WO2013005621A1

WO2013005621A1 - Palladium complex and method for producing same, method for producing vinyl ether compound, and method for collecting palladium complex

Info

Publication number: WO2013005621A1
Application number: PCT/JP2012/066396
Authority: WO
Inventors: 橋爪知弘; 原田伸彦
Original assignee: 株式会社ダイセル
Priority date: 2011-07-01
Filing date: 2012-06-27
Publication date: 2013-01-10
Also published as: CN103635480A; JPWO2013005621A1; KR20140041711A

Abstract

Provided is a palladium complex having high heat resistance and a high activity on a transvinylation reaction. This palladium complex is represented by formula (1). L¹Pd(CH₂COOR¹)X (1) [In formula (1), L¹ represents a bidentate ligand having at least two nitrogen atoms in the molecule; X represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or a tetrafluoroborate group; R¹ represents a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, a heteroaryl group, a polyoxyalkylene residue represented by [R^bO-(R^aO)_rR^a-], or a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group or a heteroaryl group each of which has at least one substituent selected from the group consisting of a hydroxy group, a carbonyl group, a cyano group, an alkoxy group, an oxetanyl group and a vinyloxy group; R^a represents an alkylene group; R^b represents a hydrogen atom, an alkyl group, an acyl group or a vinyl group; and r represents an integer of 1 to 20.]

Description

Palladium complex and method for producing the same, method for producing vinyl ether compound, and method for recovering palladium complex

The present invention relates to a palladium complex, a method for producing the same, and a method for producing a vinyl ether compound. More specifically, the present invention relates to a palladium complex having excellent heat resistance, a method for producing the same, and a method for producing a vinyl ether compound capable of obtaining a target vinyl ether compound in a high yield by a vinyl exchange reaction. Furthermore, it is related with the method of collect | recovering the palladium complex which maintained activity with high recovery.

Until now, a vinyl exchange reaction between a vinyl ether compound (vinyl ether) and an alcohol compound (alcohol) using a palladium catalyst (Pd catalyst) is known (see Non-Patent Document 1, Patent Documents 1 and 2). Specifically, Non-Patent Document 1 and Patent Document 1 disclose that a palladium complex prepared from palladium acetate and 1,10-phenanthroline has activity in a vinyl exchange reaction. Further, in Patent Document 2, when a new vinyl ether is produced in a solution by subjecting an alcohol and an alkyl vinyl ether to a vinyl exchange reaction in the presence of a catalyst, the dissolved oxygen concentration in the solution is controlled to 10 ppm or more. It is disclosed that the yield of the vinyl exchange reaction is improved. *

JP-A-9-87224 Japanese Patent Laid-Open No. 2003-206251

When an alcohol compound that is solid at room temperature or has low solubility in an organic solvent is used as a reactant (substrate) of the above-described vinyl exchange reaction, the reaction temperature is increased in order to promote the vinyl exchange reaction uniformly in the solution. Specifically, it has been required to react at a temperature exceeding 60 ° C. On the other hand, since palladium, which is a raw material of the palladium catalyst used for the vinyl exchange reaction, is expensive, from the viewpoint of reducing the amount of the palladium catalyst used, the speed of the vinyl exchange reaction can be increased while reducing the amount of the catalyst used. For the purpose, it was required to increase the reaction temperature.

However, Non-Patent Document 1 and Patent Document 1 disclose only a specific vinyl exchange reaction at a reaction temperature of 60 ° C. or lower, and further, by performing a vinyl exchange reaction at a reaction temperature exceeding 60 ° C. No mention is made of improving the yield of the product. In addition, Patent Document 2 also discloses only a specific vinyl exchange reaction at a reaction temperature of 40 ° C. or lower.

Therefore, when the vinyl exchange reaction described in Non-Patent Document 1 and Patent Document 1 was carried out at a reaction temperature exceeding 60 ° C., the palladium catalyst was deactivated, the reaction solution turned black, and the vinyl exchange reaction was in progress. It became clear that it stopped at. Further, in the method of performing the vinyl exchange reaction while bubbling oxygen described in Patent Document 2, when the reaction temperature is increased to a temperature exceeding 60 ° C., the palladium catalyst is similarly deactivated during the reaction. It became clear to do. For this reason, the present condition is that the palladium complex with high heat resistance which is hard to deactivate even when a vinyl exchange reaction is carried out at a higher reaction temperature is required.

On the other hand, in Patent Document 2, as a method of increasing the dissolved oxygen concentration in the reaction solution in order to promote the vinyl exchange reaction, a method of performing a vinyl exchange reaction by pressurizing to 5 MPa with pure oxygen, and a hydrogen peroxide solution Two methods of carrying out the vinyl exchange reaction while dropping are disclosed. However, since the former method uses pure oxygen, in addition to the problem of safety, there is a problem that a high-pressure facility is required and the facility cost becomes high when industrially implemented. In addition, the latter method has a problem that the vinyl ether compound may be decomposed (hydrolyzed) into alcohol and acetaldehyde by moisture contained in the hydrogen peroxide solution, and both methods are sufficiently satisfactory. It wasn't the way.

Furthermore, from the viewpoint of resource saving and cost reduction, it is desirable that the catalyst in the above-described vinyl exchange reaction be reusable. In particular, when the product has a high boiling point, the product and the catalyst For example, when the catalyst and the product are separated by distillation under reduced pressure with heating, the catalyst is deteriorated and cannot be reused.

Accordingly, an object of the present invention is to provide a palladium complex which is not easily deactivated even when the reaction is carried out at a high temperature, has high heat resistance, and has high activity (catalytic ability) for vinyl exchange reaction. is there.
Another object of the present invention is to produce a palladium complex which is not easily deactivated even when the reaction is carried out at high temperature, has high heat resistance, and has high activity (catalytic ability) for vinyl exchange reaction. The object is to provide a method for producing a palladium complex.
Furthermore, the other object of this invention is to provide the manufacturing method of the vinyl ether compound which can obtain the target vinyl ether compound with a high yield.
Furthermore, another object of the present invention is to provide a method for recovering a palladium complex in which the palladium complex of the present invention can be easily recovered and the deterioration of the palladium complex during recovery is suppressed.

As a result of intensive studies to solve the above problems, the present inventors have found that a palladium complex having a specific structure is not easily deactivated even when the reaction is carried out at a high temperature (that is, excellent in heat resistance). It has been found that it has a high activity for the exchange reaction. In addition, the present inventors specify a specific divalent palladium complex, a specific bidentate ligand, and a vinyl ether compound (or a specific divalent palladium complex and a vinyl ether compound) in the presence of oxygen. It was found that a palladium complex having excellent heat resistance and high activity with respect to a vinyl exchange reaction can be obtained by a method of reacting under conditions. Furthermore, the present inventors have found that a target vinyl ether compound can be obtained in a high yield by a vinyl exchange reaction using a palladium complex having a specific structure. Furthermore, the present inventors can easily recover the palladium complex of the present invention by adding water and a specific organic solvent to the reaction solution after the vinyl exchange reaction and separating the aqueous layer, and at the time of recovery. It has been found that the degradation of the palladium complex is suppressed. The present invention has been completed based on these findings.

That is, the present invention provides a palladium complex represented by the following formula (1).

[In formula (1), L ¹ represents a bidentate ligand having two or more nitrogen atoms in the molecule. X represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or tetrafluoroborate. R ¹ is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, a heteroaryl group, [R ^b O— (R ^a O) _r R ^a — Or a polyoxyalkylene residue represented by the formula: or a hydroxyl group, a carbonyl group, a cyano group, an alkoxy group, an oxetanyl group, and a vinyloxy group, and having 1 to 18 carbon atoms having at least one substituent. A linear or branched alkyl group, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, or a heteroaryl group is shown. R ^a represents an alkylene group, R ^b represents a hydrogen atom, an alkyl group, an acyl group, or a vinyl group, and r represents an integer of 1 to 20. ]

Further, L ¹ is a bipyridine derivative or a 1,10-phenanthroline derivative, X is an acetyloxy group, R ¹ is a linear or branched alkyl group having 1 to 10 carbon atoms, or 3 to 10 carbon atoms. A cycloalkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms having one or more hydroxyl groups, a linear or branched alkyl group having 1 to 10 carbon atoms having one or more vinyloxy groups, or , [HO— (CH ₂ CH ₂ O) _s CH ₂ CH ₂ —] or [CH ₂ ═CHO— (CH ₂ CH ₂ O) _s CH ₂ CH ₂ —] Represents an integer of 1 to 4).

Further, L ¹ is 2,2′-bipyridine or 1,10-phenanthroline, and R ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Provided is a palladium complex as described above.

Further, the present invention is a method for producing a palladium complex represented by the following formula (1), which is a divalent palladium complex represented by the following formula (2), and has two or more nitrogen atoms in the molecule. A reaction step of reacting a bidentate ligand and a vinyl ether compound represented by the following formula (3) in the presence of oxygen, wherein the reaction step is allowed to react at a temperature of 20 to 60 ° C. for 0.3 hours or more. Including a first reaction step and a second reaction step after the first reaction step and further reacting at a temperature of 40 to 120 ° C. for 0.3 hours or longer, and the reaction temperature is controlled to 120 ° C. or lower throughout the reaction. A process for producing a palladium complex, which is characterized by the following steps.

[In Formula (2), X ¹ and X ² are the same or different and each represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or a tetrafluoroborate. Show. L represents a monodentate ligand having one or more nitrogen atoms in the molecule, or a bidentate ligand having two or more nitrogen atoms in the molecule. n represents an integer of 0 or more. ]

[In formula (3), R ¹ is the same as above. ]

Moreover, this invention is a manufacturing method of the palladium complex represented by following formula (1), Comprising: The bivalent palladium complex represented by following formula (2), and the vinyl ether compound represented by following formula (3) Is reacted in the presence of oxygen, and the reaction step includes a first reaction step of reacting at a temperature of 20 to 60 ° C. for 0.3 hours or more, and a further 40 to 40 after the first reaction step. And a second reaction step in which the reaction is performed at a temperature of 120 ° C. for 0.3 hours or longer, and the reaction temperature is controlled to 120 ° C. or lower throughout the reaction. .

[In Formula (2), X ¹ and X ² are the same or different and each represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or a tetrafluoroborate. Show. L represents a bidentate ligand having two or more nitrogen atoms in the molecule. n represents an integer of 1 or more. ]

[In formula (3), R ¹ is the same as above. ]

Further, L ¹ is 2,2′-bipyridine or 1,10-phenanthroline, and R ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. A method for producing the palladium complex is provided.

In the present invention, an alcohol compound represented by the following formula (4) is reacted with a vinyl ether compound represented by the following formula (5) in the presence of the palladium complex, and represented by the following formula (6). A method for producing a vinyl ether compound is provided.

[In the formula (4), R ² represents an organic group having a carbon atom at the bonding site with the oxygen atom shown in the formula, and p represents an integer of 1 or more. ]

[In the formula (5), R ³ to R ⁵ are the same or different and each represents a hydrogen atom or an organic group having a carbon atom at the bonding site with the carbon atom shown in the formula, and R ⁶ represents in the formula An organic group having a carbon atom at the bonding site with the oxygen atom. ]

[In formula (6), q represents an integer of 1 to p, and R ² to R ⁵ are the same as defined above. ]

Furthermore, as the palladium complex, a divalent palladium complex represented by the following formula (2), a bidentate ligand having two or more nitrogen atoms in the molecule, and a vinyl ether represented by the following formula (3) A first reaction step in which the compound is reacted at a temperature of 20 to 60 ° C. for 0.3 hours or more in the presence of oxygen; and after the first reaction step, further a temperature of 40 to 120 ° C. for 0.3 hours or more The vinyl ether compound using a palladium complex obtained by further isolation after reacting in a reaction step in which the reaction temperature is controlled to 120 ° C. or lower throughout the entire reaction, A manufacturing method is provided.

[In Formula (3), R ¹ represents a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, a heteroaryl group, [R ^b O— ( R ^a O) _r R ^a —] or at least one substituent selected from the group consisting of a hydroxyl group, a carbonyl group, a cyano group, an alkoxy group, an oxetanyl group, and a vinyloxy group A linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, or a heteroaryl group. R ^a represents an alkylene group, R ^b represents a hydrogen atom, an alkyl group, an acyl group, or a vinyl group, and r represents an integer of 1 to 20. ]

Further, as the above palladium complex, a divalent palladium complex represented by the following formula (2) and a vinyl ether compound represented by the following formula (3) are obtained at a temperature of 20 to 60 ° C. in the presence of oxygen. A first reaction step for reacting for 3 hours or more, and a second reaction step for reacting at a temperature of 40 to 120 ° C. for 0.3 hours or more after the first reaction step, and the reaction temperature is maintained throughout the reaction. Provided is a method for producing the above vinyl ether compound using a palladium complex obtained by further isolation after reaction in a reaction step controlled to 120 ° C. or lower.

Furthermore, as the palladium complex, a divalent palladium complex represented by the following formula (2), a bidentate ligand having two or more nitrogen atoms in the molecule, and a vinyl ether represented by the following formula (3) A first reaction step in which the compound is reacted at a temperature of 20 to 60 ° C. for 0.3 hours or more in the presence of oxygen; and after the first reaction step, further a temperature of 40 to 120 ° C. for 0.3 hours or more And a method for producing the vinyl ether compound using a palladium complex solution obtained by reacting in a reaction step in which the reaction temperature is controlled to 120 ° C. or lower throughout the reaction. .

