JP7282017B2 - Method for producing alkenyl phosphorus compound - Google Patents

Description

The present invention relates to a method for producing alkenylphosphorus compounds. More particularly, the present invention relates to a method for producing alkenyl phosphorus compounds by hydrophosphorylation reaction using a resin-supported transition metal complex as a catalyst.

Organophosphorus compounds are chemical substances that are widely used in various products such as flame retardants, plasticizers, insecticides, pharmaceuticals and agricultural chemicals, and ligands for metal complexes. In recent years, organophosphorus compounds have been attracting particular industrial attention as functional materials in the fields of constituent materials such as metal surface treatment agents and flame-retardant resins, and electronic materials.

Among organophosphorus compounds, alkenylphosphonic acid derivatives are useful precursors of the above-mentioned various chemical substances, and thus various production methods have been investigated. For example, alkenylphosphonic acid derivatives have been produced by the addition reaction of the 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 hydrophosphorylation using a catalyst in which a transition metal is immobilized on a polystyrene resin to which triphenylphosphine is bound.

Chem. Lett. 2013, 42, 1065-1067

However, in the catalyst in which a transition metal is immobilized on a polystyrene resin to which triphenylphosphine is bound, as described in Non-Patent Document 1, the phosphorus content on the resin surface is not sufficient, and it is very difficult to add the amount of phosphorus necessary for the reaction. There are problems that a large amount of resin is required for the reaction, the reaction efficiency is low, and a large amount of metal components are leached from the surface of the resin, resulting in many side reactions. Therefore, there is room for improvement in the reaction efficiency when used in the hydrophosphorylation reaction. Moreover, since the catalyst used in the hydrophosphorylation reaction is expensive and has a short life, reuse of the catalyst is desired in order to reduce production costs.

Accordingly, an object of the present invention is to provide a method for producing an alkenylphosphorus compound using a catalyst capable of efficiently proceeding a hydrophosphorylation reaction. Another object of the present invention is to recycle such catalysts.

As a result of intensive studies to solve the above problems, the present inventors have found that a hydrophosphorylation reaction is performed using a complex compound obtained by reacting a resin having a phosphine substituent on the surface with a transition metal as a catalyst. , found that an alkenyl phosphorus compound can be efficiently produced, and completed the present invention. In addition, the present inventors have found that the catalyst can be reused by reacting the used catalyst with a transition metal compound, which is a precursor of the complex compound, and have completed the present invention.

（一般式（１）中、Ｒ^１およびＲ^２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、置換若しくは非置換のシクロアルキル基、置換若しくは非置換のアラルキル基、置換若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^１およびＲ^２は、互いに結合して環状構造を形成していてもよい。）
で表されるリン化合物と、
下記一般式（２）：

（一般式（２）中、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子、置換若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。）
で表されるアルキニル化合物とを、下記一般式（３）：

（一般式（３）中、Ｒ^５は、置換もしくは非置換の炭化水素基を表し、Ｒ^６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^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、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、遷移金属との錯体化合物の存在下で反応させて、
下記一般式（４）：

（一般式（４）中、Ｒ^１およびＲ^２は、一般式（１）中のＲ^１およびＲ^２と同義であり、Ｒ^３およびＲ^４は、一般式（２）中のＲ^３およびＲ^４と同義である。）
で表されるアルケニルリン化合物を製造する方法。
［２］ 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］に記載の製造方法。
［３］ 一般式（１）および（４）中、Ｒ^１およびＲ^２は、それぞれ独立して、炭素数が１～１０の置換もしくは非置換のアルコキシ基である、［１］または［２］に記載の製造方法。
［４］ 一般式（２）および（４）中、Ｒ^３およびＲ^４は、それぞれ独立して、炭素数が１～１０の、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リール基、または置換もしくは非置換のアラルキル基である、［１］～［３］のいずれかに記載の製造方法。
［５］ 一般式（３）中、Ｒ^５は、炭素数が６～１２の炭化水素基である、［１］～［４］のいずれかに記載の製造方法。
［６］ 一般式（３）中、Ｒ^６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］～［５］のいずれかに記載の製造方法。
［７］ 一般式（３）中、Ｒ^７およびＲ^８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］～［６］のいずれかに記載の製造方法。
［８］ 前記遷移金属が、ニッケル、パラジウム、またはロジウムである、［１］～［７］のいずれかに記載の製造方法。
［９］ 一般式（４）で表されるアルケニルリン化合物を製造した後、反応液から前記錯体化合物を回収する工程と、
回収された錯体化合物を再利用して、一般式（４）で表されるアルケニルリン化合物を製造する工程をさらに含む、［１］～［８］のいずれかに記載の製造方法。
［１０］ 前記回収された錯体化合物を、錯体化合物の前駆体である遷移金属化合物により活性化する工程をさらに含む、［９］に記載の製造方法。
［１１］ 前記錯体化合物の前駆体である遷移金属化合物が、ゼロ価ニッケル化合物である、［１０］に記載の製造方法。
［１２］ 前記ゼロ価ニッケル化合物が、ビス（１，５－シクロオクタジエン）ニッケル（０）、テトラキス（トリフェニルホスフィン）ニッケル（０）、またはニッケルカルボニルである、［１１］に記載の製造方法。 That is, according to the present invention, the following inventions are provided.
[1] the following general formula (1):

