Metal phenoxide compound, catalyst for transesterification reaction, and method for producing carboxylic acid ester

Abstract

To provide a metal phenoxide compound that enables a desired carboxylate to be synthesized in high yield, a catalyst for transesterification comprising a metal phenoxide compound, and a method for producing a carboxylate.SOLUTION: A metal phenoxide compound is represented by the following formula (1) or formula (2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a metal phenoxide compound, a catalyst for transesterification, and a method for producing a carboxylic acid ester.

Background Art

[0002] Carboxylic acid esters are used in various fields such as pharmaceuticals, fragrances, and chemical products. As a method for producing a carboxylic acid ester, for example, a method of obtaining a carboxylic acid ester by performing a transesterification reaction between a methyl ester and an alcohol is used. A catalyst is used in the transesterification reaction. Examples of the catalyst for transesterification include those containing an organic onium salt of phenols having a substituent at at least one ortho position of a phenolic hydroxyl group (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the catalyst of Patent Document 1 has a problem that the yield of the target carboxylic acid ester is low.

[0005] The present invention has been made in view of the above circumstances, and an object thereof is to provide a metal phenoxide compound capable of synthesizing a target carboxylic acid ester in a high yield, a catalyst for transesterification containing the metal phenoxide compound, and a method for producing a carboxylic acid ester.

Means for Solving the Problems

[0006] The present invention has the following aspects. [1] A metal phenoxide compound represented by the following formula (1) or the following formula (2).

[0007] [Chemical formula] (In formula (1), M is Na, K or Li; X1 is a hydrocarbon group or a silyl group which may have a substituent; Y1 is any one of a hydrogen atom, a hydrocarbon group which may have a substituent, a halogen atom, a trifluoromethyl group, a nitro group, and an ester group; Z1 is a hydrocarbon group which may have a substituent. Note that the two X1 groups may be the same group or different groups, the two Y1 groups may be the same group or different groups, and the two Z1 groups may be the same group or different groups.)

[0008] [Chemical formula] (In formula (2), X2 is a hydrocarbon group or a silyl group which may have a substituent; Y2 is any one of a hydrogen atom, a hydrocarbon group which may have a substituent, a halogen atom, a trifluoromethyl group, a nitro group, and an ester group; Z2 is a hydrocarbon group which may have a substituent. Note that the two X2 groups may be the same group or different groups, the two Y2 groups may be the same group or different groups, and the two Z2 groups may be the same group or different groups.)

[0009] [2] The metal phenoxide compound according to [1], wherein X1 is a branched alkyl group.

[0010] [3] The metal phenoxide compound according to [1], wherein X2 is a branched alkyl group.

[0011] [4] A transesterification catalyst comprising the metal phenoxide compound according to any one of [1] to [3].

[0012] [5] A method for producing a carboxylic acid ester, comprising a step of carrying out a transesterification reaction by contacting an ester compound with an alcohol in the presence of a transesterification catalyst comprising at least one of a metal(I) phenoxide compound represented by the following formula (1) and a magnesium(II) phenoxide compound represented by the following formula (2):

[0013] [ka] (In formula (1), M is Na, K, or Li; X1 is a hydrocarbon group or silyl group which may have a substituent; Y1 is any one of a hydrogen atom, a hydrocarbon group which may have a substituent, a halogen atom, a trifluoromethyl group, a nitro group, and an ester group; and Z1 is a hydrocarbon group which may have a substituent. Note that the two X1 groups may be the same group or different groups, the two Y1 groups may be the same group or different groups, and the two Z1 groups may be the same group or different groups.)

[0014] [ka] (In formula (2), X2 is a hydrocarbon group or a silyl group which may have a substituent, Y2 is any one of a hydrogen atom, a hydrocarbon group which may have a substituent, a halogen atom, a trifluoromethyl group, a nitro group, and an ester group, and Z2 is a hydrocarbon group which may have a substituent. Note that the two X2 groups may be the same group or different groups, the two Y2 groups may be the same group or different groups, and the two Z2 groups may be the same group or different groups.)

[0015] [6] The method for producing a carboxylic acid ester according to [5], wherein the ester compound is a (meth)acrylic acid ester.

[0016] [7] The method for producing a carboxylic acid ester according to [5], wherein the alcohol is a primary alcohol or a secondary alcohol. [Effects of the Invention]

[0017] According to the present invention, it is possible to provide a metal phenoxide compound capable of synthesizing a target carboxylic acid ester in a high yield, a transesterification catalyst containing the metal phenoxide compound, and a method for producing a carboxylic acid ester.

Brief Description of the Drawings

[0018]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Modes for Carrying Out the Invention

[0019] Embodiments of the metal phenoxide compound, the transesterification catalyst, and the method for producing a carboxylic acid ester of the present invention will be described. Note that this embodiment is specifically described to better understand the gist of the invention, and does not limit the present invention unless otherwise specified.

[0020] [Metal Phenoxide Compound] The metal phenoxide compound according to this embodiment is represented by the following formula (1) or (2).

[0021] [ka]

[0022] In formula (1), M is Na, K, or Li, X1 is a hydrocarbon group or silyl group which may have a substituent, Y1 is any one of a hydrogen atom, a hydrocarbon group which may have a substituent, a halogen atom, a trifluoromethyl group, a nitro group, and an ester group, and Z1 is a hydrocarbon group which may have a substituent. Note that the two X1 groups may be the same group or different groups, the two Y1 groups may be the same group or different groups, and the two Z1 groups may be the same group or different groups.

[0023] Since Na, K, and Li are monovalent metals, the metal phenoxide compounds represented by the above formula (1) can also be called metal (I) phenoxide compounds, where (I) represents the valence of the metal. When M is Na, the catalyst exhibits particularly excellent catalytic activity in the transesterification reaction between a methacrylic acid ester and an alcohol.

[0024] In formula (1), X1 is a hydrocarbon group which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group may be linear, branched, or have a ring structure.

[0025] The aliphatic hydrocarbon group is not particularly limited, but may contain an unsaturated bond. Specific examples include alkyl groups, alkenyl groups, and alkynyl groups. The aromatic hydrocarbon group is not particularly limited, but may include an aryl group.

[0026] In addition, the substituent that the hydrocarbon group may have is not particularly limited, and any substituent can be mentioned. Among them, the hydrocarbon group that may have a substituent is preferably a hydrocarbon group having one or more bonds, groups or atoms selected from an ester bond, an amide bond, an ether bond, a sulfide bond, a disulfide bond, a urethane bond, a nitro group, a cyano group, a ketone group, a formyl group, an acetal group, a thioacetal group, a sulfonyl group, a silyl group, a carboxy group that may have a substituent, a halogen atom, a silicon atom, a phosphorus atom, etc.

[0027] From the viewpoints of reactivity and availability, the number of carbon atoms of the hydrocarbon group is preferably 1 or more, while preferably 20 or less, more preferably 10 or less, still more preferably 7 or less, and particularly preferably 4 or less.

[0028] Alternatively, in formula (1), X1 is a silyl group that may have a substituent. Examples of the substituent include an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group is not particularly limited, but may contain an unsaturated bond. Specifically, an alkyl group, an alkenyl group, or an alkynyl group can be mentioned. The aromatic hydrocarbon group is not particularly limited, and an aryl group can be mentioned.

[0029] Among the above, X1 is preferably an alkyl group, and an alkyl group having the above-mentioned number of carbon atoms is more preferable. Examples of such an alkyl group include alkyl groups such as a methyl group, an ethyl group, an isobutyl group, and a tert-butyl group. Among these, X1 is most preferably a branched alkyl group (branched alkyl group). As the branched alkyl group, an isobutyl group and a tert-butyl are preferable, and a tert-butyl is more preferable.

[0030] In formula (1), Y1 is any one of a hydrogen atom, a hydrocarbon group which may have a substituent, a halogen atom, a trifluoromethyl group, a nitro group, and an ester group. The hydrocarbon group which may have a substituent is not particularly limited, and examples thereof include the same groups as X1, and preferred groups also include the same groups as X1. The most preferred groups include a hydrogen atom, a linear alkyl group, or a branched alkyl group. Specifically, a hydrogen atom, a methyl group, or a tert-butyl group can be mentioned.

[0031] In formula (1), Z1 is a hydrocarbon group which may have a substituent. The hydrocarbon group which may have a substituent is not particularly limited, and examples thereof include the same groups as X1, and preferred groups also include the same groups as X1. The most preferred groups include a linear alkyl group, a branched alkyl group, and an aryl group. Specifically, a methyl group or a tert-butyl group can be mentioned.

[0032] The metal (I) phenoxide compound represented by formula (1) exhibits excellent catalytic activity in the transesterification reaction between an ester compound and an alcohol.

[0033] As a preferred form of the metal (I) phenoxide compound represented by the above formula (1), specifically, a sodium (I) phenoxide compound represented by the following formula (3) can be mentioned.

[0034]

Chemical formula

[0035] In formula (3), t-Bu represents a tert-butyl group.

[0036] The sodium (I) phenoxide compound represented by the above formula (3) exhibits particularly excellent catalytic activity in the transesterification reaction between a methacrylic acid ester and an alcohol.

[0037]

Chemical formula

[0038] In formula (2), X2 is a hydrocarbon group or a silyl group which may have a substituent, Y2 is any one of a hydrogen atom, a hydrocarbon group which may have a substituent, a halogen atom, a trifluoromethyl group, a nitro group, and an ester group, and Z2 is a hydrocarbon group which may have a substituent. Note that the two X2 groups may be the same group or different groups, the two Y2 may be the same group or different groups, and the two Z2 may be the same group or different groups.

[0039] Since Mg is a divalent metal, the metal phenoxide compound represented by the above formula (2) can also be referred to as a magnesium (II) phenoxide compound. (II) represents the valence of magnesium.

[0040] Regarding X2, examples of the hydrocarbon group which may have a substituent include the hydrocarbon groups which may have the substituents exemplified for X1 in formula (1), and the preferred groups are also the same as those of X1, and the branched alkyl group is most preferred.

[0041] Regarding X2, examples of the silyl group include the silyl groups which may have the substituents exemplified for X1 in formula (1).

[0042] In formula (2), Y2 is any one of a hydrogen atom, a hydrocarbon group which may have a substituent, a halogen atom, a trifluoromethyl group, a nitro group, and an ester group. Examples of the hydrocarbon group which may have a substituent include the same groups as Y1 in formula (1), and the preferred groups are also the same as those of Y1.

[0043] In formula (2), Z2 is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include the same groups as Z1 in formula (1), and the preferred groups are also the same as those of Z1.

[0044] The magnesium (II) phenoxide compound represented by the formula (2) exhibits excellent catalytic activity in the transesterification reaction between an ester compound and an alcohol.

[0045] As a preferred form of the magnesium (II) phenoxide represented by the above formula (2), specifically, a magnesium (II) phenoxide compound represented by the following formula (4) and a magnesium (II) phenoxide compound represented by the following formula (5) can be mentioned.

[0046] [Chemical formula]

[0047] [Chemical formula]

[0048] In the formulas (4) and (5), t-Bu represents a tert-butyl group.

[0049] The magnesium (II) phenoxide compounds represented by the above formulas (4) and (5) exhibit particularly excellent catalytic activity in the transesterification reaction between a methacrylic acid ester and an alcohol.

[0050] According to the metal phenoxide compound according to this embodiment, a catalyst for transesterification reaction capable of synthesizing a target carboxylic acid ester in a high yield can be obtained.

[0051] [Method for producing metal phenoxide compound] [Method for producing metal (I) phenoxide compound represented by formula (1)] As a method for producing the metal (I) phenoxide compound represented by the above formula (1), there is no particular limitation as long as the target metal (I) phenoxide compound can be obtained, and it can be produced by a known method. For example, boron trifluoride diethyl etherate is added to anhydrous acetone containing a phenol represented by the following formula (6), which has a substituent corresponding to X1 at the 2-position and a substituent corresponding to Y1 at the 4-position, and the mixture is stirred at room temperature (25°C) for 6 to 24 hours. Next, alcohol is added to the mixture at 0°C and stirred for 1 hour. The resulting suspension is then filtered, and the crude product is washed with alcohol at 0°C. The crude product is then dissolved in chloroform and further purified by silica gel column chromatography to obtain a compound represented by the following formula (7). As the alcohol, methanol, ethanol, etc. can be used.

[0052] [ka]

[0053] [ka]

[0054] Next, a metal(I) alkoxide is added to the anhydrous tetrahydrofuran containing the compound represented by formula (7), and the mixture is stirred at room temperature (25°C) for 15 minutes to 1 hour. The volatile substances are then removed, and the residue is dried at room temperature (25°C) under reduced pressure for 2 to 6 hours to obtain a yellow compound. The resulting yellow compound is the metal(I) phenoxide compound represented by the above formula (1). The mixing ratio of the metal(I) alkoxide to the compound represented by the above formula (7) is preferably 2:1 by molar ratio. As the metal(I) alkoxide, for example, sodium methoxide, potassium methoxide, or lithium methoxide can be used.

