WO2003068391A1 - Catalyseur d'hydrogenation et procede de production d'alcenes - Google Patents

Catalyseur d'hydrogenation et procede de production d'alcenes Download PDF

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Publication number
WO2003068391A1
WO2003068391A1 PCT/JP2003/001355 JP0301355W WO03068391A1 WO 2003068391 A1 WO2003068391 A1 WO 2003068391A1 JP 0301355 W JP0301355 W JP 0301355W WO 03068391 A1 WO03068391 A1 WO 03068391A1
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same
compound
hydrogenation catalyst
substituent
general formula
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PCT/JP2003/001355
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English (en)
Japanese (ja)
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Takeshi Ohkuma
Makoto Yoshida
Ryoji Noyori
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Nagoya Industrial Science Research Institute
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Priority to AU2003207190A priority Critical patent/AU2003207190A1/en
Publication of WO2003068391A1 publication Critical patent/WO2003068391A1/fr

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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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0212—Alkoxylates
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • 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
    • B01J2531/824—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Definitions

  • the present invention relates to a method for producing a hydrogenation catalyst and an alkene compound.
  • the present invention relates to a hydrogenation catalyst for partially hydrogenating an alkyne compound to an argen compound, and a method for producing an alkene compound using the hydrogenation catalyst.
  • the present invention has been made in view of the above problems, and has as its object to provide a catalyst for partially hydrogenating an alkyne compound with high activity. Another object is to provide a catalyst which partially hydrogenates an alkyne compound to give a cis-algen compound with high selectivity. It is another object of the present invention to obtain an alkene compound from an alkyne compound in high yield using these catalysts. Still another object is to obtain a cis alkene compound from an alkyne compound with high selectivity using these catalysts. Disclosure of the invention
  • the present inventors have conducted intensive studies and found that as a hydrogenation catalyst for partially hydrogenating an alkyne compound into an alkene compound, at least one selected from the group consisting of general formulas (1) to (3) is used as a main component. Was found to have high activity.
  • n is an integer from 1 to 5, and R '' to R "may be the same or different, and may be a hydrocarbon which may have a substituent.
  • X ′ 1 and X ′ 2 are anions which may be the same or different,
  • R 2 ′ to R 24 are the same or different and may have a substituent, and Y 2 ′ to ⁇ ′′ are the same.
  • Hydrogen, an optionally substituted hydrocarbon group, a halogen, an alkoxy group, or an amino group, and X 2 ′ and X 22 may be the same or different.
  • R 3 ′ to R 36 are the same or different and may be a hydrocarbon group which may have a substituent, and X 3 ′ and X 32 are the same. Or an anion that can be different)
  • —Hydrogenation catalysts having general formulas (1) to (3) as main components can be used to produce alkene compounds by partially hydrogenating various alkyne compounds. It is difficult to obtain an alkene compound with a catalyst, and alkyne compounds can be satisfactorily partially hydrogenated to give alkene compounds in high yields, or cis alkene compounds can be given with high selectivity. Highly useful as a catalyst.
  • the — (CH 2 ) ⁇ — of the methylene chain of the general formula (1) may have a difference in selectivity and reactivity depending on its length, and is appropriately determined according to the alkyne compound as a reaction substrate.
  • the methylene chain is preferably an integer of any one of to 5, particularly preferably the methylene chain is an integer of any of 1 to 4, and more preferably 2 or 3.
  • R " ⁇ R 'hydrocarbon group which may have a substituent at 4 in the general formula (1) are aliphatic, hydrocarbon group having an alicyclic saturated or unsaturated, monocyclic or polycyclic Aromatic or araliphatic hydrocarbons, or various of these substituted hydrocarbon groups such as alkyl, alkenyl, cycloalkyl, cycloalkenyl, phenyl, trityl, xylyl, and alcohol.
  • Hydrocarbon groups such as xylphenyl, naphthyl, phenylalkyl and the like, and those hydrocarbon groups, as well as acceptable groups such as alkyl, alkenyl, cycloalkyl, aryl, alkoxy, ester, acyl, halogen, nitro, cyano, etc. that various may be selected from among those having a substituent.
