JP7349335B2 - Method for producing complex compound - Google Patents

Description

The present invention relates to a method for producing a complex compound. More specifically, the present invention relates to a simple method for producing zero-valent transition metal complex compounds useful as catalysts for hydrophosphorylation reactions.

Organophosphorus compounds are chemical substances that are widely used in various products such as flame retardants, plasticizers, insecticides, medicines and agrochemicals, and ligands for metal complexes. In recent years, organic phosphorus compounds have attracted particular attention industrially as functional materials in the fields of metal surface treatment agents, constituent materials such as flame-retardant resins, and electronic materials.

Among organic phosphorus compounds, alkenylphosphonic acid derivatives are useful precursor substances for the various chemical substances mentioned above, and therefore various production methods have been investigated heretofore. For example, alkenylphosphonic acid derivatives have been produced by addition reaction of P(O)--H bond of phosphonic acid to alkynes (hereinafter referred to as hydrophosphorylation reaction) using a catalyst. For example, Non-Patent Document 1 proposes performing a hydrophosphorylation reaction using a catalyst in which a transition metal is immobilized on a polystyrene resin bound to triphenylphosphine.

Chem. Lett. 2013, 42, 1065-1067

However, in the catalyst described in Non-Patent Document 1, in which a transition metal is immobilized on polystyrene resin bound to triphenylphosphine, the phosphorus content on the resin surface is insufficient, and it is extremely difficult to add the amount of phosphorus necessary for the reaction. There have been problems in that a large amount of resin is required, the reaction efficiency is low, and there is a lot of leaching of metal components from the resin surface, resulting in a large number of side reactions. Therefore, there was room for improvement in reaction efficiency when used in hydrophosphorylation reactions.

Therefore, it is an object of the present invention to provide complex compounds useful as catalysts for hydrophosphorylation reactions.

As a result of extensive research in order to solve the above problems, the inventors of the present invention discovered that by reacting a resin having a phosphine substituent on the surface with a divalent transition metal compound in the presence of a solvent and a reducing agent. The present inventors have discovered that it is possible to obtain a zero-valent transition metal complex compound useful as a catalyst for hydrophosphorylation reactions, and have completed the present invention.

（一般式（１）中、Ｒ^１は、置換もしくは非置換の炭化水素基を表し、Ｒ^２は、置換もしくは非置換のアルキル基または置換もしくは非置換のアリール基を示し、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子、置換もしくは非置換のアルキル基、または置換もしくは非置換のアリール基を示し、ｎおよびｍの値の合計１００％に対して、ｎの値は２０～１００％の範囲内であり、ｍの値は０～８０％の範囲内であり、＊で樹脂微粒子表面と結合している。）
で表される樹脂微粒子と、二価の遷移金属化合物とを、溶媒および還元剤の存在下で反応させて、ゼロ価の遷移金属錯体化合物を製造する方法。
［２］ 前記溶媒が、配位性溶媒である、［１］に記載の製造方法。
［３］ 前記配位性溶媒が、非プロトン性極性溶媒である、［２］の記載の製造方法。
［４］ 前記二価の遷移金属が二価のニッケル化合物である、［１］～［３］のいずれかに記載の製造方法。
［５］ 前記二価のニッケル化合物が、塩化ニッケル、酢酸ニッケル、およびそれらの水和物から選択される、［４］に記載の製造方法。
［６］ 前記還元剤が、前記遷移金属よりも陽性の金属である、［１］～［５］のいずれかに記載の製造方法。
［７］ 前記遷移金属よりも陽性の金属が、亜鉛である、［６］に記載の製造方法。
［８］ 前記樹脂微粒子中のホスフィン基と前記遷移金属の物質量比が１０：１～１：２である、［１］～［７］のいずれかに記載の製造方法。
［９］ 一般式（１）中、Ｒ^１は、炭素数が６～１２の炭化水素基である、［１］～［８］のいずれかに記載の製造方法。
［１０］ 一般式（１）中、Ｒ^２は、炭素数が１～８のアルキル基、または炭素数が５～１２のアリール基である、［１］～［９］のいずれかに記載の製造方法。
［１１］ 一般式（１）中、Ｒ^３およびＲ^４は、炭素数が１～８のアルキル基、または炭素数が５～１２のアリール基である、［１］～［１０］のいずれかに記載の製造方法。
［１２］ 前記錯体化合物が、ヒドロホスホリル化反応の触媒として用いられる、［１］～［１１］のいずれかに記載の製造方法。 That is, according to the present invention, the following inventions are provided.
[1] General formula (1) below:

