Method for producing compounds with two linked ester bonds

Abstract

This invention relates to a method for producing ester compounds with two linked ester bonds by reacting a carboxylic acid with an acrylic acid ester, and provides a novel production method that can be used at an industrially viable level (e.g., yield of 30% or more). [Solution] A method for producing a compound having two ester bonds represented by the following formula (3), comprising the step of reacting a specific carboxylic acid with a specific acrylic acid ester in the presence of a basic catalyst. TIFF2026144336000015.tif48168 (R 1 R indicates a specific substituent with 3 to 36 carbon atoms. 2 (This indicates a specific substituent with 2 to 36 carbon atoms.)

Description

[Technical Field]

[0001] This invention relates to a method for producing ester compounds in which two ester bonds are linked together. [Background technology]

[0002] Ester compounds, which consist of two linked ester bonds, are used in a variety of fields as raw materials for photoresist polymers, liquid crystal materials, thermoelectric conversion materials, inkjet inks, and pharmaceutical intermediates.

[0003] As a method for producing ester compounds in which two ester bonds are linked, for example, compounds represented by RCOOCH2CH2COOR' (where R and R' represent any monovalent group), Patent Document 1 discloses a method in which dicyclohexylcarbodiimide is used as a condensing agent to react 3-(acryloyloxy)propionic acid with N-hydroxysuccinimide in a condensation reaction. Furthermore, Non-Patent Document 1 reports that when benzoic acid and ethyl acrylate were reacted using N,N'-diphenylthiourea as a catalyst, the results were unsatisfactory. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Chinese Patent Application Publication No. 110835307 Specification [Non-patent literature]

[0005] [Non-Patent Document 1] Advanced Synthesis & Catalysis(2015),357(12),2644 [Overview of the project] [Problems that the invention aims to solve]

[0006] As a method for producing ester compounds with two linked ester bonds, the ideal method is to react a commercially available carboxylic acid with an acrylic acid ester to produce the ester compound. However, as reported in Non-Patent Document 1, it was previously considered difficult to achieve a reaction level suitable for industrial use (e.g., yield of 30% or more).

[0007] Therefore, the present invention relates to a method for producing an ester compound having two linked ester bonds by reacting a carboxylic acid with an acrylic acid ester, and aims to provide a new production method that can be used at an industrially applicable level (for example, with a yield of 30% or more). [Means for solving the problem]

[0008] To solve the above problems, the present invention proposes the following method of manufacturing.

[0009] [1] A first aspect of the present invention is a method for producing a compound having two ester bonds represented by the following formula (3), comprising the step of reacting a carboxylic acid represented by the following formula (1) with an acrylic acid ester represented by the following formula (2) in the presence of a basic catalyst.

[0010] TIFF2026144336000001.tif49168

[0011] In equation (1) above, R 1 represents a hydrocarbon group having 3 to 36 carbon atoms, and this hydrocarbon group may have one or more bonds from among oxygen-containing bonds, sulfur-containing bonds, and nitrogen-containing bonds that are not bonded to hydrogen. Furthermore, a portion of the hydrocarbon group may be substituted with a carboxyl group, a nitro group, or a halogen.

[0012] TIFF2026144336000002.tif43168

[0013] In equation (2) above, R 2represents a hydrocarbon group having 2 to 36 carbon atoms, and the hydrocarbon group may have one or more bonds selected from a bond containing oxygen, a bond containing sulfur, and a bond containing nitrogen to which no hydrogen is bonded. Further, a part of the hydrocarbon group may be substituted with a carboxy group, a nitro group or a halogen.

[0014] TIFF2026144336000003.tif48168

[0015] In the formula (3), R 1 and R 2 are each the same as R 1 and R 2 in the formulas (1) and (2).

[0016] [2] A second aspect of the present invention is the method for producing a compound having two consecutive ester bonds according to the first aspect, wherein the basic catalyst is a tertiary amine.