[0055] (Method for producing magnesium(II) phenoxide compound represented by formula (2)) As a method for producing the magnesium (II) phenoxide compound represented by the above formula (2), there are no particular restrictions as long as the target phenoxide compound can be obtained, and it can be produced by a known method. For example, in the same manner as the method for producing the metal (I) phenoxide compound represented by the above formula (1), a compound represented by the above formula (7) is obtained. However, the mixing ratio of the magnesium (II) alkoxide and the compound represented by the above formula (7) is preferably adjusted to a molar ratio of 1:1. Next, di-n-butylmagnesium is added to anhydrous tetrahydrofuran in which the compound represented by the above formula (7) is dissolved, and the mixture is stirred at room temperature (25 °C) for 15 minutes to 1 hour. Then, volatile substances are removed, and the residue is dried under reduced pressure at room temperature (25 °C) for 2 to 6 hours to obtain a white compound. The obtained white compound is the magnesium (II) phenoxide compound represented by the above formula (2). The mixing ratio of di-n-butylmagnesium and the compound represented by the above formula (7) is preferably adjusted to a molar ratio of 1:1.

[0056] [Catalyst for transesterification reaction] The catalyst for transesterification reaction according to the present embodiment is a catalyst for transesterification reaction for obtaining a carboxylic acid ester by performing a transesterification reaction between an ester compound and an alcohol, and includes the metal (I) phenoxide compound represented by the above formula (1) or the magnesium (II) phenoxide compound represented by the above formula (2).

[0057] According to the catalyst for transesterification reaction according to the present embodiment, the target carboxylic acid ester can be synthesized in a high yield.

[0058] [Method for producing carboxylic acid ester] The method for producing a carboxylic acid ester according to the present invention includes a step of performing a transesterification reaction by bringing an ester compound into contact with an alcohol in the presence of a transesterification catalyst containing at least one of the metal (I) phenoxide compound represented by the above formula (1) and the magnesium (II) phenoxide compound represented by the above formula (2), and a carboxylic acid ester is obtained by this step.

[0059] As the transesterification reaction between the ester compound and the alcohol, for example, the following formula (8) shows the chemical formula related to the transesterification reaction between a methacrylic acid ester and a primary alcohol. The following formula (9) shows the chemical formula related to the transesterification reaction between an acrylic acid ester and a primary alcohol.

[0060]

Chemical formula

[0061]

Chemical formula

[0062] In the above formulas (8) and (9), R1 and R3 are each an alkyl group having 1 or more carbon atoms. Among them, R1 and R3 are each preferably an alkyl group having 1 or more carbon atoms, on the other hand, preferably an alkyl group having 10 or less carbon atoms, more preferably an alkyl group having 6 or less carbon atoms, and particularly preferably an alkyl group having 2 or less carbon atoms. In the above formulas (8) and (9), R2 represents an alkyl group. Among them, when R2-OH is a primary alcohol, R2 is preferably an alkyl group having 2 or more carbon atoms, more preferably an alkyl group having 3 or more carbon atoms, particularly preferably an alkyl group having 4 or more carbon atoms, on the other hand, preferably an alkyl group having 30 or less carbon atoms, more preferably an alkyl group having 20 or less carbon atoms, and particularly preferably an alkyl group having 20 or less carbon atoms.

[0063] When R2-OH is a secondary alcohol, R2 is preferably an alkyl group having 3 or more carbon atoms, more preferably an alkyl group having 4 or more carbon atoms, particularly preferably an alkyl group having 5 or more carbon atoms. On the other hand, it is preferably an alkyl group having 30 or less carbon atoms, more preferably an alkyl group having 25 or less carbon atoms, and particularly preferably an alkyl group having 20 or less carbon atoms.

[0064] When R2-OH is a tertiary alcohol, R2 is preferably an alkyl group having 4 or more carbon atoms. On the other hand, it is preferably an alkyl group having 30 or less carbon atoms, more preferably an alkyl group having 25 or less carbon atoms, and particularly preferably an alkyl group having 20 or less carbon atoms.

[0065] Hereinafter, the details of the method for producing the carboxylic acid ester according to this embodiment will be described. First, a reaction vessel such as a flask is charged with at least one of a dried molecular sieve, a metal (I) phenoxide compound represented by the above formula (1), and a magnesium (II) phenoxide compound represented by the above formula (2), an ester exchange reaction catalyst, and a predetermined amount of a (meth) acrylic acid ester. After stirring the mixture at room temperature (25 ° C) for 1 to 5 minutes, alcohol is added to obtain a suspension. Next, the suspension is stirred at a predetermined reaction temperature for 30 minutes to 96 hours to carry out an ester exchange reaction between the (meth) acrylic acid ester and the alcohol. Then, the suspension is purified to obtain a carboxylic acid ester.

[0066] The (meth) acrylic acid ester is not particularly limited, but is preferably a (meth) acrylic acid ester having 1 to 10 carbon atoms in the ester moiety, more preferably a (meth) acrylic acid ester having 6 or less carbon atoms in the ester moiety, particularly preferably a (meth) acrylic acid ester having 2 or less carbon atoms in the ester moiety, and most preferably methyl methacrylate or methyl acrylate.

[0067] As the alcohol, there is no particular limitation, and monohydric alcohols or polyhydric alcohols with two or more hydroxyl groups can be mentioned.

[0068] Examples of the monohydric alcohol include primary alcohols, secondary alcohols, or tertiary alcohols. Examples of the polyhydric alcohol include diols, triols, tetraols, unstable alcohols, etc., and any of them can be used.

[0069] Although there is no particular limitation for the primary alcohol, it is preferably a primary alcohol having 2 or more carbon atoms, and on the other hand, in order to reduce the purification load of the target carboxylic acid ester, it is preferably a primary alcohol having 30 or less carbon atoms. Examples of such primary alcohols include methanol, ethanol, propane-1-ol, butane-1-ol, pentane-1-ol, hexane-1-ol, heptane-1-ol, octane-1-ol, nonane-1-ol, decane-1-ol, undecane-1-ol, dodecane-1-ol, tridecane-1-ol, tetradecane-1-ol, pentadecane-1-ol, hexadecane-1-ol, heptadecane-1-ol, octadecane-1-ol, nonadecane-1-ol, icosane-1-ol, heneicosane-1-ol, docosane-1-ol, tricosane-1-ol, tetracosane-1-ol, pentacosane-1-ol, hexacosane-1-ol, heptacosane-1-ol, octacosane-1-ol, nonacosane-1-ol, triacontane-1-ol, polycosanol, 2-methyl:2-methylpropane-1-ol, 3-methyl:3-methylbutane-1-ol, and the like. Among these, the primary alcohol is more preferably a primary alcohol having 3 or more carbon atoms, particularly preferably a primary alcohol having 4 or more carbon atoms, and on the other hand, it is more preferably a primary alcohol having 20 or less carbon atoms, particularly preferably a primary alcohol having 10 or less carbon atoms.

[0070] There are no particular limitations on the secondary alcohol, but it is preferably a secondary alcohol having 3 or more carbon atoms, more preferably a secondary alcohol having 4 or more carbon atoms, and particularly preferably a secondary alcohol having 5 or more carbon atoms, while it is preferably a secondary alcohol having 30 or less carbon atoms, more preferably a secondary alcohol having 25 or less carbon atoms, and particularly preferably a secondary alcohol having 20 or less carbon atoms. Examples of such secondary alcohols include propan-2-ol, butan-2-ol, pentan-2-ol, hexane-2-ol, heptan-2-ol, 2-methylbutan-1-ol, and the like.

[0071] The tertiary alcohol is not particularly limited, but is preferably a tertiary alcohol having 4 or more carbon atoms, more preferably a tertiary alcohol having 30 or less carbon atoms, more preferably a tertiary alcohol having 25 or less carbon atoms, and particularly preferably a tertiary alcohol having 20 or less carbon atoms. Examples of such tertiary alcohols include 1-adamantanol and tert-butanol.

[0072] The diol is not particularly limited, but is preferably a diol having 1 or more carbon atoms, more preferably a diol having 2 or more carbon atoms, while being preferably a diol having 30 or less carbon atoms, more preferably a diol having 25 or less carbon atoms, and particularly preferably a diol having 20 or less carbon atoms. Examples of such diols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,4-benzenedimethanol represented by the following formula (10), 1,6-hexanediol represented by the following formula (11), and 1,4-butynediol represented by the following formula (12).

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] The triol is not particularly limited, but is preferably a triol having 1 or more carbon atoms, more preferably a triol having 2 or more carbon atoms, and is preferably a triol having 30 or less carbon atoms, more preferably a triol having 25 or less carbon atoms. Examples of such triols include trimethylolpropane represented by the following formula (13).

[0077] [ka]

[0078] The tetraol is not particularly limited, but is preferably a tetraol having 1 or more carbon atoms, more preferably a tetraol having 2 or more carbon atoms, and is preferably a tetraol having 30 or less carbon atoms, more preferably a tetraol having 25 or less carbon atoms. Examples of such tetraols include hexane-1,2,3,6-tetraol.

[0079] The unstable alcohol refers to an alcohol having a structure that is prone to chemical reactions within the molecule. There are no particular limitations on these, but unstable alcohols having 2 or more carbon atoms are preferred, and unstable alcohols having 3 or more carbon atoms are more preferred, while unstable alcohols having 30 or less carbon atoms are preferred, and unstable alcohols having 25 or less carbon atoms are more preferred. Examples of such unstable alcohols include (R)-oxirane-2-methanol represented by the following formula (14) and allyl alcohol represented by the following formula (14).

[0080] [ka]

[0081] [ka]

[0082] Among the above alcohols, primary alcohols or secondary alcohols are preferred because of their excellent reactivity.

[0083] The compounding ratio of the (meth)acrylic acid ester to the alcohol, in other words, the molar ratio of the (meth)acrylic acid ester to the alcohol, is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and is preferably 50 or less, more preferably 30 or less. When the molar ratio of the (meth)acrylic acid ester to the alcohol is 1 or more and 50 or less, the transesterification reaction between the (meth)acrylic acid ester and the alcohol proceeds easily. The (meth)acrylic acid ester and the alcohol may each be used alone, or two or more may be used in combination. When two or more types of (meth)acrylic acid and / or alcohol are used, it is preferable that the total amount thereof is within the above range.

[0084] The transesterification reaction temperature between the (meth)acrylic acid ester and the alcohol is preferably −20° C. or higher, more preferably 10° C. or higher, and is preferably 100° C. or lower, more preferably 80° C. or lower. If the reaction temperature is −20° C. or higher, the transesterification reaction between the (meth)acrylic acid ester and the alcohol proceeds easily. Furthermore, if the reaction temperature is 100° C. or lower, the amount of energy consumed by heating can be reduced.

[0085] (Meth)acrylate and alcohol may be subjected to transesterification reaction in a solvent or without a solvent. However, considering productivity and the load of solvent recovery, it is preferably carried out without a solvent. Here, without a solvent means that the amount of the solvent relative to alcohol is 30% by mass or less.

[0086] On the other hand, when using a solvent, there is no particular limitation on the solvent. For example, benzene, toluene, xylene, n - hexane, cyclohexane, n - heptane, n - octane, n - nonane, n - decane, 1,4 - dioxane, tetrahydrofuran, tetrahydropyran, anisole, methyl - tert - butyl ether, dibutyl ether, diphenyl ether, ethylene glycol monomethyl ether, ethylene glycol mono - n - butyl ether, acetone, methyl ethyl ketone, methyl - n - butyl ketone, methyl isobutyl ketone, cyclohexanone, 2 - methylcyclohexanone, dimethylformaldehyde, dimethylacetamide, etc. may be mentioned. The solvent may be used alone or in combination of two or more.

[0087] As the metal phenoxide compound, as described above, at least one of the metal (I) phenoxide compound represented by the above formula (1) and the magnesium (II) phenoxide compound represented by the above formula (2) may be mentioned, and it may be used alone or in combination of two or more. For example, one or more metal (I) phenoxide compounds selected from the above formula (1) and one or more magnesium (II) phenoxide compounds selected from the above formula (2) may be used, or two or more of the metal (I) phenoxide compounds selected from the above formula (1) may be used, or two or more of the magnesium (II) phenoxide compounds selected from the above formula (2) may be used.

