WO1996016923A1 - Process for the preparation of an aldehyde - Google Patents

Process for the preparation of an aldehyde Download PDF

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Publication number
WO1996016923A1
WO1996016923A1 PCT/NL1995/000393 NL9500393W WO9616923A1 WO 1996016923 A1 WO1996016923 A1 WO 1996016923A1 NL 9500393 W NL9500393 W NL 9500393W WO 9616923 A1 WO9616923 A1 WO 9616923A1
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group
ligand
compound
carbon atoms
organic group
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PCT/NL1995/000393
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French (fr)
Inventor
Elmo Wissing
Antonius Jacobus Josephus Maria Teunissen
Carolina Bernedette Hansen
Petrus Wilhelmus Nicolaas Maria Van Leeuwen
Annemiek Van Rooy
Dennis Burgers
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Dsm N.V.
E.I. Du Pont De Nemours And Company
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Priority to EP95937211A priority Critical patent/EP0793636A1/en
Priority to JP8518618A priority patent/JPH10509973A/en
Priority to AU39377/95A priority patent/AU3937795A/en
Publication of WO1996016923A1 publication Critical patent/WO1996016923A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B01J31/186—Mono- or diamide derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/242—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2458—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657154—Cyclic esteramides of oxyacids of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • C07F9/65842—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring
    • C07F9/65844—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring the phosphorus atom being part of a five-membered ring which may be condensed with another ring system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Definitions

  • the invention relates to a process for preparing an aldehyde compound by hydroformylation of an ethylenically unsaturated organic compound in the presence of a catalyst system comprising of a multidentate phosphorus ligand and a Group 8-10 metal.
  • hydroformylation is meant the reaction of an unsaturated compound with hydrogen and carbon monoxide in the presence of a catalyst.
  • US-A-4769498 describes the hydroformylation of 2-butene in the presence of a homogeneous catalyst system consisting of rhodium and a bidentate phosphite ligand.
  • a disadvantage of such a process is that the selectivity to aldehydes is too low for a commercially interesting process.
  • An object of this invention is a hydroformylation process to prepare aldehydes with a higher selectivity to aldehydes than is achieved with the catalyst system of US-A-4769498.
  • the multidentate phosphorus amide ligand consists of a multivalent bridging organic group connected to at least two trivalent phosphorus-containing groups of the formula
  • R is hydrogen, an organic group, or - S0 2 R 1 , wherein R 1 is a C 1-12 organic group, and wherein remaining free bonds of said trivalent phosphorus groups are linked to a mono- or di-valent organic group.
  • Phosphorus amide compounds which are used as ligands, are described in WO-A-9303839.
  • a catalyst system consisting of rhodium and a bidentate phosphorus diamide ( (N,N'-diphenyl-ethylenediamine-P) 2 -2S,4S- pentanediol) .
  • This bidentate phosphorus diamide ligand contains structural groups in which two nitrogen atoms, in contrast to the P(N(R)-) (0-) 2 group(s) of the ligands according to the invention, are directly bonded to a phosphorus atom of the ligand.
  • WO-A-9303839 is dedicated to a process for the stereo specific preparation of optically active aldehyde compounds by using one specific stereo-isomer of the phosphorus amide ligand.
  • the phosphorus amide compound used as ligand in the process according to the invention may for example be represented by the following formula:
  • R 2 , R 3 , R 4 and R 5 are the same or different and in which either one of X or Y is a N(R) group while the other group is oxygen
  • A is a multivalent (multi is equal to k+m) organic group with 2 to 30 carbon atoms, k is at least 1, m can be 0-5 and k+m is 2-6, R 2 and R 3 together and/or R 4 and R 5 together form one, optionally substituted, divalent organic group with 2 to 30 carbon atoms or R 2 , R 3 , R 4 and R s are independently, optionally substituted, monovalent organic groups with 1 to 20 carbon atoms.
  • R is hydrogen or an organic group with 1 to
  • R 1 is an organic group with 1 to 12 carbon atoms.
  • R is hydrogen or a C ⁇ -C ⁇ alkyl group, phenyl, for example methyl, ethyl, propyl or substituted or unsubstituted aryl groups, for example phenyl and tolyl or a -SO 3 R 1 group as defined before.
  • bidentate phosphorus amide compounds used as ligand in the process according to the invention can be represented by formula (1) in which k+m is equal to 2 or by the following formula: R 2 -0 Y — A — Z O-R 4
  • A is a divalent organic group with 2 to 30 carbon atoms and in which R 2 , R 3 , R 4 , R 5 and R are the same as defined above.
  • the bridging group (A) may be for example a multivalent organic group with 2 to 30 carbon atoms. The number of valencies is in principle not bound to an upper limit.
  • An example of a multivalent bridging group are dendrimer like compounds as described in WO-A- 9314147.
  • a preferred dendrimer bridging compound has reactive -NH 2 groups which can easily react with a bis(alkoxy) or bis(aryloxy)phosphorus chloride compound to yield the ligand which can be used in the process according to the invention.
  • valencies In general the amount of valencies will be 2- 6.
  • An example of a tetravalent organic group is pentaerythritetraryl.
  • Preferred divalent organic groups are alkylene, alkylene-oxy-alkylene, arylene, arylene- (CH 2 ) y -(R 6 ) n -(CH 2 ) y -arylene, in which y is 0 or 1, n is 0 or 1 and each arylene is the same or different, substituted or unsubstituted divalent aryl radical and R 5 individually represents a divalent group selected from the group consisting of -CR 7 R 8 -, -0-, -S-, -NR 9 -, -SiR ⁇ R 11 - and -CO-, in which R 7 and R 8 individually represents hydrogen, C 1 -C 12 alkyl, phenyl, tolyl, anisyl or methoxyphenyl, wherein each R 9 , R 10 and R 11 group individually represents hydrogen or a C 1 -C l2 organic group for example ethyl, propyl, butyl, benzyl and by preference hydrogen
  • Examples of possible divalent organic bridging groups (A) include substituted and unsubstituted radicals selected from the group consisting of alkylene, alkylene-oxy-alkylene, phenylene, naphthylene, phenylene-(CH 2 ) y -(R 6 ) n -(CH 2 ) y - phenylene and naphthylene-(CH 2 ) y -(R 6 ) n -(CH 2 ) y - naphthylene-radicals, R 6 , n and y are the same as defined above.
  • divalent radicals A are -CH 2 CH 2 OCH 2 CH 2 -, 1,4-phenylene, 2,3- phenylene, 1,3-phenylene, 1,4-naphthylene, 1,5- naphthylene, 1,8-naphthylene, 2,3-naphthylene, 1,1' biphenyl-2,2 '-diyl, 2,2' biphenyl-1,1 '-diyl, 1,1' biphenyl-4,4 '-diyl, 1,1' binaphthyl-2,2 '-diyl, 2,2'- binaphthyl-1,1 '-diyl, phenylene-CH 2 -phenylene, phenylene-S-phenylene, CH 2 -phenylene-CH 2 and phenylene- CH(CH 3 )-phenylene.
  • divalent bridging group (A) has the following formula:
  • R 12 is - CY L Y 2 - wherein each Y 1 and Y 2 radical individually represents hydrogen, C x -C 12 alkyl, for example methyl, propyl, isopropyl, butyl, isodecyl, dodecyl; phenyl, methoxyphenyl, tolyl and anisyl and r has a value of 0 to 1; wherein each X 1 , X 2 , Z 1 , and Z 2 group individually is hydrogen, an alkyl radical having from 1 to 18 carbon atoms, substituted or unsubstituted aryl, alkaryl, aralkyl or alicyclic groups as defined and exemplified hereinabove, for example phenyl, benzyl, cyclohexyl and 1-methylcyclohexyl; cyano, halogen, for example Cl, Br, I; nitro, trifluoromethyl , hydroxy, carbonyloxy, amino, acyl
  • both X 1 and X 2 are groups having a steric hindrance, for example isopropyl, or more preferably tert-butyl, or greater and Z 1 and Z 2 are hydrogen, an alkyl radical, especially tert-butyl, a hydroxy radical or an alkoxy radical, especially methoxy.