[0017] [3] A third aspect of the present invention is the method for producing a compound having two consecutive ester bonds according to the first or second aspect, wherein the R 1 has a polymerizable unsaturated bond. [4] A fourth aspect of the present invention is the method for producing a compound having two consecutive ester bonds according to any one of the first to third aspects, wherein the R 2 has an unsaturated bond. [5] A fifth aspect of the present invention is the method for producing a compound having two consecutive ester bonds according to any one of the first to fourth aspects, wherein the R 2 has a halogen atom. [6] A sixth aspect of the present invention is the method for producing a compound having two consecutive ester bonds according to any one of the first to fifth aspects, wherein the R 2 is a succinimidyl group. Effects of the Invention

[0018] The manufacturing method proposed in this invention is a novel manufacturing method that has not been disclosed before, and it is possible to produce ester compounds in which two ester bonds are linked together at a level that is industrially usable (for example, yield of 30% or more). [Modes for carrying out the invention]

[0019] The present invention will be described below based on one embodiment. However, the present invention is not limited to this embodiment.

[0020] <Manufacturing method of the present invention> A method for producing a compound according to an example of an embodiment of the present invention (referred to as the "production method of the present invention") is a method for producing a compound having two ester bonds represented by the following formula (3) (referred to as the "ester compound"), and is characterized by including a step of reacting a carboxylic acid represented by the following formula (1) (referred to as the "carboxylic acid") with an acrylic acid ester represented by the following formula (2) (referred to as the "acrylic acid ester") in the presence of a basic catalyst (referred to as the "reaction step").

[0021] TIFF2026144336000004.tif49168

[0022] TIFF2026144336000005.tif43168

[0023] TIFF2026144336000006.tif48168

[0024] <This carboxylic acid> The carboxylic acid used in this reaction step is the carboxylic acid represented by formula (1) above.

[0025] In equation (1) above, R 1 This represents a hydrocarbon group having 3 to 36 carbon atoms. Examples of the "carbon groups having 3 to 36 carbon atoms" include carbon groups having 3 to 36 carbon atoms in a structure obtained by removing one hydrogen atom from a linear, branched, or cyclic saturated aliphatic hydrocarbon compound, or carbon groups having 3 to 36 carbon atoms composed of a combination of carbon groups having one or more hydrogen atoms from a linear, branched, or cyclic saturated aliphatic hydrocarbon compound. However, the definition is not limited to these examples. In particular, from the perspective of how easily the reaction proceeds, R 1 It is preferable that the hydrocarbon group has 24 or fewer carbon atoms, more preferably a hydrocarbon group with 12 or fewer carbon atoms, and even more preferably a hydrocarbon group with 8 or fewer carbon atoms.

[0026] Specific examples of the aforementioned "hydrocarbon groups having 3 to 36 carbon atoms in a structure obtained by removing one hydrogen atom from a linear, branched, or cyclic saturated aliphatic hydrocarbon compound" include, for example, alkyl groups obtained by removing one hydrogen atom from alkanes such as propyl, 2-methylpropyl, pentyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, and 2-ethylhexyl, and hydrocarbon groups obtained by removing one or more hydrogen atoms from cyclic saturated aliphatic hydrocarbon compounds having one or more ring structures, such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, decahydronaphthalene, norbornane, tetrahydrodicyclopentadiene, and adamantane. However, the examples are not limited to these.

[0027] Specific examples of hydrocarbon groups used in hydrocarbon groups having 3 to 36 carbon atoms, which are formed by the aforementioned combinations of hydrocarbon groups, include alkyl groups with a structure obtained by removing one hydrogen atom from alkanes such as methyl, ethyl, propyl, 2-methylpropyl, pentyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, and 2-ethylhexyl, as well as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexa Divalent groups with structures obtained by removing two hydrogen atoms from alkanes such as methylene, heptamethylene, octamethylene, nonamethylene, decamethylene, 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-ethyltrimethylene, ethylethylene, ethane-1,1-diyl, propane-2,2-diyl, methanetriyl, ethane-1,1,2-triyl 2-methylpropane-1,1,1- Examples include trivalent groups with a structure obtained by removing three hydrogen atoms from alkanes such as triyl, 2-methylpropane-1,1,2-triyl, 2-methylpropane-1,1,3-triyl, and 2-methylpropane-1,1,1-triyl; tetravalent carbons; and hydrocarbon groups with a structure obtained by removing one or more hydrogen atoms from cyclic saturated aliphatic hydrocarbon compounds having one or more ring structures, such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, decahydronaphthalene, norbornane, tetrahydrodicyclopentadiene, and adamantane. However, the examples are not limited to these.

