Method for producing dicarboxylic acid monoesters and dicarboxylic acid monoester salts

Abstract

The present invention addresses the problem of providing: a method for producing a dicarboxylic acid monoester, the method having excellent selectivity of the dicarboxylic acid monoester; and a novel dicarboxylic acid monoester salt. A method for producing a dicarboxylic acid monoester according to the present invention produces a dicarboxylic acid monoester represented by formula (3) or (4) by causing a dicarboxylic acid represented by formula (1) and an alcohol derivative represented by formula (2) to react with each other in a protic solvent with use of a base.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a dicarboxylic acid monoester and a dicarboxylic acid monoester salt. [Background technology]

[0002] Optical films such as optical compensation sheets and retardation films are used in various image display devices to eliminate image coloration and widen the viewing angle. Stretched birefringent films have been used as optical films, but in recent years, it has been proposed to use optical films having an optically anisotropic layer made of a liquid crystalline compound instead of stretched birefringent films.

[0003] It is known that the liquid crystal compound used to form such an optically anisotropic layer can be synthesized, for example, by utilizing an esterification reaction between a hydroxy compound for forming a skeleton located at the center of the liquid crystal compound molecule and a carboxylic acid compound for forming a side chain portion of the liquid crystal compound. As a method for synthesizing the above-mentioned carboxylic acid compounds, for example, Patent Document 1 describes a method for synthesizing a dicarboxylic acid monoester from a dicarboxylic acid (

[0092]

[0093] ). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2019 / 017444 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have studied the method for synthesizing dicarboxylic acid monoesters described in Patent Document 1 and have found that, depending on the reaction conditions, dicarboxylic acid dimonoesters are also produced as by-products, and therefore there is room for improvement in the selectivity of dicarboxylic acid monoesters.

[0006] Therefore, an object of the present invention is to provide a method for producing a dicarboxylic acid monoester which is excellent in selectivity for the dicarboxylic acid monoester, and a novel dicarboxylic acid monoester salt. [Means for solving the problem]

[0007] As a result of intensive investigations to achieve the above object, the present inventors have found that the selectivity for dicarboxylic acid monoesters can be improved by employing a reaction system using a base in a protic solvent, and have thus completed the present invention. That is, it has been found that the above object can be achieved by the following configuration.

[0008] [1] A method for producing a dicarboxylic acid monoester, comprising reacting a dicarboxylic acid represented by formula (1) described below with an alcohol derivative represented by formula (2) described below using a base in a protic solvent to produce a dicarboxylic acid monoester represented by formula (3) or (4) described below. [2] The method for producing a dicarboxylic acid monoester according to [1], wherein the protic solvent is water. [3] The method for producing a dicarboxylic acid monoester according to [1] or [2], wherein the base is an inorganic base. [4] The method for producing a dicarboxylic acid monoester according to [3], wherein the inorganic base is a Bronsted base. [5] The method for producing a dicarboxylic acid monoester according to any one of [1] to [4], wherein an alkali metal salt or alkaline earth metal salt of a dicarboxylic acid represented by formula (1) described below is formed in the reaction system and used. [6] X in the formula (2) described below 1 represents a group represented by formula (2-1) below. [7] The dicarboxylic acid represented by the formula (1) described later is a compound represented by the formula (1-1) described later, The method for producing a dicarboxylic acid monoester according to any one of [1] to [6], wherein the dicarboxylic acid monoester represented by formula (3) or (4) below is a compound represented by formula (3-1) or (4-1) below, respectively. [8] The method for producing a dicarboxylic acid monoester according to any one of [1] to [7], wherein the dicarboxylic acid represented by formula (1) below is a compound represented by formula (1-2) below. [9] The method for producing a dicarboxylic acid monoester according to any one of [1] to [8], wherein the dicarboxylic acid monoester represented by formula (3) below is a compound represented by formula (3-2) below.

[10] A dicarboxylic acid monoester salt represented by the formula (4-2) described below. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a method for producing a dicarboxylic acid monoester with excellent selectivity for the dicarboxylic acid monoester, and a novel dicarboxylic acid monoester salt. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. The following description of the components may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In addition, in this specification, each component may be a single substance corresponding to the component, or two or more substances may be used in combination. Here, when two or more substances are used in combination for each component, the content of that component refers to the total content of the substances used in combination, unless otherwise specified.

[0011] [Method of producing dicarboxylic acid monoester] The method for producing a dicarboxylic acid monoester of the present invention (hereinafter also simply referred to as "the production method of the present invention") comprises reacting a dicarboxylic acid represented by the following formula (1) with an alcohol derivative represented by the following formula (2) using a base in a protic solvent to produce a dicarboxylic acid monoester represented by the following formula (3) or (4). The formulas (1) to (4) will be described in detail later. [ka]

[0012] In the present invention, as described above, the selectivity of the dicarboxylic acid monoester can be improved by reacting the dicarboxylic acid represented by the above formula (1) with the alcohol derivative represented by the above formula (2) in a protic solvent using a base. Although the details of this are not clear, the present inventors speculate as follows. That is, in the present invention, taking into consideration that the produced dicarboxylic acid monoester is precipitated from the reaction solvent, it is considered that by using a protic solvent as the reaction solvent, after both terminals of the dicarboxylic acid are dissociated by the base, the dicarboxylic acid is precipitated from the reaction solvent at the point when only one terminal is reacted with the alcohol derivative, thereby suppressing the subsequent reaction, i.e., the production of a dicarboxylic acid diester, and therefore improving the selectivity of the dicarboxylic acid monoester. The raw materials and reaction conditions in the production method of the present invention will be described in detail below.