Further, as the above palladium complex, a divalent palladium complex represented by the following formula (2) and a vinyl ether compound represented by the following formula (3) are obtained at a temperature of 20 to 60 ° C. in the presence of oxygen. A first reaction step for reacting for 3 hours or more, and a second reaction step for reacting at a temperature of 40 to 120 ° C. for 0.3 hours or more after the first reaction step, and the reaction temperature is maintained throughout the reaction. Provided is a method for producing the above vinyl ether compound using a palladium complex solution obtained by reacting in a reaction step controlled to 120 ° C. or lower.

In the present invention, an alcohol compound represented by the following formula (4) is reacted with a vinyl ether compound represented by the following formula (5) in the presence of the palladium complex, and represented by the following formula (6). To the reaction solution after the vinyl exchange reaction that produced the vinyl ether compound is added water and an organic solvent that is a good solvent for the vinyl ether compound represented by the following formula (6) and phase-separated from water, A method for recovering a palladium complex is provided, wherein the palladium complex is recovered by separating an aqueous layer.

Since the palladium complex of the present invention has the above configuration, it is difficult to deactivate even when the reaction is carried out at a high temperature, and has high heat resistance. Moreover, it has high activity with respect to vinyl exchange reaction. For this reason, when the palladium complex of the present invention is used, the vinyl exchange reaction can be carried out at a higher temperature, and the target vinyl ether compound can be obtained in a high yield. Furthermore, the palladium complex of the present invention can be used for the vinyl exchange reaction of compounds that are difficult to react at low temperatures (for example, those that are solid at room temperature or have low solubility in solvents). It is also advantageous in that the versatility of the vinyl exchange reaction can be expanded by making it possible to use it as a reactant (substrate). Moreover, according to the method for producing a palladium complex of the present invention, a palladium complex having high heat resistance and high activity for vinyl exchange reaction can be obtained. Furthermore, according to the method for producing a vinyl ether compound of the present invention, the target vinyl ether compound can be obtained in a high yield. Furthermore, according to the method for recovering a palladium complex of the present invention, the palladium complex and the product can be easily separated, and each can be recovered in a high yield, and further, it is not necessary to apply heat during the separation. The decrease in activity of the palladium complex is suppressed.

₂ is a chart of an IR spectrum of the palladium complex [Pd (OAc) (bpy) (CH ₂ COO—n—C ₃ H ₇ )] obtained in Example 1.

[Palladium Complex of the Present Invention]
The palladium complex of the present invention is a palladium complex represented by the following formula (1).

L ¹ in the formula (1) represents a bidentate ligand (nitrogen-containing bidentate ligand) having two or more nitrogen atoms in the molecule. The nitrogen-containing bidentate ligand has two or more nitrogen atoms in the molecule, and two of these nitrogen atoms form a coordination bond with palladium (palladium metal) to form a bidentate. It is not particularly limited as long as it is a compound that can form a complex by positioning, and for example, aromatic heterocyclic rings such as bipyridine derivatives (bipyridyl derivatives) and 1,10-phenanthroline derivatives (1,10-phenanthroline derivatives) Compound; Aliphatic diamine compound such as ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine and 2,4-pentanediamine; Alicyclic diamine compound such as 1,2-cyclohexanediamine; Aromatic diamine compound; Examples thereof include cyclic diamine compounds. The bipyridine derivative means a compound having a bipyridine skeleton (bipyridyl skeleton) and includes, for example, 2,2′-bipyridine, bipyridine having a substituent, and the like. The 1,10-phenanthroline derivative means a compound having a 1,10-phenanthroline skeleton (1,10-phenanthroline skeleton), such as 1,10-phenanthroline and 1,10-phenanthroline having a substituent. included.

The substituent in the bipyridine having the above substituent and the 1,10-phenanthroline having the above substituent is not particularly limited, and examples thereof include a linear or branched alkyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. Bridged cyclic groups such as adamantyl group and norbornyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; carbon atoms of 1 to 4 such as methoxy group, ethoxy group, propyloxy group, isopropyloxy group and butyloxy group An alkoxy group having 2 to 5 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; an acyl group having 1 to 10 carbon atoms such as an acetyl group, a propionyl group and a benzoyl group; a hydroxyl group (hydroxy group); a carboxyl group Cyano group; nitro group; oxo group and the like. That is, examples of the bipyridine having the above substituent include 2,2 ′-(4,4′-dimethyl) bipyridine, 2,2 ′-(4,4′-di-t-butyl) bipyridine, Examples include '-(4,4'-di-n-nonyl) bipyridine. Examples of the 1,10-phenanthroline having the above substituent include 2-hydroxy-1,10-phenanthroline, 3-hydroxy-1,10-phenanthroline, 4-hydroxy-1,10-phenanthroline, and 5-hydroxy. -1,10-phenanthroline and the like.

Among these, L ¹ is particularly preferably a bipyridine derivative or a 1,10-phenanthroline derivative, and more preferably 2,2′-bipyridine or 1,10-phenanthroline.

In addition, the bipyridine derivative and the 1,10-phenanthroline derivative, which are immobilized on a carrier by using a bipyridine derivative or 1,10-phenanthroline derivative supported on a solid such as a polymer, silica gel, alumina, or activated carbon, are used. It is also possible to obtain the palladium complex of the invention.

X in Formula (1) represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or tetrafluoroborate (BF ₄ : tetrafluoroborate ion). Show. Examples of the acyloxy group include an acetyloxy group (OCOCH ₃ ), a propanoyloxy group (OCOC ₂ H ₅ ), and a trifluoroacetyloxy group (OCOCF ₃ ). Examples of the halogen atom include a chlorine atom (Cl), a bromine atom (Br), a fluorine atom (F), and an iodine atom (I). Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group (OSO ₂ CH ₃ ) and an ethylsulfonyloxy group. Examples of the haloalkylsulfonyloxy group include a trifluoromethanesulfonyloxy group and a nonafluorobutanesulfonyloxy group. Examples of the arylsulfonyloxy group include a toluenesulfonyloxy group (OSO ₂ C ₆ H ₄ CH ₃ ). Examples of the haloarylsulfonyloxy group include a p-chlorobenzenesulfonyloxy group. Among these, X is preferably an acyloxy group, more preferably an acetyloxy group, in terms of easy availability of raw materials.

R ¹ in the formula (1) is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, a heteroaryl group, [R ^b O— (R ^a O) _r R ^a- ] or at least one selected from the group consisting of a hydroxyl group (hydroxy group), a carbonyl group, a cyano group, an alkoxy group, an oxetanyl group, and a vinyloxy group A linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, or a heteroaryl group having the above-described substituents.

Examples of the linear or branched alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a sec-butyl group, a pentyl group, and a hexyl group. Group, octyl group and the like. Examples of the cycloalkyl group having 3 to 18 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the heteroaryl group include various heteroaromatic ring groups containing heteroatoms such as oxygen, nitrogen, and sulfur (for example, thienyl group, furyl group, pyridyl group, pyrrolyl group).

Polyoxyalkylene residues - R ^a in ^{^{[[R b O- (R a}} O) r R a]] represents an alkylene group. Examples of the alkylene group include a linear or branched alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, a propylene group, and a butylene group (more preferably a linear or branched group having 1 to 10 carbon atoms). Chain alkylene group). R ^b in the polyoxyalkylene residue represents a hydrogen atom, an alkyl group, an acyl group, or a vinyl group. Especially, as said ^Rb , a hydrogen atom and a vinyl group are preferable, for example. In the polyoxyalkylene residue, r represents the number of repeating (R ^a O) units and represents an integer of 1 to 20.

Examples of the linear or branched alkyl group having 1 to 18 carbon atoms and having at least one substituent selected from the group consisting of the hydroxyl group, carbonyl group, cyano group, alkoxy group, oxetanyl group, and vinyloxy group include For example, an alkyl group having one or more hydroxyl groups [for example, a hydroxyalkyl group such as hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, 2,2-dimethyl-3-hydroxypropyl group, etc.] Alkyl group [eg, methyloxycarbonylmethyl group, ethyloxycarbonylmethyl group, carboxymethyl group, ethyloxycarbonylethyl group, carboxyethyl group, etc.] Alkyl group having one or more cyano groups [eg, cyanomethyl group, etc.] An amine having one or more alkoxy groups Kill group (alkoxyalkyl group) [for example, linear or branched alkoxyalkyl group such as methoxymethyl group, butoxymethyl group, ethoxyethyl group, butoxyethyl group, etc.] alkyl group having one or more oxetanyl groups [ For example, 3-ethyl-3-oxetanylmethyl group] alkyl group having one or more vinyloxy groups [eg, vinyloxyethyl group, vinyloxypropyl group, vinyloxybutyl group, 2,2-dimethyl-3-vinyl An oxypropyl group, a 6-vinyloxymethylcyclohexylmethyl group, a vinyloxyalkyl group such as a 6-vinyloxycyclohexyl group, etc.], an alkyl group having two or more of the above substituents [for example, 3-hydroxymethyloxetane-3- Ilmethyl group, 3-vinyloxymethyloxetane-3 Ylmethyl group, etc.] and the like.

Examples of the cycloalkyl group having 3 to 18 carbon atoms and having at least one substituent selected from the group consisting of the hydroxyl group, carbonyl group, cyano group, alkoxy group, oxetanyl group and vinyloxy group include one or more hydroxyl groups A cycloalkyl group having a [for example, 6-hydroxymethylcyclohexylmethyl group, 6-hydroxycyclohexyl group, etc.], a cycloalkyl group having one or more carbonyl groups [for example, a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, etc.], 1 A cycloalkyl group having the above cyano group [for example, 2-cyanocyclohexyl group, 3-cyanocyclohexyl group, 4-cyanocyclohexyl group, 2-cyanocyclopentyl group, 3-cyanocyclopentyl group, etc.] one or more alkoxy groups Have A cycloalkyl group [for example, a methoxycyclohexyl group, a propoxycyclohexyl group, an octoxycyclohexyl group, etc.] a cycloalkyl group having one or more oxetanyl groups, a cycloalkyl group having one or more vinyloxy groups, two or more of the above substituents And the like, and the like.

Examples of the aryl group having at least one substituent selected from the group consisting of the hydroxyl group, carbonyl group, cyano group, alkoxy group, oxetanyl group, and vinyloxy group include an aryl group having one or more hydroxyl groups [for example, Hydroxyphenyl group, dihydroxyphenyl group, trihydroxyphenyl group, tetrahydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, etc.] aryl group having one or more carbonyl groups [eg, benzoyloxy group, naphthyloxy group, etc.] An aryl group having one or more cyano groups [eg, cyanophenyl group, cyanonaphthyl group, etc.] An aryl group having one or more alkoxy groups [eg, methoxyphenyl group, propoxyphenyl group, butoxyphenyl group, etc.], 1 Oki more Taniru aryl group having a group, one or more aryl groups having a vinyloxy group [e.g., a vinyl oxy phenyl group, an aryl group having two or more of said substituents.

Examples of the heteroaryl group having at least one substituent selected from the group consisting of the hydroxyl group, carbonyl group, cyano group, alkoxy group, oxetanyl group, and vinyloxy group include, for example, a heteroaryl group having one or more hydroxyl groups [ For example, a hydroxyfuryl group, a hydroxythienyl group, a hydroxypyridyl group, etc.] a heteroaryl group having one or more carbonyl groups, a heteroaryl group having one or more cyano groups [for example, a cyanothienyl group, a cyanopyridyl group, etc.] A heteroaryl group having one or more alkoxy groups [eg, methoxypyridyl group, propoxypyridyl group, methoxythienyl group, etc.], heteroaryl group having one or more oxetanyl groups, heteroaryl group having one or more vinyloxy groups, 2 or more types of substituents Heteroaryl group which are mentioned.

Among these, as R ¹ , a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a straight chain or branched chain having 1 to 10 carbon atoms having one or more hydroxyl groups. A chain alkyl group (a hydroxyalkyl group in which one or more hydrogen atoms of a linear or branched alkyl group having 1 to 10 carbon atoms are substituted with a hydroxyl group), and one or more vinyloxy groups having 1 to 10 carbon atoms A linear or branched alkyl group (a vinyloxyalkyl group in which one or more hydrogen atoms of a linear or branched alkyl group having 1 to 10 carbon atoms is substituted with a vinyloxy group), HO— (CH ₂ CH ₂ O) _s —CH ₂ CH ₂ — (s represents the number of repeating oxyethylene units (CH ₂ CH ₂ O) and represents an integer of 1 to 4) or CH ₂ ═CHO— (CH ₂ CH ₂ O) _s -CH ₂ H ₂ - (s is as defined above) Polyoxyethylene residue preferably represented by, in particular, a vinyl ether compound as a raw material of the palladium complex in that it is readily available, straight-chain having 1 to 6 carbon atoms Alternatively, a branched alkyl group or a cycloalkyl group having 3 to 6 carbon atoms is preferable.

The palladium complex of the present invention is a palladium complex represented by the formula (1), and more specifically has a structure (complex structure) represented by the following formula (1 ′). Since the palladium complex of the present invention has a structure represented by the following formula (1 ′), it exhibits high heat resistance and high catalytic ability for vinyl exchange reaction.