[0028] The aforementioned "carbon hydrocarbon group having 3 to 36 carbon atoms" may have one or more bonds from among a bond containing oxygen, a bond containing sulfur, and a bond containing nitrogen that does not contain hydrogen. Examples of the aforementioned "oxygen-containing bond" include ether bonds, ester bonds, and carbonyl bonds. Examples of the aforementioned "sulfur-containing bonds" include thioether bonds, thioester bonds, disulfide bonds, and thioketone bonds. Examples of the aforementioned "bonds containing nitrogen that do not contain hydrogen" include CN(-C)-C, C(=O)N(-C)-C, ON(-C)-C, and ON(-C)-C.

[0029] Furthermore, the aforementioned "carbon hydrocarbon group having 3 to 36 carbon atoms" may be partially substituted with a carboxyl group, a nitro group, or a halogen. Examples of halogens in this case include fluorine, chlorine, bromine, and iodine.

[0030] Furthermore, the R 1 In other words, the aforementioned "carbon hydrocarbon group having 3 to 36 carbon atoms" may have one or more unsaturated bonds, such as alkenyl groups, alkynyl groups, or aromatic skeletons such as benzene or naphthalene. Among these, it is preferable that the group has polymerizable unsaturated bonds, as this allows it to be used as a raw material for functional resins. Examples of "polymerizable unsaturated bonds" include vinyl groups, isopropenyl groups, and maleimide groups.

[0031] <Acrylic acid ester> The acrylic acid ester used in this reaction process is the acrylic acid ester represented by formula (2) above.

[0032] This acrylic acid ester does not contain methacrylic acid esters. It has been confirmed that using methacrylic acid esters results in very low reactivity.

[0033] In equation (1) above, R 2This represents a hydrocarbon group with 2 to 36 carbon atoms. Examples of the "carbon groups having 2 to 36 carbon atoms" include carbon groups having 2 to 36 carbon atoms that have a structure obtained by removing one hydrogen atom from a linear, branched, or cyclic saturated aliphatic hydrocarbon compound, or carbon groups having 2 to 36 carbon atoms that are composed of a combination of carbon groups having a structure obtained by removing one or more hydrogen atoms from a linear, branched, or cyclic saturated aliphatic hydrocarbon compound. However, the definition is not limited to these examples. In particular, from the perspective of how easily the reaction proceeds, R 2 It is preferable that the hydrocarbon group has 24 or fewer carbon atoms, more preferably a hydrocarbon group with 12 or fewer carbon atoms, and even more preferably a hydrocarbon group with 6 or fewer carbon atoms.

[0034] Specific examples of the aforementioned "hydrocarbon groups with 2 to 36 carbon atoms in a structure obtained by removing one hydrogen atom from a linear, branched, or cyclic saturated aliphatic hydrocarbon compound" include, for example, alkyl groups obtained by removing one hydrogen atom from alkanes such as ethyl, propyl, 2-methylpropyl, pentyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, and 2-ethylhexyl, and hydrocarbon groups obtained by removing one or more hydrogen atoms from cyclic saturated aliphatic hydrocarbon compounds having one or more ring structures, such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, decahydronaphthalene, norbornane, tetrahydrodicyclopentadiene, and adamantane. However, the examples are not limited to these.

