CN1024635C - Carbonylation catalyst system - Google Patents

Carbonylation catalyst system Download PDF

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CN1024635C
CN1024635C CN 90101125 CN90101125A CN1024635C CN 1024635 C CN1024635 C CN 1024635C CN 90101125 CN90101125 CN 90101125 CN 90101125 A CN90101125 A CN 90101125A CN 1024635 C CN1024635 C CN 1024635C
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acid
phosphine
catalyst
pyridine
compound
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CN1049462A (en
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埃特·德伦得
帕特鲁思·亨里库斯·马里·布兹拉
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Mitsubishi Chemical UK Ltd
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Shell Internationale Research Maatschappij BV
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Abstract

A catalyst system which comprises a) a Group VIII metal compound, and b) a phosphine of formula wherein R+[1] represents an aliphatic hydrocarbyl group, R+[2] represents an optionally substituted aromatic heterocyclic group having 5 or 6 ring atoms of which at least one is nitrogen, which may form part of an optionally substituted, larger condensed ring structure, and R+[3] independently has the meaning of R+[2] or represents an optionally substituted aryl group.

Description

Carbonylation catalyst system
The present invention relates to comprise the raw catelyst of phosphine, the application in alkene and alkynes carbonylation process of some new phosphine and this catalyst.
The carbonylation method of various olefinics and acetylenically unsaturated compound has been proposed in the prior art.The described J.Falbe that seen of these methods, " New Syntheses with Carbon Monoxide ", Springer Verlag, Berlin Heidelberg, New York, 1980.In general, these methods comprise alefinically unsaturated compounds and reaction of carbon monoxide, and in some cases, also with can the leave away nucleophilic compound reaction of hydrogen atom of hydrogen or band, are reflected at carbonylating catalyst and carry out under existing.In many cases, carbonylating catalyst comprises ligands such as VIII family source metal and phosphine.
Recently comprise VIII family source metal and pyridine phosphine in disclosed a kind of catalyst.
Kurti Kurtev et al, at Journal of the Chemical Society, Dalton Transactions discloses the catalyst and the application in 1-hexene carbonylation process thereof that comprise rhodium and ruthenium compound and pyridine phosphine among the 1980 Pages 55-58.
EP-A1-0259914 number open european patent application has proposed to comprise palladium compound, pyridine phosphine, the catalyst of acid and quinone and produce application in the polymer process at carbonylation of olefin.
EP-A1-0271144 number open european patent application proposed to comprise palladium compound, the catalyst of pyridine list phosphine and acid making with hydroxy-containing compounds to use in the alkynes carbonylation process.Different with EP-A1-0259914, be applicable to that allegedly the wideest definition of the phosphine of carbonylation method is restricted to the phosphine that all three phosphorus substituting groups are aryl.
EP-A1-0282142 number open european patent application proposed to use in the process that makes carbonylation of olefin with hydroxy-containing compounds and comprised palladium compound, the catalyst of pyridine list phosphine and acid.Different with EP-A1-0259914, be applicable to that allegedly the wideest definition of the phosphine of carbonylation method is restricted to the phosphine that all three phosphorus substituting groups are aryl.
EP-A2-0305012 number open european patent application has proposed to comprise palladium compound, the pyridine diphosphine, and the catalyst of acid and quinone, and produce application in the polymer process at carbonylation of olefin.
Do not have one piece to disclose phosphorus atoms and have the substituent pyridine list of general aliphatic series phosphine in the above-mentioned prior art document, also not proposing these phosphines is having any attraction aspect the carbonylating catalyst component.Really, for the catalyst that is suitable for producing polymer, promptly comprise the catalyst carbonylating catalyst in addition of quinone, above-mentioned documents is advised obviously without these phosphines.
Chem.Ber.115(9), 3085-95(1982) methyl-two-2-pyridine phosphine and dimethyl-2-pyridine phosphine disclosed.
J.Mol.Spectrosc., 34(2), 245-56(1970) normal-butyl-two-2-pyridine phosphine is disclosed.
Now unexpectedly find the general aliphatic substituent pyridine list phosphine of phosphorus atoms band as the carbonylating catalyst component, particularly effective especially in the alkynes carbonylation process.
Therefore, the present invention proposes catalyst, comprising:
A) VIII family metallic compound and
B) following formula list phosphine or its acid-addition salts
Figure 901011258_IMG2
R wherein 1Be aliphatic hydrocarbyl, R 2Be the aromatic heterocyclic radical that replaces in case of necessity, 5 or 6 annular atomses wherein arranged and wherein have at least one to be nitrogen-atoms, and can form the part of the big condensed ring structure that replaces in case of necessity, and R 3Has R respectively 1Or R 2Definition or be the aryl that replaces in case of necessity.