The palladium complex of the present invention includes a divalent palladium complex represented by the following formula (2), a bidentate ligand (nitrogen-containing bidentate ligand) having two or more nitrogen atoms in the molecule, and the following formula: The vinyl ether compound represented by (3) can be produced by a method including a step of reacting in the presence of oxygen (referred to as “reaction step”).

In the palladium complex of the present invention, in particular, n in the divalent palladium complex represented by the above formula (2) is an integer of 1 or more, and L has 2 or more nitrogen atoms in the molecule. In the case of a bidentate ligand, a step of reacting a divalent palladium complex represented by the above formula (2) and a vinyl ether compound represented by the following formula (3) in the presence of oxygen (reaction step) ).

In the formula (2), X ¹ and X ² each represent an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or tetrafluoroborate. X ¹ and X ² may be the same or different. Examples of the acyloxy group, halogen atom, alkylsulfonyloxy group, haloalkylsulfonyloxy group, arylsulfonyloxy group, and haloarylsulfonyloxy group include those exemplified as X in the above formula (1). The X ¹ or X ^2, constitute the X in the formula (1).

In formula (2), L is a monodentate ligand (nitrogen-containing monodentate ligand) having one or more nitrogen atoms in the molecule, or a bidentate ligand (containing nitrogen atom having two or more nitrogen atoms in the molecule). Nitrogen bidentate ligand). The nitrogen-containing monodentate ligand has at least one nitrogen atom in the molecule, and one of these nitrogen atoms forms a coordinate bond with palladium (palladium metal) to form a monodentate coordination. It is a compound that can form a complex. Examples of the nitrogen-containing monodentate ligand include nitrile compounds such as acetonitrile and benzonitrile, ammonia, amine compounds (including cyclic amine compounds such as imidazole and imidazoline), and aromatic heterocyclic compounds such as pyridine. It is done. Examples of the nitrogen-containing bidentate ligand include those exemplified as L ¹ in the above formula (1) (particularly bipyridine derivatives and 1,10-phenanthroline derivatives).

In formula (2), n represents an integer of 0 or more. That is, the divalent palladium complex represented by the formula (2) may or may not have L. n is not particularly limited, but is preferably 0 to 4, and more preferably 0 to 2. In addition, when n is an integer greater than or equal to 2, each L may be the same and may differ.

In particular, when L in the formula (2) is a nitrogen-containing bidentate ligand (for example, a bipyridine derivative or a 1,10-phenanthroline derivative) and n is an integer of 1 or more, as described above, The palladium complex of the present invention can be produced without using a nitrogen-containing bidentate ligand in the reaction step. However, even in such a case, a nitrogen-containing bidentate ligand may be used in the reaction step.

As the divalent palladium complex represented by the formula (2), for example, palladium acetate [Pd (OAc) ₂ ] and palladium trifluoroacetate [Pd (OCOCF ₃ ) ₂ ] are particularly easily available. , Palladium methanesulfonate [Pd (OSO ₂ CH ₃ ) ₂ ], palladium toluene sulfonate [Pd (OSO ₂ C ₆ H ₄ CH ₃ ) ₂ ], palladium chloride [PdCl ₂ ], palladium bromide [PdBr ₂ ], Palladium iodide [PdI ₂ ], bis (acetonitrile) palladium (II) dichloride [PdCl ₂ (CH ₃ CN) ₂ ], bis (benzonitrile) palladium (II) dichloride [PdCl ₂ (C ₆ H ₅ CN) ₂ ] , tetrafluoroborate tetrakis (acetonitrile) palladium _{(II) [Pd (BF 4} ) 2 (CH 3 CN) 4], 1,10- E-phenanthroline palladium dichloride, 1,10-phenanthroline palladium diacetate, 2,2'-bipyridine palladium dichloride, 2,2'-bipyridine palladium diacetate are preferred.

Examples of the nitrogen-containing bidentate ligand used as a reactant in the reaction step include those exemplified as L ¹ in the above formula (1), and in particular, bipyridine derivatives and 1,10-phenanthroline derivatives. And 2,2′-bipyridine and 1,10-phenanthroline are more preferable.

R ¹ in formula (3) is the same as described above (same as R ¹ in formula (1)), and specific examples include the above-described examples.

As the vinyl ether compound represented by the formula (3), for example, methyl vinyl ether, ethyl vinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, sec-butyl vinyl ether, Pentyl vinyl ether, hexyl vinyl ether, hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, cyclohexane dimethanol monovinyl ether, cyclohexane dimethanol divinyl ether and the like are preferable.

In the reaction step of the method for producing a palladium complex of the present invention, the divalent palladium complex represented by the formula (2), the bidentate ligand having two or more nitrogen atoms in the molecule, and the formula (3) The reaction of the vinyl ether compound represented (or the divalent palladium complex represented by formula (2) and the vinyl ether compound represented by formula (3)) is preferably allowed to proceed in solution. That is, the solution includes a divalent palladium complex represented by the formula (2), a bidentate ligand having two or more nitrogen atoms in the molecule, and a vinyl ether compound represented by the formula (3) (or A solution containing at least a divalent palladium complex represented by the formula (2) and a vinyl ether compound represented by the formula (3) (sometimes referred to as “complex preparation solution”).

In the method for producing a palladium complex of the present invention, a solvent may be used to obtain the complex preparation solution. The solvent is not particularly limited, but is preferably one that does not participate in the formation reaction of the palladium complex of the present invention. Specifically, for example, hexane, ethyl acetate, tetrahydrofuran, acetone, dimethylformamide, dimethyl sulfoxide, acetonitrile, toluene , Benzenemethanol, ethanol, propanol, butanol, diethylene glycol, triethylene glycol, tetraethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol monomethyl ether, and the like. A solvent can be used individually or in combination of 2 or more types. In addition, the manufacturing method of the palladium complex of this invention can also be implemented without using a solvent (namely, the said solution for complex preparation does not need to contain a solvent).

Although the usage-amount of the bidentate ligand (nitrogen-containing bidentate ligand) which has two or more nitrogen atoms in the said molecule | numerator is not specifically limited, 1 mol of bivalent palladium complexes represented by Formula (2) The amount is preferably 1 to 200 mol, more preferably 1.5 to 100 mol, and still more preferably 3 to 15 mol. If the amount used is less than 1 mole, the production of the palladium complex represented by the formula (1) may be insufficient. On the other hand, when the amount used exceeds 200 mol, it may be disadvantageous in terms of cost. In addition, as above-mentioned, when L in Formula (2) is a nitrogen-containing bidentate ligand and n is an integer greater than or equal to 1, it is not necessary to use a nitrogen-containing bidentate ligand. Good.

The amount of the vinyl ether compound represented by the above formula (3) is not particularly limited, but is preferably 1 to 300 mol, more preferably 1 mol relative to 1 mol of the divalent palladium complex represented by the formula (2). The amount is 5 to 200 mol, more preferably 10 to 100 mol, particularly preferably 5 to 100 mol. If the amount used is less than 1 mole, the production of the palladium complex represented by the formula (1) may be insufficient. On the other hand, when the amount used exceeds 300 moles, it may be disadvantageous in terms of cost.

In the method for producing a palladium complex of the present invention, known or commonly used additives can be used as long as the effects of the present invention are not impaired.

In the reaction step, a divalent palladium complex represented by the formula (2), a bidentate ligand having two or more nitrogen atoms in the molecule, and a vinyl ether compound represented by the formula (3) (or It is necessary to react the divalent palladium complex represented by the formula (2) and the vinyl ether compound represented by the formula (3) in the presence (coexistence) of oxygen (oxygen molecules). As a method for causing oxygen to exist, a method for bubbling oxygen in the above complex preparation solution, a method for causing oxygen to exist in the gas phase part of the reactor, hydrogen peroxide, peracetic acid, persulfuric acid, metachloroperbenzoic acid, etc. Examples thereof include a method of coexisting a compound capable of generating oxygen molecules such as an organic peroxide such as peracid and tertiary butyl hydroperoxide, but it is not particularly limited as long as oxygen can coexist. When oxygen is bubbled or oxygen is present in the gas phase of the reactor, pure oxygen may be used, or a mixed gas diluted with a gas other than oxygen such as nitrogen, helium, or argon may be used. May be. The concentration of oxygen in the mixed gas is not particularly limited, but is preferably 10% (volume%) or less from the viewpoint of safety. In the reaction step, oxygen (oxygen molecule) reacts with the vinyl ether compound represented by the above formula (3) to thereby form “CH ₂ COOR ^{1 in} the palladium complex of the present invention represented by the formula (1). "Is responsible for generating the structure."

The reaction step includes a first reaction step of reacting at a temperature of 20 to 60 ° C. for 0.3 hours or more, and a second reaction step of reacting at a temperature of 40 to 120 ° C. for 0.3 hours or more after the first reaction step. And the reaction temperature is controlled to 120 ° C. or lower throughout the reaction. Through such a reaction step, the palladium complex of the present invention can be obtained.

The temperature in the first reaction step (reaction temperature: T ₁ ) may be 20 to 60 ° C., and is not particularly limited, but is preferably 25 to 55 ° C., more preferably 30 to 50 ° C. Further, the reaction time in the first reaction step may be 0.3 hours or more, and is not particularly limited, but is preferably 0.3 to 18 hours, more preferably 0.5 to 15 hours, and still more preferably 0.00. 8-10 hours. When the reaction temperature (T ₁ ) in the first reaction step is less than 20 ° C. or the reaction time in the first reaction step is less than 0.3 hours, complex formation in the first reaction step becomes insufficient. After the second reaction step, black precipitation is likely to occur, the yield of the palladium complex of the present invention may be reduced, and it may be difficult to remove the black precipitate. The same applies when the reaction temperature (T ₁ ) in the first reaction step exceeds 60 ° C. The reaction temperature T ₁ may be always constant (substantially constant) in the first reaction step, or may be raised or lowered continuously or stepwise in the range of 20 to 60 ° C.

The temperature in the second reaction step (reaction temperature: T ₂ ) may be 40 to 120 ° C., and is not particularly limited, but is preferably 50 to 110 ° C., more preferably 60 to 100 ° C. The reaction time in the second reaction step may be 0.3 hours or longer, and is not particularly limited, but is preferably 0.3 to 18 hours, more preferably 0.5 to 15 hours, still more preferably 0.00. 8-10 hours. When the reaction temperature (T ₂ ) in the second reaction step is less than 40 ° C. or the reaction time in the second reaction step is less than 0.3 hour, the formation of the palladium complex becomes insufficient, and the palladium complex of the present invention The yield may decrease. Also, if the reaction temperature in the second reaction step (T ₂₎ exceeds 120 ° C., for susceptible to black precipitate by heating, undesirable. The reaction temperature T ₂ may be always constant (substantially constant) in the second heating step, or may be raised or lowered continuously or stepwise in the range of 40 to 120 ° C.

Reaction temperatures T ₁ in the first reaction step, the above reaction temperature T ₂ in the second reaction step may be the same temperature (substantially the same temperature), or may be different temperatures. In particular, from the viewpoint of improving the yield of the palladium complex of the present invention, the reaction temperature T ₂ is preferably higher than the reaction temperature T ₁ . “The reaction temperature T ₂ is higher than the reaction temperature T ₁ ” means that the minimum value of the reaction temperature T ₂ in the second reaction step is higher than the maximum value of the reaction temperature T ₁ in the first reaction step. Means high.

When the reaction temperature T ₁ and the reaction temperature T ₂ are both in the range of 40 to 60 ° C., the first reaction step and the second reaction step cannot be clearly distinguished. When the total reaction time at a temperature of 0 ° C. is 0.6 hours or more, the reaction step includes the first reaction step (reaction at a temperature of 20 to 60 ° C. for 0.3 hour or more) and the second reaction. And a step (a step of reacting at a temperature of 40 to 120 ° C. for 0.3 hour or more).

The reaction step may include a reaction step other than the first reaction step and the second reaction step, but the reaction temperature in the reaction step is controlled to 120 ° C. or lower throughout the reaction (over the entire reaction step). The Although not particularly limited, the reaction temperature is preferably controlled to 115 ° C. or less, more preferably 110 ° C. or less throughout the reaction. When the reaction is carried out at a temperature exceeding 120 ° C., it becomes difficult to obtain the palladium complex of the present invention.

Furthermore, it is preferable that the step of reacting (heating) at a temperature exceeding 60 ° C., which is the upper limit of the reaction temperature T ₁ in the first reaction step, is not included before the first reaction step of the reaction step.

In addition, the manufacturing method of the palladium complex of this invention may include other processes, such as the process of isolating and refine | purifying the palladium complex of this invention other than the said reaction process, for example.

The palladium complex of the present invention can be obtained by the above-described production method (the production method of the palladium complex of the present invention). The palladium complex of the present invention can be used without being isolated from the reaction product obtained by the above production method (for example, a solution containing the palladium complex of the present invention and its raw materials), or can be used in a known or conventional manner. What was isolated using purification techniques (for example, recrystallization, distillation under reduced pressure, distillation, chromatography, etc.) can also be used. In particular, by isolating the palladium complex of the present invention as a solid, it is possible to obtain a solid palladium complex catalyst for a vinyl exchange reaction that can reduce impurities and the like that inhibit the vinyl exchange reaction and is easy to handle.