[0088] The total amount of the metal (I) phenoxide compound represented by the above formula (1) and the magnesium (II) phenoxide compound represented by the above formula (2) with respect to alcohol has no particular limitation. However, in order to efficiently promote the transesterification reaction, it is preferably 0.001 mol or more, more preferably 0.003 mol or more, and particularly preferably 0.005 mol or more per 1 mol of alcohol. On the other hand, in order to reduce the purification load after the reaction, it is preferably 0.20 mol or less, more preferably 0.15 mol or less, and particularly preferably 0.10 mol or less.

[0089] In addition, in the present embodiment, the above metal phenoxide compound acts as a catalyst. However, as long as the effects of the present invention are not impaired, other catalysts may be used in combination with the metal phenoxide compound.

[0090] In addition, compounds other than the above compounds may be present in the reaction system. For example, a polymerization inhibitor may be used. There is no particular limitation on the polymerization inhibitor. For example, known polymerization inhibitors such as 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxyl (4-acetamido-TEMPO), copper (II) dimethyldithiocarbamate, phenothiazine, methoquinone, and hydroquinone can be used.

[0091] In addition, a gas that does not participate in the transesterification reaction can be blown into the reaction system. For example, the transesterification reaction can be carried out while blowing air, nitrogen, etc.

[0092] The method for purifying the above suspension is not particularly limited, and examples include purification using a silica gel column (mobile phase: hexane·methyl acetate), washing, filtration, distillation, etc. These purification methods are not particularly limited and may be carried out by generally disclosed methods.

[0093] According to the method for producing a carboxylic acid ester according to the present invention, the target carboxylic acid ester can be synthesized in a high yield.

Examples

[0094] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0095] [Production Example of 6,6'-(propane-2,2-diyl)bis(2,4-di-tert-butylphenol)] Boron trifluoride diethyl etherate (0.6 mL, 5.0 mmol) was added to anhydrous acetone (368 μL, 5.0 mmol) containing 2,4-di-tert-butylphenol (2.1 g, 10.0 mmol), and the mixture was stirred under nitrogen at room temperature (25°C) for 16 hours. Methanol was then added to the mixture at 0°C, and the mixture was stirred for 1 hour. The resulting suspension was then filtered, and the crude product was washed with methanol at 0°C. The crude product was then dissolved in chloroform and further purified by silica gel column chromatography (eluent: n-hexane:ethyl acetate = 8:1) to obtain a white compound. The compound obtained in Figure 1 1 The H-NMR spectrum of the compound obtained is shown in Figure 2. 13 The C-NMR spectrum of the obtained compound is shown below. 1 H-NMR and 13 The C-NMR measurement data is shown below. 1 H-NMR data (400MHz, solvent: CDCl3) δ(ppm): 1.28(s,18H,2C(CH3)3), 1.36(s,18H,2C(CH3)3), 1.7 3(s,6H,2CH3), 4.99(s,2H,2OH), 7.30(d,J=2.28Hz,2H,2ArH), 7.40(d,J=2.28Hz,2H,2ArH). 13 C-NMR (100MHz, solvent: CDCl3) δ (ppm): 29.0 (2C), 29.7 (6C), 31.9 (6C), 34.8 (2C), 35.3 (2 C), 40.6(1C), 119.9(2C), 124.2(2C), 130.8(2C), 137.6(2C), 143.1(2C), 151.9(2C). From the above measurement data, it was confirmed that 6,6´-(propane-2,2-diyl)bis(2,4-di-tert-butylphenol) represented by the following formula (16) was obtained. The reaction formula for synthesizing 6,6´-(propane-2,2-diyl)bis(2,4-di-tert-butylphenol) by the transesterification reaction of 2,4-di-tert-butylphenol and acetone anhydride is shown in the following formula (17).

[0096] [Chemical formula]

[0097] [Chemical formula]

[0098] [Catalyst Preparation Example 1] (Preparation of Transesterification Catalyst) Sodium methoxide (10 μL, 0.050 mmol) was added to anhydrous tetrahydrofuran (140 μL) in which 6,6´-(propane-2,2-diyl)bis(2,4-di-tert-butylphenol) (12.4 mg, 0.025 mmol) was dissolved, and the mixture was stirred at room temperature (25 °C) for 30 minutes under nitrogen. Then, volatile substances were removed, and the residue was dried at room temperature (25 °C) under reduced pressure (<5 Torr) for 3 hours to obtain a yellow compound. The 1 1H-NMR spectrum of the obtained compound is shown in Figure 3. The 13 13C-NMR spectrum of the obtained compound is shown in Figure 4. The 1 1H-NMR and 13 13C-NMR measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 1.28 (s, 18H, 2C(CH3)3), 1.36 (s, 18H, 2C(CH3)3), 1.73 (s, 6H, 2CH3), 7.30 (d, J = 2.28 Hz, 2H, 2ArH), 7.41 (d, J = 2.28 Hz, 2H, 2ArH). 13C-NMR (100MHz, solvent: CDCl3) δ (ppm): 29.0 (2C), 29.7 (6C), 31.9 (6C), 34.8 (2C), 35.3 (2 C), 40.5(1C), 119.8(2C), 124.2(2C), 130.6(2C), 137.5(2C), 143.1(2C), 151.8(2C). From the above measurement data, it was confirmed that the compound represented by the following formula (18) was obtained. The following formula (19) shows the reaction formula for synthesizing the compound represented by the following formula (18) by the reaction of 6,6'-(propane-2,2-diyl)bis(2,4-di-tert-butylphenol) with sodium methoxide.

[0099] [ka]

[0100] [ka]

[0101] [Catalyst Production Example 2] (Production of Transesterification Catalyst) Di-n-butylmagnesium (Bu2Mg, 1.0 M heptane solution, 100 μL, 0.10 mmol) was added to 6,6'-(propane-2,2-diyl)bis(2,4-di-tert-butylphenol) (49.6 mg, 0.10 mmol) in anhydrous tetrahydrofuran (200 μL). The mixture was stirred under nitrogen at room temperature (25 °C) for 30 minutes. The volatiles were then removed, and the residue was dried under reduced pressure (<5 Torr) at room temperature (25 °C) for 3 hours to give a white compound. The compound obtained in Figure 5 1 The H-NMR spectrum of the compound obtained is shown in Figure 6. 13 The C-NMR spectrum of the compound obtained is shown below. 1 H-NMR and 13 The C-NMR measurement data is shown below. 11H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 1.28 (s, 18H, 2C(CH3)3), 1.36 (s, 18H, 2C(CH3)3), 1.73 (s, 6H, 2CH3), 7.30 (d, J = 2.28 Hz, 2H, ArH), 7.40 (d, J = 2.28 Hz, 2H, 2ArH). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 29.0 (2C), 29.7 (6C), 31.9 (6C), 34.8 (2C), 35.3 (2C), 40.5 (1C), 119.9 (2C), 124.2 (2C), 130.7 (2C), 137.5 (2C), 143.1 (2C), 151.8 (2C). From the above measurement data, it was confirmed that the compound represented by the following formula (20) was obtained. The reaction formula for synthesizing the compound represented by the following formula (20) by the reaction of 6,6´-(propan-2,2-diyl)bis(2,4-di-tert-butylphenol) and di-n-butylmagnesium is shown below.

[0102] [Chemical formula]

[0103] [Chemical formula]

[0104] [Catalyst Production Example 3] (Production of Transesterification Catalyst) (Production of Transesterification Catalyst) A white compound was obtained in the same manner as in Catalyst Production Example 2, except that 11.4 mg (0.10 mmol) of magnesium ethoxide was used instead of di-n-butylmagnesium. Of the obtained compound 1 1H-NMR and 13 13C-NMR measurement data are shown below. 11H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 1.28 (s, 18H, 2C(CH3)3), 1.36 (s, 18H, 2C(CH3)3), 1.73 (s, 6H, 2CH3), 7.30 (d, J = 2.28 Hz, 2H, ArH), 7.40 (d, J = 2.28 Hz, 2H, 2ArH). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 29.0 (2C), 29.7 (6C), 31.9 (6C), 34.8 (2C), 35.3 (2C), 40.5 (1C), 119.9 (2C), 124.2 (2C), 130.7 (2C), 137.5 (2C), 143.1 (2C), 151.8 (2C). From the above measurement data, it was confirmed that a compound represented by the following formula ( 20 ) was obtained.

[0105]

Chemical formula

[0106] [Preparation Example 4 of Catalyst] (Preparation of Transesterification Catalyst) 108 mg (2.0 mmol) of sodium methoxide and 440 mg (2.0 mmol) of 2,6-di-tert-butyl-4-methylphenol were dissolved in 5 mL of methanol and stirred at room temperature (25 °C) for 30 minutes. After completion of stirring, volatile substances were removed from the solution under reduced pressure, and the residue was dried at room temperature (25 °C) under reduced pressure (less than 665 Pa) for 2 hours to obtain a white compound. The 1 1H-NMR and 13 13C-NMR measurement data of the obtained compound are shown below. 1 1H-NMR data (400 MHz, solvent: DMSO-d6) δ (ppm): 1.30 (s, 18H), 2.00 (s, 3H), 6.42 (s, 2H). 1313C-NMR (100 MHz, solvent: DMSO-d6) δ (ppm): 21.6, 30.2 (6C), 34.6 (2C), 109.5, 123.6 (2C), 134.9 (2C), 167.9. From the above measurement data, it was confirmed that sodium 2,6-di-tert-butyl-4-methylphenoxide (hereinafter abbreviated as "NaOAr-1") represented by the following formula (23) was obtained.

[0107]

Chemical formula

[0108] [Catalyst Production Example 5] (Production of Transesterification Catalyst) 228.9 mg (2.0 mmol) of magnesium ethoxide (hereinafter abbreviated as "Mg(OEt)2") and 881 mg (4.0 mmol) of 2,6-di-tert-butyl-4-methylphenol were dissolved in 5 mL of methanol and stirred at room temperature (25 °C) for 30 minutes. After completion of stirring, volatile substances were removed from the solution under reduced pressure, and the residue was dried at room temperature (25 °C) under reduced pressure (less than 665 Pa) for 2 hours to obtain a white compound. For the obtained compound 1 1H-NMR and 13 13C-NMR measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: benzene-d6) δ (ppm): 1.38 (s, 36H), 2.25 (s, 6H), 7.06 (s, 4H). 13 13C-NMR (100 MHz, solvent: benzene-d6) δ (ppm): 21.5 (2C), 30.5 (12C), 34.4 (4C), 125.9 (4C), 128.5 (2C), 136.0 (4C), 152.1 (2C). From the above measurement data, it was confirmed that magnesium 2,6-di-tert-butyl-4-methylphenoxide (hereinafter abbreviated as "Mg(OAr)2") represented by the following formula (24) was obtained.

[0109] [Chemical formula]

[0110] [Catalyst Production Example 6] (Production of Transesterification Catalyst) A white compound was obtained in the same manner as in Catalyst Production Example 5, except that 2 mL (1.0 mol / L heptane solution, 2.0 mmol) of di-n-butylmagnesium was used instead of magnesium ethoxide. For the obtained compound, 1 1H-NMR and 13 13C-NMR measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: benzene-d6) δ (ppm): 1.38 (s, 36H), 2.25 (s, 6H), 7.06 (s, 4H). 13 13C-NMR (100 MHz, solvent: benzene-d6) δ (ppm): 21.5 (2C), 30.5 (12C), 34.4 (4C), 125.9 (4C), 128.5 (2C), 136.0 (4C), 152.1 (2C). From the above measurement data, it was confirmed that Mg(OAr)2 represented by the above formula (24) was obtained.

[0111] [Example 1] (Production of Carboxylic Acid Ester) Into a flask, add 400 mg of dried molecular sieve 5Å, 12.4 mg (0.025 mmol) of the sodium (I) phenoxide compound represented by the above formula (18), 1.49 mL (at room temperature (25 °C)) (14 mmol) of methyl methacrylate (hereinafter sometimes abbreviated as "MMA"), 0.42 mg (0.0020 mmol) of 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxyl as a polymerization inhibitor, and 18.8 mg (0.20 mmol) of dimethyl sulfone as an internal standard substance. After stirring the mixture at room temperature (25 °C) for 1 minute, add 0.206 mL (2.0 mmol) of benzyl alcohol (hereinafter sometimes abbreviated as "BnOH") to obtain a suspension. The suspension was then stirred at room temperature (25° C.) for 10 minutes. The progress of the reaction was monitored by thin layer chromatography. After the completion of the reaction was confirmed by thin layer chromatography, a portion of the suspension was sampled to determine the yield. 1 The purity was determined by H-NMR (CDCl3) and was found to be over 99%. The sample used to determine the yield was returned to the suspension, and the resulting suspension was purified directly on a silica gel column (mobile phase: hexane / methyl acetate) to obtain the compound of Example 1. The obtained compound 1 H-NMR, 13 The C-NMR, IR and HRMS measurement data are shown below. 1 H-NMR data (400MHz, solvent: CDCl3) δ (ppm): 1.97 (s, 3H), 5.20 (s, 2H), 5.59 (s, 1H), 6.16 (s, 1H), 7.30-7.40 (m, 5H). 13 C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 18.5, 66.5, 125.9, 128.1 (2C), 128.2, 128.6 (2C), 136.2, 136.3, 167.3. IR(neat)3034, 2957, 1719, 1637, 1454, 1319, 1294, 1159cm -1 . HRMS(DART+) calculation for C 11 H 13 O2 [M+H] + 177.0916, found 177.0912. From the above measurement data, it was confirmed that benzyl methacrylate represented by the following formula (25) was obtained. The following formula (26) shows the reaction formula for synthesizing benzyl methacrylate by the transesterification reaction of methyl methacrylate and benzyl alcohol. The yield of the target product was calculated by separating it from by-products using silica gel column chromatography and then directly measuring its mass using an electronic balance, and was found to be over 99%.

