JP2021046365A - METHOD FOR PRODUCING α,β-UNSATURATED CARBOXYLIC ACID DERIVATIVE - Google Patents

Abstract

To provide a method for producing α,β-unsaturated carboxylic acid derivative that is advantageous in a cost and efficient.SOLUTION: A method for producing α,β-unsaturated carboxylic acid derivative including: a process of allowing metal lactone compound and alkyl halide having the carbon number of 1 to 6 to react to obtain α,β-unsaturated carboxylic acid derivative and either or both of hydrogen iodide and hydrogen bromide; and a process of allowing either or both of the hydrogen iodide and hydrogen bromide and alcohol having the carbon number of 1 to 6 to react to regenerate the alkyl halide.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an α, β-unsaturated carboxylic acid derivative.

In recent years, _{many methods of using CO 2} as a raw material for chemical synthesis have been proposed for the purpose of reducing greenhouse gases such as _{carbon dioxide (CO 2).} As one of them, it has been proposed to produce an unsaturated carboxylic acid derivative such as an acrylic acid derivative using _{CO 2 and an alkene as raw materials.}

For example, Non-Patent Document 1 describes the synthesis of α, β-unsaturated carboxylic acid derivatives using _{CO 2 and alkene as raw materials.} Specifically, the nickel complex is reacted with ethylene to obtain an ethylene-nickel complex, and then the ethylene-nickel complex is _{reacted with CO 2} to form a nickel-lactone complex. Then, it is described that methyl acrylate, which is an α, β-unsaturated carboxylic acid derivative, was synthesized by reacting the nickel-lactone complex with methyl iodide or trifluoromethanesulfonic acid.

Fritz E. Kuhn et. Al., Liberation of methyl acrylate from metallalactone complexes via M-O ring opening (M = Ni, Pd) with methylation agents, New J. Chem., 2013, 37, 3512-3517

According to the method described in Non-Patent Document 1, at least an equimolar amount of methyl iodide or trifluoromethanesulfonic acid is required with the target product, methyl acrylate. Although not described in Non-Patent Document 1, when a nickel-lactone complex is reacted with, for example, methyl iodide, in addition to the target product, methyl acrylate, an equal molar amount of hydrogen iodide with methyl acrylate is added. It is thought to be born.

That is, according to the method of Non-Patent Document 1, it is necessary to use an expensive methyl iodide or trifluoromethanesulfonic acid in an equimolar amount with the target methyl acrylate, which is disadvantageous in terms of cost. In addition, it is not efficient because it is necessary to treat harmful hydrogen iodide produced as a by-product.

Therefore, an object of the present invention is to provide an efficient method for producing an α, β-unsaturated carboxylic acid derivative, which is advantageous in terms of cost.

The present inventors have conducted diligent research to solve the above problems. As a result, the metal lactone compound was reacted with either one or both of the hydrocarbons iodide and the hydrocarbon bromide having 1 to 6 carbon atoms, and the α, β-unsaturated carboxylic acid derivative and hydrogen iodide and The step of obtaining either one or both of hydrogen bromide and one or both of the hydrogen iodide and the hydrogen bromide are reacted with an alcohol having 1 to 6 carbon atoms to cause the hydrocarbon and hydrogen bromide. We have found that the above problems can be solved by using a method for producing an α, β-unsaturated carboxylic acid derivative, which comprises a step of regenerating one or both of the above-mentioned hydrogen bromide, and the present invention has been made. It came to be completed.

That is, the present invention has the following configurations.
[1] The metal lactone compound represented by the following formula (1) is reacted with either one or both of hydrogen iodide and hydrogen bromide having 1 to 6 carbon atoms, and α, β-unsaturated. The step of obtaining one or both of the carboxylic acid derivative and hydrogen iodide and hydrogen bromide, and the reaction of one or both of the hydrogen iodide and the hydrogen bromide with an alcohol having 1 to 6 carbon atoms. A method for producing an α, β-unsaturated carboxylic acid derivative, which comprises a step of regenerating one or both of the iodide hydrocarbon and the bromide hydrocarbon.

［式中、Ｍは、遷移金属であり、Ｌは、それぞれ独立して、単座配位子であるか、又はＬは共働して二座配位子を形成し、Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２はそれぞれ独立に水素原子、又は炭素数が１〜８のアルキル基である。］
［２］ 遷移金属錯体と、アルケンと、二酸化炭素と、を反応させて前記金属ラクトン化合物を得る工程をさらに含む、［１］に記載のα，β−不飽和カルボン酸誘導体の製造方法。
［３］ 前記金属ラクトン化合物が下記式（２）で表される、［１］又は［２］に記載のα，β−不飽和カルボン酸誘導体の製造方法。

[In the formula, M is a transition metal and L is a monodentate ligand, respectively, or L cooperates to form a bidentate ligand, R ¹¹ , R ¹² , R ²¹ and R ²² are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms. ]
[2] The method for producing an α, β-unsaturated carboxylic acid derivative according to [1], further comprising a step of reacting a transition metal complex with an alkene and carbon dioxide to obtain the metal lactone compound.
[3] The method for producing an α, β-unsaturated carboxylic acid derivative according to [1] or [2], wherein the metal lactone compound is represented by the following formula (2).

［式中、Ｍは、遷移金属であり、Ｘは、それぞれ独立して、窒素原子、又はリン原子であり、Ｒ^１は、それぞれ独立して、脂肪族炭化水素基、芳香族炭化水素基、複素芳香環基、又は窒素含有基であり、Ｒ^２及びＲ^３は、それぞれ独立して、脂肪族炭化水素基、芳香族炭化水素基、又は複素芳香環基であり、この際、２つのＲ^１は互いに結合して環構造を形成していてもよく、同一のＸ原子に結合するＲ^１、Ｒ^２、及びＲ^３が一体となって環構造を形成していてもよく、Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２は上記と同様である。］
［４］ 前記金属ラクトン化合物が下記式（３）で表される、［３］に記載のα，β−不飽和カルボン酸誘導体の製造方法。

[In the formula, M is a transition metal, X is an independent nitrogen atom or a phosphorus atom, and R ¹ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, respectively. a heteroaromatic ring group, or a nitrogen-containing group, R ² and R ³ are each independently an aliphatic hydrocarbon group, aromatic hydrocarbon group or a heteroaromatic ring group, this time, two R ¹ may be bonded to form a ring structure, R ^1, R ^2, and R ³ which bind to the same X atoms may form a ring structure together, R ^11, R ¹² , R ²¹ , and R ²² are the same as described above. ]
[4] The method for producing an α, β-unsaturated carboxylic acid derivative according to [3], wherein the metal lactone compound is represented by the following formula (3).

［式中、Ｍは、遷移金属であり、Ｘは、それぞれ独立して、窒素原子、又はリン原子であり、Ｒ^２、及びＲ^３は、それぞれ独立して、脂肪族炭化水素基、芳香族炭化水素基、又は複素芳香環基であり、Ａ^１は、単結合、二価の脂肪族炭化水素基、二価の芳香族炭化水素基、二価の複素芳香環基、又は二価の窒素含有基であり、この際、同一のＸ原子に結合するＡ^１、Ｒ^２、及びＲ^３が一体となって環構造を形成していてもよく、Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２は上記と同様である。］
［５］ 前記Ｘの少なくとも１つが窒素原子であり、前記窒素原子に結合するＡ^１、Ｒ^２、及びＲ^３が一体となって複素芳香環が形成される、［４］に記載のα，β−不飽和カルボン酸誘導体の製造方法。
［６］ 前記Ｘの少なくとも１つがリン原子であり、前記リン原子に結合するＲ^２及びＲ^３の少なくとも一つが、炭素数３以上の脂肪族炭化水素基、炭素数６以上の芳香族炭化水素基、又は炭素数３以上の複素芳香環基である、［４］又は［５］に記載のα，β−不飽和カルボン酸誘導体の製造方法。
［７］ 前記金属ラクトン化合物が下記式（４）〜（６）からなる群から選択される少なくとも１つを含む［４］〜［６］のいずれか一項に記載のα，β−不飽和カルボン酸誘導体の製造方法。

[In the formula, M is a transition metal, X is an independently nitrogen atom or a phosphorus atom, and R ² and R ³ are independently aliphatic hydrocarbon groups and aromatics, respectively. It is a hydrocarbon group or a heteroaromatic ring group, and A ¹ is a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent heteroaromatic ring group, or a divalent nitrogen. It is an containing group, and at this time, A ¹ , R ² , and R ³ bonded to the same X atom may be integrally formed to form a ring structure, and R ¹¹ , R ¹² , R ²¹ , and R ^22. Is the same as above. ]
[5] The α, according to [4], wherein at least one of the X is a nitrogen atom, and A ¹ , R ² , and R ^{3 bonded to the nitrogen atom are integrated to form a heteroaromatic ring.} A method for producing a β-unsaturated carboxylic acid derivative.
[6] At least one of the X is a phosphorus atom, ^{and at least one of R 2} and R ³ bonded to the phosphorus atom is an aliphatic hydrocarbon group having 3 or more carbon atoms and an aromatic hydrocarbon having 6 or more carbon atoms. The method for producing an α, β-unsaturated carboxylic acid derivative according to [4] or [5], which is a group or a heteroaromatic ring group having 3 or more carbon atoms.
[7] The α, β-unsaturated according to any one of [4] to [6], wherein the metal lactone compound contains at least one selected from the group consisting of the following formulas (4) to (6). A method for producing a carboxylic acid derivative.