(In general formula (1), R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted represents an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group, and R ¹ and R ² may combine with each other to form a cyclic structure.)
A phosphorus compound represented by
The following general formula (2):

(In general formula (2), R ³ and R ⁴ 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 represents 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 .)
and an alkynyl compound represented by the following general formula (3):

(In general formula (3), R ⁵ represents a substituted or unsubstituted hydrocarbon group, R ⁶ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, R ⁷ and R ⁸ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group; is within the range of , and the value of m is within the range of 0 to 80%, and * is bonded to the resin fine particle surface.)
is reacted in the presence of a complex compound of a resin fine particle represented by and a transition metal,
The following general formula (4):

(In general formula (4), R ¹ and R ² are synonymous with R ¹ and R ² in general formula (1), R ³ and R ⁴ are R ³ and R in general formula (2) ⁴ is synonymous.)
A method for producing an alkenyl phosphorus compound represented by
[2] The production method according to [1], wherein the substance amount ratio of the phosphine groups in the resin fine particles and the transition metal is 10:1 to 1:2.
[3] In general formulas (1) and (4), R ¹ and R ² are each independently a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms [1] or [2] The manufacturing method described in .
[4] In general formulas (2) and (4), R ³ and R ⁴ are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group having 1 to 10 carbon atoms; Or the production method according to any one of [1] to [3], which is a substituted or unsubstituted aralkyl group.
[5] The production method according to any one of [1] to [4], wherein R ⁵ in general formula (3) is a hydrocarbon group having 6 to 12 carbon atoms.
[6] The formula according to any one of [1] to [5], wherein R ⁶ is an alkyl group having 1 to 8 carbon atoms or an aryl group having 5 to 12 carbon atoms in general formula (3). Production method.
[7] Any one of [1] to [6], wherein R ⁷ and R ⁸ in general formula (3) are an alkyl group having 1 to 8 carbon atoms or an aryl group having 5 to 12 carbon atoms The manufacturing method described in .
[8] The production method according to any one of [1] to [7], wherein the transition metal is nickel, palladium, or rhodium.
[9] After producing the alkenyl phosphorus compound represented by the general formula (4), a step of recovering the complex compound from the reaction solution;
The production method according to any one of [1] to [8], further comprising a step of producing the alkenylphosphorus compound represented by the general formula (4) by reusing the recovered complex compound.
[10] The production method according to [9], further comprising the step of activating the recovered complex compound with a transition metal compound that is a precursor of the complex compound.
[11] The production method according to [10], wherein the transition metal compound that is the precursor of the complex compound is a zerovalent nickel compound.
[12] The production method according to [11], wherein the zerovalent nickel compound is bis(1,5-cyclooctadiene)nickel(0), tetrakis(triphenylphosphine)nickel(0), or nickelcarbonyl. .

According to the present invention, an alkenyl phosphorus compound can be efficiently produced by performing a hydrophosphorylation reaction using a complex compound obtained by reacting a resin having a phosphine substituent on the surface with a transition metal as a catalyst. can. In particular, the hydrophosphorylation reaction can be efficiently carried out under heating temperature conditions of room temperature or higher. In addition, since the life of the catalyst is long and the catalyst can be reused, the manufacturing cost can be reduced.

FIG. 4 is a diagram showing an IR spectrum of fine resin particles (I). FIG. 4 is a diagram showing an IR spectrum of fine resin particles (II). FIG. 4 is a diagram showing an IR spectrum of fine resin particles (III). FIG. 4 is a diagram showing an IR spectrum of an oxidized product of fine resin particles (IV).

[Method for Producing Alkenyl Phosphorus Compound]
(Hydrophosphorylation reaction)
In the method for producing an alkenyl phosphorus compound of the present invention, an alkenyl phosphorus compound is produced by subjecting a phosphorus compound and an alkynyl compound, which are starting materials, to a hydrophosphorylation reaction in the presence of a catalyst. According to the method for producing an alkenyl phosphorus compound of the present invention, an alkenyl phosphorus compound can be efficiently synthesized under heating temperature conditions of room temperature or higher.

（一般式（１）中、Ｒ^１およびＲ^２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^１およびＲ^２は、互いに結合して環状構造を形成していてもよい。） (Phosphorus compound)
A phosphorus compound represented by the following general formula (1) can be used as a starting material for the hydrophosphorylation reaction.

(In general formula (1), R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted represents an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group, and R ¹ and R ² may combine with each other to form a cyclic structure.)

In general formula (1), the alkyl group, alkoxy group, cycloalkyl group, aralkyl group, aryl group, and aryloxy group of R ¹ and R ² preferably have 1 to 10 carbon atoms. In addition, the number of carbon atoms of the substituent is not included in the above number of carbon atoms. For example, R ¹ and R ² 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 group, cycloalkyl groups such as cyclohexyl group, benzyl group, aralkyl group such as phenethyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, aryloxy group such as phenoxy group mentioned. Among these, R ¹ and R ² are each independently preferably a substituted or unsubstituted alkoxy group.

In general formula (1), examples of substituents that R ¹ and R ² 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. groups, acyloxy groups, carboxy groups, cyano groups, nitro groups, hydroxy groups, mercapto groups, oxo groups, and the like. The number of carbon atoms contained in the substituent is preferably 1-6, more preferably 1-4, still more preferably 1-3.

（一般式（２）中、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、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。） (alkynyl compound)
Alkynyl compounds represented by the following general formula (2) can be used as starting materials for the hydrophosphorylation reaction.