  • R and R '2, R' 3 and R '4 form a ring
  • R to R ′ 4 are preferably alkyl, cycloalkyl or phenyl which may have a substituent, among which alkyl (for example, carbon Numerals 1 to 5), cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, and alkoxyphenyl (alkoxy is, for example, having 1 to 5 carbon atoms) are particularly preferable. Further, "it is preferable that all to R 14 are the same.
  • R Anion in, X '2 are fluorine, chlorine, bromine, may be a halogen such as iodine A carboxylate such as an acetate And alkoxy such as methoxy and ethoxy.
  • the hydrocarbon group which may have a substituent in R 2 ′ to R ′′ in the general formula (2) is an aliphatic or alicyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group. It may be an aromatic or araliphatic hydrocarbon or any of these substituted hydrocarbon groups, for example, alkyl, alkenyl, cycloalkyl, cycloalkenyl, phenyl, trityl, xylyl, alkoxyphenyl, In addition to hydrocarbon groups such as naphthyl and phenylalkyl, and these hydrocarbon groups, there are also allowable groups such as alkyl, alkenyl, cycloalkyl, aryl, alkoxy, ester, acyl, halogen, halogen, cyano, etc.
  • R 2 ′ and R 22 and when R 23 and R 24 form a ring, R 2 ′ and R 22 , R 23 and R 24 may combine to form a carbon chain, alkyl on the carbon chain, an alkenyl, a cycloalkyl, Ariru, alkoxy, ester, Ashiru old xylene, halogen atom, nitro, such Shiano group
  • R "to R” may be alkyl, cycloalkyl or a substituent.
  • Phenyl which may be possessed is preferred, and among them, alkyl (for example, having 1 to 5 carbon atoms), cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, and alkoxy phenyl (for example, alkoxy has 1 to 5 carbon atoms) are preferred. It is particularly preferable that all of R "to R" are the same.
  • hydrocarbon group which may have a substituent in to Y "of the general formula (2) Similar to R 2 ' ⁇ R “supra, aliphatic, having a saturated or unsaturated hydrocarbon group of alicyclic, monocyclic or polycyclic aromatic or araliphatic hydrocarbons, or a substituent may be any species of these hydrocarbon groups, Y 2 ' ⁇ Y "if forms a ring, for example Y 2' and Upsilon 22, Upsilon 22 and Upsilon" or ⁇ 23 and Upsilon "binds To form a carbon chain on which alkyl, alkenyl, cycloalkyl, aryl, Those having various allowable substituents such as lucoxy, ester, acyl, halogen, nitrogen, cyano and the like may be selected.
  • anion at X 2 ′ and X 22 in the general formula (2) may be a halogen such as fluorine, chlorine, bromine or iodine, or a carboxylate such as acetate, Alkoxy such as methoxy and ethoxy may be used.
  • the hydrocarbon group which may have a substituent in R 3 ′ to R 36 in the general formula (3) is an aliphatic or alicyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group. It may be an aromatic or araliphatic hydrocarbon, or various of these substituted hydrocarbon groups.
  • alkyl, alkenyl, cycloalkyl, aryl, hydrocarbon groups such as alkyl, alkenyl, cycloalkyl, cycloalkenyl, phenyl, tril, xylyl, alkoxyphenyl, naphthyl and phenylalkyl, and these hydrocarbon groups, It may be selected from those having various acceptable substituents such as alkoxy, ester, acyl, halogen, nitrogen, cyano and the like.
  • R "to R 36 are ⁇ alkyl, optionally phenyl which may have a cycloalkyl or substituents rather preferred, of which alkyl (Eg, C 1-5), cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, and alkoxyphenyl (alkoxy is, eg, C 1-5) are particularly preferred.
  • X 3 in the general formula (3) ', Anion in X 32 are fluorine, chlorine, bromine, may be a halogen such as iodine, may be a Karubokishire Bok such Asete one Bok, main Bok alkoxy, alkoxy such as E Bok alkoxy It may be.
  • the palladium complex which is a starting material for synthesizing the phosphine-palladium complexes represented by the general formulas (1) to (3), has a valence of zero, one, two, three, and even higher valences. Can be used. In the case of using 0-valent and 1-valent palladium complexes, it is necessary to oxidize palladium by the final stage. You. When a divalent complex is used, a phosphine-palladium complex represented by general formulas (1) to (3) can be synthesized by reacting a palladium complex with a phosphine ligand.
  • the reaction between the starting material palladium complex and the phosphine ligand is a Aromatic hydrocarbon solvents such as pentane and xylene; aliphatic hydrocarbon solvents such as pentane and hexane; halogen-containing hydrocarbon solvents such as methylene chloride; ether solvents such as ether and tetrahydrofuran; methanol, ethanol, 2 —Alcohol solvents such as propanol, butanol, benzyl alcohol, etc., acetonitrile, N, N-dimethylacetamide (DMA), N, N-dimethylformamide (DMF), N— In organic solvents containing heteroatoms such as methylpyrrolidone and dimethylsulfoxide (DMSO), the reaction temperature is 100. The reaction is carried out at a temperature between C and