[0013] [Dicarboxylic acid] The dicarboxylic acid used in the production method of the present invention is a dicarboxylic acid represented by the following formula (1). [ka]

[0014] In the above formula (1), W represents a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a divalent heterocyclic group having 2 to 20 carbon atoms, or a group in which two or more groups of the same or different types selected from the group consisting of these groups are linked by a single bond or a divalent linking group. However, the hydrogen atoms contained in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the heterocyclic group may be replaced by halogen atoms, -R w1 , -OR w1 , optionally substituted with a cyano group or a nitro group, R w1 represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

[0015] In the above formula (1), examples of the divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms represented by one embodiment of W include groups represented by the following formulae (W-7) to (W-19). Furthermore, examples of the divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms represented by one embodiment of W include groups represented by the following formulae (W-1) to (W-6). Furthermore, examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by one embodiment of W include groups represented by the following formulae (W-20) to (W-27). Furthermore, the divalent heterocyclic group having 2 to 20 carbon atoms represented by one embodiment of W may be either aromatic or non-aromatic, but is preferably a divalent aromatic heterocyclic group from the viewpoint of further improving the degree of orientation. Atoms other than carbon that constitute a divalent aromatic heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom. When an aromatic heterocyclic group has multiple atoms that constitute the ring other than carbon, these atoms may be the same or different. Specific examples of the divalent aromatic heterocyclic group include a pyridylene group (pyridine-diyl group), a pyridazine-diyl group, an imidazole-diyl group, a thienylene (thiophene-diyl group), a quinolylene group (quinoline-diyl group), an isoquinolylene group (isoquinoline-diyl group), an oxazole-diyl group, a thiazole-diyl group, an oxadiazole-diyl group, a benzothiazole-diyl group, a benzothiadiazole-diyl group, a phthalimido-diyl group, a thienothiazole-diyl group, a thiazolothiazole-diyl group, a thienothiophene-diyl group, and a thienoxazole-diyl group. [ka] JPEG0007727709000004.jpg23148 JPEG0007727709000005.jpg23148 JPEG0007727709000006.jpg26148

[0016] As described above, W in the above formula (1) may be a group in which two or more groups of the same or different types selected from the group consisting of divalent aliphatic hydrocarbon groups having 1 to 13 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and divalent heterocyclic groups having 2 to 20 carbon atoms are linked together via a single bond or a divalent linking group. Here, "two or more groups of the same kind" refers to, for example, two or more groups selected from divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, and "two or more groups of different kinds" refers to, for example, two or more groups selected from divalent aliphatic hydrocarbon groups having 1 to 13 carbon atoms and divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms. Examples of the divalent linking group include -CO-, -O-, -S-, -C(=S)-, and -CR 11 R 12 -, -CR 13 =CR 14 -, -C≡C-, -NR 15 -, -N=CR 16-, -N=N-, or a divalent linking group consisting of a combination of two or more of these. 11 ~R 16 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. Specifically, -CO-, -O-, -CO-O-, -C(=S)O-, -CR 11 R 12 -, -CR 11 R 12 -CR 11 R 12 -, -O-CR 11 R 12 -, -CR 11 R 12 -O-CR 11 R 12 -,-CO-O-CR 11 R 12 -, -O-CO-CR 11 R 12 -, -CR 11 R 12 -O-CO-CR 11 R 12 -, -CR 11 R 12 -CO-O-CR 11 R 12 -, -NR 15 -CR 11 R 12 -, and -CO-NR 15 - is preferably mentioned.

[0017] W in the above formula (1) preferably has a ring structure. Specifically, W in the above formula (1) is preferably a group in which two or more groups, the same or different, selected from the group consisting of the above-mentioned divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms, divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and divalent heterocyclic groups having 2 to 20 carbon atoms are linked by a single bond or a divalent linking group, more preferably a group in which two or more groups selected from divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms are linked by a single bond or a divalent linking group, and even more preferably a group in which two or more groups selected from divalent alicyclic hydrocarbon groups having 3 to 13 carbon atoms are linked by a single bond.

[0018] In the present invention, the dicarboxylic acid represented by the above formula (1) is preferably a compound represented by the following formula (1-1), because this results in good optical properties when made into a film. [ka]

[0019] In the above formula (1-1), R 1 and R 2 each independently represents a ring structure. Also, L 1 represents a single bond or a divalent linking group. Furthermore, n represents an integer of 0 to 2. However, when n represents 2, there are multiple R 2 and L 1 may be the same or different from each other.