(In general formula (2), R ³ and R ⁴ 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 represents 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 (2), the alkyl group, cycloalkyl group, aralkyl group, aryl group, heteroaryl group, alkenyl group, alkoxy group, and aryloxy group of R ³ and R ⁴ have 1 to 10 carbon atoms. is preferred. In addition, the number of carbon atoms of the substituent is not included in the above number of carbon atoms. For example, R ³ and R ⁴ 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, and cyclo groups such as cyclohexyl group. Alkyl group, benzyl group, aralkyl group such as phenethyl group, phenyl group, tolyl group, xylyl group, aryl group such as naphthyl group, 1-butenyl group, 2-butenyl group, 1,3-butadienyl group, pentenyl group, hexenyl group alkenyl groups such as groups; alkoxy groups such as methoxy groups, ethoxy groups and butoxy groups; and aryloxy groups such as phenoxy groups. Among these, R ³ and R ⁴ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group having 1 to 10 carbon atoms. is preferred.

In general formula (2), examples of substituents that R ³ and R ⁴ 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. groups, acyloxy groups, carboxy groups, cyano groups, nitro groups, hydroxy groups, mercapto groups, oxo groups, and the like. The number of carbon atoms contained in the substituent is preferably 1-6, more preferably 1-4, still more preferably 1-3.

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

(Complex compound (catalyst))
As the catalyst used for the hydrophosphorylation reaction, a complex compound (resin-supported transition metal complex) of a resin fine particle described in detail below and a transition metal can be used. Since such a complex compound has a high concentration of phosphine substituents on the surface of the resin fine particles, the hydrophosphorylation reaction can proceed efficiently under a temperature condition of room temperature or higher.

（一般式（３）中、Ｒ^５は、置換もしくは非置換の炭化水素基を表し、Ｒ^６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^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、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 fine resin particles forming the complex compound are represented by the following general formula (3).

(In general formula (3), R ⁵ represents a substituted or unsubstituted hydrocarbon group, R ⁶ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, R ⁷ and R ⁸ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group; is within the range of , and the value of m is within the range of 0 to 80%, and * is bonded to the resin fine particle surface.)

In general formula (3), the substituted or unsubstituted hydrocarbon group for R ⁵ is preferably a hydrocarbon group having 6 to 12 carbon atoms. In addition, the number of carbon atoms of the substituent is not included in the above number of carbon atoms. Examples of hydrocarbon groups having 6 to 12 carbon atoms include alkylene groups such as hexylene group, heptylene group and octylene group, cycloalkylene groups such as cyclohexylene group, aromatic hydrocarbon groups such as phenylene group and naphthylene group, and the like. mentioned. Among these, ^R5 is preferably an aromatic hydrocarbon group, more preferably a phenylene group.

In general formula (3), the substituted or unsubstituted alkyl group for R ⁶ is preferably an alkyl group having 1 to 8 carbon atoms, and the substituted or unsubstituted aryl group is an aryl group having 5 to 12 carbon atoms. groups are preferred. In addition, the number of carbon atoms of the substituent is not included in the above number of carbon atoms. Examples of alkyl groups 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 and hexyl group. . The aryl group having 5 to 12 carbon atoms includes phenyl group, tolyl group, xylyl group, naphthyl group and the like. Among these, ^R6 is preferably an aromatic hydrocarbon group, more preferably a phenyl group.

In general formula (3), the substituted or unsubstituted alkyl group for R ⁷ and R ⁸ is preferably an alkyl group having 1 to 8 carbon atoms, and the substituted or unsubstituted aryl group is preferably 5 to 8 carbon atoms. Twelve aryl groups are preferred. In addition, the number of carbon atoms of the substituent is not included in the above number of carbon atoms. Examples of alkyl groups 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 and hexyl group. . The aryl group having 5 to 12 carbon atoms includes phenyl group, tolyl group, xylyl group, naphthyl group and the like. Among these, ^R7 and ^R8 are each independently preferably a hydrogen atom, a methyl group, or a phenyl group.

In general formula (3), examples of substituents that R ⁵ , R ⁶ , R ⁷ and R ⁸ may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a heterocyclic group, alkylidene group, amino group, silyl group, acyl group, acyloxy group, carboxy group, cyano group, nitro group, hydroxy group, mercapto group, oxo group and the like. The number of carbon atoms contained in the substituent is preferably 1-6, more preferably 1-4, still more preferably 1-3. Also, R ⁵ , R ⁶ , R ⁷ and R ⁸ may have a fluorine atom.

Specific examples of the resin represented by general formula (3) include resins represented by the following formula.

In the general formula (3), the value of n is 20 to 100%, preferably 50 to 100%, more preferably 80 to 100% with respect to the total 100% of the values of n and m, The value of m is 0-80%, preferably 0-50%, more preferably 0-20%.

The fine resin particles represented by formula (3) can be produced by the following method. For example, in a nitrogen atmosphere, Merrifield resin and an alkali metal organophosphorus compound or a trivalent organophosphorus compound having an ester bond are added to a reaction vessel, and reacted at -20 to 150°C for 1 to 48 hours. Resin microparticles can be produced. The Merrifield resin is a styrene/chloromethylstyrene crosslinked resin. Examples of alkali metal organophosphorus compounds include sodium diphenylphosphide and sodium methylphenylphosphide. Examples of trivalent organophosphorus compounds having an ester bond include triethyl phosphite and methyl diphenylphosphite.

