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WO2003018192A2 - Procede de preparation de 2-propylheptanol - Google Patents

Procede de preparation de 2-propylheptanol Download PDF

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Publication number
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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WO
WIPO (PCT)
Prior art keywords
hydrogen
alkyl
formula
aryl
cycloalkyl
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PCT/EP2002/009455
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German (de)
English (en)
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WO2003018192A3 (fr
Inventor
Wolfgang Ahlers
Rocco Paciello
Thomas Mackewitz
Martin Volland
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Basf Aktiengesellschaft
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2002324067A priority Critical patent/AU2002324067A1/en
Publication of WO2003018192A2 publication Critical patent/WO2003018192A2/fr
Publication of WO2003018192A3 publication Critical patent/WO2003018192A3/fr

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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B01J31/1855—Triamide derivatives thereof
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    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B01J31/186—Mono- or diamide derivatives thereof
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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    • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
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    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
    • C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
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    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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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.

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Abstract

La présente invention concerne un procédé destiné à la préparation de 2-propylheptanol, faisant intervenir l'hydroformylation de butène, une condensation aldolique des produits d'hydroformylation ainsi obtenus, et leur hydratation catalytique. L'invention a également pour objet de nouveaux catalyseurs impliqués dans l'étape d'hydroformylation, et leur utilisation.
PCT/EP2002/009455 2001-08-24 2002-08-23 Procede de preparation de 2-propylheptanol WO2003018192A2 (fr)

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AU2002324067A AU2002324067A1 (en) 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

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DE10141494 2001-08-24
DE10141494.3 2001-08-24

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WO2003018192A2 true WO2003018192A2 (fr) 2003-03-06
WO2003018192A3 WO2003018192A3 (fr) 2003-11-13

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WO2004026803A1 (fr) * 2002-09-13 2004-04-01 Basf Aktiengesellschaft Procede de production de dialdehydes et/ou de monoaldehydes ethyleniquement insatures par hydroformylation de composes ethyleniquement insatures
WO2005009934A3 (fr) * 2003-07-23 2005-04-07 Basf Ag Procede d'hydroformylation en deux etapes
WO2005039762A1 (fr) * 2003-10-23 2005-05-06 Basf Aktiengesellschaft Stabilisation de catalyseurs d'hydroformylation a base de ligands phosphoramidite
WO2005120704A1 (fr) 2004-06-12 2005-12-22 Lg Chem. Ltd. Composition de catalyseur contenant du phosphore et processus de d'hydroformylation faisant appel a cette composition
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JP2007507340A (ja) * 2004-06-12 2007-03-29 エルジー・ケム・リミテッド 燐を含む触媒組成物及びそれを利用したヒドロホルミル化の方法
WO2006128434A3 (fr) * 2005-06-02 2007-08-30 Studiengesellschaft Kohle Mbh DIPHOSPHONITES CHIRAUX UTILISES EN TANT QUE LIGANDS DANS LA REDUCTION ENANTIOSELECTIVE DE CETONES, DE ß-CETO-ESTERS, DE ET CETIMINES, CATALYSEE PAR DU RUTHENIUM
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EP1486481A3 (fr) * 2003-03-25 2010-01-27 Basf Se Procédé d'hydroformylation
US8519084B2 (en) 2008-06-16 2013-08-27 Basf Se Use of a C11 diol or C11 diol mixture for producing polymers
EP2740535A1 (fr) * 2012-12-04 2014-06-11 Dow Technology Investments LLC Ligands bidentates pour hydroformylation d'éthylène
DE102013214378A1 (de) 2013-07-23 2015-01-29 Evonik Industries Ag Phosphoramiditderivate in der Hydroformylierung von olefinhaltigen Gemischen
WO2017150337A1 (fr) 2016-03-01 2017-09-08 株式会社クラレ Procédé de production de composé dialdéhyde
WO2018228879A1 (fr) 2017-06-13 2018-12-20 Basf Se Procédé d'hydroformylation pour produire des dérivés de 1,6-hexanediol
US10315975B2 (en) 2015-07-10 2019-06-11 Basf Se Method for the hydroformylation of 2-substituted butadienes and the production of secondary products thereof, especially ambrox
US10647651B2 (en) 2015-10-12 2020-05-12 Basf Se Hydroformylation process for producing 1,6-disubstituted hexane derivatives