  • the amount of the phosphine-palladium complex varies depending on the reaction vessel and economics.
  • the molar ratio S / C (S is a substrate, C is a catalyst) can be used in the range of 100 to 500 000, and is preferably used in the range of 100 to 100 000.
  • a reaction substrate is used in a reaction solvent in the presence of a base or a reducing agent and in the presence of hydrogen or a compound that donates hydrogen.
  • Alkene compounds can be partially hydrogenated to produce alkene compounds in high yield.
  • a cis alkene compound can be produced with high yield and / or high selectivity from an internal alkyne compound, and a terminal alkene compound can be produced with high yield from a terminal alkyne compound.
  • examples of the base include alkali metal salts such as a hydroxyl group, an alkoxy group, a mercapto group, and a naphthyl group or an earth metal salt, and specifically, KOH, CH 3 OK And t-Bu OK.
  • examples of the reducing agent include sodium borohydride and aluminum lithium hydride.
  • the amount of the base or the reducing agent is not particularly limited, but may be, for example, in the range of 0.5 to 100 equivalents of the phosphine-palladium complex represented by the general formulas (1) to (3). It may be determined as appropriate.
  • an appropriate solvent such as a protic solvent, an aprotic solvent, a coordinating solvent, or a mixed solvent thereof can be used.
  • Examples of the protonic solvent include alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, tert-butanol, and benzyl alcohol, water, and mixed solvents thereof.
  • Examples of non-protonic solvents include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as pentane and hexane, octogen-containing hydrocarbon solvents such as methylene chloride, ethers, tetrahydrofuran, and the like. And the like, or a mixed solvent thereof.
  • the coordinating solvent examples include heterodimer, N, N-dimethylacetamide (DMA), N, N-dimethylformamide (DMF), N-methylpyrrolidone, and dimethylsulfoxide (DMSO).
  • Examples thereof include an organic solvent containing atoms or a mixed solvent thereof.
  • the reaction solvent is preferably DMF or DMF and an alcohol solvent (particularly tert-butanol).
  • the pressure of hydrogen in this partial hydrogenation reaction is sufficient to be 0.5 atm due to the extremely high activity of the present catalyst system, it is preferably in the range of 200 atm in consideration of economical efficiency, and preferably 3 atm. A range of ⁇ 100 atm is desirable, but high activity can be maintained even at 50 atm or less considering the economics of the whole process. It is possible.
  • the reaction temperature is preferably from ⁇ 15 to 100 ° C. in consideration of economy, but the reaction can be carried out at around 20 to 45 at room temperature.
  • the reaction time varies depending on the reaction conditions such as the concentration of the reaction substrate, temperature and pressure, but the reaction is completed in a few minutes to several days.
  • additives include N, N, N ', N'tetramethylethylenediamine (TMEDA), N, N'-dimethylethylenediamine, ethylene glycol, N, N-dimethyl
  • TEDA trimetramethylethylenediamine
  • N, N'-dimethylethylenediamine ethylene glycol
  • N, N-dimethyl examples include aminoethanol, phenol, aniline, benzonitrile, p-nitrophenol, triphenylphosphinoxide, trifluroethanol, water or quinoline.
  • the phosphine-palladium complex represented by any of the general formulas (1) to (3) for example, an alkyne compound having a hydroxyl group, an alkyne compound having a halogen, an alkyne compound having an ester, and an alkyne compound having a protected hydroxyl group
  • alkyne compounds having various functional groups such as alkyne compounds having an amino group, alkynyl ketones, and enynes
  • FIG. 1 is a structural formula of the phosphine-palladium complex synthesized in Examples 1 to 9,
  • FIG. 2 is a table of reaction conditions and reaction results of Examples 10 to 18;
  • FIG. 3 is a table of reaction conditions and reaction results of Examples 19 to 33;
  • FIG. 4 is a table showing the reaction conditions and the reaction results of Examples 34 to 51, and
  • FIG. 5 is a table showing the reaction conditions and the reaction results of Examples 52 to 58.
  • FIG. 1 shows the structural formulas of the phosphine-palladium (II) complexes synthesized in Examples 1 to 9.
  • 1,2-bis (dimethylphosphino) benzene was prepared as follows. That is, THF (50 mL) was placed in a 250 mL Schlenk-type reaction tube equipped with a stir bar coated with polytetrafluoroethylene under an argon atmosphere, and then lithium aluminum hydride (3 9 g, 10 2.8 mm 0 I) was added. The reaction solution was cooled to 178 ° C, and trimethylsilane (12.9 mL, 102.5 mmo I) was carefully added dropwise using a syringe, followed by stirring at room temperature for 2 hours. .