(In general formula (1), R ¹ represents a substituted or unsubstituted hydrocarbon group, R ² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, R ³ and R ⁴ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and the value of n is 20 to 100% with respect to the total of 100% of the values of n and m. The value of m is within the range of 0 to 80%, and the * indicates that it is bonded to the surface of the resin fine particles.)
A method for producing a zero-valent transition metal complex compound by reacting resin fine particles represented by the above with a divalent transition metal compound in the presence of a solvent and a reducing agent.
[2] The manufacturing method according to [1], wherein the solvent is a coordinating solvent.
[3] The manufacturing method according to [2], wherein the coordinating solvent is an aprotic polar solvent.
[4] The manufacturing method according to any one of [1] to [3], wherein the divalent transition metal is a divalent nickel compound.
[5] The manufacturing method according to [4], wherein the divalent nickel compound is selected from nickel chloride, nickel acetate, and hydrates thereof.
[6] The production method according to any one of [1] to [5], wherein the reducing agent is a metal that is more positive than the transition metal.
[7] The manufacturing method according to [6], wherein the metal more positive than the transition metal is zinc.
[8] The production method according to any one of [1] to [7], wherein the ratio of the amount of phosphine groups to the transition metal in the resin fine particles is 10:1 to 1:2.
[9] The production method according to any one of [1] to [8], wherein in general formula (1), R ¹ is a hydrocarbon group having 6 to 12 carbon atoms.
[10] In the general formula (1), R ² is an alkyl group having 1 to 8 carbon atoms or an aryl group having 5 to 12 carbon atoms, according to any one of [1] to [9]. Production method.
[11] In general formula (1), R ³ and R ⁴ are an alkyl group having 1 to 8 carbon atoms or an aryl group having 5 to 12 carbon atoms, any one of [1] to [10] The manufacturing method described in.
[12] The production method according to any one of [1] to [11], wherein the complex compound is used as a catalyst for a hydrophosphorylation reaction.

According to the present invention, it is possible to provide a method for producing a zero-valent transition metal complex compound useful as a catalyst for a hydrophosphorylation reaction. The zero-valent transition metal complex compound of the present invention, as a catalyst, can efficiently advance the hydrophosphorylation reaction at a temperature of room temperature or higher. Furthermore, since the complex compound of the present invention can use inexpensive commercially available materials as raw materials, manufacturing costs can be reduced.

FIG. 3 is a diagram showing an IR spectrum of resin fine particles (I). FIG. 3 is a diagram showing an IR spectrum of resin fine particles (II).

[Method for producing complex compound]
The method for producing a complex compound of the present invention involves reacting resin fine particles represented by the following general formula (1) with a divalent transition metal compound in the presence of a reducing agent to produce a zero-valent transition metal complex compound. It includes a step of synthesizing. The zero-valent transition metal complex compound obtained by the method for producing a complex compound of the present invention can be used as a catalyst for a hydrophosphorylation reaction. The zero-valent transition metal complex compound has a phosphine substituent at a high concentration on the surface of the resin fine particles, so that the hydrophosphorylation reaction can proceed efficiently at a temperature of room temperature or higher.

（一般式（１）中、Ｒ^１は、置換もしくは非置換の炭化水素基を表し、Ｒ^２は、置換もしくは非置換のアルキル基または置換もしくは非置換のアリール基を示し、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子、置換もしくは非置換のアルキル基、または置換もしくは非置換のアリール基を示し、ｎおよびｍの値の合計１００％に対して、ｎの値は２０～１００％の範囲内であり、ｍの値は０～８０％の範囲内であり、＊で樹脂微粒子表面と結合している。） (Resin fine particles)
The resin fine particles used in the method for producing a complex compound are represented by the following general formula (1).

(In general formula (1), R ¹ represents a substituted or unsubstituted hydrocarbon group, R ² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, R ³ and R ⁴ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and the value of n is 20 to 100% with respect to the total of 100% of the values of n and m. The value of m is within the range of 0 to 80%, and the * indicates that it is bonded to the surface of the resin fine particles.)