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WO2003066642A1 (fr) * 2002-02-08 2003-08-14 Basf Aktiengesellschaft Chelates de phosphore
WO2004026803A1 (fr) * 2002-09-13 2004-04-01 Basf Aktiengesellschaft Procede de production de dialdehydes et/ou de monoaldehydes ethyleniquement insatures par hydroformylation de composes ethyleniquement insatures
US7145042B2 (en) 2002-09-13 2006-12-05 Basf Aktiengesellschaft Method for producing dialdehydes and or ethylenically unsaturated monoaldehydes by hydroformylating ethylenically unsaturated compounds
EP1486481A3 (fr) * 2003-03-25 2010-01-27 Basf Se Procédé d'hydroformylation
WO2005009934A3 (fr) * 2003-07-23 2005-04-07 Basf Ag Procede d'hydroformylation en deux etapes
WO2005039762A1 (fr) * 2003-10-23 2005-05-06 Basf Aktiengesellschaft Stabilisation de catalyseurs d'hydroformylation a base de ligands phosphoramidite
US8110709B2 (en) 2003-10-23 2012-02-07 Basf Se Stabilization of hydroformylation catalysts based on phosphoramide ligands
CN1871066B (zh) * 2003-10-23 2011-06-22 巴斯福股份公司 基于磷酰胺配体的加氢甲酰化催化剂的稳定
EP1755781A4 (fr) * 2004-06-12 2009-05-13 Lg Chemical Ltd Composition de catalyseur contenant du phosphore et processus de d'hydroformylation faisant appel a cette composition
EP1755782A4 (fr) * 2004-06-12 2009-05-06 Lg Chemical Ltd Composition de catalyseur contenant du phosphore et procede d'hydroformylation dans lequel ladite composition est utilisee
JP2007508131A (ja) * 2004-06-12 2007-04-05 エルジー・ケム・リミテッド 燐を含む触媒組成物及びそれを利用したヒドロホルミル化の方法
JP2007507340A (ja) * 2004-06-12 2007-03-29 エルジー・ケム・リミテッド 燐を含む触媒組成物及びそれを利用したヒドロホルミル化の方法
WO2005120704A1 (fr) 2004-06-12 2005-12-22 Lg Chem. Ltd. Composition de catalyseur contenant du phosphore et processus de d'hydroformylation faisant appel a cette composition
US8524628B2 (en) 2004-06-12 2013-09-03 Lg Chem, Ltd. Phosphorus-containing catalyst composition and hydroformylation process using the same
WO2006045597A1 (fr) * 2004-10-26 2006-05-04 Basf Aktiengesellschaft Ligands destines a l'hydroformulation asymetrique
WO2006128434A3 (fr) * 2005-06-02 2007-08-30 Studiengesellschaft Kohle Mbh DIPHOSPHONITES CHIRAUX UTILISES EN TANT QUE LIGANDS DANS LA REDUCTION ENANTIOSELECTIVE DE CETONES, DE ß-CETO-ESTERS, DE ET CETIMINES, CATALYSEE PAR DU RUTHENIUM
US9266808B2 (en) 2006-11-30 2016-02-23 Basf Se Method for the hydroformylation of olefins
WO2008065171A1 (fr) * 2006-11-30 2008-06-05 Basf Se Procédé pour l'hydroformulation d'oléfines
DE102008002530A1 (de) 2007-06-28 2009-01-02 Basf Se Verfahren zur Herstellung von Alkansäureglycidestern
US8519084B2 (en) 2008-06-16 2013-08-27 Basf Se Use of a C11 diol or C11 diol mixture for producing polymers
EP2740535A1 (fr) * 2012-12-04 2014-06-11 Dow Technology Investments LLC Ligands bidentates pour hydroformylation d'éthylène
CN104822456A (zh) * 2012-12-04 2015-08-05 陶氏技术投资有限责任公司 用于氢甲酰化乙烯的双齿配位体
WO2014088800A1 (fr) * 2012-12-04 2014-06-12 Dow Technology Investments Llc Ligands bidentés pour l'hydroformylation de l'éthylène
US9795952B2 (en) 2012-12-04 2017-10-24 Dow Technology Investments Llc Bidentate ligands for hydroformylation of ethylene
DE102013214378A1 (de) 2013-07-23 2015-01-29 Evonik Industries Ag Phosphoramiditderivate in der Hydroformylierung von olefinhaltigen Gemischen
US10315975B2 (en) 2015-07-10 2019-06-11 Basf Se Method for the hydroformylation of 2-substituted butadienes and the production of secondary products thereof, especially ambrox
US10647651B2 (en) 2015-10-12 2020-05-12 Basf Se Hydroformylation process for producing 1,6-disubstituted hexane derivatives
WO2017150337A1 (fr) 2016-03-01 2017-09-08 株式会社クラレ Procédé de production de composé dialdéhyde
WO2018228879A1 (fr) 2017-06-13 2018-12-20 Basf Se Procédé d'hydroformylation pour produire des dérivés de 1,6-hexanediol
US10941092B2 (en) 2017-06-13 2021-03-09 Basf Se Hydroformylation process for producing 1,6-hexanediol derivatives

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