The estimated formation mechanism of the palladium complex of the present invention is shown below. Note that palladium acetate [Pd (OAc) ₂ ] is used as the divalent palladium complex represented by the formula (2), and 2,2′-bipyridine is used as a bidentate ligand having two or more nitrogen atoms in the molecule. An example in which normal propyl vinyl ether is used as the vinyl ether compound represented by the formula (3) is shown, but the formation reaction of the palladium complex of the present invention proceeds by the same mechanism when other raw materials are used. It is thought to do.

[Method for producing vinyl ether compound of the present invention]
A catalyst for a vinyl exchange reaction in which the palladium complex of the present invention is exchanged between a hydrogen atom of a hydroxyl group of an alcohol compound (compound having a hydroxyl group) and a vinyl group of a vinyl ether compound (compound having a vinyl ether group) to form a new vinyl ether compound. By using it as a (vinyl exchange reaction catalyst), the target vinyl ether compound can be obtained in high yield. In the present specification, a method of producing a vinyl ether compound by a vinyl exchange reaction using the palladium complex of the present invention may be referred to as “a method for producing a vinyl ether compound of the present invention”.

That is, the method for producing the vinyl ether compound of the present invention specifically includes an alcohol compound represented by the following formula (4) and a vinyl ether compound represented by the following formula (5) in the presence of the palladium complex of the present invention. In which a vinyl ether compound represented by the following formula (6) is produced.

R ² in the formula (4) represents an organic group (organic residue) having a carbon atom at the bonding site with the oxygen atom shown in the formula. The organic group in R ² may be an organic group that is non-reactive with respect to the vinyl exchange reaction in the method for producing a vinyl ether compound of the present invention and has a carbon atom at the bonding site with an oxygen atom shown in the formula. Although it does not specifically limit, For example, the organic group etc. which contain a hydrocarbon group and / or a heterocyclic group are mentioned.

The hydrocarbon group and heterocyclic group include a hydrocarbon group and a heterocyclic group having a substituent. The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these groups are bonded.

Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, decyl group, and dodecyl group. An alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 3 carbon atoms), such as a vinyl group, an allyl group, or a 1-butenyl group, preferably 2 to 10, more preferably Preferred are alkenyl groups having 2 to 3); alkynyl groups having 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as ethynyl group and propynyl group. Examples of the alicyclic hydrocarbon group include 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and cyclooctyl group. A cycloalkyl group of 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as a cyclopentenyl group and a cyclohexenyl group; a perhydronaphthalen-1-yl group, norbornyl Group, adamantyl group, tetracyclo [4.4.0.1 ^2,5 . And a bridged cyclic hydrocarbon group such as 1 ^7,10 ] dodecan-3-yl group. Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 14 (preferably 6 to 10) carbon atoms such as a phenyl group and a naphthyl group. Examples of the group in which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group are bonded include cycloalkyl-alkyl groups such as a cyclopentylmethyl group, a cyclohexylmethyl group, and a 2-cyclohexylethyl group (for example, a C _3-20 Cycloalkyl-C _1-4 alkyl group, etc.). Examples of the group in which the aliphatic hydrocarbon group and the aromatic hydrocarbon group are bonded include, for example, an aralkyl group (for example, a C _7-18 aralkyl group), an alkyl-substituted aryl group (for example, about 1 to 4 groups). And a phenyl group or a naphthyl group substituted with a C _1-4 alkyl group.

The hydrocarbon group includes various substituents such as halogen atoms, oxo groups, hydroxyl groups, substituted oxy groups (for example, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, etc.), carboxyl groups, substituted oxycarbonyls. Group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc. May be. The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis (for example, acyl group, alkoxycarbonyl group, organic silyl group, alkoxyalkyl group, oxacycloalkyl group, etc.). In addition, an aromatic or non-aromatic heterocyclic ring may be condensed with a ring of an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

Examples of the substituted or unsubstituted carbamoyl group include an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, acetyl group, benzoyl group, etc. A carbamoyl group having an acyl group or the like, or an unsubstituted carbamoyl group. Examples of the substituted or unsubstituted amino group include methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, s-butyl groups, t-butyl groups and other alkyl groups, acetyl groups, and benzoyl groups. And an amino group having an acyl group, etc., or an unsubstituted amino group.

The heterocyclic ring constituting the heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. Examples of such a heterocycle include a heterocycle containing an oxygen atom as a heteroatom (for example, a 3-membered ring such as an oxirane ring, a 4-membered ring such as an oxetane ring, a furan, tetrahydrofuran, oxazole, γ-butyrolactone ring, etc. 5-membered ring, 6-membered ring such as 4-oxo-4H-pyran, tetrahydropyran, morpholine ring, condensed ring such as benzofuran, 4-oxo-4H-chromene, chroman ring, 3-oxatricyclo [4.3. 1.1 ^4,8] undecane-2-one ring, 3-oxatricyclo [4.2.1.0 ^4,8] bridged rings such as nonane-2-one ring), a sulfur atom as a hetero atom Heterocycles containing (for example, 5-membered ring such as thiophene, thiazole, thiadiazole ring, 6-membered ring such as 4-oxo-4H-thiopyran ring, condensed ring such as benzothiophene ring, etc. , Hetero rings containing a nitrogen atom as a hetero atom (for example, 5-membered rings such as pyrrole, pyrrolidine, pyrazole, imidazole and triazole rings, 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, piperidine and piperazine rings, indole and indoline) Quinoline, acridine, naphthyridine, quinazoline, condensed rings such as purine rings, etc.). The heterocyclic group includes, in addition to the substituents that the hydrocarbon group may have, an alkyl group (eg, a C _1-4 alkyl group such as a methyl or ethyl group), a cycloalkyl group, an aryl group It may have a substituent such as (for example, phenyl, naphthyl group). The nitrogen atom constituting the heterocyclic ring is a conventional protective group (for example, an alkoxy group, an alkoxycarbonyl group, an alkenyloxycarbonyl group, an aralkyloxycarbonyl group, an aralkyl group, an acyl group, an arylsulfonyl group, an alkylsulfonyl group, etc.) It may be protected by.

R ² may be an organic group composed of one or more hydrocarbon groups and / or heterocyclic groups and one or more linking groups. Examples of the linking group include an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond (—CONH—), a carbonyl group (—CO—), and the like. Examples include a group in which two or more are bonded.

P in the formula (4) represents an integer of 1 or more. p is not particularly limited, but can be appropriately selected from the range of 1 to 4, for example.

Examples of the alcohol compound represented by the formula (4) include methanol, ethanol, n-propanol, i-propanol, n-butanol, t-butanol, pentanol, hexanol, heptanol, octanol, allyl alcohol, phenol, An alcohol having one hydroxyl group such as benzyl alcohol, 3-methyloxetane-3-ylmethanol, 3-ethyloxetane-3-ylmethanol (ie, an alcohol in which p in formula (4) is 1); ethylene glycol, 1 , 2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3,3-bishydroxymethyloxetane, oxetane dimethanol, 1,4 -Cyclohexanedimethanol, 2-hydroxy A mixture of 6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane and 3-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane (ONB), 1,6- Examples thereof include alcohols having two or more hydroxyl groups such as cyclohexanedimethanol, 1,4-cyclohexanediol, and neopentyl glycol (that is, alcohols in which p in formula (4) is an integer of 2 or more).

Equation ⁽⁵⁾ R ³ ~ R 5 in ^{^{(R 3, R 4, R}} 5) are the same or different, the binding site of the hydrogen atoms or carbon atoms indicated in formula an organic group having a carbon atom Show. As the organic group, without inhibiting the vinyl exchange reaction, and yet may be any organic radical having a carbon atom at the bonding site to the carbon atom indicated in the formula is not particularly limited, for example, organic in the R ² Specific examples include alkyl groups such as methyl, ethyl, pentyl, isopentyl, butyl (n-butyl), isobutyl, s-butyl, and t-butyl groups. Groups; alkenyl groups such as vinyl, allyl, butenyl, hexenyl, decenyl, and cyclohexenyl; and aryl groups such as phenyl, naphthyl, tolyl, xylyl, and ethylphenyl. Among these, as R ³ to R ⁵ , a hydrogen atom is preferable, and it is particularly preferable that R ³ to R ⁵ are all hydrogen atoms.

R ⁶ in the formula (5) represents an organic group having a carbon atom at the bonding site with the oxygen atom shown in the formula. As the organic group, without inhibiting the vinyl exchange reaction may be any organic radical having a carbon atom at a bonding site with an oxygen atom shown in the formula is not particularly limited, similarly to the organic group in the R ² Can be mentioned. Examples of the organic group for R ⁶ include an alkyl group, an alkenyl group, and an aryl group, and more specifically, the same groups as those exemplified for R ³ to R ⁵ above can be given.

Examples of the vinyl ether compound represented by the formula (5) include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, pentyl vinyl ether, hexyl. Examples include vinyl ether, methyl isopropenyl vinyl ether, ethyl isopropenyl vinyl ether, allyl vinyl ether, phenyl vinyl ether, and benzyl vinyl ether.

The reaction of the alcohol compound represented by the above formula (4) and the vinyl ether compound represented by the formula (5) in the presence of the palladium complex of the present invention (vinyl exchange reaction) is carried out in the presence or absence of a solvent. Can be implemented. The solvent is not particularly limited, but is preferably a solvent that is non-reactive with respect to the vinyl exchange reaction. For example, hexane, ethyl acetate, tetrahydrofuran, acetone, dimethylformamide, dimethyl sulfoxide, acetonitrile, toluene, ethylene glycol dimethyl ether (monoglyme) , Diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), methylene chloride, chloroform, 2-butanone and the like. A solvent can be used individually or in combination of 2 or more types.

Although the usage-amount of the vinyl ether compound represented by the said Formula (5) changes with kinds etc. of a reaction material and is not specifically limited, It is 0. 0 with respect to 1 mol of hydroxyl groups which the alcohol compound represented by Formula (4) has. The amount is preferably 1 to 100 mol, more preferably 1 to 50 mol, still more preferably 2 to 20 mol. If the amount used is less than 0.1 mol, the yield of the target vinyl ether may be reduced. On the other hand, if the amount used exceeds 100 moles, it may be disadvantageous in terms of cost.

The amount of the palladium complex of the present invention varies depending on the type of reaction product, reaction temperature, and the like, and is not particularly limited, but is preferably 0.0001 to 50 mol with respect to 1 mol of the vinyl ether compound represented by the formula (5). More preferably, it is 0.01 to 10 mol, and still more preferably 0.1 to 5 mol. If the amount used is less than 0.0001 mol, the yield of the target vinyl ether may decrease. On the other hand, when the amount used exceeds 50 mol, it may be disadvantageous in terms of cost.

In the method for producing a vinyl ether compound of the present invention, the palladium complex of the present invention is isolated (for example, obtained by further isolation after the reaction step in the method of producing the palladium complex of the present invention described above). Palladium complex) can also be used, and a solution containing the palladium complex of the present invention (palladium complex solution) (for example, a palladium complex solution obtained by the reaction step in the method for producing a palladium complex of the present invention described above) can be used. You can also.

In the method for producing the vinyl ether compound of the present invention, in addition to the alcohol compound represented by the formula (4), the vinyl ether compound represented by the formula (5), and the palladium complex of the present invention, the palladium complex of the present invention is further added. A bidentate ligand (nitrogen-containing bidentate ligand, particularly bipyridine derivative, 1,10-phenanthroline derivative) having two or more nitrogen atoms in the molecule constituting may be added. By further addition of the nitrogen-containing bidentate ligand, the palladium catalyst of the present invention can be more effectively present in the reaction system, and the vinyl exchange reaction tends to proceed more stably. Although it does not specifically limit as addition amount (usage amount) of the said nitrogen-containing bidentate ligand, It is preferable to set it as more than 0 mol and 100 mol or less with respect to 1 mol of palladium complexes of this invention, More preferably 1 to 80 mol. When the nitrogen-containing bidentate ligand is added in excess of 100 moles with respect to the palladium complex of the present invention, it may be disadvantageous in terms of cost.

The reaction temperature (reaction temperature for vinyl exchange reaction) in the method for producing a vinyl ether compound of the present invention is not particularly limited, but is preferably −10 to 100 ° C., more preferably 0 to 80 ° C. When the reaction temperature is less than −10 ° C., a sufficient reaction rate may not be obtained. When the reaction temperature exceeds 100 ° C., formation of reaction by-products may be promoted or the palladium catalyst may be deactivated. . The reaction temperature may be kept substantially constant from the start of the reaction to the end of the reaction, or may be changed stepwise within the above temperature range, for example.

In particular, in the method for producing a vinyl ether compound of the present invention, by using the palladium complex of the present invention as a catalyst, for example, even when a higher reaction temperature (for example, 60 ° C. or higher) is used to increase the reaction rate, Since black precipitates and catalyst deactivation are unlikely to occur, the productivity of the target vinyl ether compound is improved.

The reaction time (reaction time for carrying out the vinyl exchange reaction) in the method for producing the vinyl ether compound of the present invention varies depending on the type of the reactant and is not particularly limited, but is appropriately selected from the range of 0.6 to 100 hours, for example. be able to.

The reaction pressure in the method for producing a vinyl ether compound of the present invention (reaction pressure for carrying out a vinyl exchange reaction) is not particularly limited, and may be carried out at normal pressure, or under reduced pressure or under pressure. In particular, normal pressure is preferable in that the production process is not complicated.