［式中、Ｍは、遷移金属であり、Ｒ^２及びＲ^３は、それぞれ独立して、脂肪族炭化水素基、芳香族炭化水素基、又は複素芳香環基であり、Ａ^１は、単結合、二価の脂肪族炭化水素基、二価の芳香族炭化水素基、二価の複素芳香環基、又は二価の窒素含有基であり、Ａ^２は、単結合、二価の脂肪族炭化水素基、二価の芳香族炭化水素基、二価の複素芳香環基、又は二価の窒素含有基であり、Ａ^３は、単結合、二価の脂肪族炭化水素基、二価の芳香族炭化水素基、二価の複素芳香環基、又は二価の窒素含有基であり、Ｒ^４は、それぞれ独立して、水素原子、脂肪族炭化水素基、芳香族炭化水素基、又は複素芳香環基であり、Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２は上記と同様である。］
［８］ 前記金属ラクトン化合物を得る工程の反応を、１０気圧以下の圧力で行う、［２］〜［７］のいずれか一項に記載のα，β−不飽和カルボン酸誘導体の製造方法。

[In the formula, M is a transition metal, R ² and R ³ are independently aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or heteroaromatic ring groups, and A ¹ is a single bond. , A divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent heteroaromatic ring group, or a divalent nitrogen-containing group, and A ² is a single-bonded, divalent aliphatic hydrocarbon. hydrogen group, a divalent aromatic hydrocarbon group, a divalent heterocyclic aromatic ring group, or a divalent nitrogen-containing group, a ³ is a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic family hydrocarbon group, a divalent heterocyclic aromatic ring group, or a divalent nitrogen-containing group, R ⁴ are each independently hydrogen atom, an aliphatic hydrocarbon group, aromatic hydrocarbon group, or a heteroaromatic It is a ring group, and R ¹¹ , R ¹² , R ²¹ , and R ²² are the same as described above. ]
[8] The method for producing an α, β-unsaturated carboxylic acid derivative according to any one of [2] to [7], wherein the reaction in the step of obtaining the metal lactone compound is carried out at a pressure of 10 atm or less.

According to the present invention, it is possible to provide an efficient method for producing an α, β-unsaturated carboxylic acid derivative, which is advantageous in terms of cost.

Hereinafter, the present invention will be described in detail.
The method for producing the α, β-unsaturated carboxylic acid of the present embodiment is one of a metal lactone compound represented by the following formula (1), a hydrogen iodide having 1 to 6 carbon atoms, and a hydrocarbon bromide. , Or both to obtain one or both of the α, β-unsaturated carboxylic acid derivative and hydrogen iodide and hydrogen bromide (hereinafter, also referred to as step 1), and the hydrogen iodide. And any one or both of the hydrogen bromide and an alcohol having 1 to 6 carbon atoms are reacted to regenerate either one or both of the hydrogen iodide and the hydrogen bromide (hereinafter, hereinafter). (Also referred to as step 2) and.

前記式（１）中、Ｍは、遷移金属であり、Ｌは、それぞれ独立して、単座配位子であるか、又はＬは共働して二座配位子を形成する。Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２はそれぞれ独立に水素原子、又は炭素数が１〜８のアルキル基である。

In the above formula (1), M is a transition metal, L is a monodentate ligand independently of each other, or L cooperates to form a bidentate ligand. R ¹¹ , R ¹² , R ²¹ and R ²² are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.

The method for producing the metal lactone compound represented by the formula (1) is not particularly limited, but a method for producing it by reacting _{a transition metal complex described later with an alkene and carbon dioxide (CO 2) is preferable.} Details of the metal lactone compound represented by the formula (1) will be described later.

(Step 1)
In step 1, the metal lactone compound represented by the above formula (1) is reacted with either one or both of hydrogen iodide hydrocarbon and hydrogen bromide having 1 to 6 carbon atoms, and α, β-non is formed. This is a step of obtaining one or both of α, β-unsaturated carboxylic acid ester, hydrogen iodide, and hydrogen bromide, which are saturated carboxylic acid derivatives. Hereinafter, hydrocarbons having 1 to 6 carbon atoms and hydrocarbons bromide are collectively referred to as "hydrocarbons iodide (bromide)".
The carbon number of the iodide (bromide) hydrocarbon may be appropriately selected according to the target α, β-unsaturated carboxylic acid ester, but is preferably 1 to 6, preferably 1 to 5. It is more preferably 1 to 4.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a benzyl group and the like, and these groups may have a substituent such as a hydroxyl group and a halogen group. Of these, an alkyl group is particularly preferable as the hydrocarbon group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl and a tert-butyl group, and the alkyl group may be a methyl group, an ethyl group, a propyl group or a tert-butyl group. It is preferably an ethyl group, especially preferably an ethyl group.
Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, a 3-butenyl group, a 2-pentenyl group, a 2-hexenyl group and the like, and a vinyl group and an allyl group are preferable, and a vinyl group is used. Is particularly preferable.

The number of iodine atoms or bromine atoms in the iodide (bromide) hydrocarbon may be plural, but is usually one. Further, it is preferable to use an iodide hydrocarbon from the viewpoint that the reaction with the metal lactone compound proceeds sufficiently and the yield of the α, β-unsaturated carboxylic acid derivative is improved.

That is, as the iodide (bromide) hydrocarbon in the present embodiment, methyl iodide, ethyl iodide, propyl iodide, isopropyl iodide, n-butyl iodide, isobutyl iodide, and tert-butyl iodide are preferable. , Methyl iodide, ethyl iodide, propyl iodide, tert-butyl iodide are more preferred, and ethyl iodide is particularly preferred.

The amount of iodide (bromide) hydrocarbon used is preferably 0.2 to 10.0 mol, more preferably 0.5 to 7.0 mol, with respect to 1 mol of the metal lactone compound. , 1.0-5.0 mol, more preferably.
When the amount of iodide (bromide) hydrocarbon used is equal to or higher than the lower limit of the above range, the reaction between the metal lactone compound and the iodide (bromide) hydrocarbon proceeds sufficiently, and the α, β-unsaturated carboxylic acid The yield of the acid derivative is improved. When the amount of iodide (bromide) hydrocarbon used is not more than the upper limit of the above range, the formation of impurities can be suppressed.

The reaction temperature in step 1 is not particularly limited as long as it has the effect of the present invention, but is preferably 0 to 120 ° C, more preferably 20 to 100 ° C, and even more preferably 20 to 80 ° C. ..
When the reaction temperature is at least the lower limit of the above range, the reaction between the metal lactone compound and the iodide (bromide) hydrocarbon proceeds sufficiently, and the yield of the α, β-unsaturated carboxylic acid derivative is improved. When the reaction temperature is not more than the upper limit of the above range, the thermal decomposition of the transition metal complex which is a catalyst described later can be suppressed, and the production cost can be reduced.
The reaction pressure in step 1 is not particularly limited as long as it has the effect of the present invention, but is usually preferably 10 atm or less, preferably 8 atm or less, and 1 to 5 atm in absolute pressure. More preferred.

The reaction of step 1 is preferably carried out using a solvent. In a preferred embodiment, it is preferable to carry out the reaction by introducing a metal lactone compound and an iodide (bromide) hydrocarbon into a solvent containing a transition metal complex.
The solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran (THF); dimethylformamide; dimethylsulfoxide and the like. Of these, THF and toluene are preferably used. These solvents may be used alone or in combination of two or more.

The reaction form of step 1 is not particularly limited, and may be carried out in a batch manner or in a continuous manner.
When the batch method is used, it is preferable to introduce a metal lactone compound and an iodide (bromide) hydrocarbon into the solvent and carry out the reaction. When the reaction is carried out in a continuous manner, it is preferable to carry out the reaction by charging a metal lactone compound in a solvent and continuously introducing an iodide (bromide) hydrocarbon.
Further, as the reaction device, a known reaction device can be appropriately used depending on the reaction type to be adopted.
The reaction atmosphere can be a nitrogen, argon, or helium atmosphere.

The reaction of step 1 is preferably carried out by adding an iodide (bromide) hydrocarbon to the reaction solution obtained in step 1-A described later.