Found catalyst of the present invention activity in alkene and alkynes carbonylation process very high and in the alkynes carbonylation process reaction speed fast especially.And, found catalyst selectivity height of the present invention; When making raw material, to the selectivity height of β-carbonylation product with alkynes; When making raw material with alkene, to alpha-carbonyl product selectivity height, and the latter is surprising especially.
Found that the catalyst that comprises quinone among the present invention has activity when producing polymer with alefinically unsaturated compounds and carbon monoxide carbonylation.
In formula (1) phosphine, any aliphatic hydrocarbyl generally contains 1-30, and preferred 1-12 is particularly up to 5 carbon atoms.Also can be thiazolinyl, as vinyl, pi-allyl or cyclobutenyl, but be preferably alkyl.Preferred alkyl is a methyl, ethyl, and propyl group, isopropyl, the 1-butyl, 2-methyl-2-propyl group (tert-butyl group), 1-amyl group and 1-hexyl are preferably the group that contains up to 5 carbon atoms especially.
In formula (I) phosphine, at least one is preferably imino nitrogen atom in the annular atoms.
Here " imino nitrogen atom " means suc as formula two N-and comprises the nitrogen-atoms of representing in the aromatic heterocycle substituent structure formula of this atom.For example, if aromatic substituent is a pyridine radicals, then the aromatic substituent structural formula is
Figure 901011258_IMG3
The aromatic heterocycle substituting group example of imido-nitrogen-atoms is a pyridine radicals, pyrazinyl, quinolyl, isoquinolyl, pyrimidine radicals, pyridazinyl, cinnolines base, triazine radical, quinoxalinyl and quinazolyl.Preferred substituents is pyridine radicals and pyrimidine radicals.
Preferably at least one is an imino nitrogen atom in the annular atoms, and open by a bridge carbon atom and phosphorus atoms.For example, if the aromatic heterocycle substituting group is a pyridine radicals, then preferably on its 2, link to each other with phosphorus atoms by carbon atom.Therefore, the substituent preferred example of the aromatic heterocycle of imido-nitrogen-atoms is the 2-pyridine radicals, 2-pyrazinyl, 2-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 2-pyrimidine radicals, 3-pyridazinyl, 3-cinnolines base, 2-triazine radical, 2-quinoxalinyl, and 2-quinoline quinoline base.Be preferably the 2-pyridine radicals especially, 2-pyrimidine radicals and 2-triazine radical.R 2Be the pyridine radicals that replaces in case of necessity, particularly obtained good result during the 2-pyridine radicals.
At R 3When being not one of above-mentioned aromatic heterocyclic radical, then be aliphatic hydrocarbyl or the aryl that replaces in case of necessity.
The aryl of Qu Daiing generally contains less than 18 ring carbon atoms and is preferably the phenyl that replaces in case of necessity in case of necessity, but also can be anthryl or the naphthyl that replaces in case of necessity.
R 3Be preferably pyridine radicals, alkyl or the phenyl that replaces must be respectful the time.
Herein, mentioning in case of necessity the group that replaces preferably means and does not replace or by one or more substituent groups, substituting group is selected from hydroxyl, halogen (particularly chlorine and fluorine), alkoxyl (is preferably 1-5 carbon alkyl, particularly methoxyl group and ethyoxyl), dialkyl amido (particularly dimethylamino and diethylamino), single, two and trihalomethyl group, as trifluoromethyl, a trichloromethyl and a chloromethyl, and alkyl (is preferably 1-5 carbon alkyl, methyl particularly, ethyl, propyl group, isopropyl and the tert-butyl group.
Replacing the aromatic heterocyclic radical example is 6-methyl-2-pyridine radicals, 6-methoxyl group-2-pyridine radicals, 3-methyl-2-pyridine radicals, 4-methyl-2-pyridine radicals and 4,6-dimethyl-2-pyridine radicals.The substituted aryl example is the 4-methoxyphenyl, 3-aminomethyl phenyl and 2-fluorophenyl.
The example of formula (1) phosphine is:
Two (normal-butyl)-2-pyridine phosphines,
Dimethyl 2-pyridine phosphine,
Aminomethyl phenyl 2-pyridine phosphine,
Normal-butyl tert-butyl group 2-pyridine phosphine,
Normal-butyl (4-methoxyphenyl) (2-pyridine) phosphine and
Methyl two (2-pyridine) phosphine.
