WO2003068391A1

WO2003068391A1 - Hydrogenation catalyst and process for production of alkenes

Info

Publication number: WO2003068391A1
Application number: PCT/JP2003/001355
Authority: WO
Inventors: Takeshi Ohkuma; Makoto Yoshida; Ryoji Noyori
Original assignee: Nagoya Industrial Science Research Institute
Priority date: 2002-02-12
Filing date: 2003-02-10
Publication date: 2003-08-21
Also published as: AU2003207190A1; JP2003236386A

Abstract

The conversion of an internal alkyne into a cis-alkene or that of a terminal alkyne into a terminal alkene can be carried out by conducting partial hydrogenation of an alkyne as the substrate with a catalytic amount of [1,2-bis(diphenyl- phosphino)propane]palladium chloride in a mixed solvent consisting of DMF and an alcohol in the presence of potassium t-butoxide or sodium borohydride and in the presence of hydrogen.

Description

Specification

TECHNICAL FIELD 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. Background branch art

Conventionally, in the partial hydrogenation reaction of an alkyne compound to an alkene compound, a study using a transition metal catalyst such as palladium or nickel has been conducted. For example, H. Lind Iar performs partial hydrogenation of alkyne compounds using a catalyst prepared by poisoning metal palladium supported on calcium carbonate with lead acetate, and highly selectively converts cis-alkene compounds. Reported that it could be obtained. This catalyst is currently commonly used for its high activity and high cis selectivity.

However, some catalytic hydrogenations using metal complexes using alkyne compounds having various functional groups as substrates have been reported.However, there are few research examples and the applicable range is limited. ing. In addition, many of these compounds, when stirred for a long time, reduce the product alkene compound to produce an alkane compound, or the cis alkene compound isomerizes to give a more stable trans alkene compound. Have the drawbacks. Therefore, there has been a demand for the development of a catalyst for partially hydrogenating an alkyne compound with high activity and a catalyst for partially hydrogenating an alkyne compound to give a cis-alkene compound with high selectivity. 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.

_R 13 _R 14

(In the general formula (1), 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,

—In the general formula (2), R ² ′ to R ²⁴ are the same or different and may have a substituent, and Y ² ′ to 丫 ″ 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. A good anion,

In the general formula (3), 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 ) _π— 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. Usually, 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. . Also, 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. with its, if R and R ^'2, R' ³ and R ^'4 form a ring, R R ^12, R ^'3 and R "may combine to form a carbon chain, alkyl on the carbon chain, alkenyl Le, cycloalkyl, Ariru, alkoxy, ester, Ashiru old alkoxy, halogen atom, Two Bok port, Those having various allowable substituents such as a cyano group may be selected. Here, in consideration of the ease of synthesis and the ease of availability, 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. Further, X in the general formula (1)" 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. And 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 In consideration of the ease of synthesis and the ease of availability, 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. Also, the 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丫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. Further, the 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. For example, 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. Here, considering the synthesis of Chasse of and availability if put pyramid, etc., 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. When a trivalent or tetravalent palladium complex is used as the starting material, the reduction of the palladium atom is required by the final stage. 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 200 ° C. to obtain a phosphine-palladium complex.

When the phosphine-palladium complex represented by any of the general formulas (1) to (3) is used as a partial hydrogenation catalyst for an alkyne compound, 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.

Using the phosphine-palladium complex represented by any of the general formulas (1) to (3), 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. In addition, 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. Can be.

Here, 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. In addition, 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. As the reaction solvent, 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. Can be 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. Examples of the coordinating solvent 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. Here, the reaction solvent is preferably DMF or DMF and an alcohol solvent (particularly tert-butanol).

Although 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.

In this partial hydrogenation reaction, further additives may be added. Such additives include N, N, N ', N'tetramethylethylenediamine (TMEDA), N, N'-dimethylethylenediamine, ethylene glycol, N, N-dimethyl Examples include aminoethanol, phenol, aniline, benzonitrile, p-nitrophenol, triphenylphosphinoxide, trifluroethanol, water or quinoline. By adding these additives, depending on the reaction system, it is possible to suppress the isomerization of the cis-alkene compound to the trans-argen compound or to suppress the over-reduction of the alkene compound to the alkane compound. Can be.

