CN1174545A - Process for preparation of aldehyde - Google Patents

Process for preparation of aldehyde Download PDF

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CN1174545A
CN1174545A CN 95197346 CN95197346A CN1174545A CN 1174545 A CN1174545 A CN 1174545A CN 95197346 CN95197346 CN 95197346 CN 95197346 A CN95197346 A CN 95197346A CN 1174545 A CN1174545 A CN 1174545A
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ligand
group
compound
phosphamide
organic group
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E·威辛
A·J·J·M·托尼森
C·B·汉森
P·W·N·M·范利文
A·范鲁伊
D·伯格斯
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Koninklijke DSM NV
EIDP Inc
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DSM NV
EI Du Pont de Nemours and Co
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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
    • B01J31/186—Mono- or diamide derivatives thereof
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    • 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
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    • 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
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    • 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
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    • 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
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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    • 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
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    • 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
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    • 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
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    • 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
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

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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 provided that at least one group of formula (B) is present, wherein R is hydrogen, an organic group, or -SO2R<1>, wherein R<1> is a C1-12 organic group, and wherein remaining free bonds of said trivalent phosphorus groups are linked to a mono- or divalent organic group.

Description

The preparation method of aldehyde
The present invention relates in the presence of catalyst system, the method for the preparing aldehyde by hydroformylation compound by unsaturated ethylene thiazolinyl organic compound, described catalyst system contains the metal of multiple tooth phosphorus ligand and 8～10 families.
Described hydroformylation reaction is meant the reaction of unsaturated compound and hydrogen and carbon monoxide in the presence of catalyzer.
United States Patent (USP)-A-4769498 has described this method.United States Patent (USP)-A-4769498 has described in the presence of the homogeneous catalyst system that contains rhodium and bidentate phosphites ligand, the hydroformylation reaction of 2-butylene.
The shortcoming of this method is the too low incompatibility industrial applications of the selectivity of aldehyde.
The purpose of this invention is to provide a kind of hydroformylation process for preparing aldehyde, the aldehyde selectivity of this method is higher than the aldehyde selectivity that catalyst system reached of United States Patent (USP)-A-4769498.
The realization of this purpose of the present invention is that multiple tooth phosphamide ligand is made up of the multivalence bridging organic group that is connected to the trivalent phosphorus-containing groups shown in two following formulas at least:
Figure A9519734600041
Condition is to have at least the group of a formula [B] to exist, wherein R be hydrogen, organic group or-SO 2R 1, R wherein 1Be C 1-12Organic group, and remaining free linkage of described trivalent phosphorus-containing groups links to each other with the organic group of monovalence or divalence.
Have been found that the selectivity of aldehyde is higher than the selectivity that United States Patent (USP)-A-4769498 reached when preparing aldehyde with method of the present invention.
Some compound that can be used as bidentate phosphamide ligand of the present invention is described among United States Patent (USP)-A-5147910,5147909 and 5075483.All these reference are only narrated and are contained trivalent P (N (R)-) in the chemical structure (O-) 2The phosphamide compound of group has effective stabilization to organic materials such as polymkeric substance.There is not one piece of reference to propose the part that these phosphamide compounds can be used as unsaturated ethylene alkenyl compound hydroformylation catalyst system effectively.
WO-A-9303839 has described the phosphamide compound as ligand.In this patent application, cinnamic asymmetric hydroformylation reaction has been described, (form by (N, the 2-2S of N '-phenylbenzene-quadrol-P), 4S-pentanediol) by rhodium and bidentate phosphorus diamide for wherein used catalyst system.The building stone of this bidentate phosphorus diamide ligand and ligand P of the present invention (N (R)-) are (O-) 2The group difference, two nitrogen-atoms are bonded directly on the phosphorus atom of ligand.But obviously, use this class phosphorus diamide ligand after, compare with the method for United States Patent (USP)-A-4769498, the selectivity of aldehyde does not improve.In addition, WO-A-9303839 is devoted to carry out with a kind of stereotaxis isomer of phosphamide ligand the exploitation of the stereotaxis preparation method of photolytic activity aldehyde cpd.
The phosphamide compound that is used as the ligand of the inventive method for example can be represented by the formula: R wherein 2, R 3, R 4And R 5Can be identical or inequality, and among X or the Y any be N (R) base, and another group is an oxygen, and A is multivalence (valence mumber the equals k+m) organic group of 2～30 carbon atoms, and k is 1 at least, and m can be 0～5, and k+m is 2～6, R 2And R 3Together and/or R 4And R 5Form (the optional replacement) divalent organic group that 2～30 carbon atoms are arranged together, or R 2, R 3, R 4And R 5Be (the optional replacement) any monovalent organic radical group that 1～20 carbon atom is arranged independently of one another.