In the general formula (1), the substituted or unsubstituted hydrocarbon group for R ¹ is preferably a hydrocarbon group having 6 to 12 carbon atoms. Note that the above carbon number does not include the carbon number of the substituent. Examples of hydrocarbon groups having 6 to 12 carbon atoms include alkylene groups such as hexylene groups, heptylene groups, and octylene groups, cycloalkylene groups such as cyclohexylene groups, and aromatic hydrocarbon groups such as phenylene groups and naphthylene groups. Can be mentioned. Among these, R ¹ is preferably an aromatic hydrocarbon group, more preferably a phenylene group.

In general formula (1), the substituted or unsubstituted alkyl group for R ² is preferably an alkyl group having 1 to 8 carbon atoms, and the substituted or unsubstituted aryl group is preferably an aryl group having 5 to 12 carbon atoms. Groups are preferred. Note that the above carbon number does not include the carbon number of the substituent. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, etc. . Examples of the aryl group having 5 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, and naphthyl group. Among these, R ² is preferably an aromatic hydrocarbon group, and more preferably a phenyl group.

In general formula (1), the substituted or unsubstituted alkyl group for R ³ and R ⁴ is preferably an alkyl group having 1 to 8 carbon atoms, and the substituted or unsubstituted aryl group is preferably a carbon number 5 to 8. 12 aryl groups are preferred. Note that the above carbon number does not include the carbon number of the substituent. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, etc. . Examples of the aryl group having 5 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, and naphthyl group. Among these, it is preferable that R ³ and R ⁴ are each independently a hydrogen atom, a methyl group, or a phenyl group.

In general formula (1), examples of substituents that R ¹ , R ² , R ³ , and R ⁴ may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a heterocyclic group, Examples include an alkylidene group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group. Further, the number of carbon atoms contained in the substituent is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. Moreover, R ¹ , R ² , R ³ , and R ⁴ may have a fluorine atom.

Specific examples of the resin represented by general formula (1) include resins represented by the following formula.

In general formula (1), the value of n is 20 to 100%, preferably 50 to 100%, more preferably 80 to 100%, with respect to the total of 100% of the values of n and m, The value of m is 0 to 80%, preferably 0 to 50%, more preferably 0 to 20%.

The resin fine particles represented by the general formula (3) can be produced by the following method. For example, by adding Merrifield resin and an alkali metal organic phosphorus compound or a trivalent organic phosphorus compound having an ester bond into a reaction vessel under a nitrogen atmosphere, and reacting at -20 to 150°C for 1 to 48 hours, Resin fine particles can be produced. Note that Merrifield resin refers to styrene/chloromethylstyrene crosslinked resin. Examples of the alkali metal organic phosphorus compounds include sodium diphenyl phosphide and sodium methylphenyl phosphide. Examples of the trivalent organic phosphorus compound having an ester bond include triethyl phosphite, methyl diphenylphosphinate, and the like.

In addition, ethenylphenylmethylmagnesium chloride and halogenated phosphine were added to a reaction vessel under a nitrogen atmosphere, and phosphinylmethylstyrene obtained by reacting at 0 to 100°C for 1 to 48 hours, styrene, and a crosslinking agent were suspended. Resin fine particles can be produced by performing turbid polymerization.

Since the resin fine particles are bonded to the surface of the resin fine particles with *, the phosphorus content on the surface is high, preferably 1.3 mmol/g or more, more preferably 2.0 mmol/g or more, and even more preferably 2.0 mmol/g or more. It is .5 mmol/g or more. The phosphorus content on the surface of the resin fine particles can be measured by elemental analysis, the adsorption amount of an organic halide compound, and redox titration.

The resin fine particles can be adjusted to a desired particle size by classifying them by conventionally known methods or adjusting reaction conditions. Although the size of the resin fine particles is not particularly limited, the average particle size is preferably 1 to 1000 μm, more preferably 10 to 100 μm, and even more preferably from the viewpoint of ease of forming a complex with a transition metal. is 30 to 75 μm. The average particle diameter of the resin fine particles can be measured using a laser diffraction type particle size distribution measuring device or a sieving method (JIS K 0069:1992).