In the method for producing a vinyl ether compound of the present invention, the atmosphere in which the vinyl exchange reaction is carried out is not particularly limited, and can be carried out in any atmosphere such as in an inert gas (for example, nitrogen) or in the air.

The method for producing the vinyl ether compound of the present invention is not particularly limited, and can be carried out by any of a batch method (batch method), a semi-batch method, and a continuous flow method. For example, when the production method of the vinyl ether compound of the present invention is carried out in a batch system, for example, an alcohol compound represented by the formula (4) and a vinyl ether compound represented by the formula (5) are added to a batch reactor. The palladium complex of the present invention and, if necessary, a nitrogen-containing bidentate ligand, a solvent and the like are charged, and further, heated and stirred as necessary.

The method for producing a vinyl ether compound of the present invention includes, for example, solvent distillation under reduced pressure, distillation, recrystallization, chromatography, etc. for isolating the vinyl ether compound represented by formula (6) after completion of the vinyl exchange reaction. A purification step for carrying out the above may be included.

According to the method for producing a vinyl ether compound of the present invention, at least one hydrogen atom of the hydroxyl group of the alcohol compound represented by the formula (4) is converted into a vinyl group (R ³ R ⁴ C = A vinyl ether compound represented by the formula (6) substituted (exchanged) with CR ⁵ —) is obtained. That is, q in the formula (6) represents an integer of 1 to p, and R ² to R ⁵ (R ² , R ³ , R ⁴ , R ⁵ ) are the same as the above (formula (4) and formula ( The same as R ² to R ⁵ in 5). Specifically, for example, when p is 1, q indicates 1, and when p is 2, q indicates 1 or 2.

The vinyl ether compound represented by the formula (6) is a raw material for fine chemicals such as pharmaceuticals and agricultural chemicals, a raw material for functional resins (for example, resist resins, optical resins, transparent resins, cross-linked resins, etc.), curing for cationic polymerization. It can be applied to agents.

[Method for recovering palladium complex of the present invention]
After the vinyl ether compound is produced by the method for producing the vinyl ether compound of the present invention, the palladium complex of the present invention is recovered from the reaction solution after the vinyl exchange reaction, and the recovered palladium complex is used in the method for producing the vinyl ether compound. Use). The method for recovering the palladium complex of the present invention is not particularly limited, and any known or conventional catalyst recovery method can be used. Specifically, for example, in Japanese Patent Application Laid-Open No. 9-087224, in a method for producing ethyl vinyl ether by reacting ethanol with methyl vinyl ether using palladium, a nitrogen bidentate ligand and a nitrogen compound as a catalyst, A method is disclosed in which the product ethyl vinyl ether, the raw material methyl vinyl ether, and ethanol are removed from the reaction solution later by distillation under reduced pressure to recover the catalyst as a residue, and the recovered catalyst is reused in the reaction. In the present invention, a palladium complex can be recovered and reused by the same method.

However, when the vinyl ether compound as a product in the vinyl ether compound of the present invention has a relatively high boiling point, the palladium complex of the present invention is deactivated by heating when the product is removed from the reaction solution by distillation under reduced pressure. There is a case. For example, when the product is heated at a high temperature (for example, about 90 ° C.) in order to distill off the vinyl ether compound under reduced pressure, the residue turns black, and a vinyl exchange reaction is performed using the residue as a catalyst. However, it has been found that no catalytic activity is exhibited. Therefore, from the viewpoint of suppressing such a decrease in the catalytic activity of the palladium complex, the palladium complex of the present invention is obtained by reacting the reaction solution obtained by the method for producing the vinyl ether compound of the present invention (in the presence of the palladium complex of the present invention, the formula (Reaction solution after reacting the alcohol compound represented by (4) with the vinyl ether compound represented by formula (5) to produce the vinyl ether compound represented by formula (6)) Water, which is a good solvent for the palladium complex, and an organic solvent which is a good solvent for the vinyl ether compound represented by the formula (6) and phase-separates from water (hereinafter sometimes simply referred to as “organic solvent”) In addition, it is then preferably recovered by a method of recovering by separating the aqueous layer (sometimes referred to as “recovery method of palladium complex of the present invention”).

The organic solvent to be added to the reaction solution is not particularly limited as long as it is a good solvent for the vinyl ether compound represented by the formula (6) and phase-separated from water. For example, pentane, hexane , Heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane and other aliphatic hydrocarbons (linear or branched aliphatic hydrocarbons); cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, etc. Examples include alicyclic hydrocarbons (cyclic aliphatic hydrocarbons); aromatic hydrocarbons such as toluene and xylene. Among these, saturated aliphatic hydrocarbons are preferable, and saturated aliphatic hydrocarbons having 5 to 7 carbon atoms (for example, pentane, hexane, heptane, cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, etc.) are more preferable.

The amount of water added to the reaction solution is not particularly limited, but is preferably 1 to 200 parts by weight, more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the reaction solution. If the amount of water used is less than 1 part by weight, the recovery rate of the palladium complex may be reduced. On the other hand, if the amount of water used exceeds 200 parts by weight, it may be economically disadvantageous, for example, because it takes a long time to remove water in the subsequent vinyl exchange reaction.

The amount of the organic solvent added to the reaction solution is not particularly limited, but is preferably 1 to 500 parts by weight, more preferably 10 to 200 parts by weight with respect to 100 parts by weight of the reaction solution. When the amount of the organic solvent used is less than 1 part by weight, the recovery rate of the palladium complex may decrease. On the other hand, if the amount of the organic solvent to be used exceeds 500 parts by weight, it may be economically disadvantageous in terms of equipment and organic solvent costs.

The ratio of water and organic solvent added to the reaction solution ([water / organic solvent]: weight basis) is not particularly limited, but is preferably 0.01 / 1 to 10/1, more preferably 0.1 / 0.1. It is 1 to 3/1, more preferably 0.15 / 1 to 2/1. If the ratio of the water and the organic solvent used is out of the above range, the separation efficiency between the palladium complex of the present invention and the product may be lowered.

Next, the palladium complex of the present invention contained in the reaction solution, the raw material (the alcohol compound represented by the formula (4), the vinyl ether compound represented by the formula (5)), and the product (the vinyl ether represented by the formula (6)) In order to distribute the compound) and the solvent into the aqueous layer and the organic layer, it is preferable to stir the reaction solution (the reaction solution to which water and the organic solvent have been added). For the stirring, a known or conventional stirrer can be used.

Thereafter, the reaction solution to which water and an organic solvent have been added is allowed to stand or centrifuged to separate the water layer and the organic layer. Since the palladium complex of the present invention has a very high solubility in water, most of it is distributed in the aqueous layer. On the other hand, the vinyl ether compound represented by the formula (5) as a raw material and the vinyl ether compound represented by the formula (7) as a product are highly soluble in an organic solvent, so that most of them are distributed to the organic layer. . Therefore, the palladium complex of the present invention can be recovered by separating the aqueous layer from the reaction solution. The palladium complex of the present invention can be used (reused) in the next vinyl exchange reaction as it is in the state of an aqueous solution (separated aqueous layer), or can be used in a known or conventional method (for example, recrystallization, column chromatography, etc.). It is also possible to use it isolated from an aqueous solution by the above method. In addition, although the alcohol compound represented by the formula (6), the solvent, the ligand, and the like, which are raw materials, are distributed to the water layer or the organic layer depending on the structure, they are distributed to the water layer. In this case, the aqueous layer (aqueous solution) can be used for the next reaction as it is.

According to the method for recovering a palladium complex of the present invention, the palladium complex and the product can be easily separated and recovered, and further, since it is not necessary to apply heat during the separation, the palladium recovered as an aqueous layer (aqueous solution) is obtained. Reduction of the activity of the complex is suppressed. The palladium complex recovery method of the present invention is an economically advantageous method.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1
[Preparation of palladium complex]
In a 30 mL flask, put 0.405 g (1.8 mmol) of palladium acetate [Pd (OAc) ₂ ], 2.80 g (18 mmol) of 2,2′-bipyridine [bpy], and 3.6 g (61 mmol) of normal propanol. The mixture was stirred at room temperature until the palladium acetate was dissolved. Next, after adding 12 g (140 mmol) of normal propyl vinyl ether, heating was performed at a liquid temperature of 50 ° C. for 1 hour while bubbling in air at a flow rate of 120 mL / min (referred to as “first heating step”). Subsequently, the liquid temperature was raised to 60 ° C. and heated for 1 hour, and then refluxed at a liquid temperature of 65 ° C. for 4 hours (referred to as “second heating step”). As a result, the resulting solution (reaction solution) was red, and no black precipitate was observed. After cooling the said solution to room temperature, it concentrated at the water bath temperature of 40 degreeC using the rotary evaporator. To the obtained concentrated liquid, 0.8 g of ethyl acetate and 0.4 g of acetone are added to precipitate yellow crystals. The crystals are separated, washed with ethyl acetate and acetone, dried under vacuum, and palladium. 0.296 g (0.70 mmol, yield: 39%) of the complex [Pd (OAc) (bpy) (CH ₂ COO-n—C ₃ H ₇ )] was obtained.
The peak of ¹ H-NMR spectrum of the palladium complex [Pd (OAc) (bpy) (CH ₂ COO—n—C ₃ H ₇ )] obtained above is as follows.
¹ H-NMR (DMSO, 400 MHz): δ 0.85 ppm (t, 3H), 1.51 ppm (q, 2H), 1.93 ppm (s, 3H), 2.16 ppm (s, 2H), 3.80 ppm ( t, 2H), 7.77 ppm (t, 2H), 8.29 ppm (m, 3H), 8.58 ppm (d, 2H), 8.94 ppm (d, 2H)
FIG. 1 shows the IR spectrum of the palladium complex [Pd (OAc) (bpy) (CH ₂ COO-n—C ₃ H ₇ )] obtained above (measurement conditions: KBr tablet, transmission, measurement resolution 4 cm ^−1). The chart of the number of scans 16 times and the measurement gain 2) is shown.

Example 2
[Preparation of palladium complex]
A palladium complex [Pd (OAc) (bpy) (CH ₂ COO-n—) was prepared by carrying out the same operation as in Example 1 except that 14 g (140 mmol) of normal butyl vinyl ether was used instead of normal propyl vinyl ether. C ₄ H _9)] was obtained (yield: 0.314 g (0.72 mmol), yield: 40%).
The peak of ¹ H-NMR spectrum of the palladium complex [Pd (OAc) (bpy) (CH ₂ COO-n—C ₄ H ₉ )] obtained above is as follows.
¹ H-NMR (DMSO, 400 MHz): δ 0.82 ppm (t, 3H), 1.30 ppm (q, 2H), 1.47 ppm (t, 2H), 1.93 ppm (s, 3H), 2.16 ppm ( s, 2H), 3.84 ppm (t, 2H), 7.77 ppm (t, 2H), 8.29 ppm (m, 3H), 8.58 ppm (d, 2H), 8.94 ppm (d, 2H)

Example 3
[Preparation of palladium complex]
A palladium complex [Pd (OAc) was obtained by carrying out the same operation as in Example 1 except that 3.24 g (18 mmol) of 1,10-phenanthroline [phen] was used instead of 2,2′-bipyridine. (Phen) (CH ₂ COO-n—C ₃ H ₇ )] was obtained (yield: 0.273 g (0.61 mmol), yield: 34%).
The peak of ¹ H-NMR spectrum of the palladium complex [Pd (OAc) (phen) (CH ₂ COO-n—C ₃ H ₇ )] obtained above is as follows.
¹ H-NMR (DMSO, 400 MHz): δ 0.85 ppm (t, 3H), 1.51 ppm (q, 2H), 2.01 ppm (s, 3H), 2.35 ppm (s, 2H), 3.83 ppm ( t, 2H), 8.06 ppm (m, 2H), 8.18 ppm (s, 2H), 8.62 ppm (d, 1H), 8.85 ppm (dd, 2H), 9.22 ppm (d, 1H)

Example 4
[Preparation of palladium complex]
Example 1 except that 14 g (140 mmol) of normal butyl vinyl ether was used instead of normal propyl vinyl ether, and 3.24 g (18 mmol) of 1,10-phenanthroline was used instead of 2,2′-bipyridine. The palladium complex [Pd (OAc) (phen) (CH ₂ COO-n—C ₄ H ₉ )]] was obtained by performing the same operation as in (Yield: 0.373 g (0.81 mmol), Yield : 45%).
The peak of ¹ H-NMR spectrum of the palladium complex [Pd (OAc) (phen) (CH ₂ COO-n—C ₄ H ₉ )] obtained above is as follows.
¹ H-NMR (DMSO, 400 MHz): δ 0.82 ppm (t, 3H), 1.30 ppm (q, 2H), 1.47 ppm (t, 2H), 2.01 ppm (s, 3H), 2.35 ppm ( s, 2H), 3.87 ppm (t, 2H), 8.06 ppm (m, 2H), 8.18 ppm (s, 2H), 8.62 ppm (d, 1H), 8.85 ppm (dd, 2H), 9.22 ppm (d, 1H)