  • R 11 represents a methylene(-CH 2 - ⁇ bridging group or an alkylidene(-CHR 13 -) bridging group wherein R 13 is an alkyl radical of 1 to 12 carbon atoms as defined above for Y 1 .
  • R 13 is preferably methyl (R 12 is -CHCH 3 -) or a substituted aryl group, for example methoxyphenyl.
  • Divalent organic groups for R 2 and R 3 together and/or R 4 and R 5 together can be the same as described above for bridging group (A).
  • the preferences for the bridging group also apply for these divalent groups.
  • the divalent group is defined according to formula (3).
  • More preferred divalent organic groups for R 2 and R 3 in case X is a N(R) group and/or for R 4 and R 5 in case 0 is a N(R) group in formula (2) are represented by the following formula (presented with the N(R), P and -0- groups)
  • E 1 and E 2 are the same or different and in which E 1 en E 2 are hydrogen or a monovalent organic group with 1 to 11 carbon atoms or in which E 1 and E 2 together are one divalent organic group with 3 to 11 carbon atoms or R and E 2 together are one divalent organic group with 3 to 12 carbon atoms and E 1 is hydrogen or a monovalent organic group as defined above.
  • the possible remaining group bonded to the carbon atom(s) in formula (3a) is hydrogen.
  • Possible monovalent organic groups are alkyl, aralkyl, alkaryl or aryl groups, for example methyl, ethyl, propyl, tert-butyl, phenyl, benzyl or tolyl.
  • Divalent groups for E 1 and E 2 can be C 3 -C 5 alkylene groups, for example propylene or butylene or can be so choosen that E 1 , E 2 and the two carbon atoms of formula (3a) form a conjugated ring structure of 6 carbon atoms which ring may be substituted with for example methyl, ethyl, propyl or phenyl groups.
  • Examples for divalent organic groups for R and E 2 are, optionally substited, C 3 -C 10 alkylene groups, for example propylene, butylene or pentylene.
  • R 5 can more specifically be monovalent alkyl groups of 1 to 20 carbon atoms, cycloalkyl groups of 5 to 12 carbon atoms, aryl groups of 5 to 20 carbon atoms and alkaryl groups of 6 to 20 carbon atoms.
  • Examples of the monovalent organic group are methyl, ethyl, isopropyl, butyl, isodecyl, dodecyl, phenyl, tolyl and anisyl.
  • the monovalent group has the following structure:
  • Ligand (1) to (24) examples of compounds to be used as ligands in the process according to the invention are Ligand (1) to (24) as presented below.
  • Ph is a phenyl group
  • Me is a methyl group
  • tBu is a tert-butyl group
  • OMe is a methoxy group in these formulas.
  • the phosphorus amide compounds which are used as ligands in this invention can be prepared as described in EP-A-42359 and in S.D. Pastor et al. , J. Am. Chem. Soc. 110, 6547 (1988) and S.D. Pastor et al. , Helv. Chim. Acta 76, 900 (1991).
  • the ethylenically unsaturated organic compound has usually 2 to 20 carbon atoms.
  • Examples of possible ethylenically unsaturated organic compound are linear terminal olefinic hydrocarbons for example ethylene, propylene, 1-butene, 1,3-butadiene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1- eicosene and 1-dodecene; branched terminal olefinic hydrocarbons for example isobutene and 2-methyl-l- butene; linear internal olefinic hydrocarbons for example cis- and trans-2-butene, cis- and trans-2- hexene, cis- and trans-3-hexene, cis- and trans-2- octene and cis- and trans-3-octene; branched internal olefinic hydrocarbons for example 2,3-dimethyl-2- butene, 2-
  • Examples of the olefinic compound substituted with a hydrocarbon group containing an unsaturated hydrocarbon group include olefinic compounds containing an aromatic substituent such as styrene, ⁇ - methylstyrene and allylbenzene; and diene compounds such as 1,5-hexadiene, 1,7-octadiene and norbornadiene.
  • the ethylenically unsaturated organic compound can be substituted with one or more functional groups containing a heteroatom, for example oxygen, sulfur, nitrogen and phosphor.
  • these substituted ethylenically unsaturated organic compounds are vinyl methyl ether, methyl oleate, allyl alcohol, oleyl alcohol, 3-methyl-3-buten-l-ol, methyl 3- pentenoate, methyl 4-pentenoate, 3-pentenoic acid, 4- pentenoic acid, 3-pentenenitrile, 4-pentenenitrile, 3- hydroxy-l,7-octadiene, l-hydroxy-2,7-octadiene, 1- methoxy-2,7-octadiene, 7-octen-l-al, hexa-1-en-l-ol, acrylonitrile, acrylic acid esters for example methylacrylate, methacrylic acid esters for example methylmethacrylate, vinyl acetate and l-acetoxy-2,
  • Preferred substrates are pentenenitrile, pentenoic acid and Ci-Cj alkyl pentenoate ester compounds, for example 3-pentene nitrile, 3-pentenoic acid, methyl-3-pentenoate, ethyl-3-pentenoate and methyl 4-pentenoate. These compounds are preferred because the resulting terminal aldehyde compounds can be advantageously used in the preparation of Nylon-6 and Nylon-6.6 intermediates. An example of such use is described in US-A-4731445.
  • the branched aldehyde compounds obtained by the process according to the invention can be used to prepare branched lactams in an analogous method as described in the aforementioned US patent.
  • the catalyst system can be prepared by mixing a suitable Group 8-10 (according to the new IUPAC notation) metal compound with the phosphorus amide compound optionally in a suitable solvent in accordance with well known complex-forming methods.
  • the solvent will generally be the solvent used in the hydroformylation.
  • Suitable Group 8-10 metal compounds are hydrides, halides, organic acid salts, inorganic acid salts, oxides, carbonyl compounds and amine compounds of these metals. Examples of suitable Group 8-10 metals are cobalt, ruthenium, rhodium, palladium, platinum, osmium and iridium.
  • Group 8-10 metal compounds are ruthenium compounds for example Ru 3 (CO) 12 , Ru(N0 3 ) 3 , RuCl 3 (Ph 3 P) 3 and Ru(acac) 3 ; palladium compounds for example PdCl 2 , Pd(OAc) 2 , Pd(acac) 2 , PdCl 2 (COD) and PdCl 2 (Ph 3 P) 2 ; osmium compounds for example Os 3 (CO) 12 and OsCl 3 ; iridium compounds for example Ir 4 (CO) 12 and IrS0 4 ; platinum compounds for example K 2 PtCl 4 , PtCl 2 (PhCN) 2 and Na 2 PtCl 6 .6H 2 0; cobalt compounds for example CoCl 2 Co(N0 3 ) 2 , Co(OAc) 2 and Co 2 (CO) 8 ; and rhodium compounds for example RhCl 3 ,
  • the Group 8-10 metal compounds are not necessarily limited to the above listed compounds.
  • rhodium is used as Group 8-10 metal because the speed of reaction is higher than in case one of the other metals is used.
  • the amount of Group 8-10 metal is not specially limited, but is optionally selected so that favourable results can be obtained in respect of catalyst activity and economy.
  • concentration of Group 8-10 metal in the reaction medium is between 10 and 10.000 ppm and more preferably between 100-1000 ppm calculated as free metal.
  • the molar ratio multidentate phosphorus amide ligand to Group 8-10 metal of the catalyst system is not specially limited, but is preferably selected so that favorable results can be obtained in respect to catalyst activity and aldehyde selectivity. This ratio is generally from about 0.5 to 100 and preferably from 1 to 10 (mol ligand/mol metal).
  • the reaction medium may be the mixture of reactants of the hydroformylation itself, such as the starting unsaturated compound, the aldehyde product and/or by-products.
  • an ej ⁇ tra solvent suitable examples are saturated hydrocarbons such as naphtha, kerosine, mineral oil and cyclohexane and aromatics, for example toluene, benzene, xylene, ethers, for example diphenyl ether, tetrahydrofuran, ketones, for example cyclohexanone and nitriles, for example benzonitrile and texanol® (Union Carbide).