(Divalent transition metal compound)
The divalent transition metal compound used in the method for producing a complex compound is preferably a divalent nickel compound. Examples of divalent nickel compounds include nickel chloride (NiCl ₂ ), nickel acetate (Ni(OAc) ₂ ), bis(cyclopentadienyl)nickel (abbreviated as NiCp ₂ ), nickel bromide (NiBr ₂ ), and iodine. nickel oxide (NiI ₂ ), 1,2-bis(dimethylamino)ethane nickel chloride (abbreviated as Ni(TMEDA)Cl ₂ ), 1,2-bis(diphenylphosphino)ethane nickel chloride, nickel naphthenate, and these Examples include hydrates. Among these, the divalent transition metal compound is preferably nickel chloride (NiCl ₂ ), nickel acetate (Ni(OAc) ₂ ), and hydrates thereof. These divalent transition metal compounds form a complex with the coordinating solvent and are eluted into the solvent, and are reduced to zero-valent transition metal compounds using the reducing agent described below, thereby reducing the phosphine present on the surface of the resin particles. The result is a transition metal compound having a weaker ligand than that of the transition metal compound, and a complex compound of the transition metal compound and the resin fine particles can be formed.

(solvent)
As the solvent used in the method for producing the complex compound, a coordinating solvent can be used. As the coordinating solvent, it is preferable to use an aprotic polar solvent. Examples of the aprotic polar solvent include cyclic ethers (tetrahydrofuran, dioxane, etc.), ketones (acetone, 2-butanone, acetylacetone, etc.), and linear ethers (diethyl ether, ethylene glycol dimethyl ether, etc.). By using a coordinating solvent as a solvent, the solvent coordinates and forms a complex with the divalent nickel compound, increasing its solubility in the solvent, increasing its reactivity with reducing agents (including metals), and further increasing the coordinating solvent and the divalent nickel compound. This has the effect of promoting ligand exchange with phosphine on the surface of the resin fine particles and promoting complex formation on the surface of the resin fine particles.

(Reducing agent)
As the reducing agent used in the method for producing a complex compound, a metal more positive than the above-mentioned transition metals can be used. As the metal that is more positive than the above transition metals, it is preferable to use zinc, aluminum, iron, etc. Further, as the reducing agent, sodium borohydride, lithium aluminum hydride, hydrazine, etc. can also be used.

(Reaction conditions)
The substance ratio of the phosphine group to the transition metal compound in the resin fine particles is not particularly limited as long as a complex compound can be formed, but it is preferably 10:1 to 1:2, more preferably 8:1 to 1:1. , more preferably 5:1 to 2:1. Further, the amount of the reducing agent added is not particularly limited as long as it can reduce the transition metal compound, but for example, it is preferably 0.5 to 5 mol, more preferably 0.8 to 2.0 mol, per 1 mol of the transition metal compound. and more preferably 1.0 to 1.1 mol.

The reaction temperature between the resin fine particles and the transition metal compound is not particularly limited, but in consideration of reaction efficiency, reaction rate, and by-products, it is preferably 0 to 100°C, more preferably 20 to 80°C, and Preferably it is 30-60°C.

The reaction time of the resin fine particles and the transition metal compound is not particularly limited, but in consideration of reaction efficiency, reaction rate, and by-products, it is preferably 10 minutes to 24 hours, more preferably 1 to 20 hours, More preferably, the time is 4 to 18 hours.

The reaction between the resin particles and the transition metal compound is preferably carried out under an inert gas atmosphere in consideration of reaction efficiency, reaction rate, and by-products. As the inert gas, it is preferable to use nitrogen, argon, or the like.

[Hydrophosphorylation reaction]
The complex compound obtained by the above production method can be suitably used as a catalyst for a hydrophosphorylation reaction. In particular, an alkenyl phosphorus compound can be efficiently synthesized from a phosphorus compound and an alkynyl compound as raw materials under a temperature condition of room temperature or higher.

（一般式（２）中、Ｒ^５およびＲ^６は、それぞれ独立して、置換もしくは非置換のアルキル基、置換もしくは非置換のアルコキシ基、置換もしくは非置換のシクロアルキル基、置換もしくは非置換のアラルキル基、置換もしくは非置換のアリール基、または置換もしくは非置換のアリールオキシ基を示す。また、Ｒ^５およびＲ^６は、互いに結合して環状構造を形成していてもよい。） As a raw material for the hydrophosphorylation reaction, a phosphorus compound represented by the following general formula (2) can be used.