[0112] [Chemical formula]

[0113] [Chemical formula]

[0114] [Comparative Example 1] (Production of Carboxylic Acid Ester) A compound of Comparative Example 1 was obtained in the same manner as in Example 1, except that 12.2 mg (0.050 mmol) of the above NaOAr-1 was used instead of the sodium (I) phenoxide compound represented by the above formula (18), and the suspension was stirred at room temperature (25 °C) for 30 minutes. For the obtained compound, 1 1H-NMR, 13 13C-NMR, IR, and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 1.97 (s, 3H), 5.20 (s, 2H), 5.59 (s, 1H), 6.16 (s, 1H), 7.30 - 7.40 (m, 5H). 13 [[ID=3!]]13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 18.5, 66.5, 125.9, 128.1 (2C), 128.2, 128.6 (2C), 136.2, 136.3, 167.3. IR (neat) 3034, 2957, 1719, 1637, 1454, 1319, 1294, 1159 cm -1 . HRMS (DART+) calcd for C 11 H 13 O2 [M + H] + 177.0916, found 177.09!2. From the above measurement data, it was confirmed that benzyl methacrylate represented by the above formula (25) was obtained. The yield exceeded 99%.

[0115] It should be noted that there seems to be a small error in the "13C-NMR" line where "13!" is written instead of "13". This has been corrected in the translation as "13C".A comparison between Example 1 and Comparative Example 1 revealed that the reaction time (stirring time of the suspension) in Example 1 was shorter than that in Comparative Example 1, and that the sodium (I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0116] [Example 2] (Production of carboxylic acid esters) The compound of Example 2 was obtained in the same manner as in Example 1, except that 313 mg (2.0 mmol) of rel-(1R,2S,5R)-2-isopropyl-5-methylcyclohexanol represented by the following formula (27) was used instead of benzyl alcohol, and the suspension was stirred at room temperature (25°C) for 30 minutes. The obtained compound 1 H-NMR, 13 The C-NMR and IR measurement data were consistent with those described in the literature (ACS Catal. 2021, 11, 199-207), confirming that the ester of methyl methacrylate and rel-(1R,2S,5R)-2-isopropyl-5-methylcyclohexanol represented by the following formula (28) was obtained. The yield was over 99%.

[0117] [ka]

[0118] [ka]

[0119] Comparative Example 2 (Production of carboxylic acid esters) The compound of Comparative Example 2 was obtained in the same manner as in Example 2, except that 12.2 mg (0.050 mmol) of NaOAr-1 was used instead of the sodium(I) phenoxide compound represented by the formula (18) above, and the suspension was stirred at room temperature (25°C) for 3 hours. The obtained compound 1 H-NMR, 13The measurement data of 13C-NMR and IR were consistent with those described in the literature (ACS Catal. 2021, 11, 199-207), confirming that the ester of methyl methacrylate and rel-(1R,2S,5R)-2-isopropyl-5-methylcyclohexanol represented by the above formula (28) was obtained. The yield exceeded 99%.

[0120] From the comparison between Example 2 and Comparative Example 2, it was found that Example 2 had a shorter reaction time (stirring time of the suspension) than Comparative Example 2, and the sodium (I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0121] [Example 3] (Production of Carboxylic Acid Ester) The compound of Example 3 was obtained in the same manner as in Example 1, except that 769 mg (2.0 mmol) of cholesterol represented by the following formula (29) was used instead of benzyl alcohol, and the suspension was stirred at room temperature (25 °C) for 15 hours. Of the obtained compound 1 1H-NMR, 13 The measurement data of 13C-NMR, IR, and HRMS are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 0.68 (s, 3H), 0.86 (d, J = 6.6 Hz, 3H), 0.87 (d, J = 6.6 Hz, 3H), 0.92 (d, J = 6.4 Hz, 3H), 0.95 - 1.69 (m, 24H), 1.77 - 2.04 (m, 8H), 2.36 (d, J = 8.2 Hz, 2H), 4.67 (m, 1H), 5.38 (d, J = 4.6 Hz, 1H), 5.53 (m, 1H), 6.08 (s, 1H). 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 12.0, 18.5, 18.9, 19.5, 21.2, 22.7, 23.0, 24.0, 24.4, 27.9, 28.2, 28.4, 32.0, 32.1, 36.0, 36.3, 36.8, 37.2, 38.3, 39.7, 39.9, 42.5, 50.2, 56.3, 56.8, 74.4, 122.8, 125.1, 137.0, 139.9, 167.0. IR(KBr)2947, 1718, 1638, 1467, 1375, 1324, 1295, 1171, 1012cm -1 . HRMS(EI) calculation for C 31 H 50 O2[M] + 454.3811, found 454.3818. From the above measurement data, it was confirmed that cholesteryl methacrylate represented by the following formula (30) was obtained. The yield was over 99%.

[0122] [ka]

[0123] [ka]

[0124] Comparative Example 3 (Production of carboxylic acid esters) The compound of Comparative Example 3 was obtained in the same manner as in Example 3, except that 12.2 mg (0.050 mmol) of NaOAr-1 was used instead of the sodium(I) phenoxide compound represented by the formula (18) above, and the suspension was stirred at room temperature (25°C) for 24 hours. The obtained compound 1 H-NMR, 13 The measurement data of C-NMR, IR and HRMS are shown below. 11H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 0.68 (s, 3H), 0.86 (d, J = 6.6 Hz, 3H), 0.87 (d, J = 6.6 Hz, 3H), 0.92 (d, J = 6.4 Hz, 3H), 0.95 - 1.69 (m, 24H), 1.77 - 2.04 (m, 8H), 2.36 (d, J = 8.2 Hz, 2H), 4.67 (m, 1H), 5.38 (d, J = 4.6 Hz, 1H), 5.53 (m, 1H), 6.08 (s, 1H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 12.0, 18.5, 18.9, 19.5, 21.2, 22.7, 23.0, 24.0, 24.4, 27.9, 28.2, 28.4, 32.0, 32.1, 36.0, 36.3, 36.8, 37.2, 38.3, 39.7, 39.9, 42.5, 50.2, 56.3, 56.8, 74.4, 122.8, 125.1, 137.0, 139.9, 167.0. IR (KBr) 2947, 1718, 1638, 1467, 1375, 1324, 1295, 1171, 1012 cm -1 . HRMS (EI) calcd for C 31 H 50 O2 [M] + 454.3811, found 454.3818. From the above measurement data, it was confirmed that cholesteryl methacrylate represented by the above formula (30) was obtained. The yield was 94%.

[0125] From the comparison between Example 3 and Comparative Example 3, it was found that Example 3 had a shorter reaction time (stirring time of the suspension) and a higher yield than Comparative Example 3, and the sodium (I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0126] [Example 4] (Production of Carboxylic Acid Ester) Instead of benzyl alcohol, 278 mg (2.0 mmol) of 8-methyl-8-azabicyclo[3.2.1]octan-3-ol represented by the following formula (31) was used, and the suspension was stirred at room temperature (25 °C) for 12 hours. Otherwise, the compound of Example 4 was obtained in the same manner as in Example 1. The 1 1H-NMR, 13 13C-NMR, IR and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 1.73 (d, J = 15.0 Hz, 2H), 1.91 - 2.10 (m, 4H), 1.96 (s, 3H), 2.15 (dt, J = 15.0, 4.1 Hz, 2H), 2.29 (s, 3H), 3.11 (brs, 2H), 5.06 (t, J = 5.3 Hz, 1H), 5.57 (s, 1H), 6.09 (s, 1H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 18.3, 25.7 (2C), 36.7 (2C), 40.5 (2C), 59.8, 67.7, 125.2, 136.9, 166.7. IR (neat) 2943, 1715, 1448, 1316, 1296, 1170, 1063, 1036 cm -1 . HRMS (FAB+) calcd for C 12 11 20 H + 16 From the above measurement data, it was confirmed that (1R,3r,5S)-8-methyl-8-azabicyclo[3.2.1]octan-3-yl methacrylate represented by the following formula (32) was obtained. The yield exceeded 99%.

[0127]

Chemical formula

[0128]

Chemical formula

[0129] Comparative Example 4 (Production of carboxylic acid esters) The compound of Comparative Example 4 was obtained in the same manner as in Example 4, except that 12.2 mg (0.050 mmol) of NaOAr-1 was used instead of the sodium(I) phenoxide compound represented by the formula (18) above, and the suspension was stirred at room temperature (25°C) for 24 hours. The obtained compound 1 H-NMR, 13 The measurement data of C-NMR, IR and HRMS are shown below. 1 H-NMR data (400MHz, solvent: CDCl3) δ(ppm): 1.73(d,J=15.0Hz,2H), 1.91-2.10(m,4H), 1.96(s,3H), 2.15( dt,J=15.0,4.1Hz,2H), 2.29(s,3H), 3.11(brs,2H), 5.06(t,J=5.3Hz,1H), 5.57(s,1H), 6.09(s,1H). 13 C-NMR (100MHz, solvent: CDCl3) δ (ppm): 18.3, 25.7 (2C), 36.7 (2C), 40.5 (2C), 59.8, 67.7, 125.2, 136.9, 166.7. IR(neat)2943, 1715, 1448, 1316, 1296, 1170, 1063, 1036cm -1 . HRMS(FAB+) calculation for C 12 H 20 NO2[M+H] + 210.1494, found 210.1485. From the above measurement data, it was confirmed that (1R,3r,5S)-8-methyl-8-azobicyclo[3.2.1]octan-3-yl methacrylate represented by the above formula (32) was obtained. The yield was 88%.

[0130] From the comparison between Example 4 and Comparative Example 4, it was found that Example 4 had a shorter reaction time (stirring time of the suspension) and a higher yield than Comparative Example 4, and the sodium (I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0131] [Example 5] (Production of Carboxylic Acid Ester) The compound of Example 5 was obtained in the same manner as in Example 1, except that 309 mg (2.0 mmol) of isoborneol represented by the following formula (33) was used instead of benzyl alcohol, and the suspension was stirred at room temperature (25 °C) for 10 minutes. Of the obtained compound 1 1H-NMR, 13 13C-NMR, IR and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 0.85 (s, 3H), 0.86 (s, 3H), 1.02 (s, 3H), 1.07 - 1.21 (m, 2H), 1.57 (m, 1H), 1.67 - 1.88 (m, 4H), 1.93 (s, 3H), 4.71 (m, 1H), 5.52 (d, J = 1.4 Hz, 1H), 6.07 (s, ɪH). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 11.5, 18.4, 19.9, 20.1, 27.1, 33.7, 38.9, 45.1, 47.0, 48.9, 81.2, 125.0, 136.9, 166.9. IR (neat) 2955, 2879, 1717, 1638, 1455, 1327, 1298, 1163, 1054 cm -1 . HRMS (FAB+) calcd for C 14 18H 22 NaO2 [M+Na] + 245.1517, found 245.1509. From the above measurement data, it was confirmed that isobornyl methacrylate represented by the following formula (34) was obtained. The yield exceeded 99%.

[0132]

Chem.

[0133]

Chem.

[0134] [Comparative Example 5] (Production of Carboxylic Acid Ester) A compound of Comparative Example 5 was obtained in the same manner as in Example 5, except that 12.2 mg (0.050 mmol) of the above NaOAr-1 was used instead of the sodium (I) phenoxide compound represented by the above formula (18), and the suspension was stirred at room temperature (25 °C) for 30 minutes. For the obtained compound, 1 1H-NMR, 13 13C-NMR, IR and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 0.85 (s, 3H), 0.86 (s, 3H), 1.02 (s, 3H), 1.07 - 1.21 (m, 2H), 1.57 (m, 1H), 1.67 - 1.88 (m, 4H), 1.93 (s, 3H), 4.71 (m, 1H), 5.52 (d, J = 1.4 Hz, 1H), 6.07 (s, 1H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 11.5, 18.4, 19.9, 20.1, 27.1, 33.7, 38.9, 45.1, 47.0, 48.9, 81.2, 125.0, 136.9, 166.9. IR (neat) 2955, 2879, 1717, 1638, 1455, 1327, 1298, 1163, 1054 cm -1 . HRMS (FAB+) calcd for C 14 H 22 NaO2 [M + Na] + 245.1517, found 245.1509. From the above measurement data, it was confirmed that isobornyl methacrylate represented by the above formula (34) was obtained. The yield was 95%.