[0035] Specific examples of hydrocarbon groups used in hydrocarbon groups having 2 to 36 carbon atoms, which are formed by the aforementioned combinations of hydrocarbon groups, include alkyl groups with a structure obtained by removing one hydrogen atom from alkanes such as methyl, ethyl, propyl, 2-methylpropyl, pentyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, and 2-ethylhexyl, as well as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexa Divalent groups with structures obtained by removing two hydrogen atoms from alkanes such as methylene, heptamethylene, octamethylene, nonamethylene, decamethylene, 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-ethyltrimethylene, ethylethylene, ethane-1,1-diyl, propane-2,2-diyl, methanetriyl, ethane-1,1,2-triyl 2-methylpropane-1,1,1- Examples include trivalent groups with a structure obtained by removing three hydrogen atoms from alkanes such as triyl, 2-methylpropane-1,1,2-triyl, 2-methylpropane-1,1,3-triyl, and 2-methylpropane-1,1,1-triyl; tetravalent carbons; and hydrocarbon groups with a structure obtained by removing one or more hydrogen atoms from cyclic saturated aliphatic hydrocarbon compounds having one or more ring structures, such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, decahydronaphthalene, norbornane, tetrahydrodicyclopentadiene, and adamantane. However, the examples are not limited to these.

[0036] The aforementioned "carbon hydrocarbon group having 2 to 36 carbon atoms" may have one or more bonds from among a bond containing oxygen, a bond containing sulfur, and a bond containing nitrogen that does not contain hydrogen. Examples of the aforementioned "oxygen-containing bond" include ether bonds, ester bonds, and carbonyl bonds. Examples of the aforementioned "sulfur-containing bonds" include thioether bonds, thioester bonds, disulfide bonds, and thioketone bonds. Examples of the aforementioned "bonds containing nitrogen that do not contain hydrogen" include C(=O)N(-C)-C, ON(-C)-C, and ON(-C)-C. Examples of the aforementioned "bonds containing nitrogen that do not contain hydrogen" include CN(-C)-C, C(=O)N(-C)-C, ON(-C)-C, and ON(-C)-C.

[0037] Furthermore, the aforementioned "carbon hydrocarbon group having 2 to 36 carbon atoms" may be partially substituted with a carboxyl group, a nitro group, or a halogen. Examples of halogens in this case include fluorine, chlorine, bromine, and iodine.

[0038] The aforementioned R 2 In other words, the "carbon hydrocarbon group having 2 to 36 carbon atoms" may have one or more unsaturated bonds, such as an alkenyl group, an alkynyl group, or an aromatic skeleton such as benzene or naphthalene. Among these, those having unsaturated bonds, or those in which a portion is substituted with halogens, are preferred because they facilitate the progress of the desired reaction.

[0039] Furthermore, the R 2 In other words, the aforementioned "carbon hydrocarbon group having 2 to 36 carbon atoms" is preferably one that has a halogen atom, as this facilitates the progress of the desired reaction. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Therefore, the R 2In other words, the "carbon hydrocarbon group having 2 to 36 carbon atoms" is preferably a phenyl group, a succinimidyl group, or a group partially substituted with fluorine, with the succinimidyl group being more preferred.

[0040] R 1 and R 2 As for the combinations, the combinations described as preferred above are preferred.

[0041] <Composition Ratio> In this reaction step, the mixing ratio of the carboxylic acid and the acrylic acid ester is preferably such that the molar ratio of the acrylic acid ester is 0.1 to 10 moles per mole of the carboxylic acid, and more preferably 0.2 moles or more or 6 moles or less, and more preferably 0.3 moles or more or 4 moles or less.

[0042] <Catalyst> In this reaction step, it is preferable to react the carboxylic acid with the acrylic acid ester in the presence of a basic catalyst. In this invention, "basic catalyst" refers to a catalyst that exhibits basicity, and can promote the reaction by binding to the acidic portion of the reactants, reducing the acidity, and lowering the energy barrier of the reaction.