  • the reaction conditions to conduct the hydroformylation according to the invention are the same as used in a conventional process, described for example in US-A-4769498, and will be dependent of the particular starting ethylenically unsaturated organic compound.
  • the temperature can be from room temperature to 200 °C and preferably from 50 to 150 °C.
  • the pressure is from normal pressure to 20 MPa and preferably from 0.15 to 10 MPa and more preferably from 0.2 to 5 MPa.
  • the pressure is generally the result of the combined hydrogen and carbon monoxide partial pressure. Extra inert gasses may however be present.
  • the molar ratio hydrogen : carbon monoxide is generally between 10:1 and 1:10 and preferably between 1:1 and 6:1.
  • the invention also relates to a catalyst system comprising a Group 8-10 metal and, by preference a racemic mixture of, the multidentate phosphorus amide ligand as here described.
  • the phosphorus amide compounds used as ligands of this catalyst system can be represented by formula (1-2).
  • the groups X, Y, Z, 0, A, R, R 1 -R 13 and E 1 -E 2 can be the same as defined above.
  • a preferred catalyst system according to the invention is a catalyst system comprising the phosphorus amide ligand in which the Group 8-10 metal is rhodium. These catalyst systems are advantageous when used for hydroformylating internally ethylenically unsaturated organic compounds to aldehydes as explained above.
  • the catalyst system can also for example be used as a hydrogenation-, polymerisation-, isomerisation- and carbonylation catalyst.
  • the invention is also directed to a new group of phosphorus amide compounds, which can be advantageously used as ligands in the homogeneously catalysed hydroformylation of ethylenically unsaturated organic compounds as described above.
  • This new group of phosphorus amide compounds can be represented by the following general formula
  • R 2 , R 3 , A, R, E 1 and E 2 are the same as defined above and k is 1-5.
  • the end group consisting of N(R), C, C, E 1 , E 2 and 0 in formula (4a) is the same as the corresponding group of formula (3a).
  • Ligand (12) examples of these new compounds are the above described Ligands (1), (3) and (12).
  • a preferred compound is Ligand (12).
  • the compounds according to formula (4a) can be for example prepared in an analogous manner as described in Example 13 of US-A-4748261 in which instead of two equivalent of the phenol derivative (p- chlorophenol) an equal molar amount of an amino-alcohol derivative, for example ephedrine is used.
  • Another class of new phosphorus amide compounds to which this invention is directed can be represented by the following formula
  • R 2 , R 3 , R3 4 , R 5 and A are the same as defined above.
  • These compounds can be advantageously used as ligands in the homogeneously catalysed hydroformylation of ethylenically unsaturated organic compounds as described above.
  • Examples of these new compounds are the above described Ligands (9), (10) and (11) and the compounds which are used as ligands in Example IV of this invention.
  • Compounds according to formula (4b) can be prepared by mixing in an organic solvent a phosphorus halogenide compound (corresponding with the (R ⁇ OHR 2 ⁇ )?- or (R 3 0) (R 4 0)P-group) with 2 equivalents of an alkylamine, for example triethylamine, and 0.5 equivalent of a diamine which corresponds with the - N(R)-A-N(R)-group of formula (4b), for example N,N'- dimethylethylenediamine. After filtration and evaporation of the solvent the compounds are obtained as white solids. Subsequent crystallization results in a pure white crystalline compound.
  • the invention will be elucidated with the following non limiting examples.
  • Ligand (1) (see the description for a reference to Ligand (1) and other Ligands used in the Examples) was prepared in an analogous manner as described in Example 13 of US-A-4748261 in which instead of 2 molar amounts of para-chlorophenol, an equal molar amount of ephedrine was used.
  • the triethylamine-hydrochloride precipitate, formed in the final step of the reaction was removed by filtration. The residue was washed with two 50 ml portions of toluene. The combined filtrate and washes was concentrated to give an offwhite solid. The solid was crystallized from toluene/acetonitrile to give a 71% yield of the ligand according formula of ligand (1).
  • Ligand (3) was prepared by dissolving 18.6 gr of 2.4-di-tert-butyl phenol in 500 ml of toluene, of which 50 ml was distilled off azeotropically to remove traces of moisture. The solution was cooled to room temperature and 1 molar equivalent of triethyl amine (9.1 g) was added. To the mechanically stirred mixture 0.5 equivalent of PC1 3 (6.2 g) were added. The immediately formed suspension was stirred for 3 hours at 60°C. Subsequently, 4.55 g of triethyl amine and
  • Ligand (9) starts similar to the synthesis of Ligand (3).
  • Ligand (9) was formed upon stirring the mixture at 50°C for 4 hours. The work-up procedure was the same as described for Ligand (1). After crystallization Ligand (9) was obtained as white solid in 89% yield.
  • Ligand (12) was prepared from p-anisylidene- 1,l-bis(2-naphtol) in an analogous manner as described for Ligand (1). The ligand (12) was obtained as a white solid in 84% yield.
  • Ligand (16) was prepared in an analogous manner as described for ligand (1) using N-tosyl-2- amino-2-phenylethanol as aminoalcohol.
  • Ligand (17) was prepared in an analogous manner as described for ligand (1) using N-tert-butyl 2-aminoethanol.
  • Ligand (18) was prepared in an analogous manner as described for ligand (9) using 2,4-di-tert- butylphenol and N,N'-dimethylethanediamine.
  • Hastelloy-C-steal autoclave (Parr) was charged with a mixture of 5.8 mg (2.25 x 10 "5 mol) of rhodium dicarbonyl acetylacetonate and 45 mg (4.80 x 10 "5 mol) of the phosphorus amide Ligand (1) in 60 ml toluene under nitrogen atmosphere.
  • the autoclave was heated to 90°C in 1 hour and pressurized to 0.5 MPa with a H 2 /CO (2/1 (mol/mol)) mixture.
  • Example I was repeated with a bisphoshite ligand (A) as also used in example 14 of US-A-4769498 The results are presented in Table 1.
  • Example I was repeated with a bisphosphite ligand (B) as shown below (see also US-A-4769498) . The results are presented in Table 1.
  • B bisphosphite ligand
  • L/Rh is molar ratio of ligand and rhodium
  • S ald is selectivity in % to aldehyde calculated as molar amount of aldehyde on total mol of products formed
  • Example lib
  • Example Ila was repeated with a phosphorus amide ligand, Ligand (12) and a ligand/Rh ratio of 2.9.
  • Example II was repeated with the phosphorus diamide ligand of Example 7 of O-A-9303839:
  • Example Illa-d Example Ila was repeated with the phosphorus amide ligands of the general structure according to formula 8a-8d.
  • the synthesis of Ligand 8a-8d are described in S.D. Pastor et al. , J. Am. Chem. Soc. 110, 6547 (1988) and S.D. Pastor et al.. Helv. Chim. Acta 76, 900 (1991).
  • Example Ila was repeated with the phosphorus amide ligands of the general structure according to formula 9 and with various ligand/Rh ratios (mol/mol).
  • the synthesis of the ligands according to the general formula (9) were all prepared in a similar manner as described for Ligand (9) by using the appropriate diamine bridge corresponding with the -N(R)-A-N(R)- group of formula (3c).
  • the ligand/Rh ratio and the results are presented in Table 3.
  • Example Va-b Example Ila was repeated with 2.5 g of a mixture of cis and trans 2-octene ( 22 mmol) instead of methyl 3-pentenoate. The results are given in Table 4.
  • a 181 ml stainless steel autoclave was filled with 2 ml of a toluene solution containing 0.008 mmol Rh(CO) 2 acac, 5 equivalents of the used ligand (see Example III for ligand 8b, 8c and 8d) and 18 ml toluene.
  • the autoclave was pressurized to 1.5 MPa CO/H 2 (1/1 mol/mol) and the temperature was raised to 80°C. After stabilization of the temperature 20 mmol 1- octene and 1 ml decane (internal standard) was injected into the reactor. The pressure was further increased to 2.0 MPa CO/H 2 (1/1 mol/mol).
