claims 9 to 11 for hydroformylation, carbonylation, hy-
40 drocyanierung oder Hydrierung.40 drocyanation or hydrogenation.
45 45
PCT/EP2002/009455 2001-08-24 2002-08-23 Method for the production of 2-propylheptanol and hydroformylating catalysts and the further use thereof for carbonylation, hydrocyanation and hydrogenation WO2003018192A2 (en)

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