(In general formula (2), R ⁵ and R ⁶ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyl group, It represents an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group. Also, R ⁵ and R ⁶ may be bonded to each other to form a cyclic structure.)

In general formula (2), the number of carbon atoms in the alkyl group, alkoxy group, cycloalkyl group, aralkyl group, aryl group, and aryloxy group of R ⁵ and R ⁶ is preferably 1 to 10. Note that the above carbon number does not include the carbon number of the substituent. For example, R ⁵ and R ⁶ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, and hexyl group, methoxy group, and ethoxy group. , alkoxy groups such as butoxy groups, cycloalkyl groups such as cyclohexyl groups, aralkyl groups such as benzyl groups and phenethyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, naphthyl groups, and aryloxy groups such as phenoxy groups. Can be mentioned.

In general formula (2), examples of substituents that R ⁵ and R ⁶ may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkylkoxy group, a heterocyclic group, an alkylidene group, and a silyl group. , acyl group, acyloxy group, carboxy group, cyano group, nitro group, hydroxy group, mercapto group, and oxo group. Further, the number of carbon atoms contained in the substituent is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3.

（一般式（３）中、Ｒ^７およびＲ^８は、それぞれ独立して、水素原子、置換もしくは非置換のアルキル基、置換もしくは非置換のシクロアルキル基、置換もしくは非置換のアラルキル基、置換もしくは非置換のアリール基、置換もしくは非置換のヘテロアリール基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアルコキシ基、置換もしくは非置換のアリールオキシ基、または置換もしくは非置換のシリル基を示す。） As a raw material for the hydrophosphorylation reaction, an alkynyl compound represented by the following general formula (3) can be used.

(In general formula (3), R ⁷ and R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or Indicates an unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, or substituted or unsubstituted silyl group .)

In general formula (3), the number of carbon atoms in the alkyl group, cycloalkyl group, aralkyl group, aryl group, heteroaryl group, alkenyl group, alkoxy group, and aryloxy group of R ⁷ and R ⁸ is 1 to 10. is preferred. Note that the above carbon number does not include the carbon number of the substituent. For example, R ⁷ and R ⁸ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, hexyl group, and cyclohexyl group such as cyclohexyl group. Alkyl group, aralkyl group such as benzyl group, phenethyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, 1-butenyl group, 2-butenyl group, 1,3-butadienyl group, pentenyl group, hexenyl group Examples thereof include alkenyl groups such as groups, alkoxy groups such as methoxy groups, ethoxy groups, and butoxy groups, and aryloxy groups such as phenoxy groups.

In general formula (3), examples of the substituents that R ⁷ and R ⁸ may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a heterocyclic group, an alkylidene group, a silyl group, and an acyl group. group, acyloxy group, carboxy group, cyano group, nitro group, hydroxy group, mercapto group, and oxo group. Further, the number of carbon atoms contained in the substituent is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3.

The material ratio of the phosphorus compound represented by general formula (2) and the alkynyl compound represented by general formula (3) as raw materials for the hydrophosphorylation reaction is preferably 10:1 to 0.1:1. , more preferably 3:1 to 0.7:1, still more preferably 1.1:1 to 0.9:1.

The amount of the complex compound (catalyst) used in the hydrophosphorylation reaction is not particularly limited as long as the reaction proceeds sufficiently, but it is preferably 0.001 to 0.5 mol per mol of the phosphorus compound as the raw material, More preferably 0.01 to 0.1 mol, still more preferably 0.025 to 0.05 mol.

The reaction temperature of the hydrophosphorylation reaction is not particularly limited, but in consideration of reaction efficiency, reaction rate, and by-products, it is preferably 50 to 120 °C, more preferably 50 to 80 °C, and even more preferably The temperature is 50-60°C.

The reaction time of the hydrophosphorylation reaction is not particularly limited, but in consideration of reaction efficiency, reaction rate, and by-products, it is preferably 30 minutes to 40 hours, more preferably 1 hour to 24 hours, and Preferably it is 4 to 18 hours.

The hydrophosphorylation reaction may be performed in an organic solvent or in the absence of a solvent. The organic solvent used in the hydrophosphorylation reaction is not particularly limited, and examples thereof include alcohols, ethers, hydrocarbons, ketones, esters, aromatic hydrocarbons, and the like.