[0135] From the comparison between Example 5 and Comparative Example 5, it was found that Example 5 had a shorter reaction time (stirring time of the suspension) and a higher yield than Comparative Example 5, and the sodium (I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0136] [Example 6] (Production of Carboxylic Acid Ester) A compound of Example 6 was obtained in the same manner as in Example 1, except that 289 mg (2.0 mmol) of 5-nonanol represented by the following formula (35) was used instead of benzyl alcohol, and the suspension was stirred at room temperature (25 °C) for 30 minutes. Of the obtained compound 1 1H-NMR, 13 The measurement data of 13C-NMR and IR were consistent with those described in the literature (ACS Catal. 2021, 11, 199-207), and it was confirmed that nonan-5-yl octyl methacrylate represented by the following formula (36) was obtained. The yield exceeded 99%.

[0137] [Chemical Formula]

[0138] [Chemical Formula]

[0139] [Comparative Example 6] (Production of Carboxylic Acid Ester) A compound of Comparative Example 6 was obtained in the same manner as in Example 6, except that 12.2 mg (0.050 mmol) of the above NaOAr-1 was used instead of the sodium (I) phenoxide compound represented by the above formula (18), and the suspension was stirred at room temperature (25 °C) for 3 hours. The obtained compound's 1 1H-NMR, 13 13C-NMR and IR measurement data were consistent with those described in the literature (ACS Catal. 2021, 11, 199 - 207). Thus, it was confirmed that nonan-5-yl octyl methacrylate represented by the above formula (36) was obtained. The yield was 99%.

[0140] From the comparison between Example 6 and Comparative Example 6, it was found that Example 6 had a shorter reaction time (stirring time of the suspension) and a higher yield than Comparative Example 6, and the sodium(I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0141] [Example 7] (Production of carboxylic acid ester) A compound of Example 7 was obtained in the same manner as in Example 1, except that 649 mg (2.0 mmol) of quinine represented by the following formula (37) was used instead of benzyl alcohol, and the suspension was stirred at room temperature (25 °C) for 3 hours. The obtained compound's 1 1H-NMR, 13 13C-NMR and IR measurement data were consistent with those described in the literature (ACS Catal. 2021, 11, 199 - 207). Thus, it was confirmed that the methacrylic acid ester of quinine represented by the following formula (38) was obtained. The yield exceeded 99%.

[0142] [Chemical formula]

[0143] [Chemical formula]

[0144] [Comparative Example 7] (Production of carboxylic acid ester) Instead of the sodium (I) phenoxide compound represented by the above formula (18), 12.2 mg (0.050 mmol) of the above NaOAr-1 was used, and the suspension was stirred at room temperature (25 °C) for 6 hours. Otherwise, the same procedure as in Example 7 was carried out to obtain the compound of Comparative Example 7. For the obtained compound 1 the 1H-NMR 13 C-NMR and IR measurement data were consistent with those described in the literature (ACS Catal. 2021, 11, 199-207). Thus, it was confirmed that the methacrylic acid ester of the quinine represented by the above formula (38) was obtained. The yield exceeded 99%.

[0145] From the comparison between Example 7 and Comparative Example 7, it was found that Example 7 had a shorter reaction time (stirring time of the suspension) than Comparative Example 7, and the sodium (I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0146] [Example 8] (Production of Carboxylic Acid Ester) Instead of benzyl alcohol, geraniol represented by the following formula (39), 309 mg (2.0 mmol) was used, and the suspension was stirred at room temperature (25 °C) for 10 minutes. Otherwise, the same procedure as in Example 1 was carried out to obtain the compound of Example 8. For the obtained compound 1 the 1H-NMR 13 C-NMR, IR and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 1.60 (s, 3H), 1.68 (s, 3H), 1.72 (s, 3H), 1.94 - 1.96 (m, 3H), 2.03 - 2.14 (m, 4H), 4.67 (d, J = 7.3 Hz, 2H), 5.08 (tm, J = 6.9 Hz, 1H), 5.38 (tm, J = 6.9 Hz, 1H), 5.55 (m, 1H), 6.10 (m, 1H). 1313C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 16.6, 17.8, 18.5, 25.8, 26.4, 39.6, 61.8, 118.6, 123.9, 125.4, 131.9, 136.7, 142.1, 167.7. IR (neat) 2926, 1719, 1638, 1451, 1377, 1313, 1293, 1162, 1010 cm -1 . HRMS (DART+) calcd for C 14 H 23 O2 [M+H] + 223.1698, found 223.1696. From the above measurement data, it was confirmed that geranyl methacrylate represented by the following formula (40) was obtained. The yield exceeded 99%.

[0147] [Chemical formula]

[0148] [Chemical formula]

[0149] [Comparative Example 8] (Production of Carboxylic Acid Ester) A compound of Comparative Example 8 was obtained in the same manner as in Example 8, except that 12.2 mg (0.050 mmol) of the above NaOAr-1 was used instead of the sodium (I) phenoxide compound represented by the above formula (18), and the suspension was stirred at room temperature (25 °C) for 1 hour. The 1 1H-NMR, 13 13C-NMR, IR, and HRMS measurement data of the obtained compound are shown below. 11H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 1.60 (s, 3H), 1.68 (s, 3H), 1.72 (s, 3H), 1.94 - 1.96 (m, 3H), 2.03 - 2.14 (m, 4H), 4.67 (d, J = 7.3 Hz, 2H), 5.08 (tm, J = 6.9 Hz, 1H), 5.38 (tm, J = 6.9 Hz, 1H), 5.55 (m, 1H), 6.10 (m, 1H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 16.6, 17.8, 18.5, 25.8, 26.4, 39.6, 61.8, 118.6, 123.9, 125.4, 131.9, 136.7, 142.1, 167.7. IR (neat) 2926, 1719, 1638, 1451, 1377, 1313, 1293, 1162, 1010 cm -1 . HRMS (DART+) calcd for C 14 H 23 O2 [M + H] + 223.1698, found 223.1696. From the above measurement data, it was confirmed that geranyl methacrylate represented by the above formula (40) was obtained. The yield exceeded 99%.

[0150] From the comparison between Example 8 and Comparative Example 8, it was found that Example 8 had a shorter reaction time (stirring time of the suspension) than Comparative Example 8, and the sodium (I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0151] [Example 9] (Production of Carboxylic Acid Ester) Except that 200 mg (2.0 mmol) of 2,2,2-trifluoroethanol represented by the following formula (41) was used instead of benzyl alcohol and 24.8 mg (0.050 mmol) of the sodium (I) phenoxide compound represented by the above formula (18) was used, and the suspension was stirred at room temperature (25 °C) for 24 hours, the compound of Example 9 was obtained in the same manner as in Example 1. Of the obtained compound1 1H-NMR 13 The measurement data of 13C-NMR and IR were consistent with those described in the literature (ACS Catal. 2021, 11, 199 - 207), confirming that 2,2,2-trifluoroethyl methacrylate represented by the following formula (42) was obtained. The yield was 93%.

[0152] [Chemical formula]

[0153] [Chemical formula]

[0154] [Comparative Example 9] (Production of Carboxylic Acid Ester) A compound of Comparative Example 9 was obtained in the same manner as in Example 9, except that 24.4 mg (0.10 mmol) of the above NaOAr-1 was used instead of the sodium(I) phenoxide compound represented by the above formula (18). For the obtained compound 1 1H-NMR 13 The measurement data of 13C-NMR and IR were consistent with those described in the literature (ACS Catal. 2021, 11, 199 - 207), confirming that 2,2,2-trifluoroethyl methacrylate represented by the above formula (42) was obtained. The yield was 88%.

[0155] From the comparison between Example 9 and Comparative Example 9, it was found that Example 9 had a higher yield than Comparative Example 9, and the sodium(I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0156] [Example 10] (Production of Carboxylic Acid Ester) The compound of Example 10 was obtained in the same manner as in Example 1, except that 180 mg (2.0 mmol) of 1,4-butanediol represented by the following formula (43) was used instead of benzyl alcohol and the suspension was stirred at room temperature (25°C) for 20 minutes. The obtained compound 1 H-NMR, 13 The C-NMR and IR measurement data were consistent with those described in the literature (ACS Catal. 2021, 11, 199-207), confirming that butane-1,4-diylbis(2-methylacrylate) represented by the following formula (44) was obtained. The yield was over 99%.

[0157] [ka]

[0158] [ka]

[0159] [Comparative Example 10] (Production of carboxylic acid esters) The compound of Comparative Example 10 was obtained in the same manner as in Example 10, except that 12.2 mg (0.050 mmol) of NaOAr-1 was used instead of the sodium(I) phenoxide compound represented by the formula (18) above, and the suspension was stirred at room temperature (25°C) for 1 hour. The obtained compound 1 H-NMR, 13 The C-NMR and IR measurement data were consistent with those described in the literature (ACS Catal. 2021, 11, 199-207), confirming that butane-1,4-diylbis(2-methylacrylate) represented by the above formula (44) was obtained. The yield was over 99%.

[0160] From the comparison between Example 10 and Comparative Example 10, it was found that Example 10 had a shorter reaction time (stirring time of the suspension) than Comparative Example 10, and the sodium (I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0161] [Example 11] (Production of Carboxylic Acid Ester) Instead of benzyl alcohol, 276 mg (2.0 mmol) of 1,4-benzenedimethanol represented by the following formula (45) and 24.8 mg (0.050 mmol) of the sodium (I) phenoxide compound represented by the above formula (18) were used, and the suspension was stirred at room temperature (25 °C) for 2 hours. Otherwise, the same procedure as in Example 1 was followed to obtain the compound of Example 11. For the obtained compound 1 1H-NMR, 13 13C-NMR, IR and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 1.97 (s, 6H), 5.20 (s, 4H), 5.59 (m, 2H), 6.16 (s, 2H), 7.38 (s, 4H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 18.5 (2C), 66.2 (2C), 126.1 (2C), 128.4 (4C), 136.2 (2C), 136.3 (2C), 167.3 (2C). IR (KBr) 2966, 2931, 1701, 1635, 1456, 1373, 1319, 1295, 1156 cm -1 . HRMS (FAB+) calcd for C 16 18 18 20NaO4 [M+Na] + 297.1103, found 297.1099. From the above measurement data, it was confirmed that 1,4-phenylenebis(methylene)bis(2-methacrylate) represented by the following formula (46) was obtained. The yield exceeded 99%.

[0162] [Chemical formula]

[0163] [Chemical formula]

[0164] [Comparative Example 11] (Production of Carboxylic Acid Ester) A compound of Comparative Example 11 was obtained in the same manner as in Example 11, except that 24.4 mg (0.10 mmol) of the above NaOAr-1 was used instead of the sodium (I) phenoxide compound represented by the above formula (18), and the suspension was stirred at room temperature (25 °C) for 5 hours. Of the obtained compound 1 1H-NMR, 13 13C-NMR, IR, and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 1.97 (s, 6H), 5.20 (s, 4H), 5.59 (m, 2H), 6.16 (s, 2H), 7.38 (s, 4H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 18.5 (2C), 66.2 (2C), 126.1 (2C), 128.4 (4C), 136.2 (2C), 136.3 (2C), 167.3 (2C). IR (KBr) 2966, 2931, 1701, 1635, 1456, 1373, 1319, 1295, 1156 cm -1 . HRMS (FAB+) calcd for C 16 H 18 NaO4 [M+Na] + 297.1103, found 297.1099. From the above measurement data, it was confirmed that 1,4-phenylenebis(methylene)bis(2-methacrylate) represented by the above formula (46) was obtained. The yield exceeded 99%.

[0165] A comparison of Example 11 and Comparative Example 11 revealed that the reaction time (stirring time of the suspension) in Example 11 was shorter than that in Comparative Example 11, and that the sodium (I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0166] [Example 12] (Production of carboxylic acid esters) The compound of Example 12 was obtained in the same manner as in Example 1, except that 300 mg (2.0 mmol) of triethylene glycol represented by the following formula (47) and 24.8 mg (0.050 mmol) of the sodium(I) phenoxide compound represented by the above formula (18) were used instead of benzyl alcohol, and the suspension was stirred at room temperature (25°C) for 20 minutes. The obtained compound 1 H-NMR, 13 The C-NMR and IR measurement data were consistent with those described in the literature (ACS Catal. 2021, 11, 199-207), confirming that triethylene glycol dimethacrylate represented by the following formula (48) was obtained. The yield was over 99%.