(Step 2)
In step 2, one or both of hydrogen iodide (by-product) and hydrogen bromide obtained in step 1 are reacted with an alcohol having 1 to 6 carbon atoms to form the iodide (bromide). This is a process of regenerating hydrocarbons. The regenerated iodide (bromide) hydrocarbon can be used again in the reaction with the metal lactone compound in step 1. Hereinafter, hydrogen iodide and hydrogen bromide are collectively referred to as "hydrogen iodide (hydrogen bromide)".
That is, the hydrocarbon group in the iodide (bromide) hydrocarbon used in step 1 and the hydrocarbon group in the alcohol used in step 2 are the same. For example, when ethyl iodide is used as the iodide (bromide) hydrocarbon in step 1, the alcohol used in step 2 is ethanol. Therefore, the carbon number of the alcohol used in the step 2 is 1 to 6, preferably 1 to 5, and more preferably 1 to 4.
Examples of such alcohols include methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, isobutyl alcohol, tert-butyl alcohol and the like, and may be methanol, ethanol, 1-propanol and tert-butyl alcohol. Ethanol is preferable, and ethanol is particularly preferable.

The amount of alcohol used is preferably 1.0 mol, more preferably 1.0 to 5.0 mol, and 1.0 to 2. It is more preferably 0 mol.
When the amount of alcohol used is at least the lower limit of the above range, the reaction between hydrogen iodide (hydrogen bromide) and alcohol proceeds sufficiently, and the yield of hydrocarbon (hydrogen bromide) is improved. When the amount of alcohol used is not more than the upper limit of the above range, the side reaction between the alcohol and the metal lactone compound can be suppressed.

The reaction temperature in step 2 is not particularly limited as long as it has the effect of the present invention, but is preferably 0 to 120 ° C, more preferably 20 to 100 ° C, and even more preferably 20 to 90 ° C. ..
When the reaction temperature is at least the lower limit of the above range, the reaction between hydrogen iodide (hydrogen bromide) and alcohol proceeds sufficiently, and the yield of hydrocarbon (hydrogen bromide) is improved. When the reaction temperature is not more than the upper limit of the above range, the thermal decomposition of the catalyst can be suppressed and the production cost can be reduced.
The reaction pressure in step 2 is not particularly limited as long as it has the effect of the present invention, but is usually preferably 10 atm or less, preferably 8 atm or less, and 1 to 5 atm in absolute pressure. More preferred.

The reaction in step 2 is preferably carried out using a solvent. In a preferred embodiment, it is preferable to carry out the reaction by introducing hydrogen iodide (hydrogen bromide) and an alcohol having 1 to 6 carbon atoms into the solvent.
The solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran (THF); dimethylformamide; dimethylsulfoxide and the like. Of these, THF and toluene are preferably used. These solvents may be used alone or in combination of two or more.

The reaction form of step 2 is not particularly limited, and may be carried out in a batch manner or in a continuous manner.
When the batch method is used, it is preferable to introduce hydrogen iodide (hydrogen bromide) and an alcohol having 1 to 6 carbon atoms into the solvent to carry out the reaction. When the reaction is carried out in a continuous manner, it is preferable to charge hydrogen bromide in a solvent and continuously introduce an alcohol having 1 to 6 carbon atoms to carry out the reaction.
The reaction atmosphere can be a nitrogen, argon, or helium atmosphere.

The reaction in step 2 is preferably carried out by adding an alcohol having 1 to 6 carbon atoms to the reaction solution obtained in step 1.

(Method for producing metal lactone compound)
In the method for producing an α, β-unsaturated carboxylic acid derivative of the present embodiment, the metal lactone compound represented by the above formula (1) reacts with a _{transition metal complex, an alkene, and carbon dioxide (CO 2).} It is preferable that it is obtained by allowing it to be allowed to grow. That is, the method for producing an α, β-unsaturated carboxylic acid derivative of the present embodiment is a step of reacting a transition metal complex, an alkene, and carbon dioxide to obtain the metal lactone compound (hereinafter, step 1-A). It is also preferable to further include).

The reaction sequence of the transition metal complex, the alkene, and carbon dioxide is as follows: First, the transition metal complex and the alkene are reacted to obtain an alkene-metal complex, and the metal complex is reacted with carbon dioxide to obtain a metal lactone. It is preferable to obtain a compound.

(Step 1-A)
Step 1-A is a step of reacting a transition metal complex with an alkene and carbon dioxide to obtain a metal lactone compound represented by the above formula (1).

(Transition metal complex)
Transition metal complexes usually include transition metals and ligands.
The transition metal is not particularly limited as long as it has the effect of the present invention, but is an element belonging to Group 6 of the periodic table such as chromium (Cr), molybdenum (Mo), tungsten (W); 7 such as ruthenium (Re). Elements belonging to Group 8; Elements belonging to Group 8 such as iron (Fe) and Ruthenium (Ru); Elements belonging to Group 9 such as cobalt (Co) and Rhodium (Rh); Nickel (Ni), Palladium (Pd), Platinum Examples include elements belonging to Group 10 such as (Pt). Of these, the transition metals are preferably nickel, molybdenum, cobalt, iron, rhodium, ruthenium, palladium, platinum, renium and tungsten, preferably nickel, molybdenum, palladium, platinum, cobalt, iron, rhodium and ruthenium. It is more preferable, and nickel and palladium are further preferable. The transition metal may be used alone or in combination of two or more.

The ligand may be monodentate or polydentate such as bidentate or tridentate, but an appropriate coordination is provided so as to leave a coordination site for _{CO 2 and the compound to react with it on the metal.} It is desirable to select a position. For example, when the active metal is nickel, it is preferable to use a bidentate ligand, and when it is cobalt, it is preferable to use a tridentate ligand.

The ligand may contain at least one atom or atomic group selected from the group consisting of a phosphorus atom, a nitrogen atom, an oxygen atom, and a carben group as an atom or an atomic group coordinating with the transition metal. Good. The ligand can be selected from, for example, phosphine, phosphite, amine, and N-heterocyclic carbene. In the ligand, at least one atom or atomic group coordinating with the transition metal is preferably at least one selected from the group consisting of a phosphorus atom, an amine and a carbene group, and any one of a phosphorus atom and an amine. More preferably, one or both.

When the ligand contains at least one phosphorus atom coordinated to the transition metal, it is preferred that at least one group is attached to the phosphorus atom via a secondary or tertiary carbon atom. More preferably, at least two groups are attached to the phosphorus atom via a secondary or tertiary carbon atom. Suitable groups attached to the phosphorus atom via a secondary or tertiary carbon atom include, for example, adamantyl, tert-butyl, cyclohexyl, sec-butyl, isopropyl, phenyl, trill, xylyl, mesityl, naphthyl, etc. Fluolenyl and anthracenyl. Of these, a group having a high electron donating property is desirable, and specifically, tert-butyl and cyclohexyl are preferable.

When the ligand contains at least one N-heterocyclic carbene coordinated to the transition metal, preferably at least one group is at least one α-nitrogen atom of the carbene group via a secondary or tertiary carbon atom. Is bound to. Suitable groups attached to the nitrogen atom via the tertiary carbon atom are, for example, adamantyl, tert-butyl, isopropyl, phenyl, 2,6-diisopropylphenyl, adamantyl, tert-butyl, 2,6. -Preferably diisopropylphenyl.