  • the reaction was performed batchwise and no additional CO or H 2 was added during the reaction.
  • the composition was analyzed by gas chromatography and the results are presented in Table 5.
  • the ligand/rhodium ratio varied in which the rhodium concentration was kept the same as in Example I. The results are presented in Table 6.
  • a ligand with a dendrimer bridging compound with 32 end groups as represented with the following formula (10) was prepared as follows. To 6.08 g (29.5 mmol 2,4-di-tert-butylphenol) in 350 ml toluene which was dried azeotropically, 10 ml of triethyl amine and subsequently 2.02 g (14.7 mmol) PC1 3 were added. After stirring overnight 5 ml triethylamine and 0.307 mmol of dendrimer PA 32 (as prepared in Example VII- of O-A-9314147) in 250 ml of toluene were added. After stirring overnight, the reaction mixture was filtered over A1 2 0 3 twice. The solvent was evaporated and the ligand was purified by crystallistion from acetonitril and ethanol (twice). On average 90% of the N-groups were linked with the below group in the resulting compound.
  • Example IX Example VII was repeated with a ligand according to formula (10).
  • the phosphorus/rhodium (mol atoms P/mol rhodium) ratio was 4.
  • the selectivity to aldehydes was 97% at 5% conversion after 18.5 hours of reaction.

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Abstract

Process for preparing an aldehyde compound by hydroformylation of an ethylenically unsaturated organic compound in the presence of a catalyst system comprising of a multidentate phosphorous ligand and a Group 8-10 metal, wherein the multidentate phosphorus amide ligand consists essentially of a multivalent bridging organic group connected to at least two trivalent phosphorus-containing groups of formulas (A) and (B) provided that at least one group of formula (B) is present, wherein R is hydrogen, an organic group, or -SO2R1, wherein R1 is a C¿1-12? organic group, and wherein remaining free bonds of said trivalent phosphorus groups are linked to a mono- or divalent organic group.

Description

PROCESS FOR THE PREPARATION OF AN ALDEHYDE
The invention relates to a process for preparing an aldehyde compound by hydroformylation of an ethylenically unsaturated organic compound in the presence of a catalyst system comprising of a multidentate phosphorus ligand and a Group 8-10 metal. With hydroformylation is meant the reaction of an unsaturated compound with hydrogen and carbon monoxide in the presence of a catalyst.
Such a process is described in US-A-4769498. US-A-4769498 describes the hydroformylation of 2-butene in the presence of a homogeneous catalyst system consisting of rhodium and a bidentate phosphite ligand. A disadvantage of such a process is that the selectivity to aldehydes is too low for a commercially interesting process.
An object of this invention is a hydroformylation process to prepare aldehydes with a higher selectivity to aldehydes than is achieved with the catalyst system of US-A-4769498.
This object of the invention is achieved in that the multidentate phosphorus amide ligand consists of a multivalent bridging organic group connected to at least two trivalent phosphorus-containing groups of the formula
[A] - 0 - P - 0 -
0
I and
[B] - 0 - P - 0 N - R
I provided that at least one group of formula [B] is present, wherein R is hydrogen, an organic group, or - S02R1, wherein R1 is a C1-12 organic group, and wherein remaining free bonds of said trivalent phosphorus groups are linked to a mono- or di-valent organic group. _
It has been found that when an aldehyde is prepared with the process according to the invention the selectivity to aldehyde is higher than the selectivity achieved with the process of US-A-4769498. Some of the compounds that can be used as bidentate phosphorus amide ligands according to the invention are described in US-A-5147910, US-A-5147909 and US-A-5075483. All of these references describe phosphorus amide compounds with chemical structures comprising trivalent P(N(R)-) (0-)2 groups to be effective in stabilizing organic materials such as polymers. None of these references suggest that these phosphorus amide compounds could be advantageously used as part of a catalyst system for the hydroformylation of ethylenically unsaturated organic compounds.
Phosphorus amide compounds, which are used as ligands, are described in WO-A-9303839. In this patent application the asymmetric hydroformylation of styrene is described in which a catalyst system is used consisting of rhodium and a bidentate phosphorus diamide ( (N,N'-diphenyl-ethylenediamine-P)2-2S,4S- pentanediol) . This bidentate phosphorus diamide ligand contains structural groups in which two nitrogen atoms, in contrast to the P(N(R)-) (0-)2 group(s) of the ligands according to the invention, are directly bonded to a phosphorus atom of the ligand. It appears however that when this kind of phosphorus diamide ligand is used the selectivity to aldehydes does not improve compared to the process of US-A-4769498. Furthermore, WO-A-9303839 is dedicated to a process for the stereo specific preparation of optically active aldehyde compounds by using one specific stereo-isomer of the phosphorus amide ligand.
The phosphorus amide compound used as ligand in the process according to the invention may for example be represented by the following formula:
R2-0 O --vR*
\ /
P-Y- -O-P (1)
/ \
R3-X O-R5 m
in which R2, R3, R4 and R5 are the same or different and in which either one of X or Y is a N(R) group while the other group is oxygen, A is a multivalent (multi is equal to k+m) organic group with 2 to 30 carbon atoms, k is at least 1, m can be 0-5 and k+m is 2-6, R2 and R3 together and/or R4 and R5 together form one, optionally substituted, divalent organic group with 2 to 30 carbon atoms or R2, R3, R4 and Rs are independently, optionally substituted, monovalent organic groups with 1 to 20 carbon atoms. R is hydrogen or an organic group with 1 to
11 carbon atoms or -SO^1 in which R1 is an organic group with 1 to 12 carbon atoms. Preferably R is hydrogen or a C^-C^ alkyl group, phenyl, for example methyl, ethyl, propyl or substituted or unsubstituted aryl groups, for example phenyl and tolyl or a -SO3R1 group as defined before.
One class of bidentate phosphorus amide compounds used as ligand in the process according to the invention can be represented by formula (1) in which k+m is equal to 2 or by the following formula: R2-0 Y — A — Z O-R4
\ / \ /
P P ( 2 )
/ \ R3-X D-R5
in which at least one of X, Y, Z or 0 is a N(R) group, the remaining of X, Y, Z and 0 being oxygen, in which one or both phosphor atom(s) is at most bonded to only one nitrogen atom, A is a divalent organic group with 2 to 30 carbon atoms and in which R2, R3, R4, R5 and R are the same as defined above.
The bridging group (A) may be for example a multivalent organic group with 2 to 30 carbon atoms. The number of valencies is in principle not bound to an upper limit. An example of a multivalent bridging group are dendrimer like compounds as described in WO-A- 9314147. A preferred dendrimer bridging compound has reactive -NH2 groups which can easily react with a bis(alkoxy) or bis(aryloxy)phosphorus chloride compound to yield the ligand which can be used in the process according to the invention.
In general the amount of valencies will be 2- 6. An example of a tetravalent organic group is pentaerythritetraryl.
Preferred divalent organic groups are alkylene, alkylene-oxy-alkylene, arylene, arylene- (CH2)y-(R6)n-(CH2)y-arylene, in which y is 0 or 1, n is 0 or 1 and each arylene is the same or different, substituted or unsubstituted divalent aryl radical and R5 individually represents a divalent group selected from the group consisting of -CR7R8-, -0-, -S-, -NR9-, -SiR^R11- and -CO-, in which R7 and R8 individually represents hydrogen, C1-C12 alkyl, phenyl, tolyl, anisyl or methoxyphenyl, wherein each R9, R10 and R11 group individually represents hydrogen or a C1-Cl2 organic group for example ethyl, propyl, butyl, benzyl and by preference hydrogen, methyl or phenyl.