[0167] [ka]

[0168] [ka]

[0169] [Comparative Example 12] (Production of carboxylic acid esters) The compound of Comparative Example 12 was obtained in the same manner as in Example 12, except that 24.4 mg (0.10 mmol) of NaOAr-1 was used instead of the sodium(I) phenoxide compound represented by the formula (18) above, and the suspension was stirred at room temperature (25°C) for 30 minutes. The obtained compound 1 H-NMR, 13The measurement data of 13C-NMR and IR were consistent with those described in the literature (ACS Catal. 2021, 11, 199-207), confirming that triethylene glycol dimethacrylate represented by the above formula (48) was obtained. The yield exceeded 99%.

[0170] From the comparison between Example 12 and Comparative Example 12, it was found that Example 12 had a shorter reaction time (stirring time of the suspension) than Comparative Example 12, and the sodium(I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0171] [Example 13] (Production of Carboxylic Acid Ester) Instead of benzyl alcohol, 268 mg (2.0 mmol) of trimethylolpropane represented by the following formula (49) and 24.8 mg (0.050 mmol) of the sodium(I) phenoxide compound represented by the above formula (18) were used, and the suspension was stirred at room temperature (25 °C) for 38 hours. Otherwise, the same procedure as in Example 1 was followed to obtain the compound of Example 13. For the obtained compound 1 1H-NMR, 13 13C-NMR, IR and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 0.95 (t, J = 7.8 Hz, 3H), 1.58 (q, J = 7.8 Hz, 2H), 1.94 (s, 9H), 4.16 (s, 6H), 5.58 (s, 3H), 6.09 (s, 3H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 7.5, 18.3 (3C), 23.5, 41.2, 64.4 (3C), 126.1 (3C), 136.0 (3C), 167.0 (3C). IR (neat) 2967, 1724, 1638, 1455, 1322, 1294, 1154 cm -1 . HRMS (FAB+) calcd for C 18 H 26NaO6[M+Na] + 361.1627, found 361.1623. From the above measurement data, it was confirmed that 2-ethyl-2-((methacryloyloxy)methyl)propane-1,3-diyl bis(2-methacrylate) represented by the following formula (50) was obtained. The yield exceeded 99%.

[0172]

Chemical formula

[0173]

Chemical formula

[0174] [Comparative Example 13] (Production of Carboxylic Acid Ester) A compound of Comparative Example 13 was obtained in the same manner as in Example 13, except that 24.4 mg (z0.10 mmol) of the above NaOAr-1 was used instead of the sodium(I) phenoxide compound represented by the above formula (18), and the suspension was stirred at room temperature (25 °C) for 48 hours. For the obtained compound 1 1H-NMR, 13 13C-NMR, IR and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 0.95 (t, J = 7.8 Hz, 3H), 1.58 (q, J = 7.8 Hz, 2H), 1.94 (s, 9H), 4.16 (s, 6H), 5.58 (s, 3H), 6.09 (s, 3H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 7.5, 18.3 (3C), 23.5, 41.2, 64.4 (3C), 126.1 (3C), 136.0 (3C), 167.0 (3C). IR (neat) 2967, 1724, 1638, 1455, 1322, 1294, 1154 cm -1 . HRMS(FAB+) calcd for C 18 H 26 NaO6[M+Na] + 361.1627, found 361.1623. From the above measurement data, it was confirmed that 2-ethyl-2-((methacryloyloxy)methyl)propane-1,3-diyl bis(2-methacrylate) represented by the above formula (50) was obtained. The yield was 99%.

[0175] From the comparison between Example 13 and Comparative Example 13, it was found that Example 13 had a shorter reaction time (stirring time of the suspension) and a higher yield than Comparative Example 13, and the sodium(I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0176] From the results of Examples 1 to 13 and the results of Comparative Examples 1 to 13, it was found that the sodium(I) phenoxide compound represented by the above formula (18) had higher catalytic activity than the above NaOAr-1.

[0177] [Example 14] (Production of Carboxylic Acid Ester) To a flask, 400 mg of dried molecular sieve 5Å, 47.5 mg (0.10 mmol) of the magnesium(II) phenoxide compound represented by the above formula (20), 1.26 mL (at room temperature (25 °C)) (14 mmol) of methyl acrylate (hereinafter sometimes abbreviated as "MA"), 1.2 mg (0.0040 mmol) of copper(II) bis(dimethyldithiocarbamate) as a polymerization inhibitor, and 18.8 mg (0.20 mmol) of dimethyl sulfone as an internal standard substance were added. After stirring the mixture at room temperature (25 °C) for 1 minute, 0.206 mL (2.0 mmol) of benzyl alcohol (hereinafter sometimes abbreviated as "BnOH") was added to obtain a suspension. Next, the suspension was stirred at room temperature (25 °C) for 20 minutes. The progress of the reaction was monitored by thin layer chromatography. After the completion of the reaction was confirmed by thin layer chromatography, a portion of the suspension was sampled to determine the yield. 1 The purity was determined by H-NMR (CDCl3) and was found to be over 99%. The sample used to determine the yield was returned to the suspension, and the resulting suspension was purified directly on a silica gel column (mobile phase: hexane / methyl acetate) to obtain the compound of Example 14. The obtained compound 1 H-NMR, 13 The measurement data of C-NMR, IR and HRMS are shown below. 1 H-NMR data (400MHz, solvent: CDCl3) δ (ppm): 5.19 (s, 2H), 5.84 (dd, J = 10.4, 1.6Hz, 1H) , 6.16(dd,J=17.4,10.5Hz,1H), 6.44(dd,J=17.2,1.4Hz,1H), 7.31-7.41(m,5H). 13 C-NMR (100MHz, solvent: CDCl3) δ (ppm): 66.4, 128.3 (2C), 128.4 (2C), 128.7 (2C), 131.2, 135.9, 166.1. IR(neat)3034, 2954, 1953, 1725, 1634, 1455, 1406, 1295, 1269, 1186, 1049cm -1 . HRMS(FAB+) calculation for C 10 H 10 O2[M] + 162.0681, found 162.0680. From the above measurement data, it was confirmed that benzyl acrylate represented by the following formula (51) was obtained. The following formula (52) shows the reaction formula for synthesizing benzyl acrylate by the transesterification reaction of methyl acrylate and benzyl alcohol. The yield of the target product was calculated by separating it from by-products using silica gel column chromatography and then directly measuring its mass using an electronic balance, and was found to be over 99%.

[0178] [Chemical formula]

[0179] [Chemical formula]

[0180] [Comparative Example 14] (Production of Carboxylic Acid Ester) A compound of Comparative Example 14 was obtained in the same manner as in Example 14, except that 46.3 mg (0.10 mmol) of the above Mg(OAr)2 was used instead of the magnesium (II) phenoxide compound represented by the above formula (20), and the suspension was stirred at room temperature (25 °C) for 1 hour. For the obtained compound 1 1H-NMR, 13 13C-NMR, IR, and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 5.19 (s, 2H), 5.84 (dd, J = 10.4, 1.6 Hz, 1H), 6.16 (dd, J = 17.4, 10.5 Hz, 1H), 6.44 (dd, J = 17.2, 1.4 Hz, 1H), 7.31 - 7.41 (m, 5H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 66.4, 128.3 (2C), 128.4 (2C), 128.7 (2C), 131.2, 135.9, 166.1. IR (neat) 3034, 2954, 1953, 1725, 1634, 1455, 1406, 1295, 1269, 1186, 1049 cm -1 . HRMS (FAB+) calcd for C 10 H 10 O2 [M] + 162.0681, found 162.0680. From the above measurement data, it was confirmed that benzyl acrylate represented by the above formula (51) was obtained. The yield exceeded 99%.

[0181] From the comparison between Example 14 and Comparative Example 14, it was found that Example 14 had a shorter reaction time (stirring time of the suspension) than Comparative Example 14, and the magnesium (II) phenoxide compound represented by the above formula (20) had higher catalytic activity than the above Mg(OAr)2.

[0182] [Example 15] (Production of Carboxylic Acid Ester) The compound of Example 15 was obtained in the same manner as in Example 14, except that 373 mg (2.0 mmol) of 1-dodecanol represented by the following formula (53) was used instead of benzyl alcohol, and the suspension was stirred at room temperature (25 °C) for 30 minutes. Of the obtained compound 1 1H-NMR, 13 13C-NMR, IR and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 0.88 (t, J = 6.9 Hz, 3H), 1.24 - 1.42 (m, 18H), 1.63 - 1.70 (m, 2H), 1.95 (s, 3H), 4.14 (t, J = 6.9 Hz, 2H), 5.55 (m, 1H), 6.10 (s, 1H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 14.3, 18.5, 22.8, 26.1, 28.7, 29.4, 29.5, 29.8 (3C), 29.9, 32.1, 65.0, 125.3, 136.7, 167.6. IR (neat) 2921, 2854, 1719, 1638, 1467, 1321, 1296, 1165 cm -1 . HRMS (FAB+) calcd for C 16 15 31 28O2 [M + H] + 255.2324, found 255.2324. From the above measurement data, it was confirmed that dodecyl methacrylate represented by the following formula (54) was obtained. The yield exceeded 99%.

[0183] [ka]

[0184] [ka]

[0185] [Comparative Example 15] (Production of carboxylic acid esters) The compound of Comparative Example 15 was obtained in the same manner as in Example 15, except that 46.3 mg (0.10 mmol) of Mg(OAr)2 was used instead of the magnesium(II) phenoxide compound represented by the formula (20) above, and the suspension was stirred at room temperature (25°C) for 1 hour. The obtained compound 1 H-NMR, 13 The measurement data of C-NMR, IR and HRMS are shown below. 1 H-NMR data (400MHz, solvent: CDCl3) δ (ppm): 0.88 (t, J = 6.9 Hz, 3H), 1.24-1.42 (m, 18H), 1.63-1.70(m,2H), 1.95(s,3H), 4.14(t,J=6.9Hz,2H), 5.55(m,1H), 6.10(s,1H). 13 C-NMR (100MHz, solvent: CDCl3) δ (ppm): 14.3, 18.5, 22.8, 26.1, 28.7, 29.4, 29.5, 29.8 (3C), 29.9, 32.1, 65.0, 125.3, 136.7, 167.6. IR(neat)2921, 2854, 1719, 1638, 1467, 1321, 1296, 1165cm -1 . HRMS(FAB+) calculation for C 16 H 31 O2 [M+H] + 255.2324, found 255.2324. From the above measurement data, it was confirmed that dodecyl methacrylate represented by the above formula (54) was obtained. The yield exceeded 99%.

[0186] From the comparison between Example 15 and Comparative Example 15, it was found that Example 15 had a shorter reaction time (stirring time of the suspension) than Comparative Example 15, and the magnesium (II) phenoxide compound represented by the above formula (20) had higher catalytic activity than the above Mg(OAr)2.

[0187] [Example 16] (Production of Carboxylic Acid Ester) A compound of Example 16 was obtained in the same manner as in Example 14, except that 228 mg (2.0 mmol) of thiophene-2-ylmethanol represented by the following formula (55) was used instead of benzyl alcohol, and the suspension was stirred at room temperature (25 °C) for 2 hours. Of the obtained compound 1 1H-NMR 13 13C-NMR, IR, and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 5.35 (s, 2H), 5.85 (dd, J = 10.6, 1.4 Hz, 1H), 6.14 (dd, J = 17.4, 10.5 Hz, 1H), 6.45 (dd, J = 17.4, 1.4 Hz, 1H), 6.99 (dd, J = 5.0, 3.2 Hz, 1H), 7.12 (d, J = 3.7 Hz, 1H), 7.33 (dd, J = 5.0, 1.4 Hz, 1H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 60.7, 126.9, 127.0, 128.2, 128.4, 131.5, 137.9, 165.9. IR (neat) 3108, 2954, 1725, 1634, 1441, 1407, 1295, 1261, 1183 cm -1 . HRMS (DART+) calcd for C8H8O2S [M] + 168.0245, found 168.0246. From the above measurement data, it was confirmed that thiophene-2-ylmethyl acrylate represented by the following formula (56) was obtained. The yield exceeded 99%.