The preferred acid addition salts of the phosphine of general formula (I) comprises sulfate, sulfonate; The arylsulphonate that the hydrocarbyl sulfonate that replaces in the time of if necessary replaces if necessary the time, as benzene sulfonate, tosilate or naphthalene sulfonate, alkylsulfonate of Qu Daiing such as alkylsulfonate in case of necessity, as methane sulfonates or tert-butyl group sulfonate, or the alkylsulfonate such as the 2-hydroxypropanesulfonic acid salt trifluoro-methanyl sulfonate that replace, chlorosulfonate or fluoro sulfonate; Phosphate, as orthophosphates, pyrophosphate or benzenephosphonic acid salt; Carboxylate, as chloracetate, DCA, trichloroacetate, trifluoroacetate, oxalates or terephthalate; Or perhalide, as perchlorate.
VIII family metal example is iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum
VIII family metallic compound is preferably from palladium, and rhodium and ruthenium salt wherein are preferably palladium salt, particularly divalence palladium salt.Can there be homogeneous phase and heterogeneous metal compound, but be preferably the homogeneous phase compound.Suitable compound is a nitrate, and sulfate and per molecule carbon containing are no more than 12 alkanoic acid such as acetate and are preferably acid chloride especially.Also can preferably adopt VIII family metal and above-mentioned described any acid is become when speaking of formula (I) phosphine salt, particularly palladium salt.And the available metal complex compound as being example with the palladium, can be acetoxyacetone acid palladium, tetrakis triphenylphosphine palladium, two (three adjacent methylphosphine) palladium acetate, two (diphenylphosphine) palladium acetate, or two (triphenylphosphine) palladium sulfate.The example of the suitable heterogeneous pattern of VIII family metallic compound be metal in conjunction with on the routine active carbon and metal be attached on the ion-exchanger, as contain on the ion exchange resin of sulfonate radical.Catalyst of the present invention preferably also comprises Bronsted acid.The Bronsted acid function provides Bronsted acid.Therefore, Bronsted acid generally forms on the spot.Preferably Bronsted acid is one of related acid of the phosphonic acids addition salts of above-mentioned general formula (I).For example, also may be acid-exchange resin, for example sulfonation ion exchange resin, or boronic acid derivatives such as H (B(O 2C 6H 4) 2) or H (B(OC 6H 4CO 2) 2).
As can be seen, the catalyst that comprises the acid-addition salts of general formula (I) phosphine comprises Bronsted acid inevitably.
When catalyst comprised Bronsted acid, 18 ℃ recorded in the pKa(aqueous solution of Bronsted acid) generally be lower than 6, preferably be lower than 4.5, as be lower than 4, more preferably less than 2.Best pKa depends on the specific carbonylation that catalyst participates in.
The best of Bronsted acid and phosphine is than the specific carbonylation that depends on that catalyst participates in.Phosphine mol number/mol Bronsted acid is generally 0.1-5.0, and preferred 0.1-10 is 0.25-4 more preferably.
The ratio of catalyst Chinese style of the present invention (I) phosphine mol number/gram atom VIII family metal is not crucial, and this depends on sees body VIII family's metal and carbonylation, and preferably than being 1-1000,2-5000 more preferably is as 10-100.
Our U.S. Patent application 9002508.9 was submitted to February 5 nineteen ninety, and is wherein open and claimed:
Carbonylating catalyst, comprising:
A) VIII family source metal;
B) have the phosphine source of the aromatic substituent of imido-nitrogen-atoms;
C) proton source; With
D) alkyl sulfonate ion source, and the application of this carbon monoxide-olefin polymeric in the carbonylation of unsaturated compounds process.
Catalyst of the present invention is made in liquid phase.One or more of the reactant that liquid phase can be easily participated in by catalyst constitute.On the other hand, also can be solvent, also can constitute by one of catalyst component.
Catalyst of the present invention can be homogeneous phase or heterogeneous, is preferably heterogeneous.
Catalyst of the present invention can make with common methods.Therefore, can be with VIII family metallic compound, the phosphine of general formula (I) and Bronsted acid in case of necessity combine in liquid phase.On the other hand, also can be in liquid phase the acid-addition salts of VIII family metallic compound and general formula (I) combine.In addition, also can combine being the VIII family metallic compound of VIII family metal complex and the phosphine and/or the Bronsted acid of general formula (I).
As mentioned above, three kinds of phosphines of formula (I) have seen Chem.Ber., 115(9), and 3085-95(1982) with J.Mol.Spectrosc 34(2), 245-56(1970).All the other phosphines of formula (I) it is believed that it is novel.Therefore, the present invention also proposes above-mentioned formula (I) phosphine or its acid-addition salts, is methyl-two-2-pyridine phosphine, dimethyl-2-pyridine phosphine, and except normal-butyl-two-2-pyridine phosphine.