[0020] R in the above formula (1-1) 1 and R 2 The ring structure represented by is not particularly limited as long as it is a ring structure contained in the above-mentioned divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and divalent heterocyclic group having 2 to 20 carbon atoms.

[0021] Examples of the ring structure include an aromatic hydrocarbon ring, an aromatic heterocyclic ring, an aliphatic hydrocarbon ring, and an aliphatic heterocyclic ring, each of which may have a substituent. Specific examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring. Specific examples of the aromatic heterocycle include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring. Specific examples of the aliphatic hydrocarbon ring include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclododecane ring, and a cyclodocosane ring. Specific examples of the aliphatic heterocycle include pyrrolidine, oxolane, thiolane, piperidine, oxane, thiane, piperazine, morpholine, quinuclidine, pyrrolidine, azetidine, oxetane, aziridine, dioxane, and pentamethylene sulfide.

[0022] Among these, R in the above formula (1-1) is particularly preferred because it provides good optical properties when made into a film. 1 and R 2 is preferably an aromatic ring (particularly a benzene ring) having 6 or more carbon atoms which may have a substituent, or a cycloalkane ring having 6 or more carbon atoms which may have a substituent, more preferably a cyclohexane ring (for example, a 1,4-cyclohexylene group), and even more preferably a trans-1,4-cyclohexylene group.

[0023] Examples of the substituent that the aromatic hydrocarbon ring may have include an alkyl group, an alkoxy group, an aryl group, a halogen atom, an ester group, and a mercapto group. The alkyl group is, for example, preferably a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a cyclohexyl group, etc.), still more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or a t-butyl group. The alkoxy group is, for example, preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.), still more preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group or an ethoxy group. The aryl group is preferably an aryl group having 6 to 15 carbon atoms, more preferably a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, a naphthyl group, an anthryl group, or a 9,10-dimethoxyanthryl group, and still more preferably a phenyl group. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms and chlorine atoms being preferred. Examples of the ester group include a methyl ester group, an ethyl ester group, a propyl ester group, a hexyl ester group, an octyl ester group, a dodecyl ester group, and a stearyl ester group, and among these, a methyl ester group or an ethyl ester group is preferred.

[0024] R in the above formula (1-1) 1 and R 2 Suitable examples of the ring structures include the ring structures exemplified above, and combinations of the ring structures and substituents exemplified above, such as the ring structures shown below. In the ring structures shown below, * indicates the bonding position. [ka] [ka]

[0025] L in the above formula (1-1) 1 Examples of the divalent linking group represented by one embodiment of the formula include -CO-, -O-, -S-, -C(=S)-, -CR 11 R 12 -, -CR 13 =CR 14 -, -C≡C-, -NR 15 -, -N=CR 16 -, -N=N-, or a divalent linking group consisting of a combination of two or more of these. 11 ~R 16 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. Specifically, -CO-, -O-, -CO-O-, -C(=S)O-, -CR 11 R 12 -, -CR 11 R 12 -CR 11 R 12 -, -O-CR 11 R 12 -, -CR 11 R 12 -O-CR 11 R 12 -,-CO-O-CR 11 R 12 -, -O-CO-CR 11 R 12 -, -CR 11 R 12 -O-CO-CR 11 R 12 -, -CR 11 R 12 -CO-O-CR 11 R 12 -, -NR 15 -CR 11 R 12 -, and -CO-NR 15 - is preferably mentioned.

[0026] In the present invention, L in the above formula (1-1) 1 is preferably a single bond, or -O-, -CO-O- or -O-CO-, and more preferably a single bond.

[0027] As mentioned above, n in the above formula (1-1) represents an integer of 0 to 2, preferably 0 or 1, and more preferably 1.

[0028] In the present invention, the dicarboxylic acid represented by the above formula (1) is preferably a compound represented by the following formula (1-2), because the optical properties of the film obtained are good and the selectivity of the dicarboxylic acid monoester is further improved. [ka]

[0029] In the above formula (1-2), p represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0. Furthermore, s represents an integer of 1 to 3, preferably 1 or 2, and more preferably 2. However, when s represents 2 or 3, multiple p's may be the same or different.

[0030] Specific examples of the dicarboxylic acid represented by the above formula (1) include compounds represented by the following formula: [ka] JPEG0007727709000012.jpg6863

[0031] [Alcohol derivatives] The alcohol derivative used in the production method of the present invention is an alcohol derivative represented by the following formula (2). [ka]

[0032] In the above formula (2), X 1 represents a halogen atom, an alkylsulfonyloxy group which may have a substituent, an arylsulfonyloxy group which may have a substituent, or a heteroarylsulfonyloxy group which may have a substituent. Also, SP 1 represents a linear or branched alkylene group having 1 to 12 carbon atoms, or a divalent linking group in which one or more -CH2- groups constituting the linear or branched alkylene group having 1 to 12 carbon atoms are substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, and Q represents a substituent. Also, P 1 represents a hydrogen atom or a polymerizable group.