[0188] [Chemical formula]

[0189] [Chemical formula]

[0190] [Comparative Example 16] (Production of Carboxylic Acid Ester) A compound of Comparative Example 16 was obtained in the same manner as in Example 16, except that 46.3 mg (0.10 mmol) of the above Mg(OAr)2 was used instead of the magnesium(II) phenoxide compound represented by the above formula (20), and the suspension was stirred at room temperature (25 °C) for 3 hours. For the obtained compound, 1 1H-NMR, 13 13C-NMR, IR, and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 5.35 (s, 2H), 5.85 (dd, J = 10.6, 1.4 Hz, 1H), 6.14 (dd, J = 17.4, 10.5 Hz, 1H), 6.45 (dd, J = 17.4, 1.4 Hz, 1H), 6.99 (dd, J = 5.0, 3.2 Hz, 1H), 7.12 (d, J = 3.7 Hz, 1H), 7.33 (dd, J = 5.0, 1.4 Hz, 1H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 60.7, 126.9, 127.0, 128.2, 128.4, 131.5, 137.9, 165.9. IR (neat) 3108, 2954, 1725, 1634, 1441, 1407, 1295, 1261, 1183 cm -1 . HRMS (DART+) calcd for C8H8O2S [M] + 168.0245, found 168.0246. From the above measurement data, it was confirmed that thiophene-2-ylmethyl acrylate represented by the above formula (56) was obtained. The yield exceeded 99%.

[0191] From the comparison between Example 16 and Comparative Example 16, it was found that Example 16 had a shorter reaction time (stirring time of the suspension) than Comparative Example 16, and the magnesium (II) phenoxide compound represented by the above formula (20) had higher catalytic activity than the above Mg(OAr)2.

[0192] [Example 17] (Production of Carboxylic Acid Ester) A compound of Example 17 was obtained in the same manner as in Example 14, except that (1R)-myrtenol (304 mg, 2.0 mmol) represented by the following formula (57) was used instead of benzyl alcohol, and the suspension was stirred at room temperature (25 °C) for 15 hours. Of the obtained compound 1 1H-NMR, 13 The measurement data of 13C-NMR and IR were consistent with those described in the literature (ACS Catal. 2021, 11, 199 - 207), and it was confirmed that (1R)-myrtenyl acrylate represented by the following formula (58) was obtained. The yield exceeded 99%.

[0193]

Chemical formula

[0194]

Chemical formula

[0195] [Comparative Example 17] (Production of Carboxylic Acid Ester) The compound of Comparative Example 17 was obtained in the same manner as in Example 17, except that 46.3 mg (0.10 mmol) of Mg(OAr)2 was used instead of the magnesium(II) phenoxide compound represented by the formula (20) above, and the suspension was stirred at room temperature (25°C) for 24 hours. The obtained compound 1 H-NMR, 13 The C-NMR and IR measurement data were consistent with those described in the literature (ACS Catal. 2021, 11, 199-207), confirming that (1R)-myrtenyl acrylate represented by the above formula (58) was obtained. The yield was 99%.

[0196] A comparison of Example 17 and Comparative Example 17 revealed that Example 17 had a shorter reaction time (stirring time of the suspension) and a higher yield than Comparative Example 17, and that the magnesium(II) phenoxide compound represented by the above formula (20) had a higher catalytic activity than the above Mg(OAr)2.

[0197] [Example 18] (Production of carboxylic acid esters) The compound of Example 18 was obtained in the same manner as in Example 14, except that 309 mg (2.0 mmol) of geraniol represented by the above formula (39) was used instead of benzyl alcohol and the suspension was stirred at room temperature (25°C) for 20 minutes. The obtained compound 1 H-NMR, 13 The measurement data of C-NMR, IR and HRMS are shown below. 1 H-NMR data (400MHz, solvent: CDCl3) δ(ppm): 1.60(s,3H), 1.68(s,3H), 1.72(s,3H), 2.03-2.14(m,4H), 4.68(d,J=7.4Hz,2H) , 5.08(m,1H), 5.38(m,1H), 5.82(dd,J=10.5,1.4Hz,1H), 6.13(dd,J=17.0,10.0Hz,1H), 6.41(dd,J=17.4,1.4Hz,1H). 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 16.6, 17.8, 25.8, 26.4, 39.7, 61.6, 118.3, 123.8, 128.7, 130.7, 132.0, 142.5, 166.4. IR(neat)2968, 2925, 2857, 1725, 1636, 1445, 1407, 1378, 1294, 1270, 1184, 1045cm -1 . HRMS(DART+) calculation for C 14 H 23 O2 [M+H] + 223.1698, found 223.1696. From the above measurement data, it was confirmed that geranyl acrylate represented by the following formula (59) was obtained. The yield was over 99%.

[0198] [ka]

[0199] [Comparative Example 18] (Production of carboxylic acid esters) The compound of Comparative Example 18 was obtained in the same manner as in Example 18, except that 46.3 mg (0.10 mmol) of Mg(OAr) was used instead of the magnesium(II) phenoxide compound represented by the formula (20) above, and the suspension was stirred at room temperature (25°C) for 1 hour. The obtained compound 1 H-NMR, 13 The measurement data of C-NMR, IR and HRMS are shown below. 1 H-NMR data (400MHz, solvent: CDCl3) δ(ppm): 1.60(s,3H), 1.68(s,3H), 1.72(s,3H), 2.03-2.14(m,4H), 4.68(d,J=7.4Hz,2H) , 5.08(m,1H), 5.38(m,1H), 5.82(dd,J=10.5,1.4Hz,1H), 6.13(dd,J=17.0,10.0Hz,1H), 6.41(dd,J=17.4,1.4Hz,1H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 16.6, 17.8, 25.8, 26.4, 39.7, 61.6, 118.3, 123.8, 128.7, 130.7, 132.0, 142.5, 166.4. IR (neat) 2968, 2925, 2857, 1725, 1636, 1445, 1407, 1378, 1294, 1270, 1184, 1045 cm -1 . HRMS (DART+) calcd for C 14 H 23 O2 [M+H] + 223.1698, found 223.1696. From the above measurement data, it was confirmed that geranyl acrylate represented by the above formula (59) was obtained. The yield exceeded 99%.

[0200] From the comparison between Example 18 and Comparative Example 18, it was found that Example 18 had a shorter reaction time (stirring time of the suspension) than Comparative Example 18, and the magnesium (II) phenoxide compound represented by the above formula (20) had higher catalytic activity than the above Mg(OAr)2.

[0201] [Example 19] (Production of Carboxylic Acid Ester) An Example 19 compound was obtained in the same manner as in Example 14, except that 148 mg (2.0 mmol) of oxirane-2-methanol represented by the following formula (60) was used instead of benzyl alcohol, and the suspension was stirred at room temperature (25 °C) for 6 hours. The 1 1H-NMR, 13 13C-NMR and IR measurement data were consistent with those described in the literature (ACS Catal. 2021, 11, 199 - 207), and it was confirmed that oxirane-2-yl acrylate represented by the following formula (61) was obtained. The yield was 15%.

[0202] [Chemical formula]

[0203] [Chemical Formula]

[0204] [Example 20] (Production of Carboxylic Acid Ester) The compound of Example 20 was obtained in the same manner as in Example 19, except that the suspension was stirred at room temperature (25 °C) for 25 hours. For the obtained compound 1 1H-NMR, 13 13C-NMR and IR measurement data were consistent with those described in the literature (ACS Catal. 2021, 11, 199 - 207), confirming that the oxiran-2-yl acrylate represented by the above formula (61) was obtained. The yield was 33%.

[0205] [Comparative Example 19] (Production of Carboxylic Acid Ester) The compound of Comparative Example 19 was obtained in the same manner as in Example 19, except that 46.3 mg (0.10 mmol) of the above Mg(OAr)2 was used instead of the magnesium (II) phenoxide compound represented by the above formula (20), and the suspension was stirred at room temperature (25 °C) for 18 hours. For the obtained compound 1 1H-NMR, 13 13C-NMR and IR measurement data were consistent with those described in the literature (ACS Catal. 2021, 11, 199 - 207), confirming that the oxiran-2-yl acrylate represented by the above formula (61) was obtained. The yield was 8%.

[0206] From the comparison between Example 19 and Comparative Example 19, it was found that Example 19 had a shorter reaction time (stirring time of the suspension) and a higher yield than Comparative Example 19, and the magnesium (II) phenoxide compound represented by the above formula (20) had higher catalytic activity than the above Mg(OAr)2. Further, from the comparison between Example 20 and Comparative Example 19, it was found that Example 20 had a higher yield than Comparative Example 19, and the phenoxide compound represented by the above formula (20) had higher catalytic activity than the above Mg(OAr)2.

[0207] [Example 21] (Production of Carboxylic Acid Ester) The compound of Example 21 was obtained in the same manner as in Example 14, except that isoborneol represented by the above formula (33), 309 mg (2.0 mmol), was used instead of benzyl alcohol, and the suspension was stirred at room temperature (25 °C) for 11 hours. For the obtained compound, 1 1H-NMR, 13 13C-NMR, IR and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 0.85 (d, J = 3.2 Hz, 6H), 1.01 (s, 3H), 1.07 - 1.21 (m, 2H), 1.57 (m, 1H), 1.67 - 1.87 (m, 4H), 4.75 (dd, J = 7.3, 3.7 Hz, 1H), 5.79 (dd, J = 10.5, 1.4 Hz, 1H), 6.09 (dd, J = 17.4, 10.5 Hz, 1H), 6.34 (dd, J = 17.4, 1.4 Hz, 1H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 11.5, 19.9, 20.2, 27.1, 33.8, 38.8, 45.1, 47.0, 48.9, 81.2, 129.3, 130.0, 165.8. IR (neat) 2956, 2879, 1720, 1636, 1619, 1455, 1406, 1390, 1296, 1199, 1109 cm -1 . HRMS (ESI+) calcd for C 13 H 20 NaO2 [M + Na]+ 231.1356, found 231.1353. It was confirmed that isobornyl acrylate represented by the following formula (62) was obtained from the above measurement data. The yield exceeded 99%.

[0208] [Chemical formula]

[0209] [Comparative Example 20] (Production of Carboxylic Acid Ester) A compound of Comparative Example 20 was obtained in the same manner as in Example 21, except that 46.3 mg (0.10 mmol) of the above Mg(OAr)2 was used instead of the magnesium (II) phenoxide compound represented by the above formula (20). For the obtained compound 1 1H-NMR, 13 13C-NMR, IR and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 0.85 (d, J = 3.2 Hz, 6H), 1.01 (s, 3H), 1.07 - 1.21 (m, 2H), 1.57 (m, 1H), 1.67 - 1.87 (m, 4H), 4.75 (dd, J = 7.3, 3.7 Hz, 1H), 5.79 (dd, J = 10.5, 1.4 Hz, 1H), 6.09 (dd, J = 17.4, 10.5 Hz, 1H), 6.34 (dd, J = 17.4, 1.4 Hz, 1H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 11.5, 19.9, 20.2, 27.1, 33.8, 38.8, 45.1, 47.0, 48.9, 81.2, 129.3, 130.0, 165.8. IR (neat) 2956, 28x79, 1720, 1636, 1619, 1455, 1406, 1390, 1296, 1199, 1109 cm -1 . HRMS (ESI+) calcd for C 13 H 20NaO2[M+Na] + 231.1356, found 231.1353. From the above measurement data, it was confirmed that isobornyl acrylate represented by the above formula (62) was obtained. The yield was 72%.

[0210] From the comparison between Example 21 and Comparative Example 20, it was found that Example 21 had a higher yield than Comparative Example 20, and the magnesium (II) phenoxide compound represented by the above formula (20) had higher catalytic activity than the above Mg(OAr)2.

[0211] [Example 22] (Production of Carboxylic Acid Ester) A compound of Example 22 was obtained in the same manner as in Example 14, except that 313 mg (2.0 mmol) of rel-(1R,2S,5R)-2-isopropyl-5-methylcyclohexanol represented by the above formula (27) was used instead of benzyl alcohol, and the suspension was stirred at room temperature (25 °C) for 24 hours. Of the obtained compound 1 1H-NMR, 13 The measurement data of 13C-NMR and IR were consistent with those described in the literature (ACS Catal. 2021, 11, 199 - 207). Therefore, it was confirmed that the ester of methyl acrylate and rel-(1R,2S,5R)-2-isopropyl-5-methylcyclohexanol represented by the following formula (63) was obtained. The yield exceeded 99%.

[0212] [Chemical Formula]

[0213] [Comparative Example 21] (Production of Carboxylic Acid Ester) Instead of the magnesium (II) phenoxide compound represented by the above formula (20), 46.3 mg (0.10 mmol) of the above Mg(OAr)2 was used, and the suspension was stirred at room temperature (25 °C) for 48 hours. Otherwise, in the same manner as in Example 22, the compound of Comparative Example 21 was obtained. For the obtained compound 1 1H-NMR 13 [[ID=!6]]13C-NMR and IR measurement data were consistent with those described in the literature (ACS Catal. 2021, 11, 199 - 207). Thus, it was confirmed that the ester of methyl acrylate represented by the above formula (63) and rel-(1R,2S,5R)-2-isopropyl-5-methylcyclohexanol was obtained. The yield was 90%.