The hydrophosphorylation reaction is preferably carried out under an inert gas atmosphere in consideration of reaction efficiency, reaction rate, and by-products. As the inert gas, it is preferable to use nitrogen, argon, or the like.

（一般式（４）中、Ｒ^５およびＲ^６は、一般式（２）中のＲ^５およびＲ^６と同義であり、Ｒ^７およびＲ^８は、一般式（２）中のＲ^７およびＲ^８と同義である。） In the present invention, an alkenylphosphorus compound represented by the following general formula (4) can be obtained by a hydrophosphorylation reaction.

(In general formula (4), R ⁵ and R ⁶ are synonymous with R ⁵ and R ⁶ in general formula (2), and R ⁷ and R ⁸ are R 7 and R ⁶ in general formula (2). It is synonymous with ^8. )

EXAMPLES The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

<Synthesis of complex compound>
[Example 1]
Under a nitrogen atmosphere, 40 mL of tetrahydrofuran (THF) and 10.5 g of triphenylphosphine were added to a reaction vessel and stirred well. Subsequently, 7.36 g of metallic sodium dispersion (sodium content: approximately 25% by mass, average particle diameter of metallic sodium fine particles: 10 μm, manufactured by Kobelco Eco-Solutions Co., Ltd., SD) was added to the reaction vessel, and the temperature was then heated to 25°C. The mixture was stirred for 18 hours to obtain sodium diphenyl phosphide (Ph ₂ P-Na).

（上記式中、ｎおよびｍの値の合計１００％に対して、ｎの値は５０％であり、ｍの値は５０％
である。） Under a nitrogen atmosphere, 9.8 g of Merrifield resin (manufactured by Sigma-Aldrich Japan LLC, 4.4 mmol Cl/g, crosslinking agent: divinylbenzene 1 mol%) was added to the reaction vessel in which the above sodium diphenylphosphinide was prepared. The reaction was carried out at 60°C for 15 hours. After the reaction, 20 mL of 2-propanol was added dropwise to the reaction solution over 1 hour. The precipitate was taken out into the air from this suspension and washed three times with 20 mL of THF, three times with 20 mL of purified water, and once with 20 mL of acetone. It was dried under reduced pressure at 60° C. for 18 hours to obtain resin fine particles (I) represented by the following formula.

(In the above formula, the value of n is 50% and the value of m is 50% with respect to the total of 100% of the values of n and m.
It is. )

The phosphorus content on the surface of the obtained resin fine particles (I) was measured by the organic halide adsorption method described below, and was found to be 2.34 mmol/g.
(Surface phosphorus content measurement method using organic halide adsorption method)
100 mg of resin fine particles and 2.0 mL of a 5.5% by mass benzyl bromide THF solution were weighed into a vial and stirred at 60° C. for 18 hours. The supernatant liquid was extracted, and the amount of benzyl bromide adsorbed was calculated using an internal standard method (standard substance diphenyl ether) using GC-FID to determine the phosphorus content of the resin particles.

The obtained fine resin particles (I) were passed through a 300 mesh sieve, and what passed through was collected, yielding 15.9 g of pale yellow fine resin particles.

In a reaction vessel, 6.0 mmol of the obtained resin fine particles (I), 1.5 mmol of nickel chloride (NiCl ₂ ), and 1.55 mmol of zinc powder as a reducing agent were mixed at 60° C. for 8 hours in the presence of 4 mL of THF. The reaction gave complex compound (I). In addition, since zinc chloride (ZnCl ₂ ) was produced as a by-product, the complex compound (I) was washed with THF to remove the by-product.

The obtained resin fine particles (I) were measured by IR. The obtained IR spectrum is shown in FIG. When the IR spectrum was checked, the peak derived from C-Cl (wave number: 1295 cm ^-1 ) contained in the raw material Merrifield resin disappeared, and the generation of a peak derived from PC (wave number: 694 cm ^-1 ) was confirmed. Ta. In addition, it was confirmed that vinyl phosphorus was produced by coordinating with Ni in the above. From these results, it can be said that chemical bonds of phosphorus were formed on the surface of the resin particles.

[Example 2]
In a reaction vessel, 6.0 mmol of the resin fine particles (I) obtained in Example 1, 1.5 mmol of nickel acetate tetrahydrate (Ni(OAc) _{2.4H 2} O), and 1.5 mmol of zinc powder as a reducing agent were added. 55 mmol was reacted at 60° C. for 6 hours in the presence of 4 mL of THF to obtain complex compound (II). Although zinc acetate was produced as a by-product, the next step was carried out without purification.