[0033] X in the above formula (2) 1Examples of the halogen atom represented by one embodiment of the formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom or a chlorine atom is preferred, and a chlorine atom is more preferred. Also, X 1 Examples of the alkylsulfonyloxy group represented by one embodiment of the above include a methanesulfonyloxy group. Also, X 1 Examples of the arylsulfonyloxy group represented by one embodiment of the formula (1) include a toluenesulfonyloxy group and a benzenesulfonyloxy group. Also, X 1 Examples of the heteroarylsulfonyloxy group represented by one embodiment of the above include a thiophenesulfonyloxy group. The substituents that the alkylsulfonyloxy group may have include R 1 and R 2 In the description of the above, the same substituents as those that may be possessed by the aromatic hydrocarbon rings exemplified as ring structures can be mentioned.

[0034] In the present invention, X in the above formula (2) 1 is preferably a group represented by the following formula (2-1) because this further improves the selectivity for dicarboxylic acid monoesters. [ka]

[0035] In the above formula (2-1), * represents SP in the above formula (2). 1 represents the bonding position with Also, R 4 represents an alkyl group, an aryl group, or a heteroaryl group, which may have a substituent. Here, the alkyl group is preferably, for example, a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a cyclohexyl group, etc.), still more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or a t-butyl group. Furthermore, the aryl group is preferably, for example, an aryl group having 6 to 15 carbon atoms, more preferably a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, a naphthyl group, an anthryl group, or a 9,10-dimethoxyanthryl group, and still more preferably a phenyl group or a tolyl group. Examples of the heteroaryl group include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzthiazolyl, naphthothiazolyl, benzoxazolyl, m-carbazolyl, and azepinyl. The substituents that the alkyl group may have include R 1 and R 2 In the description of the above, the same substituents as those that may be possessed by the aromatic hydrocarbon rings exemplified as ring structures can be mentioned.

[0036] SP in the above formula (2) 1 Suitable examples of the linear or branched alkylene group having 1 to 12 carbon atoms represented by one embodiment of the formula (1) include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group, and a heptylene group. 1 As described above, may be a divalent linking group in which one or more of -CH2- constituting a linear or branched alkylene group having 1 to 12 carbon atoms are substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, and examples of the substituent represented by Q include R 1 and R 2In the description of the above, the same substituents as those that may be possessed by the aromatic hydrocarbon rings exemplified as ring structures can be mentioned.

[0037] P in the above formula (2) 1 The polymerizable group represented by one embodiment of (1) is not particularly limited, but is preferably a polymerizable group capable of radical polymerization or cationic polymerization. As the radical polymerizable group, a known radical polymerizable group can be used, and preferred examples include an acryloyloxy group or a methacryloyloxy group. In this case, it is known that the polymerization rate of the acryloyloxy group is generally fast, and from the viewpoint of improving productivity, the acryloyloxy group is preferred, but a methacryloyloxy group can also be used as the polymerizable group. As the cationically polymerizable group, known cationically polymerizable groups can be used, and specific examples thereof include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group. Among them, an alicyclic ether group or a vinyloxy group is preferred, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferred. Particularly preferred examples of the polymerizable group include polymerizable groups represented by any of the following formulae (P-1) to (P-20).

[0038] [ka]

[0039] In the present invention, P in the above formula (2) 1 is preferably a polymerizable group, more preferably a polymerizable group represented by the above formula (P-1) or (P-2).

[0040] In the above formula (2), SP 1 -P 1 Suitable examples of the group represented by the formula include the groups shown below. In the structures shown below, * indicates X 1 represents the bonding position with [ka]

[0041] Specific examples of the alcohol derivative represented by the above formula (2) include compounds represented by the following formula: [ka] JPEG0007727709000018.jpg1445 JPEG0007727709000019.jpg33107 JPEG0007727709000020.jpg46166

[0042] 〔reaction〕 In the production method of the present invention, a dicarboxylic acid represented by the above formula (1) is reacted with an alcohol derivative represented by the above formula (2) in a protic solvent using a base to produce a dicarboxylic acid monoester represented by the formula (3) or (4) described below.

[0043] <Protic Solvents> A protic solvent is a solvent that dissociates and releases a proton, such as water, alcohols, and fatty acids. Specific examples of the protic solvent include: water; Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol aliphatic alcohols such as 3-heptanol, 1-octanol, 2-octanol, 2-methyl-1-hexanol, 1-nonanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, α-terpineol, abietinol, and fusel oil; 2-Methoxyethanol, 2-ethoxyethanol, 2-(methoxymethoxy)ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, 2-phenoxyethanol, 2-(benzyloxy)ethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol those with multiple functional groups such as ethanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, polypropylene glycol, diacetone alcohol, 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1,2-propanediol, 1,3-dichloro-2-propanol, 2,2,2-trifluoroethanol, 3-hydroxypropionitrile, 2-aminoethanol, 2-(diethylamino)ethanol, 2-(diethylamino)ethanol, diethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanolamine, and 2,2'-thiodiethanol; Diols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, glycerin, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, and 1,2,6-hexanetriol; phenols such as phenol, cresol, o-cresol, m-cresol, p-cresol, and xylenol; General formula [CF3-(CF2) x -(CH2) y—OH], where x=1 to 20, y=0 to 19, and x+y is 20 or less, and alcohols substituted with halogen such as fluorine. These solvents may be used alone or in combination of two or more.