Example 5
[Preparation of palladium complex]
The palladium complex [Pd (OAc) (bpy) (CH ₂ COO-i-C) was obtained by carrying out the same operation as in Example 1 except that 12 g (140 mmol) of isopropyl vinyl ether was used instead of normal propyl vinyl ether. ₃ H _7)] was obtained (yield: 0.312 g (0.74 mmol), yield: 41%).
The peak of ¹ H-NMR spectrum of the palladium complex [Pd (OAc) (bpy) (CH ₂ COO-i-C ₃ H ₇ )] obtained above is as follows.
¹ H-NMR (DMSO, 400 MHz): δ 1.14 ppm (d, 6H), 1.93 ppm (s, 3H), 2.16 ppm (s, 2H), 4.03 ppm (m, 1H), 7.77 ppm ( t, 2H), 8.29 ppm (m, 3H), 8.58 ppm (d, 2H), 8.94 ppm (d, 2H)

Example 6
[Preparation of palladium complex]
A palladium complex [Pd (OAc) (bpy) (CH ₂ COO-i-) was obtained by carrying out the same operation as in Example 1 except that 14 g (140 mmol) of isobutyl vinyl ether was used instead of normal propyl vinyl ether. C ₄ H _9)] was obtained (yield: 0.252 g (0.58 mmol), yield: 32%).
The peak of ¹ H-NMR spectrum of the palladium complex [Pd (OAc) (bpy) (CH ₂ COO-i-C ₄ H ₉ )] obtained above is as follows.
¹ H-NMR (DMSO, 400 MHz): δ 0.92 ppm (d, 6H), 1.77 ppm (m, 1H), 1.93 ppm (s, 3H), 2.16 ppm (s, 2H), 3.40 ppm ( d, 2H), 7.77 ppm (t, 2H), 8.29 ppm (m, 3H), 8.58 ppm (d, 2H), 8.94 ppm (d, 2H)

Example 7
[Preparation of palladium complex]
Example 1 except that 12 g (140 mmol) of isopropyl vinyl ether was used instead of normal propyl vinyl ether, and 3.24 g (18 mmol) of 1,10-phenanthroline was used instead of 2,2′-bipyridine. By performing the same operation, a palladium complex [Pd (OAc) (phen) (CH ₂ COO-i-C ₃ H ₇ )] was obtained (yield: 0.322 g (0.72 mmol), yield: 40%).
The peak of ¹ H-NMR spectrum of the palladium complex [Pd (OAc) (phen) (CH ₂ COO-i-C ₃ H ₇ )] obtained above is as follows.
¹ H-NMR (DMSO, 400 MHz): δ 1.14 ppm (d, 6H), 2.01 ppm (s, 3H), 2.35 ppm (s, 2H), 4.03 ppm (m, 1H), 8.06 ppm ( m, 2H), 8.18 ppm (s, 2H), 8.62 ppm (d, 1H), 8.85 ppm (dd, 2H), 9.22 ppm (d, 1H)

Example 8
[Preparation of palladium complex]
Example 1 is used except that 14 g (140 mmol) of isobutyl vinyl ether is used in place of normal propyl vinyl ether, and 3.24 g (18 mmol) of 1,10-phenanthroline is used in place of 2,2′-bipyridine. By performing the same operation, a palladium complex [Pd (OAc) (phen) (CH ₂ COO-i-C ₄ H ₉ )] was obtained (yield: 0.357 g (0.774 mmol), yield: 43%).
The peak of ¹ H-NMR spectrum of the palladium complex [Pd (OAc) (phen) (CH ₂ COO-i-C ₄ H ₉ )] obtained above is as follows.
¹ H-NMR (DMSO, 400 MHz): δ 0.92 ppm (d, 6H), 1.77 ppm (m, 1H), 2.01 ppm (s, 3H), 2.35 ppm (s, 2H), 3.40 ppm ( d, 2H), 8.06 ppm (m, 2H), 8.18 ppm (s, 2H), 8.62 ppm (d, 1H), 8.85 ppm (dd, 2H), 9.22 ppm (d, 1H)

The palladium complexes obtained in Examples 1 to 8 are shown in Table 1.

Example 9
[Preparation of palladium complex]
The same operation as in Example 1 was performed except that the heating temperature in the first heating step was 25 ° C., the heating time was 1 hour, the heating temperature in the second heating step was 80 ° C., and the heating time was changed to 1 hour. As a result, Pd (OAc) (bpy) (CH ₂ COO—n—C ₃ H ₇ ) was obtained with a yield of 40%. In addition, the solution (reaction liquid) obtained as a result of heating was red, and the production | generation of black precipitation was not seen. The results are shown in Table 2.

Example 10
[Preparation of palladium complex]
The same operation as in Example 1 was performed except that the heating temperature in the first heating step was 40 ° C., the heating time was 1 hour, the heating temperature in the second heating step was changed to 80 ° C., and the heating time was changed to 1 hour. As a result, Pd (OAc) (bpy) (CH ₂ COO—n—C ₃ H ₇ ) was obtained with a yield of 38%. In addition, the solution (reaction liquid) obtained as a result of heating was red, and the production | generation of black precipitation was not seen. The results are shown in Table 2.

Example 11
[Preparation of palladium complex]
The same operation as in Example 1 was performed except that the heating temperature in the first heating step was 55 ° C., the heating time was 1 hour, the heating temperature in the second heating step was 80 ° C., and the heating time was changed to 1 hour. As a result, Pd (OAc) (bpy) (CH ₂ COO—n—C ₃ H ₇ ) was obtained with a yield of 37%. In addition, the solution (reaction liquid) obtained as a result of heating was red, and the production | generation of black precipitation was not seen. The results are shown in Table 2.

Examples 12-20
[Preparation of palladium complex]
Except that the heating temperature and heating time in the first heating step and the heating temperature and heating time in the second heating step were changed as shown in Table 2, the same operation as in Example 1 was performed, and Pd (OAc) ( bpy) was prepared _{(CH 2 COO-n-C} 3 H 7). The results are shown in Table 2.

As shown in Table 2, when the heating conditions (heating temperature and heating time) in the reaction step were controlled within the range specified by the present invention (Examples 9 to 20), the resulting palladium complex solution had a black color. The desired palladium complex could be obtained in high yield without precipitation.

Example 21
[Vinyl exchange reaction]
In a 30 mL three-necked flask equipped with a Dimroth condenser, 38.0 mg (0.09 mmol) of Pd (OAc) (bpy) (CH ₂ COO-n—C ₃ H ₇ ) obtained in Example 1, 3, 3 -Add 0.36 g (3 mmol) of bishydroxymethyloxetane, 0.186 g (1.2 mmol) of 2,2′-bipyridine, 0.52 g (6.0 mmol) of normal propyl vinyl ether, and 0.73 g of tetraglyme, When the vinyl exchange reaction was carried out by heating for 6 hours, the conversion of 3,3-bishydroxymethyloxetane was 87%, the yield of 3,3-bishydroxymethyloxetane monovinyl ether was 49%, 3,3- The yield of bishydroxymethyl oxetane divinyl ether was 38%.

Example 22
[Vinyl exchange reaction]
In a 30 mL three-necked flask equipped with a Dimroth condenser, 27.3 mg (0.12 mmol) of palladium acetate [Pd (OAc) ₂ ], 0.196 g (1.2 mmol) of 2,2′-bipyridine, 0. 71 g (8.0 mmol) and 0.95 g of tetraglyme were added and heated for 1 hour at a liquid temperature of 50 ° C. (first heating step) while bubbling air in liquid at a flow rate of 120 mL / min. After the liquid temperature was raised to 60 ° C. and heated for 1 hour, the liquid temperature was further refluxed at 65 ° C. for 4 hours (second heating step), and the palladium complex [Pd (OAc) (bpy) (CH ₂ COO-n -C ₃ H ₇ )] was prepared.
This palladium complex [Pd (OAc) (bpy) (CH ₂ COO-n—C ₃ H ₇ )] was removed from the solution, and a vinyl exchange reaction was carried out by the following procedure.
That is, the solution containing the palladium complex was placed under a nitrogen atmosphere, 0.48 g (4 mmol) of 3,3-bishydroxymethyloxetane was added, and the vinyl exchange reaction was carried out by heating at 65 ° C. for 6 hours. The conversion of 1,3-bishydroxymethyloxetane was 82%, the yield of 3,3-bishydroxymethyloxetane monovinyl ether was 52%, and the yield of 3,3-bishydroxymethyloxetane divinyl ether was 29%. .

Example 23
[Vinyl exchange reaction]
In a 30 mL three-necked flask equipped with a Dimroth condenser, palladium acetate [Pd (OAc) ₂ ] 12.1 mg (0.054 mmol), 2,2′-bipyridine 0.0795 g (0.509 mmol), normal propyl vinylether 31 g (3.6 mmol) and 1.56 g of dimethyl sulfoxide were added, and the mixture was heated at a liquid temperature of 50 ° C. for 1 hour while bubbling the mixed gas of oxygen 8 vol% and nitrogen 92 vol% at a flow rate of 10 mL / min. 1 heating step), and then heated to 60 ° C. and heated for 1 hour, and further refluxed at a liquid temperature of 65 ° C. for 4 hours (second heating step) to obtain a palladium complex [Pd (OAc) (bpy ) (CH ₂ COO-n—C ₃ H ₇ )].
This palladium complex [Pd (OAc) (bpy) (CH ₂ COO-n—C ₃ H ₇ )] was removed from the solution, and a vinyl exchange reaction was carried out by the following procedure.
That is, 1.99 g (17.1 mmol) of 1,4-cyclohexanediol and 14.6 g (170 mmol) of normal propyl vinyl ether are added to the solution containing the palladium complex, and 10 mL of a mixed gas of 8 vol% oxygen and 92 vol% nitrogen is added. The solution was heated at 65 ° C. for 16.5 hours while bubbling in the liquid at a flow rate of / min, and the vinyl exchange reaction was carried out in a reflux state. The dissolved oxygen concentration of the reaction solution during the reaction (measured with Micro Logger Oxygen Analyzer Model: 3650, manufactured by Hack Ultra Co., Ltd.) was 2 ppm or less. As a result of the reaction, the conversion of 1.4-cyclohexanediol was 71%, the yield of 1,4-cyclohexanediol monovinyl ether was 36%, and the yield of 1,4-cyclohexanediol divinyl ether was 33%.

Example 24
[Vinyl exchange reaction]
In a 30 mL three-necked flask equipped with a Dimroth condenser, 118 mg (0.52 mmol) of palladium acetate [Pd (OAc) ₂ ], 0.813 g (5.2 mmol) of 2,2′-bipyridine, 2.98 g of normal propyl vinyl ether ( 34.6 mmol) and 4.29 g of diglyme are added, and a mixed gas of 8 vol% oxygen and 92 vol% nitrogen is bubbled in the liquid at a flow rate of 10 mL / min and heated at a liquid temperature of 50 ° C. for 1 hour (first heating step) Then, the liquid temperature was raised to 60 ° C. and heated for 1 hour, and further refluxed at a liquid temperature of 65 ° C. for 4 hours (second heating step) to obtain a palladium complex [Pd (OAc) (bpy) (CH ₂ COO-n-C ₃ H ₇ )].
This palladium complex [Pd (OAc) (bpy) (CH ₂ COO-n—C ₃ H ₇ )] was removed from the solution, and a vinyl exchange reaction was carried out by the following procedure.
That is, to the solution containing the palladium complex, 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane and 3-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2. 1) 2.6 g (18.1 mmol) of a mixture of heptane (ONB) and 12.1 g (140 mmol) of normal propyl vinyl ether were added, and a mixed gas of 8 vol% oxygen and 92 vol% nitrogen was added to the liquid at a flow rate of 10 mL / min. While bubbling, the mixture was heated at 65 ° C. for 11 hours to conduct a vinyl exchange reaction under reflux. The dissolved oxygen concentration of the reaction solution during the reaction (measured with Micro Logger Oxygen Analyzer Model: 3650, manufactured by Hack Ultra Co., Ltd.) was 2 ppm or less. As a result of the reaction, the conversion rate of ONB was 95%, the yield of ONB monovinyl ether was 57%, and the yield of ONB divinyl ether was 38%.

Example 25
[Vinyl exchange reaction]
In a 30 mL three-necked flask equipped with a Dimroth condenser, 11.4 mg (0.051 mmol) of palladium acetate [Pd (OAc) ₂ ], 0.0807 g (0.52 mmol) of 2,2′-bipyridine, 0. 29 g (3.4 mmol) and 1.54 g of diglyme were added, and the mixture was heated at a liquid temperature of 50 ° C. for 1 hour while bubbling a mixed gas of oxygen 8 vol% and nitrogen 92 vol% at a flow rate of 10 mL / min. Heating step), and then the liquid temperature was raised to 60 ° C. and heated for 1 hour, and then refluxed at a liquid temperature of 65 ° C. for 4 hours (second heating step) to obtain a palladium complex [Pd (OAc) (bpy) (CH ₂ COO-n—C ₃ H ₇ )] was prepared.
This palladium complex [Pd (OAc) (bpy) (CH ₂ COO-n—C ₃ H ₇ )] was removed from the solution, and a vinyl exchange reaction was carried out by the following procedure.
That is, 2.5 g (17.3 mmol) of 1,4-cyclohexanedimethanol and 14.4 g (167 mmol) of normal propyl vinyl ether are added to the solution containing the palladium complex, and a mixed gas of 8 vol% oxygen and 92 vol% nitrogen is added. Was bubbled in the liquid at a flow rate of 10 mL / min and heated at 65 ° C. for 16.5 hours to carry out a vinyl exchange reaction under reflux. The dissolved oxygen concentration of the reaction solution during the reaction (measured with Micro Logger Oxygen Meter Model 3650 manufactured by Hack Ultra Co., Ltd.) was 2 ppm or less. As a result of the reaction, the conversion of 1,4-cyclohexanedimethanol was 99%, the yield of 1,4-cyclohexanedimethanol monovinyl ether was 26%, and the yield of 1,4-cyclohexanedimethanol divinyl ether was 73%. there were.