R be hydrogen or 1～11 carbon atom organic group or-SO 2R 1, R wherein 1It is the organic group of 1～12 carbon atom.R is hydrogen or C preferably 1～C 11Alkyl, phenyl, for example methyl, ethyl, propyl group or replacement or unsubstituted aryl, for example phenyl and tolyl, or as the SO of preceding definition 3R 1Base.
A class bidentate phosphamide compound that is used as the ligand of the inventive method can be used general formula (1) expression, and wherein k+m equals 2, or represents with following formula:
Figure A9519734600061
Wherein have at least one to be N (R) base among X, Y, Z or the Q, remaining X, Y, Z and Q are oxygen, and one of them or two phosphorus atom be nitrogen-atoms of bonding at most only, and A is the divalent organic group of 2～30 carbon atoms, and R wherein 2, R 3, R 4, R 5The same with the definition of R.
Abutment (A) can for example be the multivalence organic group of 2～30 carbon atoms.The highest valence mumber in principle without limits.The example of multivalence bridged group is a dendrimer as described in WO-A-9314147.Preferred dendroid bridging compound has reactivity-NH 2Base is easy to generate the ligand that can be used for the inventive method with the reaction of two (alcoxyls) or two (fragrant oxygen) phosphorus chloride compound.
Valence mumber generally is 2～6.An example of quadrivalent organic radical group is four aryl tetramethylolmethanes.
Preferred divalent organic group is alkylidene group, alkylidene group-oxygen-alkylidene group, arylidene, arylidene-(CH 2) y-(R 6) n-(CH 2) y-arylidene, wherein y is 0 or 1, and n is 0 or 1, and that each arylidene can be is identical or different, replacement or unsubstituted divalent aryl, R 5Representative is selected from the divalent group of following groups :-CR independently 7R 8-,-O-,-S-,-NR 9-,-SiR 10R 11-and-CO-, wherein R 7And R 8Represent hydrogen, C separately 1～C 12Alkyl, phenyl, tolyl, anisyl or p-methoxy-phenyl, wherein each R 9, R 10And R 11Base is represented hydrogen or C separately 1～C 12Organic group, for example ethyl, propyl group, butyl, benzyl are preferably hydrogen, methyl or phenyl.
The possible example of divalent organic bridging base group (A) comprises and replacing and unsubstituted group that they are selected from alkylidene group, alkylidene group-oxygen-alkylidene group, phenylene, naphthylidene, phenylene-(CH 2) y-(R 6) n-(CH 2) y-phenylene and naphthylidene-(CH 2) y-(R 6) n-(CH 2) y-naphthylidene, R 6, n and y definition the same.The more specifically example of divalent radical A is-CH 2CH 2OCH 2CH 2-, 1,4-phenylene, 2,3-phenylene, 1,3-phenylene, 1,4-naphthylidene, 1,5-naphthylidene, 1,8-naphthylidene, 2,3-naphthylidene, 1,1 '-biphenyl-2,2 '-two bases, 2,2 '-biphenyl-1,1 '-two bases, 1,1 ' biphenyl-4,4 '-two bases, 1,1 '-dinaphthalene-2,2 '-two bases, 2,2 '-dinaphthalene-1,1 '-two bases, phenylene-CH 2-phenylene, phenylene-S-phenylene, CH 2-phenylene-CH 2And phenylene-CH (CH 3)-phenylene.The general formula of preferred divalent abutment (A) is as follows: R wherein 12For-CY 1Y 2-, each Y wherein 1And Y 2Base is represented hydrogen, C separately 1～C 12Alkyl, for example methyl, propyl group, sec.-propyl, butyl, isodecyl, dodecyl; Phenyl, p-methoxy-phenyl, tolyl and anisyl, the value of r are 0～1; Each X wherein 1, X 2, Z 1And Z 2Group respectively do for oneself the alkyl of hydrogen, 1～18 carbon atom, as above-mentioned definition and the replacement that exemplifies or unsubstituted aryl, alkaryl, aralkyl or alicyclic radical, for example phenyl, benzyl, cyclohexyl and 1-methylcyclohexyl; Cyano group, halogen such as Cl, Br, I; Nitro, trifluoromethyl, hydroxyl, carbonyl oxygen base, amino, acyl group, phosphono, oxygen carbonyl, amide group, sulfinyl, alkylsulfonyl, silyl, alkoxyl group or sulfinyl.Preferred X 1And X 2Be group with steric hindrance, sec.-propyl for example, or the more preferably tertiary butyl or bigger group, Z 1And Z 2Be hydrogen, alkyl, the particularly tertiary butyl, hydroxyl or alkoxyl group, particularly methoxyl group.Preferred R 11Represent methylene radical (CH 2-) abutment or alkylidene group (CHR 13-) abutment, wherein R 13Be as the above-mentioned Y of being 1The alkyl of 1～12 carbon atom of definition.R 13Methyl (R preferably 12Be-CHCH 3-) or the aryl that replaces, for example p-methoxy-phenyl.