In addition, in a nitrogen atmosphere, ethenylphenylmethylmagnesium chloride and halogenated phosphine are added to a reaction vessel, and phosphinylmethylstyrene obtained by reacting at 0 to 100° C. for 1 to 48 hours, styrene, and a crosslinking agent are suspended. Resin microparticles can be produced by turbidity polymerization.

Since the fine resin particles are bonded to the surface of the fine resin particles with *, the phosphorus content on the surface is high, preferably 1.0 mmol/g or more, more preferably 2.0 mmol/g or more, and still more preferably 2.0 mmol/g or more. .5 mmol/g or more. The phosphorus content on the surface of the resin fine particles can be measured by elemental analysis, adsorption amount of the organic halide compound, and oxidation-reduction titration.

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

(transition metal)
Transition metals that form complex compounds include nickel, palladium, and rhodium, with nickel being preferred. In particular, by using a complex compound formed by fine resin particles and nickel as a catalyst, the hydrophosphorylation reaction can proceed efficiently under temperature conditions of room temperature (20°C) or more and less than 100°C.

The substance amount ratio of the phosphine group and the transition metal in the fine resin particles is not particularly limited as long as a complex compound can be formed, but is preferably 10:1 to 1:2, more preferably 8:1 to 1:1, More preferably 5:1 to 2:1.

(Method for producing complex compound)
The above method for producing a complex compound includes a step of reacting the fine resin particles represented by the general formula (3) with a transition metal compound in the presence of an organic solvent. The fine resin particles represented by formula (3) are as described in detail above.

The transition metal compound used in the method for producing the complex compound is preferably a nickel compound or a palladium compound, more preferably a zerovalent nickel compound. Examples of zerovalent nickel compounds include bis(1,5-cyclooctadiene)nickel(0), tetrakis(triphenylphosphine)nickel(0), nickelcarbonyl, and the like. A complex compound can be formed by using a zero-valent nickel compound that has a ligand with a weaker coordinating force than the phosphine present on the surface of the resin fine particles.

The reaction temperature between the fine resin particles and the transition metal compound is not particularly limited, but is preferably -10 to 100°C, more preferably 0 to 60°C, in consideration of reaction efficiency, reaction rate, and by-products. More preferably, it is 10 to 30°C.

The reaction time between the fine resin particles and the transition metal compound is not particularly limited, but is preferably 10 minutes to 24 hours, more preferably 1 hour to 18 hours, in consideration of reaction efficiency, reaction rate, and by-products. , more preferably 6 to 18 hours.

The organic solvent used for the reaction between the fine resin particles and the transition metal compound is not particularly limited, but examples thereof include ethers, hydrocarbons, ketones, esters, aromatic hydrocarbons, etc. Ethers such as tetrahydrofuran are preferably used. is preferred.

The reaction between the fine 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. Nitrogen, argon, or the like is preferably used as the inert gas.

(Reaction conditions)
The amount of the complex compound (catalyst) used in the hydrophosphorylation reaction is not particularly limited as long as the reaction proceeds sufficiently. 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 is preferably 50 to 120° C., more preferably 50 to 80° C., still more preferably in consideration of reaction efficiency, reaction rate and by-products. 50-60°C.

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

The hydrophosphorylation reaction may be performed in the presence of an organic solvent or in the absence of solvent. The organic solvent used in the hydrophosphorylation reaction is not particularly limited, and examples thereof include alcohols, ethers, hydrocarbons, ketones, esters 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. Nitrogen, argon, or the like is preferably used as the inert gas.

（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。） (Alkenyl Phosphorus Compound)
In the present invention, an alkenyl phosphorus compound represented by the following general formula (4) can be obtained by 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 in general formula (2). is synonymous with ^8. )

(Catalyst recovery step)
The method for producing an alkenyl phosphorus compound of the present invention can further include a step of recovering the complex compound from the reaction solution after producing the alkenyl phosphorus compound represented by general formula (4). A method for recovering the complex compound from the reaction solution is not particularly limited, and conventionally known methods such as decantation, centrifugation, and filtration can be used.

(Catalyst reuse process)
The method for producing an alkenyl phosphorus compound of the present invention includes a step of adding the complex compound recovered above into the reaction system and reusing it as a catalyst to produce an alkenyl phosphorus compound represented by the general formula (4). can further include:

(Catalyst activation step)
The method for producing an alkenyl phosphorus compound of the present invention preferably further includes a step of activating the recovered complex compound prior to the above catalyst recycling step. In the catalyst activation step, the recovered complex compound and a transition metal compound, which is a precursor of the complex compound, are allowed to react in an organic solvent, thereby regenerating the complex compound as a catalyst. The reaction conditions for the catalyst activation step include heating at preferably 0 to 100° C., more preferably 20 to 60° C., preferably 60 minutes to 24 hours, more preferably 6 to 18 hours.

Examples of the transition metal compound, which is the precursor of the complex compound used in the catalyst activation step, include the transition metal compound used in the method for producing the complex compound described above. In particular, the transition metal compound used in the method for producing the complex compound and the transition metal compound used in the catalyst activation step are preferably the same. For example, when a zero-valent nickel compound is used in the production of the complex compound, it is preferable to use the zero-valent nickel compound also in the catalyst activation step.