Comprise following formula: compound in the phosphine method for making of general formula (I):
Figure 901011258_IMG4
M wherein 1Be metallic atom or leave away atom or group, R 2aAnd R 3aBe above-mentioned R 1, R 2And R 3In two, react with following formula: compound:
M wherein 2Be metallic atom or leave away atom or group, R 1aBe R 1, R 2And R 2In remove R 2aAnd R 3aAnother, form acid-addition salts in case of necessity again.
M 1Or M 2Can be any main group metal, as alkali metal, as lithium, sodium or potassium; Alkaline-earth metal is as magnesium; Zinc; Cadmium; Benzene; Aluminium; Gallium; Indium; Thallium; Tin or lead are preferably alkali metal atom, most preferably are lithium atom.
As can be seen, at M 1Be metallic atom, formula (III) compound is M 2Represent the compound of leave away atom or group.Equally, at M 1When leaving away atom or group, general formula (III) compound is M 2Compound for metallic atom.
Leave away atom or group is preferably halogen atom, more preferably the chlorine or bromine atom.
Preferred M 2Be halogen atom, and preferred R 1aBe R 1
The reaction of formula (II) compound and formula (III) compound is generally carried out in solvent.Suitable solvents comprises liquefied ammonia and ether such as oxolane or ether, or hydrocarbon such as benzene or toluene.
This method generally at-100-100 ℃, is preferably-carries out under the 80-0 ℃.
M in the formula (III) 2For the compound of metallic atom can be used M 2For atom or the group of leaving away, as chlorine, the former respective compound of bromine or iodine makes, and wherein with metal alkyl compound, reacts as butyl lithium.
Generally just the phosphine of general formula (I) preferably contacts in solvent with suitable acid and forms acid-addition salts.
M in the formula (II) 1For the compound of chlorine or bromine can make with corresponding two and three chlorine or bromine phosphines and the reaction of formula (III) metallic compound on the spot.
M in the formula (II) 1Be alkali metal, can be as the compound of lithium with M 1Be formula (II) compound and the alkali metal pyridine of pyridine radicals, alkyl, aryl or hydride reaction make.Sometimes also can generate these formulas (II) compound on the spot, as halogen pyridine and alkali metal alkyl compound are reacted the mixture of making alkali metal pyridine and halogenated alkane, then with this mixture with two or three pyridine phosphine reactions and the alkali metal pyridine phosphide that requires at first, falsely accuse itself and halogenated alkane to react afterwards again and the alkyl pyridine phosphine that must ask.These compound method for makings of formula (II) have seen UK Patent Application No. 8923683, and on October 20th, 1989 submitted to.
As mentioned above, find that unexpectedly the present composition has excellent activity in making acetylene series or ethylenically unsaturated hydrocarbons carbonylation process.
Therefore, the present invention also proposes the application of the above-mentioned carbon monoxide-olefin polymeric of above-mentioned proposition in acetylene series or ethylenically unsaturated hydrocarbons carbonylation process.
According to a further aspect of the invention, the present invention proposes acetylene series or the carbonylation of ethylenically unsaturated compounds method, comprising acetylene series or alefinically unsaturated compounds being had under the above-mentioned catalyst existence condition and reaction of carbon monoxide in liquid phase.
Those skilled in the art are known, and known have big metering method to be suitable for acetylene series and the carbonylation of ethylenically unsaturated compounds.These methods have been divided into several reactions, and this depends on raw material.These examples of reactions are hydroformylation, so-called Reppe reaction, wherein unsaturated compound and carbon monoxide and the nucleophilic compound reaction of being with the hydrogen atom of can leaving away; And unsaturated compound and carbon monoxide carry out copolyreaction.
Acetylene series or alefinically unsaturated compounds are preferably X-alkynes or alkene.
Alefinically unsaturated compounds is preferably per molecule 2-30, is preferably 3-30 carbon and replaces or do not replace alkene or cyclenes.
Acetylenically unsaturated compound is preferably per molecule 2-20, and particularly 3-10 carbon replaces or do not replace alkynes.
Acetylene series or alefinically unsaturated compounds can contain one or more alkynes or ethylene linkage, as one, two or three alkynes or ethylene linkage.
Alkene or alkynes can be substituted, for example available halogen atom, cyano group, acyl group such as acetyl group; acyloxy such as acetoxyl group, amino as dialkyl amido, alkoxyl such as methoxyl group; haloalkyl such as trifluoromethyl, halogenated alkoxy such as trifluoromethoxy, acylamino-such as acetylamino or hydroxyl replace.Part in these groups participates in reaction, and this depends on definite reaction condition.For example, with its a little acetylene series unsaturated alcohols, 3-butine-1-alcohol for example, 4-pentyne-1-alcohol or 3-pentyne-1-alcohol carbonylation can obtain lactone.Therefore 3-butine-1-alcohol can be changed into alpha-methylene-gamma-butyrolactone.