R 2And R 3Be associated in together and/or R 4And R 5The divalent organic group that connects together can be and the identical group of above-mentioned abutment (A).The preferred base of abutment also is applicable to these divalent radicals.Divalent radical is the group shown in the general formula (3) preferably.
In the formula (2) when X be N (R) when base R 2And R 3Preferred divalent organic group, and/or when Q be N (R) when base R 4And R 5Preferred divalent organic group can be represented with following formula (exist simultaneously N (R), P and-O-group)
Figure A9519734600072
E wherein 1And E 2Be identical or different group, and E wherein 1And E 2Be any monovalent organic radical group of hydrogen or 1～11 carbon atom, or E wherein 1And E 2Form the divalent organic group of 3～11 carbon atoms together, or R and E 2Form the divalent organic group of 3～12 carbon atoms together, E 1Be hydrogen or any monovalent organic radical group as defined above.Other possible group that is bonded on the carbon atom is a hydrogen in formula (3a).Possible any monovalent organic radical group is alkyl, aralkyl, alkaryl or aryl, for example methyl, ethyl, propyl group, the tertiary butyl, phenyl, benzyl or tolyl.As E 1And E 2Divalent radical can be C 3～C 5Alkylidene group, for example propylidene or butylidene, or can so select, i.e. E 1, E 2And the conjugate ring structure of 6 carbon atoms of two carbon atoms formation of formula (3a), this ring can be replaced by for example methyl, ethyl, propyl group or phenyl.As R and E 2The example of divalent organic group the optional C that replaces is arranged 3～C 10Alkylidene group, for example propylidene, butylidene or pentylidene.
R 2, R 3, R 4And R 5Any monovalent organic radical group, more particularly can be the aryl of the cycloalkyl of the univalent alkyl of 1～20 carbon atom, 5～12 carbon atoms, 5～20 carbon atoms and the alkaryl of 6～20 carbon atoms.The example of any monovalent organic radical group is methyl, ethyl, sec.-propyl, butyl, isodecyl, dodecyl, phenyl, tolyl and anisyl.Univalent perssad preferably has following structure:
Figure A9519734600081
X wherein 1, X 2And Z 1It is previously defined group.
The examples of compounds that is used as ligand in the inventive method is shown in the formula of following (1)-(24).In these general formulas, Ph is that phenyl, Me are that methyl, tBu are the tertiary butyls, and OMe is a methoxyl group.
Figure A9519734600101
Figure A9519734600111
Figure A9519734600131
The phosphamide compound that is used as ligand among the present invention can be by the described method preparation of following document: EP-A-42359, people such as S.D.Pastor:＜American Chemical Society can will〉(J.Am.Chem.Soc) 110,6547 (1988) and people such as S.D.Pastor:＜Switzerland chemistry journal〉(Helv.Chim.Acta) 76,900 (1991).
The unsaturated ethylene thiazolinyl organic compound that is used for preparing by hydroformylation reaction aldehyde cpd has no particular limits, as long as have at least an ethene (C=C) key just passable in molecule.Unsaturated ethylene thiazolinyl organic compound has 2～20 carbon atoms usually.The possible example of unsaturated ethylene thiazolinyl organic compound comprises straight chain terminal olefine compound, for example ethene, propylene, 1-butylene, 1,3-butadiene, 1-amylene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-tetradecylene, 1-hexadecylene, 1-octadecylene, 1-icosa alkene and 1-laurylene; Side chain terminal olefine such as iso-butylene and 2-methyl-1-butene alkene; Linear internal such as suitable-and anti--2-butylene, suitable-and anti--2-hexene, genial anti--the 3-hexene, genial anti--the 2-octene and genial anti--the 3-octene; Branched internal olefins is as 2,3-dimethyl-2-butylene, 2-methyl-2-butene and 2-methyl-2-amylene; The mixture of terminal olefine and internal olefin is as the octene by the butene dimerization preparation, and light alkene comprises the isomer mixture of the olefin oligomer (dipolymer is to tetramer) of propylene, n-butene, iso-butylene etc.; With alicyclic olefin such as cyclopentenes, tetrahydrobenzene, 1-tetrahydrotoluene, cyclooctene and limonene.