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

<Synthesis of complex compound (catalyst)>
[Synthesis Example 1]
In a nitrogen atmosphere, 40 mL of tetrahydrofuran (THF) and 10.5 g of triphenylphosphine were added to the reactor and stirred well. Subsequently, 7.36 g of metallic sodium dispersion (sodium content: about 25% by mass, average particle size of metallic sodium fine particles: 10 µm, manufactured by Kobelco Eco-Solutions Co., Ltd., SD) was added to the reaction vessel, and then heated to 25°C. and stirred for 18 hours to obtain sodium diphenylphosphide (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, cross-linking agent: divinylbenzene 1 mol%) was added to the reaction vessel in which 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. A precipitate was taken out from this suspension in air and washed with 20 mL of THF three times, with 20 mL of purified water three times, and once with 20 mL of acetone. After drying under reduced pressure at 60° C. for 18 hours, fine resin particles (I) represented by the following formula were obtained.

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

The phosphorus content on the surface of the obtained resin fine particles (I) was measured by the following organic halide adsorption method and found to be 2.34 mmol/g.
(Method for measuring surface phosphorus content by 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 was removed, and the amount of adsorbed benzyl bromide was calculated by the internal standard method (standard substance diphenyl ether) using GC-FID to determine the phosphorus content of the fine resin particles.

The resulting fine resin particles (I) were passed through a 300-mesh sieve and collected to obtain 15.9 g of pale yellow fine resin particles.

In a reaction vessel under a nitrogen atmosphere, 0.21 mmol of the obtained resin fine particles (I) and 0.05 mmol of bis(1,5-cyclooctadiene)nickel (0) were added in the presence of 1.0 mL of THF. It was made to react at 25 degreeC for 6 hours. The precipitate was collected and washed with 1.0 mL of THF three times to obtain complex compound (I). At this time, when 100 mg of dimethylglyoxime was added to the supernatant of the reaction solution, almost no precipitation was observed. On the other hand, when only bis(1,5-cyclooctadiene)nickel(0) was dissolved in THF and dimethylglyoxime was added, a large amount of precipitate was deposited, so bis(1,5-cyclooctadiene) ) Nickel (0) reacted with the fine resin particles (I) to form a complex.

The obtained resin fine particles (I) were measured by IR. The IR spectrum obtained is shown in FIG. When the IR spectrum was confirmed, the C—Cl-derived peak (wavenumber: 1295 cm ⁻¹ ) contained in the raw material Merrifield resin disappeared, and the formation of the PC-derived peak (wavenumber: 694 cm ⁻¹ ) could be confirmed. rice field. In addition, it was confirmed that vinyl phosphorus was produced by coordination with Ni. From these results, it can be said that a chemical bond of phosphorus was formed on the surface of the resin fine particles.

[Synthesis Example 2]
In a nitrogen atmosphere, 132 mL of THF and 20.17 g of triphenylphosphine were added to the reactor and stirred well. Subsequently, 25.4 g of a metallic sodium dispersion (sodium content: about 25% by mass, average particle size 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 kept at 25°C. and stirred for 18 hours to obtain sodium diphenylphosphide (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 G.K., 5.5 mmol Cl/g, cross-linking 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 1 hour, and the precipitate was taken out in 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. When the phosphorus content on the surface of the obtained resin fine particles (II) was measured in the same manner as in Example 1, it was 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 100% of the values of n and m.)

In a reaction vessel, 0.21 mmol of the obtained resin fine particles (II) and 0.05 mmol of bis(1,5-cyclooctadiene)nickel (0) were mixed at 25° C. for 6 hours in the presence of 1.0 mL of THF. reacted over time. The precipitate was collected and washed with 1.0 mL of THF three times to obtain complex compound (II).

The resulting fine resin particles (II) were measured by IR. The IR spectrum obtained is shown in FIG. When the IR spectrum was confirmed, the C—Cl-derived peak (wavenumber: 1285 cm ⁻¹ ) contained in the raw material Merrifield resin disappeared, and the formation of the PC-derived peak (wavenumber: 694 cm ⁻¹ ) could be confirmed. rice field. In addition, it was confirmed that vinyl phosphorus was produced by coordination with Ni. From these results, it can be said that a chemical bond of phosphorus was formed on the surface of the resin fine particles.

[Synthesis Example 3]
In an argon gas atmosphere, 30 mL of THF and 5.0 g of methyldiphenylphosphine were added to the reactor. Next, after adding 4.8 g of a metallic sodium dispersion (sodium content: about 25% by mass, average particle size of metallic sodium fine particles: 10 μm, manufactured by Kobelco Eco-Solutions Co., Ltd., SD), the mixture was reacted at 0° C. for 18 hours. to obtain sodium methylphenyl phosphide (MePhP-Na). The yield was 70.0% as confirmed by ³¹ P NMR.