The example of alkynes is: acetylene, propine, phenylacetylene, 1-butine, 2-butine, 1-pentyne, the 1-hexin, 1-heptyne, 1-octyne, 2-octyne, 4-octyne, 1,7-18 (carbon) diine, 5-methyl-3-heptyne, 4-propyl group-valerylene, 1-three n-heptylacetylenes, benzyl acetylene and cyclohexyl-acetylene.
The example of alkene is: acetylene, propylene, styrene, 1-butylene, 2-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 2-octene, 4-octene, cyclohexene and norbornadiene.
Acetylene series and alefinically unsaturated compounds can be alkynes and alkene, as 3-methyl-3-butene-2-alkynes.
Unsaturated compound can be separately or at other reactant, carries out carbonylation as can the leave away nucleophilic compound of hydrogen atom of hydrogen or band under existing.Can leave away hydrogen atom and nucleophilic compound example of band is hydroxy-containing compounds.
Hydroxy-containing compounds is preferably alcohol, water or carboxylic acid.
Used alcohol can be fatty alcohol, and ring-shaped fat is pure or fragrant and mellow and can be with one or more substituting groups.Alcohol preferably contains up to 20 carbon/molecule.For example, can be alkanol, cyclic alkanol or phenol.Can be with one or more hydroxyls, wherein can form several products, this depends on used reactant mol ratio.
The alkanol example comprises methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol and 2-methyl isophthalic acid-propyl alcohol.
The example of phenol comprises phenol, alkyl phenol, catechol and 2, two (4-hydroxyphenyl) propane of 2-.
Other example of alcohol comprises polyalcohol, particularly low grade sugar such as glucose, fructose, mannose, galactolipin, sucrose, aldose, aldopentose, altrose, allose, talose, gulose, idose, ribose, Ah (La Bai) sugar, wood sugar, lyxose, erythrose or threose, cellulose, benzyl alcohol, 2, two (the methylol)-1-butanols of 2-, stearyl alcohol, cyclohexanol, ethylene glycol, 1,2-propane diols, 1,4-butanediol, polyethylene glycol, glycerine and 1,6-hexylene glycol.
The inventive method can be carried out with multiple carboxylic acid.For example, carboxylic acid can be aliphatic acid, and ring grease acid or aromatic acid also can be with one or more substituting groups, as the substituting group of pointing out when speaking of alkynes and alefinically unsaturated compounds.
The carboxylic acid that is preferred for the inventive method comprises the carboxylic acid that contains up to 20 carbon.Can there be one or more carboxylate radicals to exist, therefore various products of output on request, this depends on the mol ratio of used reactant.Carboxylic acid can be for example alkanecarboxylic acid or olefin carboxylic acid.The carboxylic acid example is: formic acid, acetate, propionic acid, n-butyric acie, isobutyric acid, neopentanoic acid, positive valeric acid, n-caproic acid, sad capric acid, laurate, myristic acid, palmitic acid, stearic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acids and toluic acid.The olefin carboxylic acid is acrylic acid, propiolic acid, methacrylic acid, crotonic acid, iso-crotonic acid, oleic acid, maleic acid, fumaric acid, citraconic acid and mesaconic acid.
As can be seen, unsaturated hydrocarbons and hydroxy-containing compounds can be same compound.
When hydrocarbon ethylenically unsaturated compounds and water and reaction of carbon monoxide, α, beta-unsaturated carboxylic acid just can form.If alcohol is used for replacing water, then can form α, the beta-unsaturated carboxylic acid ester.If carboxylic acid is used for replacing water, then can form α, the beta-unsaturated acid acid anhydride.Alpha-beta-unsaturated product can further react, and this depends on used reaction condition.
Find that the present composition is specially adapted to hydroxy-containing compounds the alpha-acetylenes carbonylation.
Therefore, with regard to preferred one side, the present invention also proposes α, and β-alefinically unsaturated compounds method for making is comprising having in liquid phase in the presence of the above-mentioned carbonylic catalyst alpha-acetylenes and carbon monoxide and hydroxy-containing compounds reaction.
In this method, carbonylating catalyst is preferably above-mentioned palladium catalyst, promptly comprising:
A) palladium compound,
B) phosphine of general formula (I) and
C) Bronsted acid.
Must not adopt independent solvent in the methods of the invention.