[0043] Examples of the basic catalyst include oxides, hydroxides, carbonates, and bicarbonates of alkali or alkaline earth metals such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydride, calcium hydride, potassium t-butoxide, and lithium t-butoxide; organometallic compounds such as n-butyllithium, lithium diisopropylamide, lithium hexamethyldisilazide, and bromomagnesium diisopropylamide; pyridine, triethylamine, N,N-diisopropylethylamine, N,N-dimethylbutylamine, N,N-dimethylhexylamine, N,N-dimethyloctylamine, N,N-dimethyldecylamine, N,N-dimethyldodecylamine, N,N-dimethylhexadecylamine, and N,N-dicyclohexylmethylamine. Examples of tertiary amines include N,N-dimethylcyclohexylamine, N,N-dimethylaniline, 4-dimethylaminotoluene, 2-(dimethylamino)pyridine, 4-(dimethylamino)benzonitrile, N,N-dimethylbenzylamine, 4-dimethylaminopyridine, proton sponge, (dimethylamino)acetonitrile, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 4-methylmorpholine, bis(2-morpholinoethyl) ether, triethylenediamine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonene, tris{2-(methoxymethoxy)ethyl}amine, tris[2-{(2-methoxyethoxy)methoxy}ethyl]amine, or quaternary amines such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. These can be used individually or in combination of two or more types.

[0044] Among these, tertiary amines are preferred as catalysts in terms of solubility in the reaction solution and activity. In particular, tertiary amines that do not have groups that react with acrylates, such as NH groups or OH groups, are preferred in terms of suppressing side reactions. Among these, 4-(dimethylamino)pyridine, triethylamine, triethylenediamine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonene are especially preferred.

[0045] The catalyst may be completely dissolved or partially dissolved within the reaction system.

[0046] The amount of catalyst used is preferably 0.001 to 0.5 moles per mole of the acrylic acid ester, and more preferably 0.01 moles or more, and more preferably 0.03 moles or more, from the viewpoint of ensuring the reaction proceeds smoothly. On the other hand, from the viewpoint of removing the catalyst and suppressing side reactions, the amount is preferably 0.3 moles or less, and more preferably 0.2 moles or less.

[0047] <Polymerization inhibitor> In this reaction step, it is preferable to include a polymerization inhibitor to prevent polymerization of the acrylic acid ester. Examples of such "polymerization inhibitors" include quinone-based polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and benzoquinone; alkylphenol-based polymerization inhibitors such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol; alkylated diphenylamine; N,N'-diphenyl-p-phenylenediamine; Examples of polymerization inhibitors include amine-based polymerization inhibitors such as phenothiazines, hindered amine-based polymerization inhibitors such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl, and copper dithiocarbamate-based polymerization inhibitors such as metallic copper, copper sulfate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate. These polymerization inhibitors may be used individually or in combination of two or more.

[0048] The amount of polymerization inhibitor added is preferably adjusted to 1 to 10,000 ppm by mass, more preferably 10 ppm or more or 5,000 ppm or less, and more preferably 50 ppm or more or 3,000 ppm or less, relative to the total amount (mass) of the reaction solution, for example, when adding a solvent, the total amount (mass) of the ester compound, the carboxylic acid, the basic catalyst, and the solvent.

[0049] <Solvent> In this reaction process, a solvent that is inert to the raw materials and catalyst can be used as the solvent. In this case, the "inert solvent" can be, for example, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and cyclohexane; aromatic hydrocarbons such as toluene, o-xylene, m-xylene, p-xylene, and mixed xylene; ether solvents such as diethyl ether, diisopropyl ether, and tetrahydrofuran; or ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, and methyl isobutyl ketone. These solvents may be used individually or in combination of two or more.

[0050] The amount of solvent used is preferably 1 to 100 times the total mass of the carboxylic acid and acrylic acid ester blended as raw materials, and more preferably 1 to 30 times.