[Example 3]
In a reaction vessel, 6 mol of resin fine particles (I) obtained in Example 1, 1.5 mol of nickel acetate tetrahydrate (Ni(OAc) _{2.4H 2} O), and 1.55 mol of zinc powder as a reducing agent were added. , in the presence of acetone at 60° C. for 6 hours to obtain complex compound (III). Although zinc acetate was produced as a by-product, the process proceeded to the next step without purification.

[Example 4]
Under a nitrogen atmosphere, 132 mL of THF and 20.17 g of triphenylphosphine were added to the reaction vessel and stirred well. Subsequently, 25.4 g of a metallic sodium dispersion (sodium content: approximately 25% by mass, average particle diameter of metallic sodium fine particles: 10 μm, manufactured by Kobelco Eco-Solutions Co., Ltd., SD) was added to the reaction vessel, and then heated at 25°C. The mixture was stirred for 18 hours to obtain sodium diphenyl phosphide (Ph ₂ P-Na).

（上記式中、ｎおよびｍの値の合計１００％に対して、ｎの値は１００％であり、ｍの値は０％である。） Next, 9.76 g of Merrifield resin (manufactured by Sigma-Aldrich Japan LLC, 5.5 mmol Cl/g, crosslinking agent: divinylbenzene 5 mol%, particle size 16-50 mesh) was added to the reaction vessel, and the mixture was heated at 25°C for 20 hours. After the reaction, 20 mL of 2-propanol was added dropwise over an hour, and the precipitate was taken out into the air. This precipitate was washed three times with 60 mL of THF, three times with 60 mL of water, and once with 30 mL of acetone. This was dried under reduced pressure at 60° C. for 18 hours to obtain resin fine particles (II) represented by the following formula. The phosphorus content on the surface of the obtained resin fine particles (II) was measured in the same manner as in Example 1, and was found to be 2.96 mmol/g.

(In the above formula, the value of n is 100% and the value of m is 0% with respect to the total of 100% of the values of n and m.)

In a reaction vessel, 6.0 mmol of the obtained resin fine particles (II), 1.5 mmol of nickel acetate hydrate (Ni(OAc) _{2.4H 2} O), 1.55 mmol of zinc powder as a reducing agent, and 4 mL of THF were added. The mixture was reacted for 6 hours at 60° C. to obtain complex compound (IV). Although zinc acetate was produced as a by-product, the process proceeded to the next step without purification.

The obtained resin fine particles (II) were measured by IR. The obtained IR spectrum is shown in FIG. 2. When the IR spectrum was checked, the peak derived from C-Cl (wave number: 1285 cm ^-1 ) contained in the raw material Merrifield resin disappeared, and the generation of a peak derived from PC (wave number: 694 cm ^-1 ) was confirmed. Ta. In addition, it was confirmed that vinyl phosphorus was produced by coordinating with Ni in the above. From these results, it can be said that chemical bonds of phosphorus were formed on the surface of the resin particles.

[Comparative example 1]
In a reaction vessel, 1 mL of trimethylphosphine (manufactured by ALDRICH, 1.0 mol/LTHF solution) and 68.75 mg of bis(1,5-cyclooctadiene)nickel(0) were reacted at 0° C. for 1 hour. Complex compound (V) was obtained by distilling off the solvent from this THF solution under reduced pressure.

[Comparative example 2]
Add 200 mg of 4-Diphenylphosphinomethyl Polystyrene Resin cross-linked with 2% DVB (200-400mesh) (0.5-1.0 mmol/g) (Cat. No. D2766, Tokyo Kasei Co., Ltd.) to the reaction vessel. and screws (1,5 13.8 mg of nickel (0) (cyclooctadiene) was weighed out, 1 mL of THF was added, and the mixture was stirred at 25° C. for 18 hours. The supernatant liquid was decanted, and the precipitate was washed three times with 0.5 mL of THF to obtain complex compound (VI).