As a specific example of a ligand containing at least one phosphorus atom that can be used in the present invention, as a monodentate ligand, for example, trialkylphosphine such as trimethylphosphine; tricycloalkylphosphine such as tricyclohexylphosphine (PCy3); Examples thereof include triarylphosphine such as triphenylphosphine and tri (4-fluoromethylphenyl) phosphine; triheteroarylphosphine such as tri-2-furanylphosphine; and a phosphorane ligand such as triphenylphosphine oxide.
The bidentate ligands include bis (diphenylphosphino) methane (dppm), 1,2-bis (diphenylphosphino) ethane (dppe), 1,3-bis (diphenylphosphino) propane (dppp), and 1 , 4-bis (diphenylphosphino) butane (dppb), 1,5-bis (diphenylphosphino) pentane (dpppe), 1,6-bis (diphenylphosphino) hexane, 1,1'-bis (diphenylphos) Fino) Ferrosen, 1,2-bis (dipentafluorophenylphosphino) ethane, 1,2-bis (dicyclohexylphosphino) ethane, 1,3-bis (dicyclohexylphosphino) propane, 1,4-bis (dicyclohexyl) Phosfino) butane, 1,2-bis (di-tert-butylphosphino) ethane, 1,2-bis (diphenylphosphino) benzene, 1,2-bis (bis (3,5-dimethylphenyl) phosphino) Etan, 1,3-bis (bis (3,5-dimethylphenyl) phosphino) propane, 1,4-bis (bis (3,5-dimethylphenyl) phosphino) butane, 1,2-bis (cyclohexylphosphino) Etan, 1,4-bis (bis (3,5-di-tert-butylphenyl) phosphino) butane, 1,4-bis (bis (3,5-dimethoxyphenyl) phosphino) butane, 2,2'-bis (Diphenylphosphino) -1,1'-binaphthyl, 2,2'-bis (bis (3,5-dimethylphenyl) phosphino) -1,1'-binaphthyl, (2S, 3S)-(-)-bis (Diphenylphosphino) butane, (S, S) -1,2-bis [(2-methoxyphenyl) phenylphosphino] ethane ((S, S) -DIPAMP), (R, R)-(-)- 2,3-bis (tert-butylmethylphosphino) quinoxalin (QuinoxP ^* ), (R, R) -1,2-bis (tert-butylmethylphosphino) benzene (BenzaP ^* ), 1,1,1- Tris (diphenylphosphinomethyl) ethane, 1,1,1-tris (bis (3,5-dimethylphenyl) phosphinomethyl) ethane, 1,1,1-tris (diphenylphosphino) methane, tris (2- Diphenylphosphinoethyl) phosphine, (oxydi-2,1-phenylene) bis (diphenylphosphine), 4,5-bis (diphenylphosphino) -9,9-dimethylxanthen, 4,5-bis (diphenylphosph) Ino) -9,9-dimethylxanthene and the like can be mentioned.
Examples of the tridentate ligand include bis (2-diphenylphosphinoethyl) phenylphosphine, 1,1,1-tris (diphenylphosphinomethyl) ethane and the like.
Examples of the tetradentate ligand include tris (2-diphenylphosphinoethyl) phenylphosphine and the like.
Among them, 1,2-bis (diphenylphosphino) ethane (dppe), 1,2-bis (dicyclohexylphosphino) ethane, 1,2-bis (di-tert-butylphosphino) ethane, 1,3- Bis (dicyclohexylphosphino) propane and BenzP ^* are preferred.

In addition to the above-mentioned ligands, the ligands include halides, amines, amides, oxides, phosphates, carboxylates, acetylacetonates, arylsulfonates, alkylsulfonates, hydrides, carbon monoxides, etc. Alkenes (ethylene, propene, butane, etc.), dienes (1,3-butadiene, 1.6-hexadiene, etc.), cycloalkenes (cyclohexene, etc.), cycloalkazienes (1,5-cyclooctadiene (COD), etc.), At least selected from nitriles, aromatics, heterocyclic aromatics, ethers, phosphorus trifluoride, phosphors, phosphabenzenes, and monodentate, bidentate, and polydentate phosphinites, phosphonite, phosphoramidite, and phosphite ligands. It may also have one additional ligand.
The above-mentioned ligands may be used alone or in combination of two or more.

In one embodiment, specific examples of the transition metal complex include those represented by the following formula (7).

Ｍは遷移金属であり、具体例としては上述の通りである。このうち、Ｍとしては、ニッケル原子、パラジウム原子であることが好ましい。
Ｘは、それぞれ独立して、窒素原子、又はリン原子である。
Ｙは、一酸化炭素、炭素数２〜２０のアルケン、炭素数４〜２０のジエン、炭素数３〜２０のシクロアルケン、又は炭素数４〜２０のシクロアルカジエンである。
前記炭素数２〜２０のアルケンとしては、特に制限されないが、エチレン、プロピレン、イソブテン、１，３−ブタジエン、ピペリレン、１−ブテン、２−ブテン、１−ペンテン、３−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン等が挙げられる。
前記炭素数４〜２０のジエンとしては、特に制限されないが、１，３−ブタジエン、１，３−ペンタジエン、１，４−ペンタジエン、１，４−ヘキサジエン、１，５−ヘキサジエン、２−メチル−１，３−ブタジエン等が挙げられる。
前記炭素数３〜２０のシクロアルケンとしては、特に制限されないが、シクロプロぺン、シクロブテン、シクロペンテン、シクロヘキセン、メチルシクロペンテン、エチルシクロペンテン、シクロヘキセン等が挙げられる。
前記炭素数４〜２０のシクロアルカジエンとしては、１，５−シクロオクタジエン（ＣＯＤ）等が挙げられる。

M is a transition metal, and specific examples thereof are as described above. Of these, M is preferably a nickel atom or a palladium atom.
X is independently a nitrogen atom or a phosphorus atom.
Y is carbon monoxide, an alkene having 2 to 20 carbon atoms, a diene having 4 to 20 carbon atoms, a cycloalkene having 3 to 20 carbon atoms, or a cycloalkene having 4 to 20 carbon atoms.
The alkene having 2 to 20 carbon atoms is not particularly limited, but is limited to ethylene, propylene, isobutene, 1,3-butadiene, piperylene, 1-butene, 2-butene, 1-pentene, 3-pentene, 1-hexene, and the like. Examples thereof include 1-heptene, 1-octene, 1-nonene and 1-decene.
The diene having 4 to 20 carbon atoms is not particularly limited, but is 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-. Examples thereof include 1,3-butadiene.
The cycloalkene having 3 to 20 carbon atoms is not particularly limited, and examples thereof include cyclopropene, cyclobutene, cyclopentene, cyclohexene, methylcyclopentene, ethylcyclopentene, and cyclohexene.
Examples of the cyclooctadiene having 4 to 20 carbon atoms include 1,5-cyclooctadiene (COD) and the like.

Of the above, Y is preferably carbon monoxide, an alkene having 2 to 20 carbon atoms, and a cyclooctadiene having 4 to 20 carbon atoms, preferably carbon monoxide, an alkene having 2 to 10 carbon atoms, and 4 to 4 carbon atoms. It is more preferably 10 cycloalkadiene, more preferably carbon monoxide, ethylene, 1,5-cyclooctadiene (COD), and even more preferably ethylene, 1,5-cyclooctadiene (COD). Is particularly preferable.

R ¹ is independently an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heteroaromatic ring group, or a nitrogen-containing group. Further, R ² and R ³ are independently aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or heteroaromatic ring groups. At this time, the two R ^1s may be bonded to each other to form a ring structure, and R ¹ , R ^{2 , and R 3} bonded to the same X atom are integrally formed to form a ring structure. May be good.

Examples of the aliphatic hydrocarbon group include an alkyl group having 2 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms.

The alkyl group having 2 to 20 carbon atoms is not particularly limited, but is limited to methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, 2-butyl group, sec-butyl group, tert-butyl group and n. -Pentyl group, 2-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, n -Hexyl group, 2-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group , 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethylbutyl group, 2-Ethylbutyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, 2-heptyl group, 3-heptyl group, 2-ethylpentyl group, 1-propylbutyl group, n-octyl group, 2- Examples thereof include ethylhexyl group, 2-propylheptyl group, nonyl group and decyl group.

The cycloalkyl group having 3 to 20 carbon atoms is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group.

The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include an alkoxy group (methoxy group, ethoxy group, propyloxy group, etc.), an aryl group (phenyl group, etc.), a heteroaryl group (pyridinyl group, etc.), a hydroxy group, a halogen atom (fluorine atom, chlorine atom, etc.). Bromine atom, etc.), nitro group, nitrile group, NE ¹ E ² group, NE ¹ E ² E ³⁺ group, carboxylic acid derivative group (carboxylic acid ester group such as methyloxycarbonyl group), sulfonic acid derivative group (sulfonic acid) (Ester group, sulfonamide group, etc.) and the like can be mentioned. The E ¹ , E ² , and E ³ are independently hydrogen atoms, alkyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms. .. These substituents may be contained alone or in combination of two or more.

Examples of the aromatic hydrocarbon group include an aryl group having 6 to 30 carbon atoms. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and the like.

Examples of the heteroaromatic ring group include heteroaryl groups having 1 to 30 carbon atoms, preferably 3 to 30 carbon atoms. Examples of the heteroaryl group having 1 to 30 carbon atoms include a furanyl group, a thiophenyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, an isoxazolyl group, a thiazolyl group, a thiadiazolyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group and a triazinyl group. Group, benzofuranyl group, indolyl group, thianaftenyl group, benzimidazolyl group, benzoxazolyl group, benzothiazolyl group, benzotriazolyl group, quinolyl group, isoquinolyl group, tynoryl group, quinoxalyl group, dibenzothiophenyl group, acrizyl group, phenanthrolyl group, etc. Can be mentioned.

The aromatic hydrocarbon group and the heteroaromatic ring group may have a substituent. The substituent is not particularly limited, but is an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group, a hydroxy group, a halogen atom, a nitro group, a nitrile group, and NE ¹ E ² groups. , NE ¹ E ² E ³⁺ group, carboxy group, sulfo group and the like.

The nitrogen-containing group is different from the heteroaromatic ring group, and examples thereof include NE ¹ E ² group and NE ¹ E ² E ³⁺ group. Specific examples of the NE ¹ E ² group and the NE ¹ E ² E ³⁺ group include an amino group, a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group and the like.