The example of the olefin(e) compound that replaces with the alkyl that contains unsaturated alkyl comprises olefin(e) compound such as vinylbenzene, alpha-methyl styrene and the allyl benzene that contains aromatic substituent; With diolefin as 1,5-hexadiene, 1,7-octadiene and norbornadiene.
Undersaturated vinyl organic compound can be replaced by one or several functional group who contains heteroatoms such as oxygen, sulphur, nitrogen and phosphorus.The example of the unsaturated ethylene thiazolinyl organic compound of these replacements has vinyl methyl ether, Witconol 2301, allyl alcohol, oleyl alcohol, 3-methyl-3-butene-1-alcohol, the 3-amylene-4 acid methyl ester, the 4-amylene-4 acid methyl ester, the 3-pentenoic acid, the 4-pentenoic acid, 3 pentene nitrile, allyl acetonitrile, 3-hydroxyl-1, the 7-octadiene, 1-hydroxyl-2, the 7-octadiene, 1-methoxyl group-2, the 7-octadiene, 7-octene-1-aldehyde, oneself-1-alkene-1-alcohol, vinyl cyanide, acrylate such as methyl acrylate, methacrylic ester such as methyl methacrylate, nytril-acetoxyl group-2, the 7-octadiene.
When the vinyl organic compound is as starting raw material in undersaturated, the present invention improves aldehyde, and optionally advantage is more obvious, and when these compounds are contained above-mentioned heteroatomic functional group and replace by one or several after, even more obvious.The example of these compounds as mentioned above.
Preferred Substrate is pentenenitrile, pentenoic acid and pentenoic acid C 1～C 6Alkyl ester compound, for example 3 pentene nitrile, 3-pentenoic acid, 3-amylene-4 acid methyl ester, 3-pentenoic acid ethyl ester and 4-amylene-4 acid methyl ester.Why preferred these compounds are, is because resulting terminal aldehyde group compound can be conveniently used for preparing the intermediate of nylon 6 and nylon 66.An example of this application is disclosed among United States Patent (USP)-A-4731445.According to the described similarity method of above-mentioned United States Patent (USP), the branched chain aldehyde compound that the inventive method obtains can be used for preparing the side chain lactan.
The preparation method of catalyst system comprises by well-known complex formation, randomly in suitable solvent 8～10 suitable families (by new IUPAC code name) metallic compound is mixed with phosphamide compound.Described solvent is the used solvent of hydroformylation reaction normally.8～10 suitable family's metallic compounds are hydride, halogenide, organic acid salt, inorganic acid salt, oxide compound, carbonyl compound and the amine compound of these metals.The example of 8～10 suitable family's metals comprises cobalt, ruthenium, rhodium, palladium, platinum, osmium and iridium.The example of 8～10 family's metallic compounds comprises rhodium compound such as Ru 3(CO) 12, Ru (NO 3) 3, RuCl 3(Ph 3P) 3And Ru (acac) 3Palladium compound such as PdCl 2, Pd (OAc) 2, Pd (acac) 2, PdCl 2(COD) and PdCl 2(Ph 3P) 2Osmium compound such as Os 3(CO) 12And OsCl 3Iridic compound such as Ir 4(CO) 12And IrSO 4Platinic compound such as K 2PtCl 4, PtCl 2(PhCN) 2And Na 2PtCl 66H 2O; Cobalt compound such as CoCl 2Co (NO 3) 2, Co (OAc) 2And Co (CO) 8With rhodium compound such as RhCl 3, Rh (NO 3) 3, Rh (OAc) 3, Rh 2O 3, Rh (acac) (CO) 2[Rh (OAc) (COD)] 2, Rh 4(CO) 12, Rh 6(CO) 16, RhH (CO) (Ph 3P) 3, [Rh (OAc) (CO) 2] 2[RhCl (COD)] 2(wherein " acac " is acetylacetone based; " Ac " is ethanoyl; " COD " is 1, the 5-cyclooctadiene; " Ph " is phenyl).But, be noted that 8～10 family's metallic compounds have more than and be limited to above-claimed cpd.
Rhodium preferably in 8～10 family's metals is because the speed of response of rhodium compound is higher than other metallic compound.
The consumption of 8～10 family's metals (compound) is not particularly limited, and can select arbitrarily, so that at catalyst activity with can both obtain satisfied result economically.Usually, the concentration of 8～10 family's metals in reaction medium is calculated as 10～10 by the free metal, 000ppm, more preferably 100～1000ppm.
The mol ratio of multiple tooth phosphamide ligand and 8～10 family's metals has no particular limits in the catalyst system, but is better selected, and makes to obtain satisfied result on catalyst activity and aldehyde selectivity.It is about 0.5～100 that this ratio is generally, and is preferably 1～10 (mol ligand/mol metal).