[0051] <Main reaction process> In this reaction process, possible reaction methods include, for example, a batch reaction in which all raw materials are placed in a single reactor and the reaction is completed therein; a continuous reaction in which raw materials are continuously supplied to the reactor and the reaction proceeds continuously; and a circulating reaction in which a reactor and a mixing tank are used, and the raw materials are circulated between the reactor and the mixing tank while the reaction takes place in the reactor. However, the reaction method is not limited to these methods.

[0052] The reaction temperature for this reaction step is preferably 30 to 200°C after mixing the carboxylic acid and the acrylic acid ester, and more preferably 40°C or above, or 120°C or below, with a temperature of 50°C or above, or 100°C or below. The reaction time for this reaction step, that is, the time for reacting the carboxylic acid and the acrylic acid ester, is preferably 1 to 48 hours, and more preferably 2 hours or more, or 24 hours or less. However, in terms of yield, it is desirable to monitor the reaction using NMR, gas chromatography (GC), thin-layer chromatography (TLC), etc., to ensure that the reaction is completed.

[0053] <Refining and Recovery> When the product manufactured by the present invention is used industrially, it is preferable to purify the reaction solution after the completion of this reaction step by conventional methods such as distillation, adsorbent treatment, concentration, crystallization, and washing, and then recover the product (target product).

[0054] (Distillation and purification) Methods of distillation purification include, for example, simple distillation and distillation using a multi-stage distillation column (rectification column). Distillation columns can be packed using packing materials such as stainless steel, glass, or ceramic, including Raschig rings, Lessing rings, Dickson packings, pole rings, saddles, and Sulzer packings, as well as tray columns such as perforated plate columns and bubble bell columns.

[0055] (Adsorbent treatment) The amount of impurities can be reduced by adsorbent treatment, which involves contacting the reaction solution with an adsorbent. Methods for treating adsorbents include column chromatography and methods in which the adsorbent is suspended to adsorb impurities, and then the adsorbent is separated. Examples of adsorbents include activated clay, hydrotalcite, porous polymers, ion exchange resins (cation exchange resins or anion exchange resins), activated carbon, adsorbent resins, silica gel, silica-alumina adsorbents, alumina gel, activated alumina, silicon dioxide, and zeolites.

[0056] (concentrated) Methods for concentrating the reaction solution include conventional methods such as evaporation, vacuum concentration, filtration, freeze-drying, and chromatography.

[0057] (Crystallization) Methods for crystallization include dissolving the substance in a solvent and then lowering the temperature of the solution to precipitate crystals, concentrating the solution to precipitate crystals, and adding a solvent with low solubility of the target substance. However, the method is not limited to these methods.

[0058] (Washing) The preferred cleaning method is rinsing with water. That is, One possible method involves adding the reaction product to cold water or water at a suitable temperature, stirring, filtering to remove water-soluble impurities, and then drying the product.

[0059] (collect) As described above, after the purification process, the product (target substance) can be recovered by known methods such as centrifugation, pressure filtration, vacuum filtration, or natural filtration.

[0060] <This ester compound> The manufacturing method of the present invention can yield a compound in which two ester bonds represented by formula (3) are linked together. In equation (3) above, R 1 and R 2 These are R in equations (1) and (2) above, respectively. 1 and R 2 It is identical to [the other one]. According to the manufacturing method of the present invention, the yield of the ester compound can be 30% or more, more preferably 40% or more, and more preferably 60% or more, based on the number of moles of carboxylic acid or acrylic acid ester used as a raw material.

[0061] <Explanation of terms, etc.> In this invention, when "α~β" (where α and β are arbitrary numbers) is written, unless otherwise specified, it means "α or greater and β or less," and also includes the meaning of "preferably greater than α" or "preferably less than β." Furthermore, when written as "α or greater" or "α ≤" (where α is any number), unless otherwise specified, it includes the meaning of "preferably greater than α," and when written as "β or less" or "≤β" (where β is any number), unless otherwise specified, it also includes the meaning of "preferably less than β." [Examples]

[0062] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0063] <Raw materials> The carboxylic acids, acrylic acid esters, catalysts, and polymerization inhibitors used in the following examples and comparative examples are as follows.