The expression "bonded to form a cyclic structure R ¹ each other" combines two of R ¹ each other, resulting in forming a divalent radical, with two X and M to form a ring structure Means that. ^{In addition, "R 1} , R ² , and R ³ bonded to the same X atom together form a ring structure" typically means R ¹ , R ² , which are bonded to the same X atom. and the R ³ means to form a ring structure containing a double bond. For example, there is a case where R ¹ and R ² form a 6-membered ring structure together with X, ^{and a bond of R 3} forms a double bond of a 6-membered ring.

Of these, R ¹ preferably combines with each other to form a ring structure, more preferably a 3-membered ring structure, a 4-membered ring structure, a 5-membered ring structure, or a 6-membered ring structure. It is more preferable to form a structure or a 6-membered ring structure. By R ¹ are combined to form a ring structure, the complex becomes a bidentate ligand becomes chemically stable, also, the metal by ring - conformation between the bidentate ligand is limited, When the metal lactone compound is produced, the lactone ring structure is distorted, and the cleavage of the lactone ring in step 1 is likely to proceed, which is preferable.

Further, R ² and R ³ are preferably an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group, or a heteroaromatic ring group, and preferably have 6 to 20 carbon atoms. It is more preferably a cycloalkyl group, an aromatic hydrocarbon group, or a heteroaromatic ring group, and even more preferably an alkyl group having 3 to 10 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms. When R ² and R ³ are an alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group, or a heteroaromatic ring group, the steric hindrance is large and the electron donating property is large. Is preferable because the complex reaction in Y is likely to occur.

In one embodiment, the preferred transition metal complex is represented by the following formula (8).

すなわち、前記式（７）において、Ｒ^１が互いに結合して環構造を形成している構造である。
Ｍ、Ｘ、Ｙは、前記式（７）と同様である。
また、Ｒ^２、Ｒ^３は、前記式（７）と同様である。
Ａ^１は、単結合、二価の脂肪族炭化水素基、二価の芳香族炭化水素基、二価の複素芳香環基、又は二価の窒素含有基である。この際、同一のＸ原子に結合するＡ^１、Ｒ^２、及びＲ^３が一体となって環構造を形成していてもよい。

That is, in the above formula (7), R ¹ is bonded to each other to form a ring structure.
M, X, and Y are the same as in the above formula (7).
Further, R ² and R ³ are the same as those in the above formula (7).
A ¹ is a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent heteroaromatic ring group, or a divalent nitrogen-containing group. ^{At this time, A 1} , R ² , and R ³ bonded to the same X atom may be integrated to form a ring structure.

Examples of the divalent aliphatic hydrocarbon group include an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and an alkenylene group having 2 to 20 carbon atoms.

Examples of the alkylene group having 1 to 20 carbon atoms include methylene, ethylene, propylene, isopropylene, butylene, 2-methylpropylene, pentylene and the like.
Examples of the cycloalkylene group having 3 to 20 carbon atoms include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, methylcyclohexylene and the like.
Examples of the alkenylene group having 2 to 20 carbon atoms include a vinylene group, a propenylene group and a butenylene group.

The above-mentioned divalent aliphatic hydrocarbon group may have a substituent. Examples of the substituent include those similar to the above-mentioned aliphatic hydrocarbon group. The divalent aliphatic hydrocarbon group may have a substituent alone or in combination of two or more.

Examples of the divalent aromatic hydrocarbon group include a divalent group derived from an arylene having 6 to 30 carbon atoms. Examples of the arylene group having 6 to 30 carbon atoms include a divalent group derived from benzene, toluene, xylene, naphthalene, biphenyl and terphenyl.

Examples of the divalent heteroaromatic ring group include a divalent group derived from a heteroarylene having 1 to 30 carbon atoms. Examples of the heteroarylene group having 1 to 30 carbon atoms include furan, thiophene, pyrrole, pyrazole, imidazole, isoxazole, thiazole, thiazylazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, benzofuran, indol, thianaften, benzimidazole and benzoxa. Examples include divalent groups derived from sol, benzothiazole, benzotriazole, purine, quinoline, isoquinoline, tynoline, quinoxalin, dibenzothiophene, acrydin, phenanthroline.

The above-mentioned divalent aromatic hydrocarbon group and divalent heteroaromatic ring group may have a substituent. Examples of the substituent include those described in the divalent aromatic hydrocarbon group as ^{R 1 to} R ³ of the above formula (7) and the divalent heteroaromatic ring group. The divalent aromatic hydrocarbon group and the divalent heteroaromatic ring group may each have a substituent alone or in combination of two or more.

Examples of the divalent nitrogen-containing group, -NE 4 ^- and the like. At this time, the ^{E 4} is hydrogen atom, an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, is a heteroaryl group having 1 to 30 carbon atoms ..
^{In addition, "A 1} , R ² and R ³ bonded to the same X atom together form a ring structure" typically means that A ¹ , R ² bonded to the same X atom. and the R ³ means to form a ring structure containing a double bond.

In the above formula (8), at least one of X is a nitrogen atom, and at this time, A ¹ , R ² and R ³ bonded to the nitrogen atom are integrated to form a complex aromatic ring. Is preferable. Examples of the heteroaromatic ring include a pyrrole ring, a pyrazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring. Of these, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring are preferable, and a pyridine ring is more preferable. At this time, the heteroaromatic ring may have a substituent. Examples of the substituent include an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group, hydroxy group, a halogen atom, a nitro group, a nitrile group, ^NE 1 ^{E 2} group, ^NE 1 ^{E 2 Examples} thereof include an E3 + group, a carboxy group and a sulfo group. These substituents may be used alone or in combination of two or more. Since the heteroaromatic ring of the formula (8) has a certain steric hindrance and has a high electron donating property based on a hetero atom such as a nitrogen atom, it is preferable because a complex reaction in Y is likely to occur.

Further, in the above formula (8), at least one of X is a phosphorus atom, and at this time, ^{at least one of R 2} and R ³ bonded to the phosphorus atom is an aliphatic hydrocarbon group having 3 or more carbon atoms and carbon. It is preferable to include an aromatic hydrocarbon group having 6 or more carbon atoms or a heteroaromatic ring group having 3 or more carbon atoms.

The aliphatic hydrocarbon group having 3 or more carbon atoms includes a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a 2-ethylbutyl group and a hexyl. Alkyl group having 3 to 20 carbon atoms such as group, 2-methylpentyl group, 3-methylpentyl group, heptyl group, 2-methylhexyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclo Examples thereof include a cycloalkyl group having 3 to 20 carbon atoms such as a heptyl group. At this time, the aliphatic hydrocarbon group having 3 or more carbon atoms may have a substituent. Examples of the substituent include an alkoxy group, an aryl group, a heteroaryl group, a hydroxy group, a halogen atom, a nitro group, a nitrile group, a NE ¹ E ² group, a NE ¹ E ² E ³⁺ group, a carboxylic acid derivative group, and a sulfonic acid derivative. The group etc. can be mentioned. These substituents may be used alone or in combination of two or more.

Examples of the aromatic hydrocarbon group having 6 or more carbon atoms include heteroaryl groups having 6 to 30 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl, and a biphenyl group.

Further, examples of the heteroaromatic ring group having 3 or more carbon atoms include a furanyl group, a thiophenyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, an isoxazolyl group, a thiazolyl group, a thiadiazolyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group and a pyrazinyl group. Triazinyl group, benzofuranyl group, indolyl group, thianaftenyl group, benzimidazolyl group, benzoxazolyl group, benzothiazolyl group, benzotriazolyl group, quinolyl group, isoquinolyl group, tynoryl group, quinoxalyl group, dibenzothiophenyl group, acrizyl group, phenanthrolyl group Examples thereof include heteroaryl groups having 1 to 30 carbon atoms.

At this time, the aromatic hydrocarbon group and the heteroaromatic ring group having 6 or more carbon atoms may have a substituent. Examples of the substituent include an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group, hydroxy group, a halogen atom, a nitro group, a nitrile group, ^NE 1 ^{E 2} group, ^NE 1 ^{E 2 Examples} thereof include an E3 + group, a carboxy group and a sulfo group. These substituents may be used alone or in combination of two or more.

Of the above, in the above formula (8), when at least one of X is a phosphorus atom, ^{at least one of R 2} and R ³ bonded to the phosphorus atom is an alkyl group having 4 to 8 carbon atoms and a carbon number of carbon atoms. It is preferably a cycloalkyl group having 4 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a heteroaryl group having 1 to 7 carbon atoms, and an alkyl group having 4 to 8 carbon atoms and a cycloalkyl group having 4 to 8 carbon atoms. , An aryl group having 6 to 10 carbon atoms is more preferable, an alkyl group having 4 to 8 carbon atoms and a cycloalkyl group having 4 to 8 carbon atoms are further preferable, and a cycloalkyl group having 4 to 8 carbon atoms is used. Is particularly preferable.