The selection of optional solvent is not strict.Reaction medium can be the reactant of hydroformylation reaction itself such as the mixture of initial unsaturated compound, aldehyde product and/or by product.If with the solvent that adds, suitable example comprises stable hydrocarbon such as petroleum naphtha, kerosene, mineral oil and hexanaphthene and aromatic hydrocarbons, for example toluene, benzene, dimethylbenzene, ethers such as phenyl ether, tetrahydrofuran (THF), ketone such as pimelinketone and nitrile such as benzonitrile and texanol (union carbide corporation).
Carry out the reaction conditions and the ordinary method of hydroformylation reaction of the present invention, the described method of United States Patent (USP) A-4769498 for example, used condition is identical, and reaction conditions will depend on used concrete initial unsaturated ethylene thiazolinyl organic compound.For example, temperature can be room temperature to 200 ℃, is preferably 50～150 ℃.Pressure can be preferably 0.15～10MPa, more preferably 0.2～5MPa from normal pressure to 20MPa.Pressure is the combined pressure of hydrogen and carbon monoxide pressure of tension normally.But, also can have extra rare gas element to exist.Hydrogen: the mol ratio of carbon monoxide is generally 10: 1 to 1: 10, is preferably 1: 1 to 6: 1.
The present invention also relates to a kind of catalyst system, this system comprises the racemic mixture of the metal of 8～10 families and preferably above-mentioned multiple tooth phosphamide ligand.
Can use formula (1-2) expression as the phosphamide compound of this catalyst system ligand.Radicals X, Y, Z, Q, A, R, R 1-R 13And E 1-E 2Definition the same.The preferred catalyst system of the present invention is the catalyst system that contains phosphamide ligand (wherein 8～10 family's metals are rhodium).As explained above, when be used for unsaturated in during the reaction of vinyl organic compound hydroformylation or aldehyde, this catalyst system is extraordinary.
Described catalyst system also can be used as the catalyzer of for example hydrogenation, polymerization, isomerization and carbonylation reaction.
The present invention also relates to the new phosphamide compound of a class, this compounds is that above-mentioned unsaturated ethylene thiazolinyl organic compound carries out the useful ligand of homogeneous catalysis hydroformylation reaction.The phosphamide compound that this class is new can be represented with following general formula: R wherein 2, R 3, A, R, E 1And E 2Definition the same, k is 1～5.In the formula (4a) by N (R), C, C, E 1, E 2The end group of forming with O is identical with the corresponding group of formula (3a).
The example of these new compounds is above-mentioned ligand (1), (3) and (12).Preferred compound is ligand (12).
The compound of formula (4a) for example can be by the embodiment 13 described method preparations of United States Patent (USP)-A-4748261, and wherein 2 normal phenol derivativess (para-chlorophenol) replace with the aminoalcohol derivative such as the ephedrine of equimolar amount.
The another kind of new phosphamide compound that the present invention relates to can be represented with following general formula:
Figure A9519734600181
R wherein 2, R 3, R 4, R 5The same with the definition of A.These compounds are that above-mentioned unsaturated ethylene thiazolinyl organic compound carries out the useful ligand of homogeneous catalysis hydroformylation reaction.The example of these new compounds is above-mentioned ligand (9), (10) and (11), and the compound that is used as ligand among the embodiment of the invention IV.
The method for making of formula (4b) compound is included in the organic solvent halide compound with phosphorus (corresponding to (R 1O) (R 2O) P-or (R 3O) (R 4O) P-yl) with 2 equivalent alkylamines such as triethylamine and 0.5 normal diamines (corresponding to formula (4b)-N (R)-A-N (R)-yl) is as N, N '-dimethyl-ethylenediamine mixes.Filtration and steaming obtain white solid chemical compound after falling solvent.Subsequent crystallisation obtains pure white crystals shape compound.
The present invention will illustrate with following non-limiting example.Be used as the compound of ligand in embodiment and the experiment, its method for making is as described below.Some compound is well-known in the literature and/or the commercial goods is arranged, so their method for making just no longer describes in detail.
Ligand (1)
Ligand (1) (referring to the description of the reference of other used among ligand (1) and embodiment ligand) is by the 13 described similarity methods preparations of embodiment among United States Patent (USP)-A-4748261, and wherein the para-chlorophenol of 2 molar equivalents usefulness waits the ephedrine replacement of molar equivalent.The triethylamine that is generated in the reaction final step-hydrochloride precipitation is removed with filtration method.Residue is with 2 parts of 50ml toluene wash.The filtrate and the washing lotion that merge are concentrated, obtain linen solid.The crystallization in toluene/acetonitrile of this solid obtains meeting the ligand of ligand (1) general formula, yield 71%.