One of a large amount of excessive products or reactant as alcohol, can form suitable liquid phase.But in some cases, also require to adopt independent solvent.Can adopt any natural instincts solvent for this reason.This solvent for example can comprise sulfone and sulfoxide, as methyl-sulfoxide, and diisopropyl sulfone or thiophane-2,2-dioxide (being also referred to as sulfolane), 2-methyl sulfolane, 3-methyl sulfolane, 2-methyl-4-butyl sulfolane, aromatic hydrocarbon such as benzene, toluene, dimethylbenzene; Ester such as methyl acetate and butyrolactone; Ketone such as acetone or methyl iso-butyl ketone (MIBK), ether such as anisole, 22,5,8-three oxygen nonanes (being also referred to as diethylene glycol dimethyl ether), phenyl ether and isopropyl ether and anide such as N, N-dimethylacetylamide or N-methylpyrrolidone.
The inventive method generally can be at 10-200 ℃, particularly 20-130 ℃.
The inventive method is preferably carried out under the 1-70 crust.The also available pressure that is higher than 100 crust, but generally because of the equipment requirement, do like this and there is no absorbability economically.
Hydroxy-containing compounds is that the mol ratio of unsaturated hydrocarbons can change in wide range, is generally 0.01: 1-100: 1.
VIII family metal consumption is not crucial, is preferably 10 -7-10 -1Gram atom VIII family metal/mol unsaturated compound.
The used carbon monoxide of the inventive method can be the also available inert gas of pure gas, as nitrogen dilution.Can not there be a large amount of hydrogen in the air-flow, because unsaturated hydrocarbons can be in hydrogenation under the reaction condition.In general, preferred hydrogen content is lower than 5% in the air-flow.
Another reaction of available catalyst of the present invention is to produce linear alternated polyketone, and wherein with alefinically unsaturated compounds and CO-copolymerization, this reaction also can be described as carbonylation.
Require polymer, catalyst system therefor preferably includes quinone.The example of quinone is benzoquinones, naphthoquinones and the o-quinone that replaces in case of necessity.Be preferably benzoquinones, particularly 1, the 4-phenyl ester.The ester consumption is generally 1-1000, is preferably 10-5000mol/ gram atom VIII family's metal (as palladium).
Following example describes the present invention in detail, and used in this paper and the example " selectivity " means:
(a/b)×100%
Wherein " a " requires determining of carbonyls to belong to or alefinically unsaturated compounds mol amount for changing into, and " b " is the total mol amount of the unsaturated compound that has transformed." reaction time " speech means the actual time of reacting, and is reduced illustrating by potheater pressure, does not comprise reaction any bringing out the time before.
Example
All phosphines all make in argon atmospher, steam solvent (oxolane, ether) with the benzo sodium phenate with preceding in argon gas.And outer, the allene content in the example in the used propine is less than 0.2% unless otherwise indicated.
Example 1
Two (normal-butyl)-2-pyridine phosphine method for makings
Hexane solution magnetic with 5.9ml 1.6M n-BuLi in 10 minutes stirs adding 2.5g phenyl (2-pyridine) 2P is dissolved in the 20mol oxolane and is cooled in-80 ℃ the solution.Allow resulting dark red solution temperature get back to room temperature, solution is used 21P NMR the analysis showed that and wherein contain phosphide (normal-butyl) (2-pyridine) PLi that this is unique phosphorus-containing compound (δ P=-16.3ppm).
This solution is cooled to-40 ℃ and add solution in the positive 10ml oxolane of 1.3g 1-NBB.Allow mixture get back to room temperature again, its empty steaming desolventizes, and adds 25ml ether and 10ml water.Stir after 10 minutes, tell organic facies and use 10ml extracted with diethyl ether water.The organic facies final vacuum (66Pa) that combines steams and to desolventize.The light yellow liquid that arrives use 1H, 13C and 31P NMR the analysis showed that comprising 2-phenylpyridine and (normal-butyl) 21 of (2-pyridine) P: 1(mol ratio) mixture (δ P=-19.5ppm).
Example 2
Dimethyl-2-pyridine phosphine and aminomethyl phenyl-2-pyridine phosphine method for making
Repeat example 1, just the diethyl ether solution with the 1.6M lithium methide replaces n-butyllithium solution, and replaces NBB with the 1.3g iodomethane.Product is (methyl) 2(2-pyridine radicals) P, aminomethyl phenyl 2-pyridine radicals P and 2-phenylpyridine, ratio is 70: 30: 60, (methyl) told in distillation then 2(2-pyridine radicals P).
The product physical property is δ P=-41.2ppm(dimethyl-2-pyridine radicals phosphine) and δ P=-24.1ppm(aminomethyl phenyl-2-pyridine radicals phosphine).
Example 3
The normal-butyl tert-butyl group-2-pyridine phosphine
Repeat the method for example 1, just adopt the pentane solution of tert-butyl lithium of the 1.7m of 5.6ml to replace n-butyllithium solution.It is the normal-butyl tert-butyl group-2-pyridine radicals P(δ that NMR analyzes end product P=7.4ppm).