Comparative Example 1
[Vinyl exchange reaction]
In a 30 mL three-necked flask equipped with a Dimroth condenser, 27.3 mg (0.12 mmol) of palladium acetate [Pd (OAc) ₂ ], 0.196 g (1.2 mmol) of 2,2′-bipyridine, 0. 71 g (8.0 mmol), 3,3-bishydroxymethyloxetane 0.48 g (4 mmol), and tetraglyme 0.95 g were added and heated at 65 ° C. for 6 hours under a nitrogen atmosphere to perform a vinyl exchange reaction. As a result, the conversion rate of 3,3-bishydroxymethyloxetane was 72%, the yield of 3,3-bishydroxymethyloxetane monovinyl ether was 56%, and the yield of 3,3-bishydroxymethyloxetane divinyl ether was 17%. %Met. Further, a black precipitate was formed in the solution after the reaction.

Example 26
[Recovery and recycling of palladium complexes]
(First vinyl exchange reaction)
A 30 mL three-necked flask equipped with a Dimroth condenser and a Dean-Stark dehydrator was charged with 0.3 g (1.20 mmol) of palladium acetate [Pd (OAc) ₂ ], 1.9 g (12 mmol) of 2,2′-bipyridine, normal propyl 0.71 g (8.0 mmol) of vinyl ether and 10.4 g of tetraglyme were added, and the mixture was heated at a liquid temperature of 50 ° C. for 1 hour while bubbling air at a flow rate of 120 mL / min (first heating step), and then The liquid temperature was raised to 60 ° C. and heated for 1 hour, and then refluxed at a liquid temperature of 65 ° C. for 4 hours (second heating step) to obtain a palladium complex [Pd (OAc) (bpy) (CH ₂ COO— n-C ₃ H ₇ )] was prepared.
Next, this palladium complex [Pd (OAc) (bpy) (CH ₂ COO—n—C ₃ H ₇ )] was removed from the solution, and a vinyl exchange reaction was carried out by the following procedure. That is, the solution containing the palladium complex was placed under a nitrogen atmosphere, 4.7 g (39.8 mmol) of 3,3-bishydroxymethyloxetane and 6.9 g (80.2 mmol) of normal propyl vinyl ether were added, and oxygen 8 vol. The mixture was heated at 70 ° C. for 24 hours while bubbling in a liquid at a flow rate of 130 mL / min. The dissolved oxygen concentration of the reaction solution during the reaction (measured with Micro Logger Oxygen Meter Model 3650 manufactured by Hack Ultra Co., Ltd.) was 2 ppm or less. During the reaction, in order to distill out the normal propyl alcohol produced as a by-product from the system, the weight of the extracted liquid was azeotroped with normal propyl vinyl ether and extracted from the Dean-Stark dehydrator so that the amount of the reaction liquid did not change. Minute normal propyl vinyl ether was added to the reactor. The reaction solution was sampled 8 hours, 16 hours, and 24 hours after the start of the reaction, and the yield of 3,3-bishydroxymethyloxetane divinyl ether was measured by gas chromatography (“GC-2010” manufactured by Shimadzu Corporation). When measured and calculated using, they were 44%, 71%, and 82%, respectively.
Yield (%) = 100 × [Amount of 3,3-bishydroxymethyloxetane divinyl ether produced (mol)] / [Amount of 3,3-bishydroxymethyloxetane charged (mol)]
24 g of the reaction solution (yellow solution) obtained above was allowed to cool, 8 g of hexane and 2.6 g of water were added and stirred. Then, when left still, it separated into two layers (upper layer: organic layer, lower layer: aqueous layer). When the upper layer (organic layer) and the lower layer (aqueous layer) were analyzed, the upper layer was mainly 3,3-bishydroxymethyloxetane divinyl ether, and the lower layer was mainly palladium complex, tetraglyme and 2,2′-bipyridine. Gas chromatography (“GC-2010” manufactured by Shimadzu Corporation) (however, for the palladium complex, an ICP plasma emission spectrometer (“ICP-” manufactured by Shimadzu Corporation) was used. S-7510 "), and the recovery rate of 3,3-bishydroxymethyloxetane divinyl ether in the upper layer was 97.4%, and the recovery rate of palladium complex in the lower layer was 80.1. %, The recovery rate of tetraglyme was 29.2%, and the recovery rate of 2,2′-bipyridine was 21.6%.
In addition, the recovery rate of each component in the upper layer (organic layer) and the lower layer (aqueous layer) was calculated by the following formula. The amount (weight) of each component present in each layer is determined by measuring and calculating the concentration of each component in each layer (solution) by the calibration curve method using the above apparatus, and calculating the weight of each component from the weight of each layer (solution). Calculated. The same applies to the following.
Recovery rate in water layer (%) = 100 × [each component amount (mol) in water layer] / ([each component amount (mol) in organic layer] + [each component amount (mol) in water layer] ])
Recovery rate in organic layer (%) = 100 × [each component amount in organic layer (mol)] / ([each component amount in water layer (mol)] + [each component amount in organic layer (mol) ])

(Second vinyl exchange reaction: First recycling of palladium catalyst)
To a 30 mL three-necked flask equipped with a Dimroth condenser and a Dean-Stark dehydrator, 6.09 g of the lower layer (aqueous layer) obtained in the first vinyl exchange reaction and 2.4 g of 3,3-bishydroxymethyloxetane (20 3 mmol), 3.1 g of tetraglyme, 0.7 g (4.5 mmol) of 2,2′-bipyridine, and 3.8 g (44.7 mmol) of normal propyl vinyl ether, and a mixed gas of 8 vol% oxygen and 92 vol% nitrogen. The solution was heated at 70 ° C. for 24 hours while being bubbled in the liquid at a flow rate of 130 mL / min, and a vinyl exchange reaction was carried out in a reflux state. The dissolved oxygen concentration of the reaction solution during the reaction (measured with Micro Logger Oxygen Meter Model 3650 manufactured by Hack Ultra Co., Ltd.) was 2 ppm or less. Since the reaction solution was separated into two layers at the start of the reaction, water was distilled off azeotropically while adding normal propyl vinyl ether during the reaction. The additional amount of normal propyl vinyl ether was adjusted to match the amount (weight) of distilled normal propyl vinyl ether. Also, in order to distill out the normal propyl alcohol produced as a by-product from the system, it was azeotroped with normal propyl vinyl ether and extracted from the Dean-Stark dehydrator. The reaction was carried out while adding to the reactor. The reaction solution was sampled 8 hours, 16 hours, and 24 hours after the start of the reaction, and the yield of 3,3-bishydroxymethyloxetane divinyl ether was determined by gas chromatography (“GC-2010” manufactured by Shimadzu Corporation). ) Was measured and calculated in the same manner as in the first vinyl exchange reaction, and they were 48%, 66%, and 76%, respectively.
After allowing 13.8 g of the reaction solution (yellow to brown solution) obtained above to cool, 13.8 g of hexane and 2.23 g of water were added and stirred. Then, when left still, it separated into two layers (upper layer: organic layer, lower layer: aqueous layer). When the upper layer (organic layer) and the lower layer (aqueous layer) were analyzed, 3,3-bishydroxymethyloxetane divinyl ether was mainly used for the upper layer, and palladium complex, tetraglyme, and 2,2′-bipyridine were mainly used for the lower layer. Gas chromatography (“GC-2010” manufactured by Shimadzu Corporation) (however, for palladium complexes, the ICP plasma emission spectrometer (“ICP-” manufactured by Shimadzu Corporation) was used. S-7510 "), and the recovery rate of 3,3-bishydroxymethyloxetane divinyl ether in the upper layer was 95.6%, and the recovery rate of palladium complex in the lower layer was 96.8. %, The recovery rate of tetraglyme was 47.4%, and the recovery rate of 2,2′-bipyridine was 32.6%.

(3rd vinyl exchange reaction: second recycling of palladium catalyst)
To a 30 mL three-necked flask equipped with a Dimroth condenser and a Dean-Stark dehydrator, 9.87 g of the lower layer (aqueous layer) obtained in the second vinyl exchange reaction, 2.4 g of 3,3-bishydroxymethyloxetane (20 3 mmol), 2.7 g of tetraglyme, 0.6 g (4.1 mmol) of 2,2′-bipyridine, and 3.5 g (41.5 mmol) of normal propyl vinyl ether, and mixed with 8 vol% oxygen and 92 vol% nitrogen. While the gas was bubbled in the liquid at a flow rate of 130 mL / min, it was heated at 70 ° C. for 24 hours to perform a vinyl exchange reaction under reflux. The dissolved oxygen concentration of the reaction solution during the reaction (measured with Micro Logger Oxygen Meter Model 3650 manufactured by Hack Ultra Co., Ltd.) was 2 ppm or less. During the reaction, water was distilled off azeotropically while adding normal propyl vinyl ether as in the first recycling. The additional amount of normal propyl vinyl ether was adjusted to match the amount (weight) of distilled normal propyl vinyl ether. Also, in order to distill out the normal propyl alcohol produced as a by-product from the system, it was azeotroped with normal propyl vinyl ether and extracted from the Dean-Stark dehydrator. The reaction was carried out while adding to the reactor. The reaction solution was sampled 8 hours, 16 hours, and 24 hours after the start of the reaction, and the yield of 3,3-bishydroxymethyloxetane divinyl ether was determined by gas chromatography (“GC-2010” manufactured by Shimadzu Corporation). ) And 17%, 41% and 53%, respectively, in the same manner as in the first vinyl exchange reaction.
After allowing the reaction solution (brown solution) 13.7 g obtained above to cool, 13.7 g of water and 13.7 g of hexane were added and stirred. Then, when left still, it separated into two layers (upper layer: organic layer, lower layer: aqueous layer). When the upper layer (organic layer) and the lower layer (aqueous layer) were analyzed, 3,3-bishydroxymethyloxetane divinyl ether was mainly used for the upper layer, and palladium complex, tetraglyme, and 2,2′-bipyridine were mainly used for the lower layer. Gas chromatography (“GC-2010” manufactured by Shimadzu Corporation) (however, for palladium complexes, the ICP plasma emission spectrometer (“ICP-” manufactured by Shimadzu Corporation) was used. S-7510 "), and the recovery rate of 3,3-bishydroxymethyloxetane divinyl ether in the upper layer was 96.1%, and the recovery rate of palladium complex in the lower layer was 94.3. %, The recovery rate of tetraglyme was 92.3%, and the recovery rate of 2,2′-bipyridine was 34.3%.

(4th vinyl exchange reaction: 3rd recycling of palladium catalyst)
In a 30 mL three-necked flask equipped with a Dimroth condenser and Dean-Stark dehydrator, 6.39 g of the lower layer (aqueous layer) obtained in the third vinyl exchange reaction, 1.7 g of 3,3-bishydroxymethyloxetane (14 .6 mmol), 0.5 g (2.9 mmol) of 2,2′-bipyridine, and 2.8 g (32.2 mmol) of normal propyl vinyl ether, and a mixed gas of 8 vol% oxygen and 92 vol% nitrogen at a flow rate of 130 mL / min. The solution was heated at 70 ° C. for 42 hours while bubbling in the solution, and a vinyl exchange reaction was carried out under reflux. The dissolved oxygen concentration of the reaction solution during the reaction (measured with Micro Logger Oxygen Meter Model 3650 manufactured by Hack Ultra Co., Ltd.) was 2 ppm or less. During the reaction, water was distilled off azeotropically while adding normal propyl vinyl ether as in the first and second recycling. The additional amount of normal propyl vinyl ether was adjusted to match the amount (weight) of distilled normal propyl vinyl ether. Also, in order to distill out the normal propyl alcohol produced as a by-product from the system, it was azeotroped with normal propyl vinyl ether and extracted from the Dean-Stark dehydrator. The reaction was carried out while adding to the reactor. The reaction solution was sampled 8 hours, 16 hours, 24 hours, 32 hours and 42 hours after the start of the reaction, and the yield of 3,3-bishydroxymethyloxetane divinyl ether was determined by gas chromatography (Corporation). The results were measured in the same manner as in the first vinyl exchange reaction using “GC-2010” manufactured by Shimadzu Corporation, and found to be 0%, 5%, 26%, 42%, and 55%, respectively.

As described above, the vinyl exchange reaction proceeded even when the third palladium complex was used. In the third vinyl exchange reaction and the fourth vinyl exchange reaction, there was a certain time (induction period) from the start of heating to the start of the reaction. Since the solution containing water contained water, the water in the reaction solution was azeotropically removed out of the system, and it is assumed that this corresponds to the time until the palladium complex can come into contact with the reaction substrate. . In fact, comparing the third vinyl exchange reaction with the fourth vinyl exchange reaction, the result is that the fourth vinyl exchange reaction with a large amount of water in the reaction solution at the start of the reaction has a longer induction period. It was.