When the phosphine-palladium complex represented by any of the general formulas (1) to (3) is used, 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 By partially hydrogenating alkyne compounds having various functional groups such as alkyne compounds having an amino group, alkynyl ketones, and enynes, the corresponding alkenes can be produced in a high yield or in a highly cis-selective manner. Or you can. BRIEF DESCRIPTION OF THE FIGURES

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. BEST MODE FOR CARRYING OUT THE INVENTION

Examples 1 to 9 below show examples of the synthesis of phosphine-palladium (II) complex. FIG. 1 shows the structural formulas of the phosphine-palladium (II) complexes synthesized in Examples 1 to 9.

[Example 1]

In a 20-mL Schlenk-type reaction tube equipped with a stirrer, weigh bis (acetonitol) palladium (65.4 mg, 0.25 mmoI) and place it under argon atmosphere. , 2-Dichloroethane (2 mL) and 1,2-bis (dimethylphosphino) benzene (50 mg, 0.25 mmol) were added, and the mixture was stirred in a 50 ° C oil bath for 2 hours. After cooling to room temperature, hexane (4 mL) was added to precipitate an orange precipitate. The solid obtained by suction filtration under reduced pressure (1 mmH g) chloride 1 pale orange dried to give 2- bis (dimethyl phosphinate Roh) benzene palladium _{(P d CI 2 (dmpb)} ) a.

In addition, 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. . After cooling to 30 ° C, a pre-prepared solution of tetramethyl-1,2-phenylenediphosphonate (5 • 0 g, 17.Ommo in THF (50 mL)) was injected into the syringe. Using After the dropwise addition, the mixture was stirred at room temperature for 36 hours. Degassed distilled water (25 mL) was added little by little, and then a 1 N aqueous sodium hydroxide solution (15 mL) was added. Degassed getyl ether (50 mL) was added with a syringe, stirred for 5 minutes, and allowed to stand. The organic layer was transferred by force to another Schlenk equipped with a stir bar and sodium sulfate (10 g). This extraction operation was repeated three times. The reaction solution was transferred to another Schlenk equipped with a stirrer with a force, and the solvent was distilled off under reduced pressure. The crude product was transferred to a 1 OmL eggplant-shaped flask by means of a pressure vessel, and subjected to simple distillation under reduced pressure to give colorless liquid 1,2-bis (phosphino) benzene (1.91 g, yield 7). 9.1%). Next, a 75 mL Schlenk-type reaction tube equipped with a stirrer coated with polytetrafluoroethylene was added to dimethyl ether (15 mL) degassed in an argon atmosphere and 1,2-bis (phosphine). ) Benzene (500.0 mg, 3.5 mmoI) was added. The mixture was cooled to 178 ° C., a hexane solution of 1.6 M n-butyllithium (5 mL, 8.1 mmol) was added, and the mixture was stirred for 30 minutes. Methyl iodide (0.5 mL, 8.1 mm 0 I) was added, and the mixture was stirred at room temperature for 1 hour. Cool again to −78 ° C., add 1.6 M n-butyllithium hexane solution (5.3 mL, 8.4 mm 0 I), stir for 30 minutes, and add methyl iodide ( 0.5 mL, 8.4 mmoI) was added, and the mixture was stirred at room temperature for 2 hours. Degassed distilled water (25 mL) was added with a syringe, stirred for 3 minutes, and allowed to stand. The organic layer was transferred to another Schlenk equipped with a stir bar and sodium sulfate (5 g) by force, and after stirring, transferred to another Schlenk equipped with a stir bar with force, and the solvent was distilled under reduced pressure. I left. The product was transferred to a 5-mL eggplant-shaped flask with a power flask and subjected to simple distillation under reduced pressure to form a colorless liquid of 1,2-bis (dimethylphosphino) benzene (641.9 mg, yield 92.0). %).

[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 3]

Analogously as described in Example 1 to obtain a bis chloride (Kishiruhosufino dicyclohexyl) Metanpa radium _{(P d CI 2 (dcpm)} ). The bis (hexylphosphine) methane used was manufactured by AI drich.