Ligand (3)
The method for making of ligand (3) comprises that with 18.6 grams 2, the 4-DI-tert-butylphenol compounds is dissolved in the 500ml toluene, steams 50ml with azeotropic distn, to remove the moisture content of trace.Make solution be cooled to room temperature, add 1 molar equivalent triethylamine (9.1g).Again with 0.5 normal PCl 3(6.2g) be added in the mixture that mechanical stirring.The suspension that forms was immediately stirred 3 hours down at 60 ℃.Add 4.55g triethylamine and 2.04g tetramethylolmethane subsequently in this mixture, 60 ℃ of restir 16 hours.Make this suspension be cooled to room temperature, add 3.44g 2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxaza-phospholidine (as people such as S.D.Pastor at＜Switzerland's chemistry journal〉(Helv.Chim.Acta) described in 74,1175 (1991)).Form ligand (3) 40 ℃ of stirrings after 20 hours.Finishing sequence is identical with the described method of preparation ligand (1).Through obtaining the ligand (3) of white solid, yield 75% after twice crystallization.
Ligand (9)
The initial synthetic method to ligand (3) of the synthetic method of ligand (9) is similar.Past pair (2, add 1 equivalent triethylamine and 0.5 equivalent N, N-dimethyl-ethylenediamine in the mixture of 4-two (tertiary butyl phenoxy group) phosphorus chloride and triethylamine-hydrochloride.Mixture forms ligand (9) after stirring 4 hours under 50 ℃.Finishing sequence is identical with the described method of preparation ligand (1).Obtain white solid ligand (9) after the crystallization, yield 89%.
Ligand (12)
By right-ar-methoxy-benzylidene-1,1-two (beta naphthal) prepares ligand (12) by similar methods described in ligand (1) preparation.The ligand that obtains (12) is a white solid, yield 84%.
Ligand (16)
The method for making of ligand (16) is similar to the method described in ligand (1) preparation, uses N-methyl sulphonyl-2-amino-2 phenylethyl alcohol as amino alcohol.
Ligand (17)
Ligand (17) is to prepare by the similarity method described in ligand (1) preparation with the N-tertiary butyl-2-monoethanolamine.
Ligand (18)
Ligand (18) is with 2,4-DI-tert-butylphenol compounds and N, and N '-dimethyl-ethylenediamine prepares by the similarity method described in ligand (9) preparation.
Example I
Under nitrogen atmosphere, in 150ml Hastelloy carbon steel autoclave (Parr), add 5.8mg (2.25 * 10 -5Mol) dicarbonyl rhodium acetylacetonate and 45mg (4.80 * 10 -5Mol) mixture of phosphamide ligand (1) in 60ml toluene.In 1 hour, autoclave is heated to 90 ℃ and use H 2/ CO (2/1; (mol/mol)) mixture is forced into 0.5MPa.Subsequently, inject the mixture of 5.1g (45mmol) 3-amylene-4 acid methyl ester and 1g nonane (interior mark) and toluene (cumulative volume 15ml) in the reactor.During hydroformylation, reactor pressure H 2/ CO (2/1; Mol/mol) be held constant at 0.5MPa.The composition gas chromatographic analysis of reaction mixture, the results are shown in Table 1.
Comparative Example A An
Repeat example I with the 14 used diphosphite ligands (A) of embodiment among United States Patent (USP)-A-4769498.The results are shown in Table 1.Used diphosphite ligand (A) is:
Comparative Examples B
(see that also United States Patent (USP)-A-4769498) repeats example I with the diphosphite ligand (B) shown in the following formula.The results are shown in Table 1.
Figure A9519734600202
Table 1
Embodiment Ligand ??L/Rh(1) ??S ald(2) Transformation efficiency (%) (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 the mol ratio of ligand and rhodium.
(2) S AldBe the selectivity of aldehyde, the percentage that accounts for the product total mole number with the molar weight of aldehyde is represented.
(3) transformation efficiency is that the percentage ratio that the molar weight of unsaturated compound with reaction accounts for the initial compounds integral molar quantity is represented.Numeral in the bracket is with hour reaction times of expression.
Example II a
Use the phosphamide ligand, ligand (3) repeats example I, and wherein pressure is 1.0MPa (H 2/ CO=1/1, (mol/mol)), ligand/Rh ratio is 2.8 (mol/mol).Transformation efficiency is 75% after 46 hours, the selectivity (S of aldehyde Ald) be 84.5%.
Example II b
Use the phosphamide ligand, ligand (12) repeats example II a, and wherein ligand/Rh ratio is 2.9.