[0214] From the comparison between Example 22 and Comparative Example 21, it was found that Example 22 had a shorter reaction time (stirring time of the suspension) and a higher yield than Comparative Example 21, and the magnesium (II) phenoxide compound represented by the above formula (20) had higher catalytic activity than the above Mg(OAr)2.

[0215] [Example 23] (Production of Carboxylic Acid Ester) Instead of benzyl alcohol, 236 mg (2.0 mmol) of 1,6-hexanediol represented by the following formula (64) was used, and the suspension was stirred at room temperature (25 °C) for 24 hours. Otherwise, in the same manner as in Example 14, the compound of Example 23 was obtained. For the obtained compound 1 1H-NMR 13 13C-NMR, IR, and HRMS measurement data are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 1.41 - 1.44 (m, 4H), 1.66 - 1.73 (m, 4H), 4.16 (t, J = 6.4 Hz, 4H), 5.82 (dd, J = 10.1, 1.4 Hz, 2H), 6.12 (dd, J = 17.4, 10.5 Hz, 2H), 6.40 (dd, J = 17.4, 1.4 Hz, 2H). 1313C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 25.7 (2C), 28.6 (2C), 64.6 (2C), 128.6 (2C), 130.7 (2C), 166.4 (2C). IR (neat) 2941, 2862, 1718, 1636, 1620, 1467, 1409, 1274, 1197 cm -1 . HRMS (DART+) calcd for C 12 H 19 O4 [M+H] + 227.1283, found 227.1284. From the above measurement data, it was confirmed that hexane-1,6-diyl diacrylate (3r) represented by the following formula (65) was obtained. The yield exceeded 99%.

[0216]

Chemical formula

[0217]

Chemical formula

[0218] [Comparative Example 22] (Production of Carboxylic Acid Ester) A compound of Comparative Example 22 was obtained in the same manner as in Example 23, except that 46.3 mg (0.10 mmol) of the above Mg(OAr)2 was used instead of the magnesium (II) phenoxide compound represented by the above formula (20), and the suspension was stirred at room temperature (25 °C) for 48 hours. The 1 1H-NMR, 13 13C-NMR, IR, and HRMS measurement data of the obtained compound are shown below. 11H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 1.41 - 1.44 (m, 4H), 1.66 - 1.73 (m, 4H), 4.16 (t, J = 6.4 Hz, 4H), 5.82 (dd, J = 10.1, 1.4 Hz, 2H), 6.12 (dd, J = 17.4, 10.5 Hz, 2H), 6.40 (dd, J = 17.4, 1.4 Hz, 2H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 25.7 (2C), 28.6 (2C), 64.6 (2C), 128.6 (2C), 130.7 (2C), 166.4 (2C). IR (neat) 2941, 2862, 1718, 1636, 1620, 1467, 1409, 1274, 1197 cm -1 . HRMS (DART+) calcd for C 12 H 19 O4 [M + H] + 227.1283, found 227.1284. From the above measurement data, it was confirmed that hexane-1,6-diyl diacrylate (3r) represented by the above formula (65) was obtained. The yield was 99%.

[0219] From the comparison between Example 23 and Comparative Example 22, it was found that Example 23 had a shorter reaction time (stirring time of the suspension) and a higher yield than Comparative Example 22, and the magnesium (II) phenoxide compound represented by the above formula (20) had higher catalytic activity than the above Mg(OAr)2.

[0220] [Example 24] (Production of Carboxylic Acid Ester) A compound of Example 24 was obtained in the same manner as in Example 14, except that 240 mg (2.0 mmol) of trimethylolpropane represented by the above formula (49) was used instead of benzyl alcohol, and the suspension was stirred at room temperature (25 °C) for 24 hours. The 1 1H-NMR, 13 13C-NMR, IR, and HRMS measurement data of the obtained compound are shown below. 1 1H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 0.93 (t, J = 7.8 Hz, 3H), 1.56 (q, J = 6.8 Hz, 2H), 4.18 (s, 6H), 5.86 (d, J = 10.6 Hz, 3H), 6.11 (dd, J = 17.0, 10.0 Hz, 3H), 6.41 (d, J = 17.4 Hz, 3H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 7.6, 23.3, 41.0, 64.3 (3C), 128.1 (3C), 131.3 (3C), 166.0 (3C). IR (neat) 2970, 1725, 1635, 1619, 1467, 1408, 1270, 1182, 1061 cm -1 . HRMS (DART+) calcd for C 15 H 21 O6 [M+H] + 297.1338, found 297.1340. [[ID=IO]]From the above measurement data, it was confirmed that 2-((acryloyloxy)methyl)-2-ethylpropane-1,3-diyl diacrylate represented by the following formula (66) was obtained. The yield was 90%.

[0221]

Chemical formula

[0222] [Comparative Example 23] (Production of Carboxylic Acid Ester) A compound of Comparative Example 23 was obtained in the same manner as in Example 24, except that 46.3 mg (0.10 mmol) of the above Mg(OAr)2 was used instead of the magnesium (II) phenoxide compound represented by the above formula (20). The 1 1H-NMR, 13 13C-NMR, IR and HRMS measurement data of the obtained compound are shown below. 11H-NMR data (400 MHz, solvent: CDCl3) δ (ppm): 0.93 (t, J = 7.8 Hz, 3H), 1.56 (q, J = 6.8 Hz, 2H), 4.18 (s, 6H), 5.86 (d, J = 10.6 Hz, 3H), 6.11 (dd, J = 17.0, 10.0 Hz, 3H), 6.41 (d, J = 17.4 Hz, 3H). 13 13C-NMR (100 MHz, solvent: CDCl3) δ (ppm): 7.6, 23.3, 41.0, 64.3 (3C), 128.1 (3C), 131.3 (3C), 166.0 (3C). IR (neat) 2970, 1725, 1635, 1619, 1467, 1408, 1270, 1182, 1061 cm -1 . HRMS (DART+) calcd for C 15 H 21 O6 [M + H] + 297.1338, found 297.1340. From the above measurement data, it was confirmed that 2-((acryloyloxy)methyl)-2-ethylpropane-1,3-diyl diacrylate represented by the above formula (66) was obtained. The yield was 71%.

[0223] From the comparison between Example 24 and Comparative Example 23, it was found that Example 24 had a higher yield than Comparative Example 23, and the magnesium (II) phenoxide compound represented by the above formula (20) had higher catalytic activity than the above Mg(OAr)₂.

[0224] From the results of Examples 14 to 24 and the results of Comparative Examples 14 to 23, it was found that the magnesium (II) phenoxide compound represented by the above formula (20) had higher catalytic activity than the above Mg(OAr)₂.

[0225] [Example 25] (Production of Carboxylic Acid Ester) Into a flask, 400 mg of dried molecular sieve 5 Å, 47.5 mg (0.10 mmol) of the phenoxide compound obtained in Catalyst Preparation Example 2 (hereinafter abbreviated as "Catalyst 2"), 1.26 mL (at room temperature (25 °C)) (14 mmol) of methyl acrylate, 1.2 mg (0.0040 mmol) of copper(II) bis(dimethyldithiocarbamate) as a polymerization inhibitor, and 18.8 mg (0.20 mmol) of dimethyl sulfone as an internal standard substance were added. After the mixture was stirred at room temperature (25 °C) for 1 minute, 309 mg (2.0 mmol) of isoborneol was added to obtain a suspension. Next, the suspension was stirred at room temperature (25 °C). The progress of the reaction was monitored by thin-layer chromatography. Every 1 hour, a portion of the suspension was sampled and the yield was 1 determined by 1H-NMR (CDCl3). The results are shown in Fig. 7 and Table 1.

[0226] [Example 26] (Production of Carboxylic Acid Ester) A suspension was stirred at room temperature (25 °C) in the same manner as in Example 25, except that 43.2 mg (0.10 mmol) of the magnesium(II) phenoxide compound obtained in Catalyst Preparation Example 3 (hereinafter abbreviated as "Catalyst 3") from 3,3',5,5'-tetra-tert-butyl-[1,1'-biphenyl]-2,2'-diol and di-n-butylmagnesium was used instead of Catalyst 2. The progress of the reaction was monitored by thin-layer chromatography. Every 1 hour, a portion of the suspension was sampled and the yield was 1 determined by 1H-NMR (CDCl3). The results are shown in Fig. 7 and Table 1.

[0227] [Comparative Example 24] (Production of Carboxylic Acid Ester) A suspension was stirred at room temperature (25 °C) in the same manner as in Example 25, except that 46.3 mg (0.10 mmol) of Mg(OAr)2 obtained in Catalyst Preparation Example 5 (hereinafter abbreviated as "Catalyst 5") was used instead of Catalyst 2. The progress of the reaction was monitored by thin layer chromatography. Every hour, an aliquot of the suspension was sampled to determine the yield. 1 The results were obtained by H-NMR (CDCl3), and are shown in Figure 7 and Table 1.

[0228] [Comparative Example 25] (Production of carboxylic acid esters) The suspension was stirred at room temperature (25°C) in the same manner as in Example 25, except that 46.3 mg (0.10 mmol) of Mg(OAr)2 obtained in Catalyst Production Example 6 (hereinafter referred to as "Catalyst 6") was used instead of Catalyst 2. The progress of the reaction was monitored by thin layer chromatography. Every hour, an aliquot of the suspension was sampled to determine the yield. 1 The results were obtained by H-NMR (CDCl3), and are shown in Figure 7 and Table 1.

[0229] [Table 1]

[0230] From the results shown in FIG. 7 and Table 1, it was found that catalyst 6 produced using Bu2Mg had better catalytic activity than catalyst 5 produced using Mg(OEt)2. Furthermore, catalyst 2 produced using Bu2Mg had superior catalytic activity to catalyst 6 produced using Bu2Mg, and the transesterification reaction was completed within 8 hours. On the other hand, catalyst 3 produced using Bu2Mg was found to have inferior catalytic activity to catalysts 5 and 6.

Claims

1. A metal phenoxide compound represented by the following formula (1) or the following formula (2). 【Chemical 1】 (In formula (1), M is Na, K or Li; X1 is a hydrocarbon group or a silyl group which may have a substituent; Y1 is a hydrogen atom, a hydrocarbon group which may have a substituent, a halogen atom, a trifluoromethyl group, a nitro group, or an ester group; Z1 is a hydrocarbon group which may have a substituent. Note that the two X1 groups may be the same group or different groups, the two Y1 groups may be the same group or different groups, and the two Z1 groups may be the same group or different groups.) 【Chemical 2】 (In formula (2), X2 is a hydrocarbon group or a silyl group which may have a substituent; Y2 is a hydrogen atom, a hydrocarbon group which may have a substituent, a halogen atom, a trifluoromethyl group, a nitro group, or an ester group; Z2 is a hydrocarbon group which may have a substituent. Note that the two X2 groups may be the same group or different groups, the two Y2 groups may be the same group or different groups, and the two Z2 groups may be the same group or different groups.)

2. The metal phenoxide compound according to claim 1, wherein X1 is a branched alkyl group.

3. The metal phenoxide compound according to claim 1, wherein X2 is a branched alkyl group.

4. A transesterification catalyst comprising the metal phenoxide compound according to any one of claims 1 to 3.

5. A process for producing a carboxylic acid ester, comprising a step of performing a transesterification reaction by bringing an ester compound into contact with an alcohol in the presence of a transesterification catalyst comprising at least one of a metal (I) phenoxide compound represented by the following formula (1) and a magnesium (II) phenoxide compound represented by the following formula (2). [Chemical Formula 3] (In formula (1), M is Na, K or Li; X1 is a hydrocarbon group or a silyl group which may have a substituent; Y1 is a hydrogen atom, a hydrocarbon group which may have a substituent, a halogen atom, a trifluoromethyl group, a nitro group or an ester group; Z1 is a hydrocarbon group which may have a substituent. Note that the two X1 groups may be the same group or different groups, the two Y1 groups may be the same group or different groups, and the two Z1 groups may be the same group or different groups.) [Chemical Formula 4] (In formula (2), X2 is a hydrocarbon group or a silyl group which may have a substituent; Y2 is a hydrogen atom, a hydrocarbon group which may have a substituent, a halogen atom, a trifluoromethyl group, a nitro group or an ester group; Z2 is a hydrocarbon group which may have a substituent. Note that the two X2 groups may be the same group or different groups, the two Y2 groups may be the same group or different groups, and the two Z2 groups may be the same group or different groups.)

6. The method for producing a carboxylic acid ester according to claim 5, wherein the ester compound is a (meth)acrylate.

7. The method for producing a carboxylic acid ester according to claim 5, wherein the alcohol is a primary alcohol or a secondary alcohol.

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