Examples of possible divalent organic bridging groups (A) include substituted and unsubstituted radicals selected from the group consisting of alkylene, alkylene-oxy-alkylene, phenylene, naphthylene, phenylene-(CH2)y-(R6)n-(CH2)y- phenylene and naphthylene-(CH2)y-(R6)n-(CH2)y- naphthylene-radicals, R6, n and y are the same as defined above. More specific examples of divalent radicals A are -CH2CH2OCH2CH2-, 1,4-phenylene, 2,3- phenylene, 1,3-phenylene, 1,4-naphthylene, 1,5- naphthylene, 1,8-naphthylene, 2,3-naphthylene, 1,1' biphenyl-2,2 '-diyl, 2,2' biphenyl-1,1 '-diyl, 1,1' biphenyl-4,4 '-diyl, 1,1' binaphthyl-2,2 '-diyl, 2,2'- binaphthyl-1,1 '-diyl, phenylene-CH2-phenylene, phenylene-S-phenylene, CH2-phenylene-CH2 and phenylene- CH(CH3)-phenylene.
Preferably the divalent bridging group (A) has the following formula:
Figure imgf000007_0001
in which R12 is - CYLY2- wherein each Y1 and Y2 radical individually represents hydrogen, Cx-C12 alkyl, for example methyl, propyl, isopropyl, butyl, isodecyl, dodecyl; phenyl, methoxyphenyl, tolyl and anisyl and r has a value of 0 to 1; wherein each X1, X2, Z1, and Z2 group individually is hydrogen, an alkyl radical having from 1 to 18 carbon atoms, substituted or unsubstituted aryl, alkaryl, aralkyl or alicyclic groups as defined and exemplified hereinabove, for example phenyl, benzyl, cyclohexyl and 1-methylcyclohexyl; cyano, halogen, for example Cl, Br, I; nitro, trifluoromethyl , hydroxy, carbonyloxy, amino, acyl , phosphonyl, oxycarbonyl, amido, sulfinyl, sulfonyl, silyl, alkoxy or thionyl. Preferably both X1 and X2 are groups having a steric hindrance, for example isopropyl, or more preferably tert-butyl, or greater and Z1 and Z2 are hydrogen, an alkyl radical, especially tert-butyl, a hydroxy radical or an alkoxy radical, especially methoxy. Preferably R11 represents a methylene(-CH2-} bridging group or an alkylidene(-CHR13-) bridging group wherein R13 is an alkyl radical of 1 to 12 carbon atoms as defined above for Y1. R13 is preferably methyl (R12 is -CHCH3-) or a substituted aryl group, for example methoxyphenyl.
Divalent organic groups for R2 and R3 together and/or R4 and R5 together can be the same as described above for bridging group (A). The preferences for the bridging group also apply for these divalent groups. Preferably the divalent group is defined according to formula (3).
More preferred divalent organic groups for R2 and R3 in case X is a N(R) group and/or for R4 and R5 in case 0 is a N(R) group in formula (2) are represented by the following formula (presented with the N(R), P and -0- groups)
Figure imgf000008_0001
in which E1 and E2 are the same or different and in which E1 en E2 are hydrogen or a monovalent organic group with 1 to 11 carbon atoms or in which E1 and E2 together are one divalent organic group with 3 to 11 carbon atoms or R and E2 together are one divalent organic group with 3 to 12 carbon atoms and E1 is hydrogen or a monovalent organic group as defined above. The possible remaining group bonded to the carbon atom(s) in formula (3a) is hydrogen. Possible monovalent organic groups are alkyl, aralkyl, alkaryl or aryl groups, for example methyl, ethyl, propyl, tert-butyl, phenyl, benzyl or tolyl. Divalent groups for E1 and E2 can be C3-C5 alkylene groups, for example propylene or butylene or can be so choosen that E1, E2 and the two carbon atoms of formula (3a) form a conjugated ring structure of 6 carbon atoms which ring may be substituted with for example methyl, ethyl, propyl or phenyl groups. Examples for divalent organic groups for R and E2 are, optionally substited, C3-C10 alkylene groups, for example propylene, butylene or pentylene. Monovalent organic groups for R2, R3, R4 and
R5 can more specifically be monovalent alkyl groups of 1 to 20 carbon atoms, cycloalkyl groups of 5 to 12 carbon atoms, aryl groups of 5 to 20 carbon atoms and alkaryl groups of 6 to 20 carbon atoms. Examples of the monovalent organic group are methyl, ethyl, isopropyl, butyl, isodecyl, dodecyl, phenyl, tolyl and anisyl. Preferably the monovalent group has the following structure:
Figure imgf000009_0001
in which X1, X2 and Z1 are groups as defined above.
Examples of compounds to be used as ligands in the process according to the invention are Ligand (1) to (24) as presented below. Ph is a phenyl group, Me is a methyl group, tBu is a tert-butyl group and OMe is a methoxy group in these formulas.
Ligand (1)
Figure imgf000010_0001
Ligand (2)
Figure imgf000010_0002
Li and 3
Figure imgf000010_0003
Ligand (5)
Figure imgf000011_0001
Ligand (6)
Figure imgf000011_0002
Ligand (7)
Figure imgf000011_0003
Ligand (8)
Figure imgf000011_0004
Ligand (9)
Figure imgf000012_0001
Ligand (10)
Ligand (11)
Ligand (12)
Figure imgf000012_0002
Ligand (13)
Figure imgf000013_0001
Ligand (14)
Figure imgf000013_0002
Ligand (15)
Figure imgf000013_0003
Ligand (16)
Figure imgf000013_0004
Ligand (17)
Figure imgf000014_0001
Ligand (18)
Figure imgf000014_0002
Figure imgf000014_0003
Ligand (20)
Figure imgf000014_0004
Ligand (21)
Figure imgf000015_0001
10
Ligand (22)
Figure imgf000015_0002
Ligand (23)
Figure imgf000015_0003
30
Ligand (24)
Figure imgf000015_0004
The phosphorus amide compounds which are used as ligands in this invention can be prepared as described in EP-A-42359 and in S.D. Pastor et al. , J. Am. Chem. Soc. 110, 6547 (1988) and S.D. Pastor et al. , Helv. Chim. Acta 76, 900 (1991).
The ethylenically unsaturated organic compound used in the preparation of an aldehyde compound through hydroformylation is not specially limited so long as it has at least one ethylenically (C=C) bond in the molecule. The ethylenically unsaturated organic compound has usually 2 to 20 carbon atoms. Examples of possible ethylenically unsaturated organic compound are linear terminal olefinic hydrocarbons for example ethylene, propylene, 1-butene, 1,3-butadiene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1- eicosene and 1-dodecene; branched terminal olefinic hydrocarbons for example isobutene and 2-methyl-l- butene; linear internal olefinic hydrocarbons for example cis- and trans-2-butene, cis- and trans-2- hexene, cis- and trans-3-hexene, cis- and trans-2- octene and cis- and trans-3-octene; branched internal olefinic hydrocarbons for example 2,3-dimethyl-2- butene, 2-methyl-2-butene and 2-methyl-2-pentene; mixtures of terminally olefinic and internally olefinic hydrocarbons for example octenes prepared by dimerization of butenes, olefin oligomer isomer mixture (of from dimer to tetramer) of lower olefins including propylene, n-butene, isobutene or the like; and cycloaliphatic olefinic hydrocarbons for example cyclopentene, cyclohexene, 1-methylcyclohexene, cyclooctene and limonene.
Examples of the olefinic compound substituted with a hydrocarbon group containing an unsaturated hydrocarbon group include olefinic compounds containing an aromatic substituent such as styrene, α- methylstyrene and allylbenzene; and diene compounds such as 1,5-hexadiene, 1,7-octadiene and norbornadiene.
The ethylenically unsaturated organic compound can be substituted with one or more functional groups containing a heteroatom, for example oxygen, sulfur, nitrogen and phosphor. Examples of these substituted ethylenically unsaturated organic compounds are vinyl methyl ether, methyl oleate, allyl alcohol, oleyl alcohol, 3-methyl-3-buten-l-ol, methyl 3- pentenoate, methyl 4-pentenoate, 3-pentenoic acid, 4- pentenoic acid, 3-pentenenitrile, 4-pentenenitrile, 3- hydroxy-l,7-octadiene, l-hydroxy-2,7-octadiene, 1- methoxy-2,7-octadiene, 7-octen-l-al, hexa-1-en-l-ol, acrylonitrile, acrylic acid esters for example methylacrylate, methacrylic acid esters for example methylmethacrylate, vinyl acetate and l-acetoxy-2,7- octadiene.