（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。）
反応容器中で、得られた樹脂微粒子（ＩＩＩ）０．２１ｍｍｏｌと、ビス（１，５－シクロオクタジエン）ニッケル（０）０．０５ｍｍｏｌとを、ＴＨＦの存在下で、２５℃で４時間反応させて、錯体化合物（ＩＩＩ）を得た。 3.81 g of Merrifield resin (manufactured by Sigma-Aldrich Japan G.K., 5.5 mmol Cl/g, cross-linking agent: divinylbenzene 5 mol%, particle size 16-50 mesh) was added to the prepared sodium methylphenyl phosphide, and the mixture was heated at 60°C for 23 hours. reacted over time. The supernatant liquid was removed, and 20 mL of 2-propanol was added dropwise over 1 hour. The supernatant was decanted, washed three times with 20 mL of THF, three times with 20 mL of deionized water, and 20 mL of acetone, and dried under reduced pressure at 60° C. for 18 hours to obtain resin fine particles (III) represented by the following formula. When the phosphorus content on the surface of the obtained resin fine particles (III) was measured in the same manner as in Example 1, it was 3.85 mmol/g.

(In the above formula, the value of n is 100% and the value of m is 0% with respect to the total 100% of the values of n and m.)
In a reaction vessel, 0.21 mmol of the obtained resin fine particles (III) and 0.05 mmol of bis(1,5-cyclooctadiene)nickel (0) were reacted at 25° C. for 4 hours in the presence of THF. to obtain a complex compound (III).

The obtained resin fine particles (III) were measured by IR. The obtained IR spectrum is shown in FIG. When the IR spectrum was confirmed, the C—Cl-derived peak (wavenumber: 1295 cm ⁻¹ ) contained in the raw material Merrifield resin disappeared, and the formation of the PC-derived peak (wavenumber: 694 cm ⁻¹ ) could be confirmed. rice field. In addition, it was confirmed that vinyl phosphorus was produced by coordination with Ni. From these results, it can be said that a chemical bond of phosphorus was formed on the surface of the resin fine particles.

（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。） [Synthesis Example 4]
Under a nitrogen atmosphere, 20 g of Merrifield resin (manufactured by Sigma-Aldrich Japan LLC, 5.5 mmol Cl/g, cross-linking agent: divinylbenzene 5 mol%, particle size 16-50 mesh) and triethyl phosphite ((EtO ) ₃ P) (50 mL) was added, and the mixture was heated and stirred at 130° C. for 20 hours. The precipitate was recovered from the reaction solution which was allowed to cool to room temperature, and washed with 20 mL of acetone 5 times, 20 mL of water 3 times, and 20 mL of acetone 3 times to obtain 25.08 g of pale yellow resin microparticles. Subsequently, 1.0 g of the obtained resin and 8.46 mL of lithium aluminum hydride (1 mol/LTHF solution) were reacted at 25° C. for two days. After slowly adding 2 mL of methanol to the reaction solution, the supernatant was decanted, washed 6 times with 5 mL of 10% by mass sodium hydroxide aqueous solution and 5 times with 5 mL of water, and dried under reduced pressure at 60 ° C. for 18 hours. Resin fine particles (IV) represented by were obtained. The theoretical phosphorus content on the surface of the obtained resin fine particles (IV) was 4.80 mmol/g.

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

In a reaction vessel, 2.8 mmol of the obtained resin fine particles (IV) and 0.7 mmol of bis(1,5-cyclooctadiene)nickel(0) were reacted at 25° C. for 18 hours in the presence of 2 mL of THF. The precipitate was recovered and washed with 1.0 mL of THF three times to obtain the complex compound (IV).

100 mg of the obtained resin microparticles (IV) was treated with 5.0 mL of 5% hydrogen peroxide solution and measured by IR. The IR spectrum obtained is shown in FIG. When the IR spectrum was confirmed, the C—Cl-derived peak (wavenumber: 1295 cm ⁻¹ ) contained in the raw material Merrifield resin disappeared, and the PC-derived peak (wavenumber: 703 cm ⁻¹ ) and P(O) Generation of a peak derived from —OH (wave number: 1025 cm ⁻¹ ) was confirmed. In addition, it was confirmed that vinyl phosphorus was produced by coordination with Ni. From these results, it can be said that coordination of phosphorus and nickel was formed on the surface of the fine resin particles.

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

[Synthesis Example 6]
200 mg of 4-Diphenylphosphine Polystyrene Resin cross-linked with 2% DVB (200-400 mesh) (0.5-1.0 mmol/g) (catalog number D2766, manufactured by Tokyo Kasei Co., Ltd.) and bis(1,5 -Cyclooctadiene)nickel(0) (13.8 mg) was weighed out, 1 mL of THF was added, and the mixture was stirred at 25°C for 18 hours. The supernatant was decanted, and the precipitate was washed with 0.5 mL of THF three times to obtain complex compound (VI).

<Synthesis of Alkenyl Phosphorus Compound>
[Example 1]
300 mmol of a phosphorus compound ((MeO) ₂ P(O)H) as a starting material was weighed into a reaction vessel, and 1.5 mmol of complex compound (I) was added. An acetylene balloon was attached to the reactor, and the mixture was reacted 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 the internal standard method (standard substance diphenyl ether) using GC-FID, the amount of alkenyl phosphorus compound produced per 1 mmol of Ni was 1.46 g.

[Example 2]
An alkenyl phosphorus compound ((MeO) ₂ P(O)CH=CH ₂ ) was obtained in the same manner as in Example 1, except that 1.5 mmol of the complex compound (II) synthesized above was used as a catalyst. The amount of alkenyl phosphorus compound produced per 1 mmol of Ni was 2.11 g.

[Example 3]
An alkenyl phosphorus compound ((MeO) ₂ P(O)CH=CH ₂ ) was obtained in the same manner as in Example 2, except that the reaction temperature was changed to 80°C. The amount of alkenyl phosphorus compound produced per 1 mmol of Ni was 4.57 g.