Example 4
Dimethyl-2-pyridine phosphine method for making
Repeat the method for example 2, just with 1.91g methyl (2-pyridine radicals) 2P and 0.7g iodomethane.Press example 7 and handle and get dimethyl-2-pyridine phosphine, distill purification (yield 65%) (δ then P=-41.2ppm).
Example 5
Normal-butyl (4-anisyl) (2-pyridine radicals) phosphine method for making
All operations all carries out in inert atmosphere (nitrogen or argon gas).Solvent also distills with dry before.The hexane solution of 18ml 1.6M n-BuLi is added in the 30ml ether, and mixture is cooled to-40 ℃.In mixture, stir in 20 minutes and add the solution of 4.6g 2-bromopyridine in 15ml ethanol; Between charge period, temperature remains-40 ℃.After reinforced, temperature is upgraded to-5 ℃, is incubated 5 minutes, reduce to-40 ℃ then again.Mixture is added among 7.6g 4-methoxyphenyl-two (2-pyridine radicals base) phosphine solution in 30ml THF.After reinforced, mixture is got back to room temperature, stirs 10 minutes final vacuums except that desolvating, and adds 25ml water and 25ml carrene again.After fully stirring in 5 minutes, tell the carrene phase.Water combines final vacuum except that desolvating with two parts of 50ml dichloromethane extractions, organic facies.Residue gets 4.7g(60% with distillation) yellow liquid diphenylmethane base-(6-methyl-2-pyridine) phosphine.Product performance is 31P NMR: δ P=-14.9ppm.
In this test, it is believed that the reaction of n-BuLi and 2-bromopyridine and must n-butyl bromide and the mixture of 2-pyridine radicals lithium.Then 2-pyridine radicals lithium and 4-methoxyl group-two (2-pyridine radicals) phosphines and 4-methoxyphenyl (2-pyridine radicals) lithium phosphide (with 2,2 '-two pyridines), the phosphatization lithium gets (normal-butyl) (4-anisyl) (2-pyridine radicals) phosphine with the n-butyl bromide reaction then.
Example 6
Methyl two (2-pyridine radicals) phosphine method for making
All operations carries out in inert atmosphere (nitrogen or argon gas).Solvent also distills with dry before.The 1.6M n-BuLi hexane solution of 36ml is added in the 40ml ether, and mixture is cooled to 40 ℃.In mixture, stir to add the solution of 9.2g 2-bromopyridine in the 15ml ether in 20 minutes, between charge period, temperature remains-40-40 ℃.After reinforced, temperature is upgraded to-5 ℃, is incubated 5 minutes, and then reduces to-40 ℃.The solution of 3.4g methyl dichloro phosphine in the 15ml ether is stirred adding to coagulate in the compound.After reinforced, mixture is got back to room temperature, and vacuum adds 50ml water and 50ml carrene after steaming solvent.After fully stirring in 5 minutes, tell the carrene phase.Water is with two parts of 50ml dichloromethane extractions, and the organic facies final vacuum that combines steams solvent.Residue excess distillation and 4.0g(68%) yellow liquid methyl-two (2-pyridine) phosphine.Product performance is used 31P NMR analyzes: δ P=-20.5ppm.
Example 7
Propine and carbonylation of methanol system methyl methacrylate
Method for making is as follows.To 300ml Hastellcy(registration mark) order adds 0.025mmol acid chloride (II) in the potheater, Immol butyl (4-anisyl) (2-pyridine) Phenylphosphine, 2mmol p-methyl benzenesulfonic acid, 30ml NN-methylpyrrolidone and 30ml methyl alcohol.Back adding 25ml propine deflates from potheater.Then, add carbon monoxide and reach 60 crust.Be heated to 50 ℃ after the potheater sealing.50 ℃ of reactions were analyzed with gas-liquid chromatography after 1.5 hours.The selectivity that propylene changes into methyl methacrylate reaches 98.9%, and average conversion counts 20,000mol propine/gat Pa/ hour.
Example 8
Methyl methacrylate is produced in propine and carbonylation of methanol
Repeat example 7, difference is as follows:
A) used ligand is methyl two (2-pyridine) phosphine, replaces butyl (4-anisyl) (2-pyridine) phosphine, as
B) reaction temperature is 80 ℃, replaces 50 ℃.
The selectivity that propine changes into methyl methacrylate is 99.1%, and average conversion counts 12,5000mol/ gram atom Pd/ hour.
Comparative examples A
Repeat example 8, difference is as follows:
A) used ligand is phenyl two (2-pyridine radicals) phosphine, replace methyl two (2-pyridine radicals) phosphine and
B) reaction time is 2 hours, replaces 1.5 hours.