The advantages of the invention regarding improved aldehyde selectivity are more pronounced when starting from internally ethylenically unsaturated organic compounds and even more pronounced when these compounds are substituted with one or more functional groups containing a hetero atom as described above. Examples of these compounds are described above.
Preferred substrates are pentenenitrile, pentenoic acid and Ci-Cj alkyl pentenoate ester compounds, for example 3-pentene nitrile, 3-pentenoic acid, methyl-3-pentenoate, ethyl-3-pentenoate and methyl 4-pentenoate. These compounds are preferred because the resulting terminal aldehyde compounds can be advantageously used in the preparation of Nylon-6 and Nylon-6.6 intermediates. An example of such use is described in US-A-4731445. The branched aldehyde compounds obtained by the process according to the invention can be used to prepare branched lactams in an analogous method as described in the aforementioned US patent.
The catalyst system can be prepared by mixing a suitable Group 8-10 (according to the new IUPAC notation) metal compound with the phosphorus amide compound optionally in a suitable solvent in accordance with well known complex-forming methods. The solvent will generally be the solvent used in the hydroformylation. Suitable Group 8-10 metal compounds are hydrides, halides, organic acid salts, inorganic acid salts, oxides, carbonyl compounds and amine compounds of these metals. Examples of suitable Group 8-10 metals are cobalt, ruthenium, rhodium, palladium, platinum, osmium and iridium. Examples of Group 8-10 metal compounds are ruthenium compounds for example Ru3(CO)12, Ru(N03)3, RuCl3(Ph3P)3 and Ru(acac)3; palladium compounds for example PdCl2, Pd(OAc)2, Pd(acac)2, PdCl2(COD) and PdCl2(Ph3P)2; osmium compounds for example Os3(CO)12 and OsCl3; iridium compounds for example Ir4(CO)12 and IrS04; platinum compounds for example K2PtCl4, PtCl2(PhCN)2 and Na2PtCl6.6H20; cobalt compounds for example CoCl2Co(N03)2, Co(OAc)2 and Co2(CO)8; and rhodium compounds for example RhCl3,
Rh(N03)3, Rh(OAc)3, Rh203, Rh(acac) (CO)2 [Rh(OAc) (COD) ]2, Rh4(CO)12,, Rh6(CO)16, RhH(CO)(Ph3P)3, [Rh(OAc) (C0)2]2 and [RhCl(C0D)]2 (wherein "acac" is an acetylacetonate group; "Ac" is an acetyl group; "COD" is 1,5- cyclooctadiene; and "Ph" is a phenyl group). However, it should be noted that the Group 8-10 metal compounds are not necessarily limited to the above listed compounds.
Preferably rhodium is used as Group 8-10 metal because the speed of reaction is higher than in case one of the other metals is used.
The amount of Group 8-10 metal (compound) is not specially limited, but is optionally selected so that favourable results can be obtained in respect of catalyst activity and economy. In general the concentration of Group 8-10 metal in the reaction medium is between 10 and 10.000 ppm and more preferably between 100-1000 ppm calculated as free metal.
The molar ratio multidentate phosphorus amide ligand to Group 8-10 metal of the catalyst system is not specially limited, but is preferably selected so that favorable results can be obtained in respect to catalyst activity and aldehyde selectivity. This ratio is generally from about 0.5 to 100 and preferably from 1 to 10 (mol ligand/mol metal).
The choice of an optional solvent is not critical. The reaction medium may be the mixture of reactants of the hydroformylation itself, such as the starting unsaturated compound, the aldehyde product and/or by-products. If an ejϊtra solvent is used suitable examples are saturated hydrocarbons such as naphtha, kerosine, mineral oil and cyclohexane and aromatics, for example toluene, benzene, xylene, ethers, for example diphenyl ether, tetrahydrofuran, ketones, for example cyclohexanone and nitriles, for example benzonitrile and texanol® (Union Carbide). The reaction conditions to conduct the hydroformylation according to the invention are the same as used in a conventional process, described for example in US-A-4769498, and will be dependent of the particular starting ethylenically unsaturated organic compound. For example, the temperature can be from room temperature to 200 °C and preferably from 50 to 150 °C. The pressure is from normal pressure to 20 MPa and preferably from 0.15 to 10 MPa and more preferably from 0.2 to 5 MPa. The pressure is generally the result of the combined hydrogen and carbon monoxide partial pressure. Extra inert gasses may however be present. The molar ratio hydrogen : carbon monoxide is generally between 10:1 and 1:10 and preferably between 1:1 and 6:1. The invention also relates to a catalyst system comprising a Group 8-10 metal and, by preference a racemic mixture of, the multidentate phosphorus amide ligand as here described.
The phosphorus amide compounds used as ligands of this catalyst system can be represented by formula (1-2). The groups X, Y, Z, 0, A, R, R1-R13 and E1-E2 can be the same as defined above. A preferred catalyst system according to the invention is a catalyst system comprising the phosphorus amide ligand in which the Group 8-10 metal is rhodium. These catalyst systems are advantageous when used for hydroformylating internally ethylenically unsaturated organic compounds to aldehydes as explained above.
The catalyst system can also for example be used as a hydrogenation-, polymerisation-, isomerisation- and carbonylation catalyst.
The invention is also directed to a new group of phosphorus amide compounds, which can be advantageously used as ligands in the homogeneously catalysed hydroformylation of ethylenically unsaturated organic compounds as described above. This new group of phosphorus amide compounds can be represented by the following general formula
Figure imgf000020_0001
in which R2, R3, A, R, E1 and E2 are the same as defined above and k is 1-5. The end group consisting of N(R), C, C, E1, E2 and 0 in formula (4a) is the same as the corresponding group of formula (3a).
Examples of these new compounds are the above described Ligands (1), (3) and (12). A preferred compound is Ligand (12).
The compounds according to formula (4a) can be for example prepared in an analogous manner as described in Example 13 of US-A-4748261 in which instead of two equivalent of the phenol derivative (p- chlorophenol) an equal molar amount of an amino-alcohol derivative, for example ephedrine is used.
Another class of new phosphorus amide compounds to which this invention is directed can be represented by the following formula
R2 - 0 O - R4
\ /
P - N(R) - A - N(R) - P (4b)
/ \
R3 - 0 O - R5
in which R2, R3, R34, R5 and A are the same as defined above. These compounds can be advantageously used as ligands in the homogeneously catalysed hydroformylation of ethylenically unsaturated organic compounds as described above. Examples of these new compounds are the above described Ligands (9), (10) and (11) and the compounds which are used as ligands in Example IV of this invention.
Compounds according to formula (4b) can be prepared by mixing in an organic solvent a phosphorus halogenide compound (corresponding with the (R^OHR2©)?- or (R30) (R40)P-group) with 2 equivalents of an alkylamine, for example triethylamine, and 0.5 equivalent of a diamine which corresponds with the - N(R)-A-N(R)-group of formula (4b), for example N,N'- dimethylethylenediamine. After filtration and evaporation of the solvent the compounds are obtained as white solids. Subsequent crystallization results in a pure white crystalline compound. The invention will be elucidated with the following non limiting examples.
The compounds used as ligands in the Examples and experiments were prepared as described below. Some compounds are well known from literature and/or are commercially available. Therefore their preparation is not described in detail.
Lioand (1)
Ligand (1) (see the description for a reference to Ligand (1) and other Ligands used in the Examples) was prepared in an analogous manner as described in Example 13 of US-A-4748261 in which instead of 2 molar amounts of para-chlorophenol, an equal molar amount of ephedrine was used. The triethylamine-hydrochloride precipitate, formed in the final step of the reaction was removed by filtration. The residue was washed with two 50 ml portions of toluene. The combined filtrate and washes was concentrated to give an offwhite solid. The solid was crystallized from toluene/acetonitrile to give a 71% yield of the ligand according formula of ligand (1).