[0044] In the present invention, the protic solvent is preferably water, methanol, ethanol, n-propanol, i-propanol, n-butanol, or tert-butanol, and more preferably water, because the selectivity for the dicarboxylic acid monoester is further improved. Other protic solvents such as methanol and ethanol may be used in combination with water.

[0045] <base> The base is not particularly limited, but is preferably an inorganic base from the viewpoint of solubility in a protic solvent. Specific examples of inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; and cesium fluoride. Among these inorganic bases, Bronsted bases (inorganic Bronsted bases) are preferred from the viewpoints of solubility in protic solvents, suppression of side reactions, and the like. Specific examples of inorganic Bronsted bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carbonate chlorides such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; alkaline earth metal carbonate chlorides such as calcium carbonate and barium carbonate; alkali metal hydrogen carbonate chlorides such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and cesium hydrogen carbonate; and alkali metal hydrogen phosphate chlorides such as disodium hydrogen phosphate and dipotassium hydrogen phosphate.

[0046] In the present invention, it is preferred to form an alkali metal salt or alkaline earth metal salt of the dicarboxylic acid represented by the above formula (1) in the reaction system between the dicarboxylic acid represented by the above formula (1) and the alcohol derivative represented by the above formula (2) for the reason that the operation is simple. That is, in the present invention, the reaction of the dicarboxylic acid represented by the above formula (1) with the alcohol derivative represented by the above formula (2) may be carried out in such a manner that the dicarboxylic acid represented by the above formula (1) is first converted into an alkali metal salt or alkaline earth metal salt of the dicarboxylic acid, and then the dicarboxylic acid is reacted with the alcohol derivative represented by the above formula (2).

[0047] <Reaction conditions> The reaction conditions for the dicarboxylic acid represented by the above formula (1) and the alcohol derivative represented by the above formula (2) are not particularly limited except for the use of the above-mentioned protic solvent and base, and conventionally known reaction conditions for esterification can be appropriately adopted. For example, the reaction temperature is preferably -10 to 150°C, more preferably -5 to 120°C, and even more preferably -5 to 100°C. The reaction time is preferably 10 minutes to 24 hours, more preferably 30 minutes to 10 hours, and even more preferably 1 hour to 8 hours.

[0048] In the present invention, the amount of the alcohol derivative represented by the above formula (2) used is not particularly limited, but is preferably 0.8 to 5.0 equivalents, more preferably 1.0 to 4.0 equivalents, and even more preferably 1.0 to 3.0 equivalents relative to the dicarboxylic acid represented by the above formula (1).

[0049] In the present invention, the amount of the base used is not particularly limited, but is preferably 1.0 to 5.0 equivalents, more preferably 1.5 to 3.0 equivalents, and even more preferably 1.8 to 2.5 equivalents, relative to the dicarboxylic acid represented by formula (1).

[0050] In the present invention, an additive may be added to the reaction system in order to accelerate the above-mentioned reaction. Specific examples of the additive include potassium iodide, sodium iodide, tetraalkylammonium salts (such as tetrabutylammonium chloride and tetrabutylammonium bromide), and crown ethers (such as 18-crown-6).

[0051] [Dicarboxylic acid monoester] In the production method of the present invention, a dicarboxylic acid monoester represented by the following formula (3) or (4) is produced by the above-mentioned reaction. [ka]

[0052] In the above formulas (3) and (4), W and SP 1 and P 1 is the same as defined in the above formulas (1) and (2), and specific examples thereof are also the same. In the above formula (4), M represents an alkali metal atom or an alkaline earth metal atom. In the formula (4), m represents the valence of M. However, when m represents an integer of 2 or more, the number of W, SP, or the like present in the formula (4) is not limited to 1. 1 and P 1may be the same or different from each other.

[0053] Specific examples of the alkali metal atom represented by one embodiment of M in the above formula (4) include sodium, potassium, lithium, and cesium, and among these, sodium, potassium, and lithium are preferred. Specific examples of alkaline earth metal atoms represented by one embodiment of M include calcium, strontium, and barium, with calcium and barium being preferred.

[0054] In the present invention, the dicarboxylic acid monoester represented by the above formula (3) or (4) is preferably a compound represented by the following formula (3-1) or (4-1), respectively, because the optical properties of the resulting film are improved and the selectivity of the dicarboxylic acid monoester is further improved. The compounds represented by the following formula (3-1) or (4-1) can be produced by using the compound represented by the above formula (1-1) as the dicarboxylic acid represented by the above formula (1). [ka]

[0055] In the above formulas (3-1) and (4-1), R 1 , R 2 , L 1 and n are the same as those in the above formula (1-1), and specific examples thereof are also the same. Also, SP 1 , P 1 , M and m are defined as in the above formulas (3) and (4), and specific examples thereof are also the same.