[Example 4]
An alkenyl phosphorus compound ((MeO) ₂ P(O)CH=CH ₂ ) was obtained in the same manner as in Example 1, except that 1.5 mmol of the complex compound (III) synthesized above was used as a catalyst. The amount of alkenyl phosphorus compound produced per 1 mmol of Ni was 3.48 g.

[Example 5]
An alkenyl phosphorus compound ((MeO) ₂ P(O)CH=CH ₂ ) was obtained in the same manner as in Example 1, except that 1.5 mmol of the complex compound (IV) synthesized above was used as a catalyst. The amount of alkenyl phosphorus compound produced per 1 mmol of Ni was 2.81 g.

[Comparative Example 1]
An alkenyl phosphorus compound ((MeO) ₂ P(O)CH=CH ₂ ) was obtained in the same manner as in Example 1, except that 1.5 mmol of the complex compound (V) synthesized above was used as a catalyst. The amount of alkenyl phosphorus compound produced per 1 mmol of Ni was 0.08 g.

A list of the results of Examples 1 to 5 and Comparative Example 1 is shown in Table 1.

[Example 6]
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 (I) was added. Heated and stirred at 60° C. for 3 hours to obtain an alkenyl phosphorus compound (30%: (MeO) ₂ P(O)CH═CC ₆ H ₁₃ , 70%: (MeO) ₂ P(O)C(C ₆ H ₁₃ ). = mixture of _CH2 ) was obtained. The amount of alkenyl phosphorus compound produced per 1 mmol of Ni was 4.40 g.

[Example 7]
An alkenyl phosphorus compound (64%: (MeO) ₂ P(O)CH=CH—Ph, 36%: (MeO) ₂ A mixture of P(O)CH(Ph)= _CH2 ) was obtained. The amount of alkenyl phosphorus compound produced per 1 mmol of Ni was 1.27 g.

[Example 8]
In the same manner as in Example 6, except that 2-methyl-3-butyn-2-ol was used as the starting alkynyl compound.
Alkenyl Phosphorus Compounds (37%: (MeO) ₂ P(O)CH=CH—C(CH ₃ ) ₂ OH, 63%: (MeO) ₂ P(O)C(C(CH ₃ ) ₂ OH)=CH ₂ ) was obtained. The amount of alkenyl phosphorus compound produced per 1 mmol of Ni was 1.67 g.

[Example 9]
_An alkenyl phosphorus compound ₍ 11% _: ( _CF3CH2O ) _{2P (} O) CH=CH—C ₆ H ₁₃ , 89%: (CF ₃ CH ₂ O) ₂ P(O)C(C ₆ H ₁₃ )=CH ₂ mixture) was obtained. The amount of alkenyl phosphorus compound produced per 1 mmol of Ni was 4.06 g.

[Comparative Example 2]
The reaction was carried out under the same conditions as in Example 6, except that complex compound (VI) was used instead of complex compound (I), but no product was obtained, and only 1-octyne oligomers were obtained. was taken.

A summary of the results of Examples 6-9 above is shown in Table 2.

[Example 10]
In a reaction vessel, 1 mmol of a phosphorus compound ((MeO) ₂ P(O)H) and 1 mmol of 1-octyne as starting materials were mixed in the presence of 0.05 mmol of the complex compound (I) synthesized above as a catalyst. Reaction at 60° C. for 3 hours yields alkenyl phosphorus compounds (30%: (MeO) ₂ P(O)CH═CH—C ₆ H ₁₃ , 70%: (MeO) ₂ P(O)C(C ₆ H ₁₃ )=CH ₂ ). The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 100%. After completion of the synthesis, the reaction solution was decanted and washed with 0.5 mL of THF three times to recover the complex compound (I-1) used in the synthesis.

[Example 11]
In a reaction vessel, 1 mmol of a phosphorus compound ((MeO) ₂ P(O)H) as starting materials and 1 mmol of 1-octyne were added at 60° C. in the presence of the entire amount of the complex compound (I-1) recovered above. for 7 hours to give alkenyl phosphorus compounds (64%: (MeO) ₂ P(O)CH=CH—C ₆ H ₁₃ , 34%: (MeO) ₂ P(O)C(C ₆ H ₁₃ )= _CH2 ). The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 100%. After completion of the synthesis, the reaction solution was decanted and washed with 0.5 mL of THF three times to recover the complex compound (I-2) used twice in the synthesis.

[Example 12]
In a reaction vessel, 1 mmol of a phosphorus compound ((MeO) ₂ P(O)H) and 1 mmol of 1-octyne were used as starting materials, and the entire amount of the complex compound (I-2) recovered above was used. After reacting for hours, alkenyl phosphorus compounds (64%: (MeO) ₂ P(O)CH=CH—C ₆ H ₁₃ , 34%: (MeO) ₂ P(O)C(C ₆ H ₁₃ )=CH ₂ ). The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 100%. After completion of the synthesis, the reaction solution was decanted and washed with 0.5 mL of THF three times to recover the complex compound (I-3) used three times in the synthesis.