Liσand (3)
Ligand (3) was prepared by dissolving 18.6 gr of 2.4-di-tert-butyl phenol in 500 ml of toluene, of which 50 ml was distilled off azeotropically to remove traces of moisture. The solution was cooled to room temperature and 1 molar equivalent of triethyl amine (9.1 g) was added. To the mechanically stirred mixture 0.5 equivalent of PC13 (6.2 g) were added. The immediately formed suspension was stirred for 3 hours at 60°C. Subsequently, 4.55 g of triethyl amine and
2.04 g of pentaerythritol was added to the mixture and additionally stirred for 16 hours at 60°C. The suspension was cooled to room temperature and 3.44 g of 2-chloro-3,4-dimethyl-5-phenyl-l,3,2-oxaza- phospholidine (such as described by S.D. Pastor et al. , Helv. Chim. Acta 74, 1175 (1991)) was added. Ligand (3) was formed upon stirring the mixture at 40°C for 20 hrs. The work-up procedure was the same as described for the Ligand (1). After two crystallizations the ligand (3) was obtained as a white solid in a 75% yield.
Liαand (9)
The synthesis of Ligand (9) starts similar to the synthesis of Ligand (3). To the mixture of bis(2,4- di-tert-butyl phenoxy) phosphorus chloride and triethylamine-hydrochloride was added 1 equivalent of triethylamine and 0.5 equivalent of N,N-dimethyl- ethylenediamine. Ligand (9) was formed upon stirring the mixture at 50°C for 4 hours. The work-up procedure was the same as described for Ligand (1). After crystallization Ligand (9) was obtained as white solid in 89% yield.
Liαand (12)
Ligand (12) was prepared from p-anisylidene- 1,l-bis(2-naphtol) in an analogous manner as described for Ligand (1). The ligand (12) was obtained as a white solid in 84% yield.
Ligand (16) Ligand (16) was prepared in an analogous manner as described for ligand (1) using N-tosyl-2- amino-2-phenylethanol as aminoalcohol.
Ligand (17) Ligand (17) was prepared in an analogous manner as described for ligand (1) using N-tert-butyl 2-aminoethanol.
Liαand (18) Ligand (18) was prepared in an analogous manner as described for ligand (9) using 2,4-di-tert- butylphenol and N,N'-dimethylethanediamine. Example I
A 150 ml Hastelloy-C-steal autoclave (Parr) was charged with a mixture of 5.8 mg (2.25 x 10"5 mol) of rhodium dicarbonyl acetylacetonate and 45 mg (4.80 x 10"5 mol) of the phosphorus amide Ligand (1) in 60 ml toluene under nitrogen atmosphere. The autoclave was heated to 90°C in 1 hour and pressurized to 0.5 MPa with a H2/CO (2/1 (mol/mol)) mixture. Subsequently, a mixture of 5.1 g (45 mmol) of methyl 3-pentenoate and 1 g of nonane (internal standard) with toluene (total volume of 15 ml) was injected into the reactor. The reactor pressure was kept constant during the hydroformylation at 0.5 MPa with H2/C0 (2/1; mol/mol). The composition of the reaction mixture was analysed by gas chromatography and the results are presented in Table 1.
Comparative Experiment A
Example I was repeated with a bisphoshite ligand (A) as also used in example 14 of US-A-4769498 The results are presented in Table 1. Bisphosphite ligand (A) used:
Ligand (A)
Figure imgf000024_0001
Comparative Experiment B
Example I was repeated with a bisphosphite ligand (B) as shown below (see also US-A-4769498) . The results are presented in Table 1. Ligand (B)
Figure imgf000025_0001
Table 1
Example Ligand L/Rh Sald conversion (1) (2) (%) (3)
I 1 2.1 79.5 93.1 (28h)
A A 2.1 69.0 98.4 (21h)
B B 2.2 74.9 94.3 (28h)
(1) L/Rh is molar ratio of ligand and rhodium
(2) Sald is selectivity in % to aldehyde calculated as molar amount of aldehyde on total mol of products formed
(3) conversion is molar amount of reacted unsaturated compound on total mol of starting compound expressed in %.
The numbers between brackets refer to the reaction time in hours.
Example Ila
Example I was repeated with a phosphorus amide ligand, Ligand (3), in which the pressure was 1.0 MPa (H2/CO = 1/1 (mol/mol)) and the ligand/Rh ratio of 2.8 (mol/mol). After 46 hours the conversion was 75% and the selectivity to aldehydes (Sald) was 84.5%. Example lib
Example Ila was repeated with a phosphorus amide ligand, Ligand (12) and a ligand/Rh ratio of 2.9.
After 22 hours the conversion was 86.2% and the selectivity to aldehydes (Sald) was 91.6%.
Comparative Example C
Example II was repeated with the phosphorus diamide ligand of Example 7 of O-A-9303839:
Ligand (C)
The ligand/rhodium ratio was 2.1/1 mol/mol. Sald = 76.6% at 28.2% conversion after 40 hours reaction time.
Example Illa-d Example Ila was repeated with the phosphorus amide ligands of the general structure according to formula 8a-8d. The synthesis of Ligand 8a-8d are described in S.D. Pastor et al. , J. Am. Chem. Soc. 110, 6547 (1988) and S.D. Pastor et al.. Helv. Chim. Acta 76, 900 (1991).
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000027_0001
Figure imgf000027_0002
Figure imgf000027_0003
The r esul ts ar e presented in Table 2 .
Table 2
Example Ligand L/Rh Said conversion %
Ilia 8a 1.9 91.2 22.4 (6 h)
Illb 8b 2.0 75.6 27.4 (16.5 h)
IIIC 8c 2.1 82.5 19.1 (16.5 h)
Hid 8d 2.2 81.0 47.7 (16.5 h) Example IVa-d
Example Ila was repeated with the phosphorus amide ligands of the general structure according to formula 9 and with various ligand/Rh ratios (mol/mol). The synthesis of the ligands according to the general formula (9) were all prepared in a similar manner as described for Ligand (9) by using the appropriate diamine bridge corresponding with the -N(R)-A-N(R)- group of formula (3c). The ligand/Rh ratio and the results are presented in Table 3.
Figure imgf000028_0001
W = ethyl. R_
Figure imgf000028_0002
( 9a ) R3 = Me
W
Figure imgf000028_0003
R3 H ( 9b )
W = butyl. Rl = R2
Figure imgf000028_0004
R3 - H ( 9c ) Table 3
Example ligand L/Rh S id conversion
%
IVa 9a 5 85.5 45 (21h)
IVb 9b 2 80.1 70 (21h)
IVc 9c 2 79.1 55.4 (20h)
Example Va-b Example Ila was repeated with 2.5 g of a mixture of cis and trans 2-octene ( 22 mmol) instead of methyl 3-pentenoate. The results are given in Table 4.
Table 4
Example Ligand L/Rh Sald conversion
%
Va 1 2.2 100 19.0 (5h)
Vb 9b 2 .2 99.3 49.6 (2h)
Example Vla-c
A 181 ml stainless steel autoclave was filled with 2 ml of a toluene solution containing 0.008 mmol Rh(CO)2acac, 5 equivalents of the used ligand (see Example III for ligand 8b, 8c and 8d) and 18 ml toluene. The autoclave was pressurized to 1.5 MPa CO/H2 (1/1 mol/mol) and the temperature was raised to 80°C. After stabilization of the temperature 20 mmol 1- octene and 1 ml decane (internal standard) was injected into the reactor. The pressure was further increased to 2.0 MPa CO/H2 (1/1 mol/mol). The reaction was performed batchwise and no additional CO or H2 was added during the reaction. The composition was analyzed by gas chromatography and the results are presented in Table 5.
Table 5
Example Ligand L/Rh Said conversion
Via 8b 5 99 49 (2h)
VIb 8c 5 87 72 (2h)
Vic 8d 5 88 48 (2.5h)
Example VII a-c
Example I was repeated at 1.0 MPa (CO/H2 = 1/1 mol/mol) with (a) Ligand (16), (b) Ligand (17) and (c) Ligand (18). The ligand/rhodium ratio varied in which the rhodium concentration was kept the same as in Example I. The results are presented in Table 6.