[Example 4]

In accordance with Example 1, 1 chloride to give 2- bis (diphenyl phosphine Ino) Etan palladium _{(P d CI 2 (dppe)} ). The 1,2-bis (diphenylphosphino) ethane was manufactured by Tokyo Chemical Industry.

[Example 5]

In accordance with Example 1, 1 chloride to give 2- bis (diphenyl phosphine Ino) propane palladium _{(P d CI 2 (dppp)} ). The 1,2-bis (diphenylphosphino) propane used was manufactured by Tokyo Chemical Industry Co., Ltd.

[Example 6]

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.

[Example 7]

In a 20 mL Schlenk-type reaction tube equipped with a stirrer coated with polytetrafluoroethylene, weigh potassium tetrachloride (II) (1000.0 mg, 0.31 mmoI) and distill it Water (4 mL) was added. Hemethyldiphenylphosphine (115, 0.62 mm 0 I) (manufactured by Tokyo Kasei Co., Ltd.) was weighed and stirred at room temperature for 3 hours. After adding dichloromethane (5 mL) and stirring, the aqueous layer was removed with a syringe. Hexane in organic layer Was added to precipitate a yellow precipitate, and the solid obtained by filtration was filtered under reduced pressure (

1 mmH g) in dried yellow bis (methyl diphenyl phosphine) palladium _{(P d CI 2 (M e} P h 2 P) 2, yields 1 0 7. 9 mg, yield 6 1.0) The Obtained.

[Example 8]

According to Example 1, 1,2-bis [di (3,5-xylyl) phosphino] ethanepalladium chloride was obtained. In addition, 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. A THF solution (20 mL) of bis (3,5-xylyl) phosphine (1.5 mL, 6.5 mm0 I) prepared in advance was added by a syringe to the solution at room temperature. Stir for 5 hours. Further, a THF solution (5 mL) of 1,2-dichloroethane (0.4 mL, 5.1 mmol) prepared in advance was carefully added dropwise using a syringe, and the mixture was refluxed at 80 ° C for 30 minutes. . After cooling to room temperature, distilled water (30 OmL) was added with a syringe. The solid obtained by suction filtration under reduced pressure (1 mmH g) in dried white chloride 1, 2-bis [di (3, 5-xylyl) Hosufuino] Etan palladium _{(P d CI 2 (dxpe)} , A yield of 372.1 mg (yield 11.2%) was obtained.

[Example 9]

In accordance with Example 1, 1,2-bis [di (4-methoxyphenyl) phosphino] ethanepalladium chloride was obtained. In addition, 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. Thereafter, the mixture was stirred for 1.5 hours. The reaction solution was cooled to 0 ° C, and a previously prepared solution of 1,2-bis (dichlorophosphino) ethane (302 tL, 2 mm0I) (manufactured by AI drich) in THF (2.5 m L) was added using a syringe, and the mixture was stirred at room temperature for 21 hours. After cooling to 0 ° C, a saturated aqueous ammonium chloride solution (5 OmL) was added, and the mixture was filtered through a glass filter to remove impurities. The organic layer was collected and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure to obtain an oil, and then cooled 2-propanol (5 mL) was added to precipitate a solid. 1 as a white powder by causing suction filtration and dried under reduced pressure (1 mmH g), 2-bis [di (4-menu Bok Kishifueniru) Hosufuino] Etan _{(P d CI 2 (dmppe)} , yield 44 9.1 mg, yield 43.3%).

Next, 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.

[Example 10]

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 μm, 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 11 to 18]

Using each of the phosphine-palladium (II) complexes obtained in Examples 2 to 9, the alkyne compound was partially hydrogenated under the conditions shown in FIG. 2 according to Example 10 and the results are shown in the table. An alkene compound was obtained with a conversion and cis-Z trans selectivity.

Next, 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.