[0064] (Carboxylic acid represented by formula (1)) • Methacrylic acid: Manufactured by Tokyo Chemical Industry Co., Ltd. Benzoic acid: Manufactured by Tokyo Chemical Industry Co., Ltd. • 4-carboxystyrene: Manufactured by Tokyo Chemical Industry Co., Ltd. • 4-Maleimidobutyric acid: Manufactured by Tokyo Chemical Industry Co., Ltd. • Cyclopentancarboxylic acid: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0065] (Acrylates represented by formula (2)) • NSIA: N-acrylooxysuccinimidoallyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd. • TFEA: 2,2,2-trifluoroethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd. • Allyl acrylate: Manufactured by Tokyo Chemical Industry Co., Ltd. Phenylacrylate: Manufactured by Tokyo Chemical Industry Co., Ltd. • Ethyl acrylate: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0066] (catalyst) • DMAP: 4-(dimethylamino)pyridine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Triethylamine: Manufactured by Tokyo Chemical Industry Co., Ltd. ·1,8-Diazabicyclo[5.4.0]-7-Undecene: Manufactured by Tokyo Chemical Industry Co., Ltd. • DPTU: N,N'-diphenylthiourea, manufactured by Tokyo Chemical Industry Co., Ltd.

[0067] (Polymerization inhibitor) • BHT: 2,6-di-tert-butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd. • MQ: 4-methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd.

[0068] <Identification of the obtained compound and yield of the target product> The identification of the obtained compounds and the yield of the target product were determined by the following method. The reaction solutions obtained in the examples and comparative examples were dissolved in deuterated chloroform, and 1H-NMR measurements were performed at room temperature using a JEOL Ltd. nuclear magnetic resonance spectrometer JNM-ECZ400S. The structure of the product was identified from the spectrum obtained by measurement. Furthermore, using the number of moles of carboxylic acid or acrylic acid ester used as a raw material as a reference, the molar ratios of each were calculated from the integral ratio of the number of moles of substituents of the reference compound and the integral ratio of the number of moles of substituents of the generated compound (target product), and the yield was determined. Yield (%) = Molar ratio of target product / (Molar ratio of reference compound + Molar ratio of target product + Molar ratio of by-products)

[0069] [Example 1] In a four-necked flask equipped with a reflux condenser, 7.75 g (0.09 mol) of methacrylic acid, 5.07 g (0.03 mol) of NSIA, 0.37 g (0.003 mol) of DMAP, and 6.5 mg of BHT were placed and heated in an oil bath at 80°C for 2 hours to obtain the reaction solution. Analysis of the resulting reaction solution confirmed that the compound represented by formula (4) below was obtained in a yield of 65% (NSIA standard).

[0070] Formula (4) TIFF2026144336000007.tif50168

[0071] [Example 2] In a four-necked flask equipped with a reflux condenser, 7.75 g (0.09 mol) of methacrylic acid, 5.07 g (0.03 mol) of NSIA, 0.37 g (0.003 mol) of DMAP, and 6.5 mg of BHT were placed and heated in an oil bath at 60°C for 6 hours to obtain the reaction solution. Analysis of the resulting reaction solution confirmed that the compound represented by formula (4) was obtained in a yield of 67% (NSIA standard).

[0072] [Example 3] In a four-necked flask equipped with a reflux condenser, 7.75 g (0.09 mol) of methacrylic acid, 5.07 g (0.03 mol) of NSIA, 0.30 g (0.003 mol) of triethylamine, and 7.0 mg of BHT were placed and heated in an oil bath at 80°C for 6 hours to obtain the reaction solution. Analysis of the resulting reaction solution confirmed that the compound represented by formula (4) was obtained in a yield of 64% (NSIA standard).