  • Example 2 In accordance with Example 1, 1 chloride to give 2- bis (dimethyl phosphine Ino) Etanpa radium (P d CI 2 (dmpe) ). The 1,2-bis (dimethylphosphino) ethane was manufactured by FIuka.
  • Example 1 In accordance with Example 1, to obtain a chloride 1, 4 one-bis (diphenyl phosphine Ino) pigs emissions palladium (P d CI 2 (dppb) ).
  • the 1,4-bis (diphenylphosphino) butane was manufactured by Tokyo Chemical Industry.
  • 1,2-bis [di (3,5-xylyl) phosphino] ethanepalladium chloride was obtained.
  • 1,2-bis [di (3,5-xylyl) phosphino] ethane was prepared as follows. That is, a stir bar was placed in a 500 mL two-necked flask equipped with a reflux cooler, finely cut metallic lithium (0.07 g, 10.1 mm 0 I) was added, and a septum rubber cap was added. And closed the mouth. Under an argon atmosphere, degassed hexane (5 mL) was added with a syringe, and after stirring for 5 minutes, the hexane was removed. This operation was repeated three times.
  • 1,2-bis [di (4-methoxyphenyl) phosphino] ethanepalladium chloride was obtained.
  • 1,2- [di (4-methoxyphenyl) phosphino) ethane was prepared as follows. That is, In a 100 mL two-necked flask equipped with a stirrer coated with tetrafluoroethylene, put metallic magnesium (291.5 mg, 12.Ommo), and add THF (1 A solution of 2.5 mL, prepared beforehand, of 4-bromoanisole. 5 mL, 12 mm 0 I) (manufactured by Tokyo Chemical Industry Co., Ltd.) (2.5 mL) was added dropwise with a syringe.
  • Examples 10 to 18 described below show examples of producing an alkene compound by partially hydrogenating an alkyne compound using a phosphine-palladium (II) complex of each type.
  • FIG. 2 is a table showing the reaction results of Examples 10 to 18.
  • PdCI 2 (dmpb) (l.5 mg, 4.0 moI) obtained in Example 1 was placed in a 100-mL glass-made autoclave equipped with a stirrer coated with polyethylene glycol. I weighed it. The air in the autoclave was replaced with argon, and 3-hexine (4.56 ⁇ m, 4.0 mm 01), which had been degassed by argon bubbling, 2-propanol (4 mL), and tert-Butoxy potassium solution in 2-methyl-2-propanol (1 M ) (48 L, 48 moI) was added with a syringe under a stream of argon.
  • the gas supply tube was used to connect the storage tube to the hydrogen cylinder, and the air in the introduction tube was replaced three times with 2 atmospheres of hydrogen. Subsequently, the operation of carefully introducing 5 atm of hydrogen into the storage clave and then carefully releasing it to 2 atm was repeated 10 times, and then the hydrogen pressure was set to 8 atm and the solution was violently heated at 25 ° C for 1 hour. Stirred. Conversion cis Bruno trans selectivity was determined by '3 CNMR analyzes. Conversion,>95%; cis Z transratio, 94: 6.
  • Examples 19 to 33 below show examples of producing 41-year-old octene by adding various additives and partially hydrogenating 41-year-old cutin using a phosphine-palladium (II) complex.
  • FIG. 3 is a table showing the reaction results of Examples 19 to 33.
  • PdC (dppp) 1.5 mg, 2.5 ⁇ oI synthesized in Example 5 was added to a 100 mL glass-made autoclave equipped with a stirrer coated with polyethylene glycol. I weighed it. The air in the autoclave was replaced with argon, and 4-butane cutin (373 tL, 2.54 mmoI), 2-propanol (2 m), and tert-degassed in advance by argon bubbling.
  • FIG. 4 shows the reaction conditions and reaction results at that time.
  • each alkyne compound was partially hydrogenated using a phosphine-palladium (II) complex to produce the corresponding alkyne compound.
  • FIG. 5 shows the reaction conditions and reaction results at that time.
  • the method for producing a hydrogenation catalyst and an alkene compound of the present invention can be used for obtaining carbon-carbon double bonds contained in many physiologically active substances such as fatty acids, fragrances, pheromones, and pharmaceuticals and agricultural chemicals. It can also be used for industrial synthesis of polymer raw materials such as paints and films.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne la conversion d'un alkyne interne en un cis-alcène ou la conversion d'un alkyne terminal en un alcène terminal qui peut être réalisée par le biais de l'hydrogénation partielle d'un alkyne en tant que substrat doté d'une quantité catalytique de chlorure de [1,2-bis(diphényl-phosphino)propane]palladium dans un solvant mélangé renfermant du diméthylformamide et un alcool en présence de t-butoxyde de potassium ou de borohydrure de sodium et en présence d'hydrogène.
PCT/JP2003/001355 2002-02-12 2003-02-10 Catalyseur d'hydrogenation et procede de production d'alcenes WO2003068391A1 (fr)