In one embodiment, more preferred transition metal complexes are represented by the following formulas (9) to (11).

That is, the formula (9) has a structure in which two Xs are phosphorus atoms (P) in the formula (8). Further, in the above formula (10), in the above formula (7), one X is a phosphorus atom, the other X is a nitrogen atom, and R ¹ , R ² , and R ³ bonded to the nitrogen atom are present. It is a structure in which a pyridine ring is formed as a unit. Further, the above formula (11) has a structure in which two Xs are nitrogen atoms in the above formula (7), and R ¹ , R ² , and R ³ bonded to the nitrogen atom are integrally formed to form a pyridine ring. Is.

M, X, and Y are the same as in the above formula (7).
Further, A ¹ is the same as the above formula (8).
A ² is a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent heteroaromatic ring group, or a divalent nitrogen-containing group. Normally, it may have a carbon atom number of ^{"A 1 carbon atom number -1".}
A ³ is a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent heteroaromatic ring group, or a divalent nitrogen-containing group. Normally, it may have a carbon atom number of ^{"A 1 carbon atom number-2".}

R ⁴ are each independently a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, heteroaryl group having 1 to 30 carbon atoms, Examples thereof include an alkoxy group, a hydroxy group, a halogen atom, a nitro group, a nitrile group, a NE ¹ E ² group, a NE ¹ E ² E ³⁺ group, a carboxylic acid derivative group, and a sulfonic acid derivative group. Of these, a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group, a halogen atom, and a nitro group are preferable, and a hydrogen atom and an alkyl having 2 to 20 carbon atoms are preferable. More preferably, it is a group, a cycloalkyl group having 3 to 20 carbon atoms.

Among the above, the transition metal complex preferably contains the one represented by the above formula (10), and in the above formula (10), R ² and R ³ are independently tert-butyl groups and have 3 carbon atoms, respectively. It is more preferable to include those having a cycloalkyl group of ~ 20, and it is further preferable to include those in which R ² and R ³ are cycloalkyl groups having 5 to 8 carbon atoms in the above formula (10). At this time, it is particularly preferable that ^{R 4 is a hydrogen atom.}
The above-mentioned transition metal complex may be used alone or in combination of two or more.

(Alkene)
The alkene is not particularly limited, but is limited to ethylene, propylene, isobutene, 1,3-butadiene, piperylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene. , Styrene and the like. Of these, ethylene, propylene, 1,3-diene, and styrene are preferable, and ethylene is more preferable.
These alkenes may be used alone or in combination of two or more.
The properties of the alkene may be gaseous or liquid, although it depends on the type of alkene.
The type of α, β-unsaturated carboxylic acid derivative usually obtained differs depending on the type of alkene used. For example, when ethylene is used, an acrylic acid derivative (acrylic acid ester) is usually obtained. Further, when propylene is used, a 2-butenoic acid derivative (2-butenoic acid ester) is usually obtained. Further, when 1-butene is used, a 2-ethylpropenoic acid derivative (2-ethylpropene acid ester) is usually obtained.

The amount of the alkene used is preferably 1 to 50 mol, more preferably 1.2 to 20 mol, still more preferably 1.5 to 15 mol, relative to 1 mol of the transition metal complex. It is particularly preferably 2 to 10 mol. When the amount of the alkene used is not less than the lower limit of the above range, the reaction between the transition metal complex and the alkene can be efficiently promoted, which is preferable. When the amount of alkene used is more than 1 mol (excess amount with respect to 1 mol of the transition metal complex), the reaction proceeds efficiently in step 1, which is preferable. Specifically, the alkene remaining in the reaction of step 1-A is coordinated to the transition metal complex at the same time as the α, β-unsaturated carboxylic acid is desorbed from the metal lactone compound in the step 1. As a result, an α, β-unsaturated carboxylic acid ester can be obtained, and a transition metal complex in which an alkene is coordinated with the transition metal complex can be regenerated to enable a continuous reaction. On the other hand, when the amount of alkene used is 50 mol or less, the reaction pressure can be lowered, which is preferable.

(Carbon dioxide (CO ₂ ))
CO ₂ can be used in a gaseous, liquid, or supercritical state. _{Although it is possible to use gas mixtures containing CO 2} that are available on an industrial scale, it is preferred that they are substantially free of carbon monoxide. In addition, "substantially free of carbon monoxide" means that the CO content is 100 ppm (0.01% by volume) or less with respect to 100% by volume of the gas mixture.

The _{amount of CO 2} used is 0.1 to 10 mol, preferably 0.1 to 3 mol, and more preferably 0.1 to 1.75 mol, based on 1 mol of the transition metal complex. It is more preferably 0.1 to 1.2 mol, particularly preferably 0.5 to 1.2 mol, and most preferably 0.5 to 1.0 mol. When the _{amount of CO 2} used is not less than the lower limit of the above range, the metal lactone compound can be efficiently produced. Further, when the _{amount of CO 2} used is not more than the upper limit of the above range, _{the generation of unreacted CO 2} can be prevented.
Further, in one embodiment, the _{amount of CO 2} used is preferably 1 mol or less, more preferably 0.1 to 1 mol, and 0.1 to 0 mol with respect to 1 mol of the transition metal complex. It is more preferably .95 mol.

(Inert gas)
The reaction of Step 1-A is preferably carried out in an atmosphere of an inert gas.
The inert gas is not particularly limited, and examples thereof include nitrogen gas, rare gas (helium gas, argon gas, krypton gas, etc.) and the like. These inert gases may be used alone or in combination of two or more.
The inert gas is usually added together with _{CO 2 when CO 2} is a gas. If the alkene is a gas, it may be added together with the alkene.
The amount of the inert gas used is preferably less than 50% by volume with respect to the total volume of the _{inert gas, CO 2 and the alkene.}

(solvent)
The reaction of step 1-A is preferably carried out using a solvent. In a preferred embodiment, _{it is preferable to carry out the reaction by introducing an alkene and CO 2} into a solvent containing a transition metal complex and bringing them into contact with the transition metal complex.
The solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran (THF); dimethylformamide; dimethylsulfoxide and the like. Of these, THF and toluene are preferably used. These solvents may be used alone or in combination of two or more.

(Reaction type)
The reaction form of step 1-A is not particularly limited, and may be carried out in a batch system, a semi-batch system, a continuous system, a batch system, a semi-batch system, and a continuous system. It may be done in combination.
When the batch method is used, it is preferable to introduce a transition metal complex, an alkene, and CO ₂ into a solvent to carry out the reaction. Further, in the case of performing the semi-batch method, it is preferable to prepare the transition metal complex and the alkene in the solvent in advance _{and continuously introduce CO 2} to carry out the reaction. When the continuous method is used, it is preferable to charge the transition metal complex in the solvent _{and continuously introduce the alkene and CO 2} to carry out the reaction.
In the case of continuous operation, the liquid phase of the reaction mixture is mixed while supplying the reaction raw material into a fixed bed method, a fluidized bed method, a moving bed method, a suspension bed method, a stirring mixture type or a loop type reactor. It can be carried out by various methods such as a extraction method. In the reactor of the stirred-mixed, under liquid phase conditions, when carried out in using gaseous alkenes and CO ₂ batch or continuous system, the alkene and CO _2, the reactor vapor phase and It may be supplied to either one of the liquid phase parts, or may be supplied to both the gas phase part and the liquid phase part of the reactor.
Further, as the reaction device, a known reaction device can be appropriately used depending on the reaction type to be adopted.

The reaction temperature in step 1-A is preferably 50 to 250 ° C, more preferably 80 to 200 ° C.
The reaction pressure in step 1-A is usually preferably 50 atm or less, more preferably 10 atm or less, further preferably 2 to 10 atm, and 3 to 10 atm in absolute pressure. Is particularly preferred.

In the present embodiment, the metal lactone compound obtained in step 1-A is not isolated from the solvent, iodide (bromide) hydrocarbon is added to the reaction solution of step 1-A, and step 1 is subsequently carried out. Is preferable. In Non-Patent Document 1 described above, a nickel-lactone compound is once isolated from a solvent, the nickel-lactone compound is dispersed in dichloromethane as a solvent, and methyl iodide is added to the obtained dispersion. Alternatively, it is described that methyl acrylate, which is an α, β-unsaturated carboxylic acid derivative, was synthesized by adding trifluoromethanesulfonic acid. When the nickel-lactone compound is isolated once and redispersed in the solvent, the nickel-lactone compound is suspended in the solvent. On the other hand, as described above, when Step 1-A and Step 1 are carried out continuously, the metal lactone compound dissolves well in the solvent in Step 1 and is difficult to precipitate, so that it reacts with iodide (bromed) hydrocarbons. The properties are improved, and the yield of the obtained α, β-unsaturated carboxylic acid derivative is improved.