Transformation efficiency is 86.2% after 22 hours, the selectivity (S of aldehyde Ald) be 91.6%.
Comparing embodiment C
Phosphorus diamide ligand with embodiment among the WO-A-9303839 7 repeats example II:
Ligand (C)
Ligand/Rh is than being 2.1/1mol/mol.React after 40 hours, transformation efficiency is 28.2%, S Ald=76.6%.
EXAMPLE III a-d
Phosphamide ligand with structure shown in the general formula 8a-8d repeats example II a.The synthetic method of ligand 8a-8d is as described in the following document: people such as S.D.Pastor:＜American Chemical Society can will〉(J.Am.Chem.Soc) 110,6547 (1988) and people such as S.D.Pastor:＜Switzerland chemistry journal〉(Helv.Chim.Acta) 76,900 (1991).
Figure A9519734600221
The results are shown in Table 2.Table 2
Embodiment Ligand ???L/Rh ????S ald Transformation efficiency %
????IIIa ????8a ????1.9 ????91.2 ????22.4(6h)
????IIIb ????8b ????2.0 ????75.6 ????27.4(16.5h)
????IIIc ????8c ????2.1 ????82.5 ????19.1(16.5h)
????IIId ????8d ????2.2 ????81.0 ????47.7(16.5h)
EXAMPLE IV a-d
With the phosphamide ligand of structure shown in the general formula 9, at different ligand/Rh than (mol/mol) following repetition example II a.The synthetic method of various ligands is similar to the synthetic method of ligand 9 shown in the general formula 9, comprise use to be fit to corresponding to formula (3c)-the diamines bridged bond of N (R)-A-N (R)-group.When the results are shown in Table 3 for ligand/Rh.
Figure A9519734600231
Table 3
Embodiment Ligand ??L/Rh ??S ald Transformation efficiency %
????IVa ????9a ????5 ????85.5 ????45(21h)
????IVb ????9b ????2 ????80.1 ????70(21h)
????IVc ????9c ????2 ????79.1 ????55.4(20h)
EXAMPLE V a-b
Replace the 3-amylene-4 acid methyl ester to repeat example II a with the genial anti-2-octene of 2.5g (22mmol).The result is as shown in table 4.Table 4
Embodiment Ligand ??L/Rh ??S ald Transformation efficiency %
????Va ????1 ????22 ????100 ????19.0(5h)
????Vb ????9b ????2.2 ????99.3 ????49.6(2h)
Example VI a-c
In the stainless steel autoclave of 181ml, fill to contain 0.008mmol/Rh (CO) 2The 2ml toluene solution and the 18ml toluene of acac, the once used ligand of 5 equivalents (seeing ligand 8b, 8c and the 8d of EXAMPLE III).Use CO/H 2(1/1mol/mol) autoclave is forced into 1.5MPa, temperature rises to 80 ℃.Behind the temperature-stable, in reactor, inject 20mmol 1-octene and 1ml decane (interior mark).Pressure rises to 2.0MPa CO/H again 2(1/1mol/mol).Reaction is carried out with intermittent mode, no longer additionally adds CO or H during reaction 2Form with gas chromatographic analysis, the results are shown in Table 5.Table 5
Embodiment Ligand ??L/Rh ??S ald Transformation efficiency %
????VIa ????8b ????5 ????99 ????49(2h)
????VIb ????8c ????5 ????87 ????72(2h)
????VIc ????8d ????5 ????88 ????48(2.5h)
Example VII A a-c
At pressure 1.0MPa (CO/H 2=1/1mol/mol) under, with (a) ligand (16), (b) ligand (17) and (c) ligand (18) repetition example I.Ligand/rhodium ratio changes, but wherein the concentration of rhodium keeps the same with example I.
The results are shown in Table 6.Table 6
Embodiment Ligand ??L/Rh ????S ald Transformation efficiency %
??VIIa( *) ????16 ????2.1 ????88.4 ????93.2(48h)
??VIIb ????17 ????2.2 ????85.7 ????86.2(22h)
??VIIc ????18 ????5 ????85.5 ????44.9(21h)
T=90 ℃, pressure=0.25MPa
Example VII A I
Be prepared as follows the dendroid bridged bond compound ligand that has 32 end groups shown in the formula (10) by following method.
In the solution of 350ml toluene (through azeotropic distillation drying), add 10ml triethylamine and 2.02g (14.7mmol) PCl successively toward 6.08g (29.5mmol 2, the 4-DI-tert-butylphenol compounds) 3After stirring is spent the night, add the solution of dendritic PA32 (pressing the described method preparation of example VII A of WO-A-9314147) in 250ml toluene of 5ml triethylamine and 0.307mmol.After stirring was spent the night, reaction mixture was at Al 2O 3Last filtration secondary.Steam solvent, ligand is purified by crystallization in acetonitrile and ethanol (2 times).In the gained compound, average 90% N-group links to each other with following group.