[Example 19]

PdC (dppp) (1.5 mg, 2.5 μηιoI) 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. A solution of potassium butoxy in 2-methyl-2-propanol (1 M) (31 ML, 31 Mm 0 I) and a previously prepared 1.0 M solution of TMEDA (Hanei Co., Ltd.) in 1 M 2.7 μ, and 12.7 μ.moI) were added with a syringe under a stream of argon. Use the gas inlet pipe The clave was connected to a hydrogen cylinder, and the air in the inlet tube was replaced three times with 2 atm of hydrogen. Subsequently, the operation of carefully releasing hydrogen up to 2 atm after introducing 5 atm of hydrogen into the auto crepe was repeated 10 times, then the hydrogen pressure was increased to 8 atm and the solution was vigorously stirred at 25 ° C for 30 minutes. did. Conversion (GC), 100%; cis / trans ratio, 98.2: 1.8; n-octane, 0%.

[Examples 20 to 33]

When 4-year-old cutin was partially hydrogenated under the conditions shown in FIG. 3 according to Example 19, 4-octene was obtained with the conversion and cis-Z trans selectivity shown in the table.

[Example 34-5 1]

In Examples 34 to 51, 4-octene was partially hydrogenated using phosphine-palladium (II) complex in various reaction solvents to produce 4-octene. FIG. 4 shows the reaction conditions and reaction results at that time.

[Examples 52 to 58]

In Examples 52 to 58, 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. Industrial applicability

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.

Claims

The scope of the claims

1. A hydrogenation catalyst for partially hydrogenating an alkyne compound to an alkene compound,

A hydrogenation catalyst comprising at least one selected from the group consisting of the general formulas (1) to (3) as a main component.

R <Shikabane ²

\ ノ "

(CH ₂ ) _n Pd (1)

p / ヽ X ¹²

/ \

R35 _R 36 (- In general formula (1), n is any integer of 1 ~5, R''~ R ¹⁴ may hydrocarbon which may have a well-substituent be different even in the same X '' and X ' ² are anions which may be the same or different,

In the general formula (2), R "~ R 24 is a hydrocarbon group which may have a substituent rather good be different even in the same, Y ^Z '~Y" is same as has filed May be hydrogen, a hydrocarbon group which may have a substituent, a halogen, an alkoxy group or an amino group, and X ² ′ and X ²² may be the same or different. And

2. —The hydrogenation catalyst according to claim 1, wherein in the general formula (1), n is an integer of any one of 1 to 4.

3. - In general formula (1), according to claim R "to R ^'4, which may be different even in the same, alkyl, optionally phenylene Le have a cycloalkyl or a substituent 3. The hydrogenation catalyst according to 1 or 2.

4. In the general formula (2), R ² ′ to R ²⁴ may be the same or different, and are alkyl, cycloalkyl or phenyl which may have a substituent. 4. The hydrogenation catalyst according to any one of claims 1 to 3.

5. —In the general formula (3), R ³ ′ to R ″ may be the same or different and are alkyl, cycloalkyl or phenyl which may have a substituent. 5. The hydrogenation catalyst according to any one of 1 to 4.

6. Using the hydrogenation catalyst according to any one of claims 1 to 5, 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.

Manufactures alkene compounds by partially hydrogenating alkyne compounds as reaction substrates For producing an alkene compound.

7. The method for producing an alkene compound according to claim 6, wherein the internal alkyne compound is partially hydrogenated to produce a cis alkene compound, or the terminal alkyne compound is partially hydrogenated to produce a terminal alkene compound.

8. The method for producing an alkene compound according to claim 6 or 7, wherein the hydrogenation catalyst is used in an amount of 100 to 1000 equivalents to the reaction substrate.

9. The method for producing an alkene compound according to any one of claims 6 to 8, wherein the reaction solvent is a protic solvent, an aprotic solvent, a coordinating solvent, or a mixed solvent thereof.

10. The method for producing an alkene compound according to any one of claims 6 to 9, wherein the reaction solvent is N, N-dimethylformamide or a mixed solvent of N, N-dimethylformamide and an alcohol.

1 1. Additives Ν, Ν, Ν ', Ν'-tetramethylethylenediamine, Ν, Ν'-dimethylethylenediamine, ethylene glycol, Ν, Ν-dimethylaminoethanol, phenol, aniline, The process for producing an argen compound according to any one of claims 6 to 10, wherein the partial hydrogenation is carried out by adding benzonitrile, ρ12-trophenol, triphenylphosphinoxide, trifluroylethanol, water or quinoline. .