[Example 13]
In a reaction vessel, 1 mmol of a phosphorus compound ((MeO) ₂ P(O)H) and 1 mmol of 1-octyne were used as starting materials, and the entire amount of the complex compound (I-3) recovered above was used. After reacting for hours, alkenyl phosphorus compounds (64%: (MeO) ₂ P(O)CH=CH—C ₆ H ₁₃ , 34%: (MeO) ₂ P(O)C(C ₆ H ₁₃ )=CH ₂ ). The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 67%. After completion of the synthesis, the reaction solution was decanted and washed with 0.5 mL of THF three times to recover the complex compound (I-4) used four times in the synthesis.

[Example 14]
In a reaction vessel, 1 mmol of a phosphorus compound ((MeO) ₂ P(O)H) and 1 mmol of 1-octyne were used as starting materials, and the entire amount of the complex compound (I-4) recovered above was used. The alkenylphosphorus compound was not obtained even though it was reacted for hours. After completion of the synthesis, the complex compound (I-5) used five times in the synthesis was recovered.

Next, the complex compound (I-5) recovered above and 0.07 mmol of bis(1,5-cyclooctadiene)nickel(0) were reacted at 25° C. for 18 hours in the presence of 1 mL of THF. , the complex compound (I-5) was regenerated as a catalyst.

Subsequently, in a reaction vessel, 1 mmol of a phosphorus compound ((MeO) ₂ P(O)H) as starting materials and 1 mmol of 1-octyne were added in the presence of the entire amount of the complex compound (I-5) regenerated above. , at 60° C. for 3 hours to give alkenyl phosphorus compounds (30%: (MeO) ₂ P(O)CH═CH—C ₆ H ₁₃ , 70%: (MeO) ₂ P(O)C(C ₆ H ₁₃ )=CH ₂ ). The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 100%. After completion of the synthesis, the reaction solution was decanted and washed with 0.5 mL of THF three times to recover the complex compound (I-6) used six times in the synthesis.

[Example 15]
In a reaction vessel, 1 mmol of a phosphorus compound ((MeO) ₂ P(O)H) as starting materials and 1 mmol of 1-octyne were added at 60° C. in the presence of the entire amount of the complex compound (I-6) regenerated above. for 7 hours to give alkenyl phosphorus compounds (64%: (MeO) ₂ P(O)CH=CH—C ₆ H ₁₃ , 34%: (MeO) ₂ P(O)C(C ₆ H ₁₃ )= _CH2 ). The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 100%.

Claims (12)

The following general formula (1):

(1)
(In general formula (1), R ¹ and R ² each independently represent a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms .)
A phosphorus compound represented by
The following general formula (2):

(2)
(In general formula (2), R ³ and R ⁴ are each independently a substituted or unsubstituted alkyl group , a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted indicates an aryl group .)
and an alkynyl compound represented by the following general formula (3):

(3)
(In general formula (3), R ⁵ represents a substituted or unsubstituted hydrocarbon group having 6 to 12 carbon atoms, and R ⁶ represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or an unsubstituted aryl group having 5 to 12 carbon atoms, and each of R ⁷ and R ⁸ independently represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms , or an alkyl group having 5 to 12 carbon atoms. represents a substituted or unsubstituted aryl group, wherein the value of n is in the range of 20 to 100% and the value of m is in the range of 0 to 80%, relative to the total 100% of the values of n and m. There is, and * is connected to the surface of the resin fine particles.)
and reacting in the presence of a complex compound of a resin fine particle having a phosphorus content of 1.0 mmol/g or more on the surface of the resin fine particle and a transition metal,
The following general formula (4):

(4)
(In general formula (4), R ¹ and R ² are synonymous with R ¹ and R ² in general formula (1), R ³ and R ⁴ are R ³ and R in general formula (2) ⁴ is synonymous.)
A method for producing an alkenyl phosphorus compound represented by 2. The production method according to claim 1, wherein the substance amount ratio of the phosphine groups in the resin fine particles and the transition metal is 10:1 to 1:2. The production method according to claim 1 or 2, wherein the alkoxy group in R1 and ^R2 in general formulas ( ¹ ) and (4) is a methoxy group, an ethoxy group, or a butoxy group . The production method according to any one of claims 1 to 3 , wherein R ⁵ in general formula (3) is an aromatic hydrocarbon group having 6 to 12 carbon atoms. The production method according to any one of claims 1 to 4 , wherein R ⁶ in general formula (3) is an aryl group having 5 to 12 carbon atoms. In the general formula (3), the value of n is in the range of 50 to 100%, and the value of m is in the range of 0 to 50%, with respect to the total 100% of the values of n and m. 6. The production method according to any one of 1 to 5. The production method according to any one of claims 1 to 6, wherein the phosphorus content on the surface of the resin fine particles is 2.0 mmol/g or more. The production method according to any one of claims 1 to 7, wherein the transition metal is nickel, palladium, or rhodium. After producing the alkenyl phosphorus compound represented by the general formula (4), a step of recovering the complex compound from the reaction solution;
The production method according to any one of claims 1 to 8, further comprising a step of producing the alkenylphosphorus compound represented by the general formula (4) by reusing the recovered complex compound. 10. The production method according to claim 9, further comprising the step of activating the recovered complex compound with a transition metal compound that is a precursor of the complex compound. 11. The production method according to claim 10, wherein the transition metal compound that is the precursor of the complex compound is a zerovalent nickel compound. 12. The process according to claim 11, wherein the zerovalent nickel compound is bis(1,5-cyclooctadiene)nickel(0), tetrakis(triphenylphosphine)nickel(0), or nickelcarbonyl.

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