[0073] [Example 4] In a four-necked flask equipped with a reflux condenser, 7.75 g (0.09 mol) of methacrylic acid, 5.07 g (0.03 mol) of NSIA, 0.31 g (0.002 mol) of 1,8-diazabicyclo[5.4.0]-7-undecene, and 7.0 mg of BHT were placed and heated in an oil bath at 80°C for 6 hours to obtain the reaction solution. Analysis of the resulting reaction solution confirmed that the compound represented by formula (4) was obtained in a yield of 62% (NSIA standard).

[0074] [Comparative Example 1] In a four-necked flask equipped with a reflux condenser, 7.75 g (0.09 mol) of methacrylic acid, 5.07 g (0.03 mol) of NSIA, 0.69 g (0.003 mol) of DPTU, and 7.0 mg of BHT were placed and heated in an oil bath at 80°C for 2 hours to obtain the reaction solution. Analysis of the resulting reaction solution revealed that the amount of compound represented by formula (4) was less than 1% in terms of NSIA yield.

[0075] [Examples 5-14] In a four-necked flask equipped with a reflux condenser, the carboxylic acid, acrylic acid ester, basic catalyst, and polymerization inhibitor shown in Table 1 were charged in the amounts shown in Table 1, and the reaction was carried out at 80°C for the time shown in Table 2 to obtain the reaction solution. The obtained reaction solution was analyzed, and the structure and yield of the resulting compound are shown in Table 2.

[0076] [Table 1]

[0077] [Table 2]

[0078] [Comparative Examples 2-3] In a four-necked flask equipped with a reflux condenser, the carboxylic acid, acrylic acid ester, catalyst, and polymerization inhibitor shown in Table 3 were charged in the amounts shown in Table 3 and reacted at 80°C for the time shown in Table 4. The yields of the resulting compounds are shown in Table 4.

[0079] [Table 3]

[0080] [Table 4]

[0081] (Consideration) The results from Examples 1-3, 8, 9 and Comparative Examples 1-3 showed that when N,N'-diphenylthiourea (DPTU) was used as a catalyst, the reaction activity was very low and the yield was extremely low, whereas when a basic catalyst, particularly a tertiary amine, was used, the activity was very high and the yield was high. Furthermore, other examples showed that various carboxylic acids and acrylic acid esters can be used in the production method of the present invention.

Claims

1. A method for producing a compound having two linked ester bonds represented by formula (3), comprising the step of reacting a carboxylic acid represented by formula (1) with an acrylic acid ester represented by formula (2) in the presence of a basic catalyst. (In formula (1) above, R １ (This represents a hydrocarbon group having 3 to 36 carbon atoms, and this hydrocarbon group may have one or more bonds from among oxygen-containing bonds, sulfur-containing bonds, and nitrogen-containing bonds that are not bonded to hydrogen. Furthermore, a portion of the hydrocarbon group may be substituted with a carboxyl group, a nitro group, or a halogen.) (In formula (2) above, R ２ (This represents a hydrocarbon group having 2 to 36 carbon atoms, and the hydrocarbon group may have one or more bonds from among oxygen-containing bonds, sulfur-containing bonds, and nitrogen-containing bonds that are not bonded to hydrogen. Furthermore, a portion of the hydrocarbon group may be substituted with a carboxyl group, a nitro group, or a halogen.) (In formula (3) above, R １ and R ２ These are R in formulas (1) and (2) above, respectively. １ and R ２ (It is identical to the above.)

2. A method for producing a compound having two linked ester bonds according to claim 1, characterized in that the basic catalyst is a tertiary amine.

3. The aforementioned R １ A method for producing a compound having two linked ester bonds as described in claim 1 or 2, characterized in that it has polymerizable unsaturated bonds.

4. The aforementioned R ２ A method for producing a compound having two linked ester bonds as described in claim 1 or 2, characterized by having an unsaturated bond.

5. Said R ２ characterized in that it has a halogen atom, the method for producing a compound in which two ester bonds are connected in series according to claim 1 or 2.

6. The aforementioned R ２ A method for producing a compound having two linked ester bonds according to claim 1 or 2, characterized in that the group is a succinimidyl group.

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