Table 6
Example Ligand L/Rh S.id conversion %
VIIa(*) 16 2.1 88.4 93.2 (48h)
VHb 17 2.2 85.7 86.2 (22h)
VIIc 18 5 85.5 44.9 (21h)
T= 90°C, pressure = 0.25 MPa
Example VIII
A ligand with a dendrimer bridging compound with 32 end groups as represented with the following formula (10) was prepared as follows. To 6.08 g (29.5 mmol 2,4-di-tert-butylphenol) in 350 ml toluene which was dried azeotropically, 10 ml of triethyl amine and subsequently 2.02 g (14.7 mmol) PC13 were added. After stirring overnight 5 ml triethylamine and 0.307 mmol of dendrimer PA 32 (as prepared in Example VII- of O-A-9314147) in 250 ml of toluene were added. After stirring overnight, the reaction mixture was filtered over A1203 twice. The solvent was evaporated and the ligand was purified by crystallistion from acetonitril and ethanol (twice). On average 90% of the N-groups were linked with the below group in the resulting compound.
Figure imgf000031_0001
(*) one of the 32 N-groups of the fourth generation dendrimer compound.
Example IX Example VII was repeated with a ligand according to formula (10). The phosphorus/rhodium (mol atoms P/mol rhodium) ratio was 4. The selectivity to aldehydes was 97% at 5% conversion after 18.5 hours of reaction.

Claims

C L A I S
Process for preparing an aldehyde compound by hydroformylation of an ethylenically unsaturated organic compound in the presence of a catalyst system comprising of a multidentate phosphorus ligand and a Group 8-10 metal, characterized in that the multidentate phosphorus amide ligand consists of a multivalent bridging organic group connected to at least two trivalent phosphorus- containing groups of the formula
[A] - 0 - P - 0
I
0 and
[B] - 0 - P - 0 N - R
provided that at least one group of formula [B] is present, wherein R is hydrogen, an organic group, or -SOjR1, wherein R1 is a Cx_12 organic group, and wherein remaining free bonds of said trivalent phosphorus groups are linked to a mono- or di¬ valent organic group.
Process according to claim 1, characterized in that the phosphorus amide ligand is represented by the following formula:
R2-0 O-R4
\ /
P-Y- -O-P (1)
/ \
R3-X 0-R£ m
in which each X, Y, R2, R3, R4 and R5 are the same or different and in which either one of X or Y is a N(R) group while the other group is oxygen, A is a multi-valent (multi is equal to k+m) organic group with 2 to 30 carbon atoms, k is at least 1, m can be 0-5 and k+m is 2-6, R2 and R3 together and/or R4 and R5 together form one, optionally substituted, divalent organic group with 2 to 30 carbon atoms or R2, R3, R4 and R5 are independently, optionally substituted, monovalent organic groups with 1 to 20 carbon atoms. Process according to claim 2 , characterized in that the phosphorus amide ligand is a bidentate phosphorus amide ligand with k+m is equal to 2. Process according to any one of claims 1-3, characterized in that the Group 8-10 metal is rhodium.
Process according to any one of claims 1-4, characterized in that the ethylenically unsaturated organic compound is an internally ethylenically unsaturated organic compound. Process according to claim 5, characterized in that the internally ethylenically unsaturated organic compound is a pentenenitrile, pentenoic acid or a C -C6 alkyl pentenoate ester. Multidentate phosphorus amide compound, characterized in that the compound is represented by the following general formula
Figure imgf000033_0001
in which R2, R3, A and R are as defined in claim 2, k is 1-5 and E1 and E2 are the same or different and in which E1 and E2 are hydrogen or a monovalent organic group with 1 to 11 carbon atoms or in which E1 and E2 are one divalent organic group with 3 to 11 carbon atoms or R and E2 are one divalent organic group with 3 to 12 carbon atoms and E1 is hydrogen or a monovalent organic group with 1 to 11 carbon atoms, in which the possible remaining group bonded to the carbon atoms (C) is hydrogen. 8. Bidentate phosphorus amide compound, characterized in that the compound is represented by the following general formula
R2 - 0 O - R4
\ /
P - N(R) - A - N(R) - P (3c) / \
R3 - 0 O - R5
in which R2, R3, A, R4 and R5 are the same as defined in claim 2. 9. Catalyst system comprising a Group 8-10 metal and a multidentate phosphorus amide ligand as described in any one of claims 1-3 or claims 7-8. 10. Catalyst system according to claim 9, characterized in that the Group 8-10 metal is rhodium.
PCT/NL1995/000393 1994-11-25 1995-11-20 Process for the preparation of an aldehyde WO1996016923A1 (en)

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US5710344A (en) * 1996-11-08 1998-01-20 E. I. Du Pont De Nemours And Company Process to prepare a linear aldehyde
US5874639A (en) * 1996-11-26 1999-02-23 Union Carbide Chemicals & Plastics Technology Corporation Metal-ligand complex catalyzed processes
US5874640A (en) * 1996-11-26 1999-02-23 Union Carbide Chemicals & Plastics Technology Corporation Metal-ligand complex catalyzed processes
US5886236A (en) * 1997-04-15 1999-03-23 Union Carbide Chemicals & Plastics Technology Corporation Process for producing aldehyde acid salts
US5886235A (en) * 1995-12-06 1999-03-23 Union Carbide Chemicals & Plastics Technology Corporation. Metal-ligand complex catalyzed processes
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US5917095A (en) * 1996-11-26 1999-06-29 Union Carbide Chemicals & Plastics Technology Corporation Metal-ligand complex catalyzed processes
US5962680A (en) * 1997-04-15 1999-10-05 Union Carbide Chemicals & Plastics Technology Corporation Processes for producing epsilon caprolactams
WO2000056451A1 (en) * 1999-03-24 2000-09-28 Basf Aktiengesellschaft Catalyst comprising a metal complex of the viii subgroup based on a phosphine amidite ligand and its utilization for hydroformylation and hydrocyanation
CN1072673C (en) * 1998-12-30 2001-10-10 化学工业部北京化工研究院 Organic phosphine compound, catalyst system composed of organic phosphine compound and application of catalyst system
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WO1998019985A1 (en) * 1996-11-08 1998-05-14 E.I. Du Pont De Nemours And Company Process to prepare a linear aldehyde
US5710344A (en) * 1996-11-08 1998-01-20 E. I. Du Pont De Nemours And Company Process to prepare a linear aldehyde
US5892119A (en) * 1996-11-26 1999-04-06 Union Carbide Chemicals & Plastics Technology Corporation Metal-ligand complex catalyzed processes
US5874640A (en) * 1996-11-26 1999-02-23 Union Carbide Chemicals & Plastics Technology Corporation Metal-ligand complex catalyzed processes
US5874639A (en) * 1996-11-26 1999-02-23 Union Carbide Chemicals & Plastics Technology Corporation Metal-ligand complex catalyzed processes
US5917095A (en) * 1996-11-26 1999-06-29 Union Carbide Chemicals & Plastics Technology Corporation Metal-ligand complex catalyzed processes
US5886236A (en) * 1997-04-15 1999-03-23 Union Carbide Chemicals & Plastics Technology Corporation Process for producing aldehyde acid salts
US5962680A (en) * 1997-04-15 1999-10-05 Union Carbide Chemicals & Plastics Technology Corporation Processes for producing epsilon caprolactams
CN1072673C (en) * 1998-12-30 2001-10-10 化学工业部北京化工研究院 Organic phosphine compound, catalyst system composed of organic phosphine compound and application of catalyst system
WO2000056451A1 (en) * 1999-03-24 2000-09-28 Basf Aktiengesellschaft Catalyst comprising a metal complex of the viii subgroup based on a phosphine amidite ligand and its utilization for hydroformylation and hydrocyanation
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WO2005047299A2 (en) * 2003-11-12 2005-05-26 Studiengesellschaft Kohle Mbh Chiral di- and triphosphites
WO2005047299A3 (en) * 2003-11-12 2005-09-09 Studiengesellschaft Kohle Mbh Chiral di- and triphosphites

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