Figure A9519734600251
(*) the 4th generation the dendritic compound 32 N-groups in one
Example I X
Ligand with formula (10) repeats example VII A.Phosphorus/rhodium (mole atom phosphorus/mole rhodium) is than being 4.Reacting after 18.5 hours, is that the selectivity of 5% o'clock aldehyde is 97% at transformation efficiency.

Claims (10)

  1. One kind in the presence of catalyst system; the method of the preparing aldehyde by hydroformylation compound by unsaturated ethylene thiazolinyl organic compound; described catalyst system contains the metal of multiple tooth phosphorus ligand and 8～10 families, it is characterized in that multiple tooth phosphamide ligand is made up of the multivalence bridging organic group that is connected to the trivalent phosphorus-containing groups shown in two following formulas at least:
    Figure A9519734600021
    Condition is to have at least the group of a formula [B] to exist, wherein R be hydrogen, organic group or-SO 2R 1, R wherein 1Be C 1-12Organic group, and remaining free linkage of described trivalent phosphorus-containing groups links to each other with the organic group of monovalence or divalence.
  2. 2. according to the method for claim 1, it is characterized in that the phosphamide ligand is by following general formula:
    Figure A9519734600022
    Wherein each X, Y, R 2, R 3, R 4And R 5Can be identical or inequality, and among X or the Y any be N (R) base, and another group is an oxygen, and A is multivalence (valence mumber the equals k+m) organic group of 2～30 carbon atoms, and k is 1 at least, and m can be 0～5, and k+m is 2～6, R 2And R 3Together and/or R 4And R 5Form (the optional replacement) divalent organic group that 2～30 carbon atoms are arranged together, or R 2, R 3, R 4And R 5Be (the optional replacement) any monovalent organic radical group that 1～20 carbon atom is arranged independently of one another.
  3. 3. according to the method for claim 2, it is characterized in that the phosphamide ligand is a bidentate phosphamide ligand, wherein k+m equals 2.
  4. 4. according to any one method in the claim 1～3, the metal that it is characterized in that 8～10 families is a rhodium.
  5. 5. according to any one method in the claim 1～4, it is characterized in that unsaturated ethylene thiazolinyl organic compound is interior unsaturated ethylene thiazolinyl organic compound.
  6. 6. according to the method for claim 5, it is characterized in that unsaturated ethylene thiazolinyl organic compound is the C of pentenenitrile, pentenoic acid or pentenoic acid in this 1-C 6Alkyl ester.
  7. 7. multiple tooth phosphamide compound is characterized in that this compound represented by following general formula:
    Figure A9519734600031
    R wherein 2, R 3, A and R fixed zhang identical with the definition in the claim 2, k is 1～5, E 1And E 2Can be identical or different, and E wherein 1And E 2Be the hydrogen or any monovalent organic radical group of 1～11 carbon atom, or E wherein 1And E 2Be the divalent organic group of 3～11 carbon atoms, or R and E 2Be the divalent organic group of 3～12 carbon atoms, and E 1Be any monovalent organic radical group of hydrogen or 1～11 carbon atom, wherein all the other groups that may be bonded on the carbon atom (C) are hydrogen.
  8. 8. bidentate phosphamide compound is characterized in that this compound represented by following general formula: R wherein 2, R 3, A, R 4And R 5Definition identical with claim 2.
  9. 9. catalyst system, it contains any one described multiple tooth phosphamide ligand in 8～10 family's metals and claim 1～3 or the claim 7～8.
  10. 10. according to the catalyst system of claim 9, it is characterized in that 8～10 family's metals are rhodiums.
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US5886235A (en) * 1995-12-06 1999-03-23 Union Carbide Chemicals & Plastics Technology Corporation. Metal-ligand complex catalyzed processes
US5710344A (en) * 1996-11-08 1998-01-20 E. I. Du Pont De Nemours And Company Process to prepare a linear aldehyde
US5917095A (en) * 1996-11-26 1999-06-29 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
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US5892119A (en) * 1996-11-26 1999-04-06 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
DE19913352A1 (en) 1999-03-24 2000-09-28 Basf Ag Catalyst comprising a complex of a metal of subgroup VIII based on a phosphinamidite ligand
DE10352757A1 (en) * 2003-11-12 2005-06-16 Studiengesellschaft Kohle Mbh Chiral di- and triphosphites

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