(Metal lactone compound)
The metal lactone compound obtained by the reaction of Step 1-A is represented by the following formula (1).

前記式（１）中、Ｍは、遷移金属であり、Ｌは、それぞれ独立して、単座配位子であるか、又はＬは共働して二座配位子を形成する。遷移金属、配位子（単座配位子、二座配位子）は上述したものが挙げられる。
Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２はそれぞれ独立に水素原子、又は炭素数が１〜８のアルキル基である。炭素数が１〜８のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、１−メチルブチル基、ｎ−ヘキシル基、２−メチルペンチル基、３−メチルペンチル基、２，２−ジメチルブチル基、２，３−ジメチルブチル基、ｎ−ヘプチル基、２−メチルヘキシル基、３−メチルヘキシル基、２，２−ジメチルペンチル基、２，３−ジメチルペンチル基、２，４−ジメチルペンチル基、３，３−ジメチルペンチル基、３−エチルペンチル基、２，２，３−トリメチルブチル基、ｎ−オクチル基、イソオクチル基、２−エチルヘキシル基等が例として挙げられる。Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２の少なくとも１つがアルキルである場合、Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２の合計の炭素数は１〜８であることが好ましく、１〜６であることがより好ましく、１〜４であることがさらに好ましい。また、Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２が全て水素原子である場合、上述の工程１における炭素数が１〜６のヨウ化（臭化）炭化水素との反応によって、アクリル酸エステルを得ることできる。
Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２は、工程１−Ａで使用するアルケンを適切に選択することによって調整することができる。例えば、Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２の全てが水素原子である金属ラクトン化合物は、遷移金属錯体と、エチレンと、二酸化炭素を反応させることにより得ることができる。

In the above formula (1), M is a transition metal, L is a monodentate ligand independently of each other, or L cooperates to form a bidentate ligand. Examples of the transition metal and the ligand (monodentate ligand, bidentate ligand) include those described above.
R ¹¹ , R ¹² , R ²¹ and R ²² are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms. The alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and isopentyl. Group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n- Heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethyl Examples include a pentyl group, a 2,2,3-trimethylbutyl group, an n-octyl group, an isooctyl group, a 2-ethylhexyl group and the like. When at least one of ^{R 11} , R ¹² , R ²¹ , and R ^{22 is alkyl, the total carbon number of R 11} , R ¹² , R ²¹ , and R ²² is preferably 1 to 8, preferably 1 to 6. It is more preferable that there is, and it is further preferable that it is 1 to 4. When R ¹¹ , R ¹² , R ²¹ , and R ²² are all hydrogen atoms, the acrylic acid ester is produced by the reaction with the iodide (bromide) hydrocarbon having 1 to 6 carbon atoms in the above step 1. You can get it.
R ¹¹ , R ¹² , R ²¹ , and R ²² can be adjusted by appropriately selecting the alkene used in step 1-A. For example, ^{a metal lactone compound in which all of R 11} , R ¹² , R ²¹ , and R ²² are hydrogen atoms can be obtained by reacting a transition metal complex with ethylene and carbon dioxide.

In one embodiment, the metal lactone compound is preferably represented by the following formula (2).

前記式（２）中、Ｍは、遷移金属であり、Ｘは、それぞれ独立して、窒素原子、又はリン原子であり、Ｒ^１は、それぞれ独立して、脂肪族炭化水素基、芳香族炭化水素基、複素芳香環基、又は窒素含有基であり、Ｒ^２及びＲ^３は、それぞれ独立して、脂肪族炭化水素基、芳香族炭化水素基、又は複素芳香環基であり、この際、２つのＲ^１は互いに結合して環構造を形成していてもよく、同一のＸ原子に結合するＲ^１、Ｒ^２、及びＲ^３が一体となって環構造を形成していてもよい。
Ｍ、Ｘ、Ｒ^１、Ｒ^２、Ｒ^３は上述の前記式（７）における例示と同様である。Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２は、前記式（１）における例示と同様である。

In the above formula (2), M is a transition metal, X is an independent nitrogen atom or a phosphorus atom, and R ¹ is an aliphatic hydrocarbon group and an aromatic hydrocarbon, respectively. hydrogen group, a heteroaromatic ring group, or a nitrogen-containing group, R ² and R ³ are each independently an aliphatic hydrocarbon group, aromatic hydrocarbon group or a heteroaromatic ring group, this time, The two R ^1s may be bonded to each other to form a ring structure, or R ¹ , R ² and R ³ bonded to the same X atom may be integrally formed to form a ring structure.
M, X, R ¹ , R ² , and R ³ are the same as those in the above-mentioned equation (7). R ¹¹ , R ¹² , R ²¹ , and R ²² are the same as those in the above equation (1).

In one embodiment, the metal lactone compound is more preferably represented by the following formula (3).

前記式（３）中、Ｍは、遷移金属であり、Ｘは、それぞれ独立して、窒素原子、又はリン原子であり、Ｒ^２、及びＲ^３は、それぞれ独立して、脂肪族炭化水素基、芳香族炭化水素基、又は複素芳香環基であり、Ａ^１は、単結合、二価の脂肪族炭化水素基、二価の芳香族炭化水素基、二価の複素芳香環基、又は二価の窒素含有基であり、この際、同一のＸ原子に結合するＡ^１、Ｒ^２、及びＲ^３が一体となって環構造を形成していてもよい。
Ｍ、Ｘ、Ｒ^２、Ｒ^３、Ａ^１は、上述の前記式（８）における例示と同様である。Ｒ^１１、Ｒ^１２、Ｒ^２１、Ｒ^２２は、前記式（１）における例示と同様である。

In the above formula (3), M is a transition metal, X is an independent nitrogen atom or a phosphorus atom, and R ² and R ³ are independent aliphatic hydrocarbon groups. , aromatic hydrocarbon group or a heteroaromatic ring group, a ¹ represents a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent heterocyclic aromatic ring group or a, It is a valent nitrogen-containing group, and at this time, A ¹ , R ² , and R ³ bonded to the same X atom may be integrally formed to form a ring structure.
M, X, R ² , R ³ , and A ¹ are the same as those in the above-mentioned equation (8). R ¹¹ , R ¹² , R ²¹ , and R ²² are the same as those in the above equation (1).

In the above formula (3), at least one of X is a nitrogen atom, and at this time, ^{it is preferable that A 1} , R ² and R ³ bonded to the nitrogen atom are integrated to form a complex aromatic ring. .. At this time, examples of the heteroaromatic ring are the same as those described in the above formula (8).

Further, in the above formula (3), at least one of X is a phosphorus atom, and at this time, ^{at least one of R 2} and R ³ bonded to the phosphorus atom is an aliphatic hydrocarbon group having 3 or more carbon atoms and carbon. It is preferable to include an aromatic hydrocarbon group having 6 or more carbon atoms and a heteroaromatic ring group having 3 or more carbon atoms. At this time, the aliphatic hydrocarbon group having 3 or more carbon atoms, the aromatic hydrocarbon group having 6 or more carbon atoms, and the heteroaromatic ring group having 3 or more carbon atoms are the same as those described in the above formula (8). Can be mentioned.

In one embodiment, the metal lactone compound is more preferably at least one selected from the group consisting of the following formulas (4) to (6).

In the formula, M is a transition metal and R ² and R ³ are independently aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or heteroaromatic ring groups, A ¹ , A ² and A, respectively. ³ are each independently a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent heterocyclic aromatic ring group, or a divalent nitrogen-containing group, R ⁴ is , Independently, hydrogen atoms, aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or heteroaromatic ring groups.
M, R ² , R ³ , A ¹ , A ² , A ³ , and R ⁴ are the same as those in the above equations (9) to (11). R ¹¹ , R ¹² , R ²¹ , and R ²² are the same as those in the above equation (1).

Of the above, the metal lactone compound is preferably represented by the above formula (5), and in the above formula (5), R ² and R ³ are independently tert-butyl groups and have 3 carbon atoms, respectively. It is more preferable to include one having a cycloalkyl group of ~ 20, and further preferably to contain one in which R ² and R ³ are cycloalkyl groups having 5 to 8 carbon atoms in the above formula (5). At this time, it is particularly preferable that ^{R 4 is a hydrogen atom.}
The above-mentioned metal lactone compound may be produced alone or in combination of two or more.