Comparative Example 2
After performing the vinyl exchange reaction in the same procedure as the first vinyl exchange reaction of Example 26, the reaction solution after completion of the reaction (yellow solution) was simply distilled under the conditions of a liquid temperature of 89 ° C. and 90 Pa to obtain a reaction solution. The product 3,3-bishydroxymethyloxetane divinyl ether was concentrated and distilled off. The reaction solution after the 3,3-bishydroxymethyloxetane divinyl ether was distilled off turned black.
The black reaction solution obtained above was used as a catalyst solution, and a vinyl exchange reaction was performed in the same procedure as the second vinyl exchange reaction in Example 26. However, the vinyl exchange reaction did not proceed at all.

The palladium complex of the present invention is not easily deactivated even when the reaction is carried out at a high temperature, has high heat resistance, and has high activity for vinyl exchange reaction. Therefore, when the palladium complex of the present invention is used, raw materials for fine chemicals such as pharmaceuticals and agricultural chemicals, raw materials for functional resins (for example, resist resins, optical resins, transparent resins, cross-linked resins, etc.), curing for cationic polymerization The target vinyl ether compound applicable to the agent and the like can be obtained in high yield.

Claims

A palladium complex represented by the following formula (1).

[In formula (1), L 1 represents a bidentate ligand having two or more nitrogen atoms in the molecule. X represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or tetrafluoroborate. R 1 is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, a heteroaryl group, [R b O— (R a O) r R a — Or a polyoxyalkylene residue represented by the formula: or a hydroxyl group, a carbonyl group, a cyano group, an alkoxy group, an oxetanyl group, and a vinyloxy group, and having 1 to 18 carbon atoms having at least one substituent. A linear or branched alkyl group, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, or a heteroaryl group is shown. R a represents an alkylene group, R b represents a hydrogen atom, an alkyl group, an acyl group, or a vinyl group, and r represents an integer of 1 to 20. ]
L 1 is a bipyridine derivative or a 1,10-phenanthroline derivative, X is an acetyloxy group, R 1 is a linear or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl having 3 to 10 carbon atoms A linear or branched alkyl group having 1 to 10 carbon atoms having one or more hydroxyl groups, a linear or branched alkyl group having 1 to 10 carbon atoms having one or more vinyloxy groups, or [ HO— (CH 2 CH 2 O) s CH 2 CH 2 —] or [CH 2 ═CHO— (CH 2 CH 2 O) s CH 2 CH 2 —] The palladium complex according to claim 1, which represents an integer of 1 to 4.
L 1 is 2,2'-bipyridine or 1,10-phenanthroline, and R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. The palladium complex according to 1 or 2.
A method for producing a palladium complex represented by the following formula (1):
A divalent palladium complex represented by the following formula (2), a bidentate ligand having two or more nitrogen atoms in the molecule, and a vinyl ether compound represented by the following formula (3) in the presence of oxygen. Including a reaction step of reacting,
The reaction step includes a first reaction step of reacting at a temperature of 20 to 60 ° C. for 0.3 hours or longer, and a second reaction step of reacting at a temperature of 40 to 120 ° C. for 0.3 hours or longer after the first reaction step. A process for producing a palladium complex, characterized in that the reaction temperature is controlled to 120 ° C. or lower throughout the reaction.

[In formula (1), L 1 represents a bidentate ligand having two or more nitrogen atoms in the molecule. X represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or tetrafluoroborate. R 1 is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, a heteroaryl group, [R b O— (R a O) r R a — Or a polyoxyalkylene residue represented by the formula: or a hydroxyl group, a carbonyl group, a cyano group, an alkoxy group, an oxetanyl group, and a vinyloxy group, and having 1 to 18 carbon atoms having at least one substituent. A linear or branched alkyl group, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, or a heteroaryl group is shown. R a represents an alkylene group, R b represents a hydrogen atom, an alkyl group, an acyl group, or a vinyl group, and r represents an integer of 1 to 20. ]

[In Formula (2), X 1 and X 2 are the same or different and each represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or a tetrafluoroborate. Show. L represents a monodentate ligand having one or more nitrogen atoms in the molecule, or a bidentate ligand having two or more nitrogen atoms in the molecule. n represents an integer of 0 or more. ]

[In formula (3), R 1 is the same as above. ]
A method for producing a palladium complex represented by the following formula (1):
A reaction step of reacting a divalent palladium complex represented by the following formula (2) and a vinyl ether compound represented by the following formula (3) in the presence of oxygen,
The reaction step includes a first reaction step of reacting at a temperature of 20 to 60 ° C. for 0.3 hours or longer, and a second reaction step of reacting at a temperature of 40 to 120 ° C. for 0.3 hours or longer after the first reaction step. A process for producing a palladium complex, characterized in that the reaction temperature is controlled to 120 ° C. or lower throughout the reaction.

[In formula (1), L 1 represents a bidentate ligand having two or more nitrogen atoms in the molecule. X represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or tetrafluoroborate. R 1 is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, a heteroaryl group, [R b O— (R a O) r R a — Or a polyoxyalkylene residue represented by the formula: or a hydroxyl group, a carbonyl group, a cyano group, an alkoxy group, an oxetanyl group, and a vinyloxy group, and having 1 to 18 carbon atoms having at least one substituent. A linear or branched alkyl group, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, or a heteroaryl group is shown. R a represents an alkylene group, R b represents a hydrogen atom, an alkyl group, an acyl group, or a vinyl group, and r represents an integer of 1 to 20. ]

[In Formula (2), X 1 and X 2 are the same or different and each represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or a tetrafluoroborate. Show. L represents a bidentate ligand having two or more nitrogen atoms in the molecule. n represents an integer of 1 or more. ]

[In formula (3), R 1 is the same as above. ]
L 1 is a bipyridine derivative or a 1,10-phenanthroline derivative, X is an acetyloxy group, R 1 is a linear or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl having 3 to 10 carbon atoms A linear or branched alkyl group having 1 to 10 carbon atoms having one or more hydroxyl groups, a linear or branched alkyl group having 1 to 10 carbon atoms having one or more vinyloxy groups, or [ HO— (CH 2 CH 2 O) s CH 2 CH 2 —] or [CH 2 ═CHO— (CH 2 CH 2 O) s CH 2 CH 2 —] The method for producing a palladium complex according to claim 4 or 5, wherein the integer represents 1 to 4.
L 1 is 2,2'-bipyridine or 1,10-phenanthroline, and R 1 is a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. 7. The method for producing a palladium complex according to any one of 4 to 6.
In the presence of the palladium complex according to any one of claims 1 to 3, an alcohol compound represented by the following formula (4) is reacted with a vinyl ether compound represented by the following formula (5), and the following formula ( A method for producing a vinyl ether compound, characterized in that the vinyl ether compound represented by 6) is produced.

[In the formula (4), R 2 represents an organic group having a carbon atom at the bonding site with the oxygen atom shown in the formula, and p represents an integer of 1 or more. ]

[In the formula (5), R 3 to R 5 are the same or different and each represents a hydrogen atom or an organic group having a carbon atom at the bonding site with the carbon atom shown in the formula, and R 6 represents in the formula An organic group having a carbon atom at the bonding site with the oxygen atom. ]

[In formula (6), q represents an integer of 1 to p, and R 2 to R 5 are the same as defined above. ]
As the palladium complex according to any one of claims 1 to 3, a divalent palladium complex represented by the following formula (2), a bidentate ligand having two or more nitrogen atoms in the molecule, and A first reaction step in which the vinyl ether compound represented by the formula (3) is reacted in the presence of oxygen at a temperature of 20 to 60 ° C. for 0.3 hours or more; and after the first reaction step, further 40 to 120 And a second reaction step in which the reaction is carried out at a temperature of 0.3 ° C. for 0.3 hours or longer, and after the reaction is carried out in a reaction step in which the reaction temperature is controlled to 120 ° C. or lower throughout the reaction, The method for producing a vinyl ether compound according to claim 8, wherein a palladium complex is used.

[In Formula (2), X 1 and X 2 are the same or different and each represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or a tetrafluoroborate. Show. L represents a monodentate ligand having one or more nitrogen atoms in the molecule, or a bidentate ligand having two or more nitrogen atoms in the molecule. n represents an integer of 0 or more. ]

[In Formula (3), R 1 represents a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, a heteroaryl group, [R b O— ( R a O) r R a —] or at least one substituent selected from the group consisting of a hydroxyl group, a carbonyl group, a cyano group, an alkoxy group, an oxetanyl group, and a vinyloxy group A linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, or a heteroaryl group. R a represents an alkylene group, R b represents a hydrogen atom, an alkyl group, an acyl group, or a vinyl group, and r represents an integer of 1 to 20. ]
As the palladium complex according to any one of claims 1 to 3, a divalent palladium complex represented by the following formula (2) and a vinyl ether compound represented by the following formula (3) are prepared in the presence of oxygen. A first reaction step of reacting at a temperature of 20 to 60 ° C. for 0.3 hours or longer, and a second reaction step of further reacting at a temperature of 40 to 120 ° C. for 0.3 hours or longer after the first reaction step. The method for producing a vinyl ether compound according to claim 8, wherein a palladium complex obtained by further isolating is used after the reaction is carried out in a reaction step in which the reaction temperature is controlled to 120 ° C. or lower throughout the reaction.

[In Formula (2), X 1 and X 2 are the same or different and each represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or a tetrafluoroborate. Show. L represents a bidentate ligand having two or more nitrogen atoms in the molecule. n represents an integer of 1 or more. ]

[In Formula (3), R 1 represents a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, a heteroaryl group, [R b O— ( R a O) r R a —] or at least one substituent selected from the group consisting of a hydroxyl group, a carbonyl group, a cyano group, an alkoxy group, an oxetanyl group, and a vinyloxy group A linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, or a heteroaryl group. R a represents an alkylene group, R b represents a hydrogen atom, an alkyl group, an acyl group, or a vinyl group, and r represents an integer of 1 to 20. ]
As the palladium complex according to any one of claims 1 to 3, a divalent palladium complex represented by the following formula (2), a bidentate ligand having two or more nitrogen atoms in the molecule, and A first reaction step in which the vinyl ether compound represented by the formula (3) is reacted in the presence of oxygen at a temperature of 20 to 60 ° C. for 0.3 hours or more; and after the first reaction step, further 40 to 120 Using a palladium complex solution obtained by reacting in a reaction step in which the reaction temperature is controlled to 120 ° C. or lower throughout the reaction Item 9. A method for producing a vinyl ether compound according to Item 8.

[In Formula (2), X 1 and X 2 are the same or different and each represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or a tetrafluoroborate. Show. L represents a monodentate ligand having one or more nitrogen atoms in the molecule, or a bidentate ligand having two or more nitrogen atoms in the molecule. n represents an integer of 0 or more. ]

[In Formula (3), R 1 represents a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, a heteroaryl group, [R b O— ( R a O) r R a —] or at least one substituent selected from the group consisting of a hydroxyl group, a carbonyl group, a cyano group, an alkoxy group, an oxetanyl group, and a vinyloxy group A linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, or a heteroaryl group. R a represents an alkylene group, R b represents a hydrogen atom, an alkyl group, an acyl group, or a vinyl group, and r represents an integer of 1 to 20. ]
As the palladium complex according to any one of claims 1 to 3, a divalent palladium complex represented by the following formula (2) and a vinyl ether compound represented by the following formula (3) are prepared in the presence of oxygen. A first reaction step of reacting at a temperature of 20 to 60 ° C. for 0.3 hours or longer, and a second reaction step of further reacting at a temperature of 40 to 120 ° C. for 0.3 hours or longer after the first reaction step. The method for producing a vinyl ether compound according to claim 8, wherein a palladium complex solution obtained by reacting in a reaction step including a reaction temperature controlled to 120 ° C or lower throughout the reaction is used.

[In Formula (2), X 1 and X 2 are the same or different and each represents an acyloxy group, a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, an arylsulfonyloxy group, a haloarylsulfonyloxy group, or a tetrafluoroborate. Show. L represents a bidentate ligand having two or more nitrogen atoms in the molecule. n represents an integer of 1 or more. ]

[In Formula (3), R 1 represents a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, a heteroaryl group, [R b O— ( R a O) r R a —] or at least one substituent selected from the group consisting of a hydroxyl group, a carbonyl group, a cyano group, an alkoxy group, an oxetanyl group, and a vinyloxy group A linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group, or a heteroaryl group. R a represents an alkylene group, R b represents a hydrogen atom, an alkyl group, an acyl group, or a vinyl group, and r represents an integer of 1 to 20. ]
In the presence of the palladium complex according to any one of claims 1 to 3, an alcohol compound represented by the following formula (4) is reacted with a vinyl ether compound represented by the following formula (5), and the following formula ( 6) Water and an organic solvent that is a good solvent for the vinyl ether compound represented by the following formula (6) and phase-separated from water with respect to the reaction solution after the vinyl exchange reaction that has produced the vinyl ether compound represented by 6) And then recovering the palladium complex by separating the aqueous layer.

[In the formula (4), R 2 represents an organic group having a carbon atom at the bonding site with the oxygen atom shown in the formula, and p represents an integer of 1 or more. ]

[In the formula (5), R 3 to R 5 are the same or different and each represents a hydrogen atom or an organic group having a carbon atom at the bonding site with the carbon atom shown in the formula, and R 6 represents in the formula An organic group having a carbon atom at the bonding site with the oxygen atom. ]

[In formula (6), q represents an integer of 1 to p, and R 2 to R 5 are the same as defined above. ]