The selectivity that propine changes into methacrylate is 98.3%, and average conversion counts 8,000mol propine/gram atom/hour.Replace aryl as if can bring advantageous effects with fat-based in the organic phosphine.
Example 9
Ethene and propionic acid carbonylation are produced propionic andydride
Method for making is as follows.To 300ml Hastellog(registration mark) magnetic stirs that order adds 0.1mmol acid chloride (II), 4mmol butyl (4-anisyl) (2-pyridine phosphine, 2mmol p-methyl benzenesulfonic acid, 20ml propionic acid and 50ml anisole (solvent) in the potheater.Be blown into ethene after from potheater, deflating, reach 20 crust until pressure.Afterwards, introduce carbon monoxide and make dividing potential drop reach 30 crust.Be heated to 90 ℃ after the potheater sealing.90 ℃ of reactions were analyzed material in the still with gas-liquid chromatography after 5 hours.It is 99.5% that conversion of ethylene becomes the selectivity of propionic andydride, and average conversion is counted 300mol ethene/gram atom Pd/ hour.
Example 10
Methyl propionate is produced in ethene and carbonylation of methanol
Repeat example 9, just add 50ml methyl alcohol, replace 20ml propionic acid and 50ml anisole.It is 99.5% that conversion of ethylene becomes the selectivity of methyl propionate, and conversion ratio is counted 200mol ethene/gram molecule Pd/ hour.
Example 11
Produce linear alternated Co/ ethylene copolymer with containing the quinone catalyst
Method for making is as follows.Stir the Hastellcy(registration mark to 250ml magnetic) add 50ml methanol solution and catalyst in the potheater, comprising 0.1mmol acid chloride (II), 3mmol butyl (4-anisyl) (2-pyridine radicals) phosphine, 2mmol p-methyl benzenesulfonic acid and 20mmol 1,4-benzoquinone.Be blown into ethene after from potheater, deflating, up to reaching 20 bar pressures.Then, introduce carbon monoxide and make dividing potential drop reach 30 crust.Be heated to 110 ℃ after the potheater sealing.110 ℃ of reactions are cooled to room temperature and release pressure after 3 hours and finish polymerisation.Leach the polymer of formation, with vacuum drying under the room temperature after the methanol wash.It is 100% that conversion of ethylene becomes the selectivity of copolymer, and yield is the 0.9g copolymer, and average yield is 30g copolymer/g Pd/ hour. 13C-NMR analyzes and learns that carbon monoxide/ethylene copolymer of making is linear alternated structure, and its repetitive is-Co-(C 2H 4)-.

Claims (5)

1, a kind of carbonylating catalyst, comprising:
A) palladium source,
B) Bronsted acid and
C) following formula phosphine:
Figure 901011258_IMG1
R wherein 1For having the alkyl of 1-12 carbon atom, R 2Be the pyridine radicals that replaces in case of necessity, and R 3Be R independently 1Or R 2Definition or the aryl that replaces in case of necessity of representative.
2, the catalyst of claim 1, wherein at least one annular atoms is imino nitrogen atom and by a bridge carbon atom itself and phosphorus atoms is separated.
3, claim 1 or 2 catalyst, wherein R 2Be the 2-pyridine radicals.
4, claim 1 or 2 catalyst, wherein R 3Be pyridine radicals, alkyl or the phenyl that replaces in case of necessity.
5, claim 1 or 2 catalyst are used for the carbonylation of acetylene series or alefinically unsaturated compounds.
CN 90101125 1989-03-03 1990-03-03 Carbonylation catalyst system Expired - Lifetime CN1024635C (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB8904860.7 1989-03-03
GB898918843A GB8918843D0 (en) 1989-08-18 1989-08-18 Organic phosphines
GB8918843.7 1989-08-18
GB8923683.0 1989-10-20
GB898923683A GB8923683D0 (en) 1989-10-20 1989-10-20 Phosphorus compounds
GB9002509.9 1990-02-05

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CN1046263C (en) * 1993-03-19 1999-11-10 国际壳牌研究有限公司 Process for the carbonylation of acetylenically unsaturated compounds

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PL3121184T3 (en) * 2015-07-23 2019-03-29 Evonik Degussa Gmbh Benzene-based diphosphine ligands for alkoxycarbonylation
PL3272732T3 (en) * 2016-07-19 2020-03-31 Evonik Degussa Gmbh Method for the alcoxy carbonylation of ethylenically unsaturated compounds with monophosphin ligands
CN109092366B (en) * 2017-06-21 2021-05-28 中国石油化工股份有限公司 Catalyst composition and preparation method of 2-butenoic acid

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