[0056] In the present invention, the dicarboxylic acid monoester represented by the above formula (3) is preferably a compound represented by the following formula (3-2) or (4-2), because the optical properties of the film formed therefrom are improved and the selectivity of the dicarboxylic acid monoester is further improved. The compounds represented by the following formula (3-2) or (4-2) can be produced by using the compound represented by the above formula (1-2) as the dicarboxylic acid represented by the above formula (1). [ka] JPEG0007727709000024.jpg2790

[0057] In the above formulas (3-2) and (4-2), p and s are defined as in the above formula (1-2), and specific examples thereof are also the same. In addition, in the above formulas (3-2) and (4-2), SP 1 is the same as defined in the above formula (3), and specific examples thereof are also the same. In addition, in the above formula (3-2), P 1 is the same as defined in the above formula (3), and specific examples thereof are also the same. In addition, in the above formula (4-2), P 2 is a polymerizable group, and specific examples thereof include P 1 The specific examples of the polymerizable group are the same as those of the embodiment of the above. In addition, in the above formula (4-2), M 1 represents sodium, potassium or lithium. In addition, in the above formula (4-2), m1 is M 1 However, if m1 is an integer of 2 or more, there are multiple P 2 , SP 1 , s and p may each be the same or different.

[0058] Specific examples of the dicarboxylic acid monoesters represented by the above formulas (3), (3-1) and (3-2) include compounds represented by the following formulas: [ka] JPEG0007727709000026.jpg26118 JPEG0007727709000027.jpg2552

[0059] Specific examples of the dicarboxylic acid monoesters (dicarboxylic acid monoester salts) represented by the above formulas (4), (4-1) and (4-2) include compounds represented by the following formulas: In the following formulas, Ma represents an alkali metal atom. [ka]

[0060] [Dicarboxylic acid monoester salt] The dicarboxylic acid monoester salt of the present invention is a compound represented by the above formula (4-2). [Example]

[0061] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0062] [Example 1] [ka]

[0063] 4-Methylsulfonyloxybutyl acrylate (I-1-b) was synthesized by a known method using 4-hydroxybutyl acrylate, methanesulfonyl chloride, and triethylamine.

[0064] As shown in the above scheme, 10.0 g (39.3 mmol) of compound (I-1-a) was added to a solution of 1.88 g (78.6 mmol) of lithium hydroxide and 190 mL of water, and the solution was dissolved by heating to 60° C. 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate (I-1-b) was added to the solution, and the mixture was stirred at 80° C. for 3 hours. At the end of the reaction, the ratio of monoester (I-1) to diester (I-1-c) was found to be 88:9 by HPLC (High Performance Liquid Chromatography) analysis, and the selectivity of the monoester was 91%. After the reaction mixture was cooled to room temperature, the precipitated solid was collected by filtration, and the resulting crude product was purified by silica gel column chromatography to obtain 6.3 g (16.5 mmol) of monoester (I-1) (yield 42%).

[0065] The obtained monoester (I-1) 1 The H-NMR (Nuclear Magnetic Resonance) is shown below. 1 H-NMR (solvent: CDCl3) δ (ppm): 1.0-1.1 (m, 6H), 1.3-1.5 (m, 4H), 1.7-1.8 (m, 8H), 2.0-2.1 (m, 4H) ),2.2(tt,1H),2.2(tt,1H),4.1(t,2H),4.2(t,2H),5.8(dd,1H),6.1(dd,1H),6.4(dd,1H)

[0066] [Comparative Example 1] The monoester (I-1) was synthesized according to the following scheme described in paragraph

[0092] of Patent Document 1 (WO 2019 / 017444). [ka]

[0067] Specifically, as shown in the above scheme, 10.0 g (39.3 mmol) of compound (I-1-a), 100 mL of N,N-dimethylacetamide (DMAc), 8.0 mL (78.6 mmol) of triethylamine, and 433 mg of 2,6-di-t-butyl-4-methylphenol were mixed at room temperature (23° C.), and 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate (I-1-b) was added to the mixture, followed by stirring at 100° C. for 5 hours. At the end of the reaction, the ratio of the monoester (I-1) to the diester (I-1-c) was found to be 40:29 by HPLC analysis, and the selectivity for the monoester was 58%. After cooling the reaction mixture to room temperature, 100 mL of 1N aqueous hydrochloric acid and 100 mL of ethyl acetate were added, followed by stirring at room temperature (23°C) for 10 minutes and filtration. The filtrate was separated, and the organic layer was washed with 10% brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. 100 mL of chloroform was added to the residue, and the resulting white crystals were filtered. The filtrate was evaporated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 4.78 g (12.6 mmol) of the monoester (I-1) (yield: 32%).

[0068] [Table 1]

[0069] The results shown in Table 1 above reveal that the synthesis method of Example 1 suppressed the production of the diester (I-1-c) and improved the selectivity for the monoester (I-1) compared to the synthesis method of Comparative Example 1.