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JP2002034427A JP2003236386A (ja) 2002-02-12 2002-02-12 水素化触媒及びアルケン化合物の製造方法

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN111774096A (zh) * 2020-07-14 2020-10-16 厦门大学 一种用硫醇类配体修饰的催化剂及其制备方法与应用

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WO2005094993A1 (fr) 2004-03-31 2005-10-13 Nagoya Industrial Science Research Institute Promoteur d’hydrogenation, catalyseur d’hydrogenation, et procede de fabrication d’alcenes
JP4576584B2 (ja) * 2005-01-31 2010-11-10 独立行政法人科学技術振興機構 リン含有高分子固定化パラジウム触媒およびその使用
US9732015B2 (en) 2015-05-29 2017-08-15 Uop Llc Process for the selective hydrogenation of acetylene to ethylene

Citations (1)

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Publication number Priority date Publication date Assignee Title
EP0560532A1 (fr) * 1992-03-09 1993-09-15 Nissan Chemical Industries Ltd. Préparation de cis-oléfines

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0560532A1 (fr) * 1992-03-09 1993-09-15 Nissan Chemical Industries Ltd. Préparation de cis-oléfines

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111774096A (zh) * 2020-07-14 2020-10-16 厦门大学 一种用硫醇类配体修饰的催化剂及其制备方法与应用
CN111774096B (zh) * 2020-07-14 2021-12-03 厦门大学 一种用硫醇类配体修饰的催化剂及其制备方法与应用

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