<Synthesis of alkenylphosphorus compounds>
[Synthesis example 1]
In a reaction vessel, 90 mmol of a phosphorus compound ((MeO) ₂ P(O)H) as a starting material and the entire amount of complex compound (I) synthesized in Example 1 were mixed. Then, an acetylene balloon was attached to the reaction device, and the reaction was carried out at 60° C. for 4 hours to obtain an alkenylphosphorus compound ((MeO) ₂ P(O)CH=CH ₂ ). As a result of measuring the amount of alkenyl phosphorus compound produced by an internal standard method (standard substance diphenyl ether) using GC-FID, the amount of alkenyl phosphorus compound produced per 1 mmol of Ni was 3.81 g.

[Synthesis example 2]
An alkenylphosphorus compound ((MeO) ₂ P(O)CH=CH ₂ ) was obtained in the same manner as in Synthesis Example 1 except that the entire amount of the complex compound (II) synthesized in Example 2 was used as a catalyst. The amount of alkenylphosphorus compound produced per mmol of Ni was 4.01 g.

[Synthesis example 3]
An alkenylphosphorus compound ((MeO) ₂ P(O)CH=CH ₂ ) was obtained in the same manner as in Synthesis Example 1 except that the entire amount of the complex compound (III) synthesized in Example 3 was used as a catalyst. The amount of alkenylphosphorus compound produced per mmol of Ni was 4.54 g.

[Synthesis example 4]
An alkenylphosphorus compound ((MeO) ₂ P(O)CH=CH ₂ ) was obtained in the same manner as in Synthesis Example 1 except that the entire amount of the complex compound (IV) synthesized in Example 4 was used as a catalyst. The amount of alkenylphosphorus compound produced per 1 mmol of Ni was 4.73 g.

[Synthesis example 5 (comparison)]
An alkenylphosphorus compound ((MeO) ₂ P(O)CH=CH ₂ ) was obtained in the same manner as in Synthesis Example 1 except that 6 mmol of the complex compound (V) synthesized above was used as a catalyst. The amount of alkenylphosphorus compound produced per 1 mmol of Ni was 0.08 g.

[Synthesis example 6 (comparison)]
1 mmol of the phosphorus compound ((MeO) ₂ P(O)H), 1 mmol of the alkynyl compound (1-octyne), and 1 mL of THF were weighed into a glass Schlenk, and 0.05 mmol of the complex compound (VI) synthesized above was added. Although the mixture was heated and stirred at 60° C. for 3 hours, no product could be obtained, and only a 1-octyne oligomer was obtained.

Table 1 shows a list of the results of Synthesis Examples 1 to 5 above.

Claims (12)

General formula (1) below:
(In general formula (1), R ¹ represents a substituted or unsubstituted hydrocarbon group, R ² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, R ³ and R ⁴ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and the value of n is 20 to 100% with respect to the total of 100% of the values of n and m. The value of m is within the range of 0 to 80%, and the * indicates that it is bonded to the surface of the resin fine particles.)
A method for producing a zero-valent transition metal complex compound by reacting resin fine particles represented by the above with a divalent transition metal compound in the presence of a solvent and a reducing agent. The manufacturing method according to claim 1, wherein the solvent is a coordinating solvent. The manufacturing method according to claim 2, wherein the coordinating solvent is an aprotic polar solvent. The manufacturing method according to any one of claims 1 to 3, wherein the divalent transition metal compound is a divalent nickel compound. The manufacturing method according to claim 4, wherein the divalent nickel compound is selected from nickel chloride, nickel acetate, and hydrates thereof. The manufacturing method according to any one of claims 1 to 5, wherein the reducing agent is a metal that is more positive than the transition metal. The manufacturing method according to claim 6, wherein the metal more positive than the transition metal is zinc. The manufacturing method according to any one of claims 1 to 7, wherein the ratio of the amount of phosphine groups to the transition metal in the resin fine particles is 10:1 to 1:2. The manufacturing method according to any one of claims 1 to 8, wherein in general formula (1), R ¹ is a hydrocarbon group having 6 to 12 carbon atoms. The manufacturing method according to any one of claims 1 to 9, wherein in general formula (1), R ² is an alkyl group having 1 to 8 carbon atoms or an aryl group having 5 to 12 carbon atoms. According to any one of claims 1 to 10, in general formula (1), R ³ and R ⁴ are an alkyl group having 1 to 8 carbon atoms or an aryl group having 5 to 12 carbon atoms. Production method. The production method according to any one of claims 1 to 11, wherein the complex compound is used as a catalyst for a hydrophosphorylation reaction.