[0070] [Example 2] A monoester (I-1) was synthesized in the same manner as in Example 1, except that sodium hydroxide was used instead of lithium hydroxide. Specifically, 10.0 g (39.3 mmol) of compound (I-1-a) was added to a solution of 3.15 g (78.6 mmol) of sodium hydroxide and 320 mL of water, and the solution was dissolved by heating to 60° C. 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate (I-1-b) was added to the solution, and the mixture was stirred at 80° C. for 3 hours. At the end of the reaction, the ratio of the monoester (I-1) to the diester (I-1-c) was found to be 35:1.2 by HPLC analysis, and the selectivity for the monoester was 97%.

[0071] [Example 3] A monoester (I-1) was synthesized in the same manner as in Example 1, except that potassium hydroxide was used instead of lithium hydroxide. Specifically, 10.0 g (39.3 mmol) of compound (I-1-a) was added to a solution of 4.41 g (78.6 mmol) of potassium hydroxide and 320 mL of water, and the solution was dissolved by heating to 60° C. 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate (I-1-b) was added to the solution, and the mixture was stirred at 80° C. for 3 hours. At the end of the reaction, the ratio of the monoester (I-1) to the diester (I-1-c) was found to be 21.1:0.8 by HPLC analysis, and the selectivity for the monoester was 96%.

[0072] [Example 4] A monoester (I-1) was synthesized in the same manner as in Example 1, except that sodium hydrogen carbonate was used instead of lithium hydroxide. Specifically, 10.0 g (39.3 mmol) of compound (I-1-a) was added to a solution of 4.25 g (78.6 mmol) of sodium bicarbonate and 320 mL of water, and the solution was dissolved by heating to 60° C. 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate (I-1-b) was added to the solution, and the mixture was stirred at 80° C. for 3 hours. At the end of the reaction, the ratio of the monoester (I-1) to the diester (I-1-c) was found to be 27.1:0.7 by HPLC analysis, and the selectivity for the monoester was 97%.

[0073] [Example 5] Similar to the scheme of Example 1, 10.0 g (39.3 mmol) of compound (I-1-a) was added to a solution of 1.88 g (78.6 mmol) of lithium hydroxide and 320 mL of water, and the mixture was heated to 60 ° C. to dissolve. After the temperature of this solution was raised to 80 ° C., 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate (I-1-b) was added, and the mixture was stirred at 80 ° C. for 2 hours. After 2 hours, an aqueous solution (4.9 mL) of 9.61 g (43.2 mmol) of 4-methylsulfonyloxybutyl acrylate (I-1-b) and 0.47 g (19.7 mmol) of lithium hydroxide was added, and the mixture was further heated and stirred at 80 ° C. for 2 hours. At the end of the reaction, the ratio of the monoester (I-1) to the diester (I-1-c) was found to be 39.7:6.3 by HPLC analysis, and the selectivity for the monoester was 86%. After the reaction mixture was cooled to room temperature, the precipitated solid was collected by filtration, washed with water, and then dried by air drying to obtain 7.84 g of compound (I-1). The content of monoester (I-1) calculated using a calibration curve was 82%, and the yield was 43%.

[0074] [Example 6] [ka]

[0075] As shown in the above scheme, 10.0 g (39.3 mmol) of compound (I-1-a) was added to a solution of 1.88 g (78.6 mmol) of lithium hydroxide and 320 mL of water, and the solution was dissolved by heating to 60° C. 14.7 g (59.0 mmol) of compound (I-2-b) was added to the solution, and the mixture was stirred at 80° C. for 3 hours. At the end of the reaction, the ratio of the monoester (I-2) to the diester (I-2-c) was analyzed by HPLC, and the selectivity of the monoester was found to be 92%. After the reaction mixture was cooled to room temperature, the precipitated solid was collected by filtration, washed with water, and then dried by blow drying to obtain 7.23 g (17.7 mmol) of the monoester (I-2) (yield 45%).

[0076] [Example 7] [ka]

[0077] As shown in the above scheme, 10.0 g (58.1 mmol) of compound (I-3-a) was added to a solution of 2.78 g (116 mmol) of lithium hydroxide and 320 mL of water, and dissolved by heating to 60° C. 24.3 g (87.1 mmol) of compound (I-3-b) was added to this solution, and the mixture was stirred at 80° C. for 3 hours. At the end of the reaction, the ratio of the monoester (I-3) to the diester (I-3-c) was analyzed by HPLC, and the selectivity of the monoester was found to be 78%.

[0078] [Example 8] [ka]

[0079] As shown in the above scheme, 10.0 g (39.3 mmol) of compound (I-1-a) was added to a solution of 1.88 g (78.6 mmol) of lithium hydroxide and 320 mL of water, and the solution was dissolved by heating to 60° C. 20.9 g (47.2 mmol) of compound (I-4-b) was added to the solution, and the mixture was stirred at 80° C. for 3 hours. At the end of the reaction, the ratio of the monoester (I-4) to the diester (I-4-c) was analyzed by HPLC, and the selectivity of the monoester was found to be 72%.