One aspect of the present invention is that in step 1-A, ethylene is used as an alkene, and the transition metal complex, ethylene, and carbon dioxide are reacted to make R ¹¹ , R ¹² , R ²¹ , and R ²² all hydrogen. An atomic metal lactone compound represented by the formula (1) is obtained, ethyl iodide is used as an iodide (bromide) hydrocarbon in step 1, and the metal lactone compound is reacted with ethyl iodide to form acrylic. It is particularly preferable to obtain ethyl iodide and hydrogen iodide, use ethanol as an alcohol in step 2, react the hydrogen iodide with ethanol, regenerate ethyl iodide, and reuse the ethyl iodide in step 1. preferable.
In this embodiment, the ethylene used in step 1-A can be obtained by dehydrating ethanol. Therefore, if a certain amount of the transition metal complex and a certain amount of ethyl iodide are prepared, it is possible to continuously produce ethyl acrylate by supplying ethanol and carbon dioxide.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1]
(1) Synthesis of MAP Ligand 2- (Methylamino) pyridine (0.459 g, 4.16 mmol) was dissolved in 15 mL of toluene, and the obtained solution was cooled to −35 ° C. N-Butyllithium (1.6 M, 2.75 mL, 4.37 mmol) was gradually added dropwise to the cooled solution. After the dropping, the mixture was stirred at room temperature for 3 hours. After cooling to −35 ° C. again, cyclohexylphosphine (0.967 g, 4.16 mmol) was added dropwise, and the mixture was stirred at 80 ° C. for 8 hours. Then, toluene was distilled off in vacuum, dissolved in pentane, and then the solution was filtered on Celite. Pentane was distilled off in vacuum to obtain the desired product (dihexylphosphino) -2-methylaminopyridine (MAP) (870 mg, 69%) represented by the following formula (12).

(2) Synthesis of (MAP) Ni (COD) metal complex which is a transition metal complex
A solution of (dihexylphosphino) -2-methylaminopyridine (MAP) (64.6 mg, 0.212 mmol) in tetrahydrofuran (THF) was added to nickel bis 1,5-cyclooctadiene (Ni (COD) ₂ ) (58. It was gradually added dropwise to a solution of 4 mg (0.212 mmol) in THF. After stirring at room temperature for 3 hours, THF was distilled off in vacuum. As a result, a transition metal complex ((MAP) Ni (COD)) represented by the following formula (13) was obtained. In the obtained transition metal complex, in the above formula (10), M is nickel, Y is 1,5-cyclooctadiene, R ² and R ³ are cyclohexyl groups, and R ⁴ is a hydrogen atom. Yes, it is a transition metal complex in which A ² is −N (CH _{3) −.}

(3) Step 1-A
Under a nitrogen atmosphere, (MAP) Ni (COD) (0.1 mmol, 47.1 mg) was weighed in a pressure-resistant NMR tube and suspended in d8-THF. A pressure-resistant NMR tube was connected to the vacuum line, and after cooling the NMR tube with liquid nitrogen, the internal gas (mainly N ₂ ) was degassed (cooling remained unchanged). Then, a gas cylinder filled with ethylene gas was connected to the vacuum line, and ethylene gas was introduced into the NMR tube (4 equivalents with respect to the transition metal complex).
Once the pressure-resistant NMR tube was returned to room temperature and allowed to stand for 10 minutes, carbon dioxide (for the transition metal complex) was placed in the pressure-resistant NMR tube using a gas cylinder filled with carbon dioxide in the same manner as in the introduction of ethylene gas. 1 equal amount) was introduced. The pressure resistant NMR tube was heated at 90 ° C. and the products were analyzed by ³¹ P-NMR and ^{1 H-NMR.} The yield of the nickel lactone compound after 24 hours was 93.0%. In the obtained nickel lactone compound, in the above formula (5), M is nickel, R ² and R ³ are cyclohexyl groups, R ⁴ is a hydrogen atom, and A ² is -N (CH ₃ )-. Is a nickel lactone compound in which R ¹¹ , R ¹² , R ²¹ and R ^{22 are hydrogen atoms.}

(4) Step 1
Ethyl iodide (15.6 mg, 0.1 mmol, 1 equivalent with respect to the nickel lactone compound) was introduced into the reaction solution obtained in Step 1-A. After the reaction at 80 ° C. for 24 hours, the ^{product was analyzed by 1} H-NMR, and the formation of ethyl acrylate was confirmed.

(5) Step 2
Ethanol (4.6 mg, 0.1 mmol) was added to the solution after the reaction, the pressure-resistant NMR tube was sealed, and the mixture was stirred at 90 ° C. for 3 hours. When the solution after the reaction ^{was analyzed by 1} H-NMR, the formation of ethyl iodide was confirmed.

[Example 2]
The reaction was carried out in the same manner as in Example 1 except that ethyl bromide was used instead of ethyl iodide. The formation of ethyl acrylate was confirmed in step 1, and the formation of ethyl bromide was confirmed in step 2. The amount of ethyl acrylate produced was smaller than that of Example 1.

[Comparative Example 1]
An attempt was made to synthesize ethyl acrylate in the same manner as in Example 1 except that ethyl chloride was used instead of ethyl iodide, but the formation of ethyl acrylate was not confirmed.

Claims (8)

An α, β-unsaturated carboxylic acid derivative is obtained by reacting a metal lactone compound represented by the following formula (1) with one or both of hydrogen iodide and hydrogen bromide having 1 to 6 carbon atoms. The step of obtaining one or both of hydrogen iodide and hydrogen bromide, and the reaction of one or both of the hydrogen iodide and the hydrogen bromide with an alcohol having 1 to 6 carbon atoms are carried out. A method for producing an α, β-unsaturated carboxylic acid derivative, which comprises a step of regenerating one or both of a hydrogen iodide hydrocarbon and the bromide hydrocarbon.

[In the formula, M is a transition metal and L is a monodentate ligand, respectively, or L cooperates to form a bidentate ligand, R ¹¹ , R ¹² , R ²¹ and R ²² are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms. ] The method for producing an α, β-unsaturated carboxylic acid derivative according to claim 1, further comprising a step of reacting a transition metal complex with an alkene and carbon dioxide to obtain the metal lactone compound. The method for producing an α, β-unsaturated carboxylic acid derivative according to claim 1 or 2, wherein the metal lactone compound is represented by the following formula (2).

[In the formula, M is a transition metal, X is an independent nitrogen atom or a phosphorus atom, and R ¹ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, respectively. a heteroaromatic ring group, or a nitrogen-containing group, R ² and R ³ are each independently an aliphatic hydrocarbon group, aromatic hydrocarbon group or a heteroaromatic ring group, this time, two R ¹ may be bonded to form a ring structure, R ^1, R ^2, and R ³ which bind to the same X atoms may form a ring structure together, R ^11, R ¹² , R ²¹ , and R ²² are the same as described above. ] The method for producing an α, β-unsaturated carboxylic acid derivative according to claim 3, wherein the metal lactone compound is represented by the following formula (3).

[In the formula, M is a transition metal, X is an independently nitrogen atom or a phosphorus atom, and R ² and R ³ are independently aliphatic hydrocarbon groups and aromatics, respectively. It is a hydrocarbon group or a heteroaromatic ring group, and A ¹ is a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent heteroaromatic ring group, or a divalent nitrogen. It is an containing group, and at this time, A ¹ , R ² , and R ³ bonded to the same X atom may be integrally formed to form a ring structure, and R ¹¹ , R ¹² , R ²¹ , and R ^22. Is the same as above. ] At least one of the Xs is a nitrogen atom
The method for producing an α, β-unsaturated carboxylic acid derivative according to claim 4, wherein a heteroaromatic ring is formed by integrating ^{A 1} , R ² , and R ³ bonded to the nitrogen atom. At least one of the X is a phosphorus atom
^{At least one of R 2} and R ³ bonded to the phosphorus atom is an aliphatic hydrocarbon group having 3 or more carbon atoms, an aromatic hydrocarbon group having 6 or more carbon atoms, or a heteroaromatic ring group having 3 or more carbon atoms. The method for producing an α, β-unsaturated carboxylic acid derivative according to claim 4 or 5. Production of the α, β-unsaturated carboxylic acid derivative according to any one of claims 4 to 6, wherein the metal lactone compound contains at least one selected from the group consisting of the following formulas (4) to (6). Method.

[In the formula, M is a transition metal, R ² and R ³ are independently aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or heteroaromatic ring groups, and A ¹ is a single bond. , A divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent heteroaromatic ring group, or a divalent nitrogen-containing group, and A ² is a single-bonded, divalent aliphatic hydrocarbon. hydrogen group, a divalent aromatic hydrocarbon group, a divalent heterocyclic aromatic ring group, or a divalent nitrogen-containing group, a ³ is a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic family hydrocarbon group, a divalent heterocyclic aromatic ring group, or a divalent nitrogen-containing group, R ⁴ are each independently hydrogen atom, an aliphatic hydrocarbon group, aromatic hydrocarbon group, or a heteroaromatic It is a ring group, and R ¹¹ , R ¹² , R ²¹ , and R ²² are the same as described above. ] The method for producing an α, β-unsaturated carboxylic acid derivative according to any one of claims 2 to 7, wherein the reaction in the step of obtaining the metal lactone compound is carried out at a pressure of 10 atm or less.