[0080] [Example 9] [ka]

[0081] As shown in the above scheme, 10.0 g (39.3 mmol) of compound (I-1-a) was added to a solution of 1.88 g (78.6 mmol) of lithium hydroxide and 320 mL of water, and the solution was dissolved by heating to 60° C. 15.4 g (47.2 mmol) of compound (I-5-b) was added to the solution, and the mixture was stirred at 80° C. for 3 hours. At the end of the reaction, the ratio of the monoester (I-2) to the diester (I-2-c) was analyzed by HPLC, and the selectivity of the monoester was found to be 75%.

[0082] [Example 10] [ka]

[0083] As shown in the above scheme, a reaction was carried out using compound (I-5-a) in the same manner as in Examples 6 to 9. At the end of the reaction, the ratio of the monoester (I-5) to the diester (I-5-c) was analyzed by HPLC, and the selectivity of the monoester was found to be 77%.

Claims

1. A method for producing a dicarboxylic acid monoester, comprising reacting a dicarboxylic acid represented by the following formula (1) with an alcohol derivative represented by the following formula (2) using a base in a protic solvent to produce a dicarboxylic acid monoester represented by the following formula (3) or (4): 【Chemical 1】 Here, in the formulas (1) to (4), W represents a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a divalent heterocyclic group having 2 to 20 carbon atoms, or a group in which two or more groups of the same or different types selected from the group consisting of these groups are linked by a single bond or a divalent linking group consisting of -CO-, -O-, -S-, -C(=S)-, -CR11R12-, -CR13=CR14-, -C≡C-, -NR15-, -N=CR16-, -N=N-, or a combination of two or more of these. R11 to R16 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. However, the hydrogen atoms contained in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the heterocyclic group may be replaced by halogen atoms, —R ｗ１ , -OR ｗ１ , optionally substituted with a cyano group or a nitro group, R ｗ１ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom. X １ represents a halogen atom, an alkylsulfonyloxy group which may have a substituent, an arylsulfonyloxy group which may have a substituent, or a heteroarylsulfonyloxy group which may have a substituent. SP １ represents a linear or branched alkylene group having 1 to 12 carbon atoms, or a —CH ２ represents a divalent linking group in which one or more -'s are substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, and Q represents a substituent. P １ represents a hydrogen atom or a polymerizable group represented by any one of formulas (P-1) to (P-14) and (P-16) to (P-20). M represents an alkali metal atom or an alkaline earth metal atom. m represents the valence of M. However, when m represents an integer of 2 or more, a plurality of W, SP, １ and P １ may be the same or different from each other. 【Chemistry 2】

2. The method for producing a dicarboxylic acid monoester according to claim 1, wherein the protic solvent is water.

3. The method for producing a dicarboxylic acid monoester according to claim 1 or 2, wherein the base is an inorganic base.

4. The method for producing a dicarboxylic acid monoester according to claim 3, wherein the inorganic base is a Bronsted base.

5. The method for producing a dicarboxylic acid monoester according to any one of claims 1 to 4, wherein an alkali metal salt or alkaline earth metal salt of the dicarboxylic acid represented by formula (1) is formed in the reaction system and used.

6. X in the formula (2) １ The method for producing a dicarboxylic acid monoester according to any one of claims 1 to 5, wherein represents a group represented by the following formula (2-1): 【Chemistry 3】 In the formula (2-1), * represents SP in the formula (2). １ represents the bonding position with R ４ represents an alkyl group, an aryl group, or a heteroaryl group, which may have a substituent.

7. The dicarboxylic acid represented by the formula (1) is a compound represented by the following formula (1-1): The method for producing a dicarboxylic acid monoester according to any one of claims 1 to 6, wherein the dicarboxylic acid monoester represented by formula (3) or (4) is a compound represented by the following formula (3-1) or (4-1), respectively: 【Chemistry 4】 In the formulas (1-1), (3-1) and (4-1), R １ and R ２ each independently represents a ring structure. L １ represents a single bond or -CO-, -O-, -S-, -C(=S)-, -CR 11 R 12 -, -CR 13=CR 14 -, -C≡C-, -NR 15 -, -N=CR 16 -, -N=N-, or a divalent linking group formed by a combination of two or more thereof. R 11 to R 16 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. n represents an integer of 0 to 2. However, when n represents 2, there are multiple R ２ and L １ may be the same or different from each other. SP １ , P １ , M and m are the same as defined in the formulas (3) and (4).

8. The method for producing a dicarboxylic acid monoester according to any one of claims 1 to 7, wherein the dicarboxylic acid represented by formula (1) is a compound represented by the following formula (1-2): 【Chemistry 5】 Here, in the formula (1-2), p represents an integer of 0 to 3; s represents an integer of 1 to 3. However, when s represents 2 or 3, multiple p's may be the same or different.

9. The method for producing a dicarboxylic acid monoester according to any one of claims 1 to 8, wherein the dicarboxylic acid monoester represented by formula (3) is a compound represented by formula (3-2): 【Chemistry 6】 Here, in the formula (3-2), p represents an integer of 0 to 3; s represents an integer of 1 to 3. However, when s represents 2 or 3, multiple p's may be the same or different. SP １ and P １ is the same as defined in the above formula (3).

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