Method for producing binaphthyl carboxylic acid

Abstract

The present invention addresses the problem of providing a method for producing binaphthyl carboxylic acid having a good hue, which is suitable as a resin raw material having excellent optical characteristics. [Solution] Provided is a 2, 3, 4-triazole compound represented by formula (2). A method for producing a 1, 1 '-binaphthyl-2, 2'-bis (carboxylmethoxy)-1, 1 '-binaphthyl body, characterized in that a 1, 1'-binaphthyl-2, 2 '-diol body represented by formula (1) is used as a starting material, and the following steps (i)-(iii) are performed in this order: (i) a step wherein the 1, 1'-binaphthyl-2, 2 '-diol body represented by formula (1) and a halogenated acetate body represented by formula (3) are reacted in a solvent to form a mixture; a step for generating a 2, 2 '-bis (alkoxycarbonylmethoxy)-1, 1'-binaphthalene body represented by formula (4) by performing an etherification reaction in an atmosphere or under a gas stream having an oxygen concentration of 6 vol% or less; (ii) a step for hydrolyzing the 2, 2 '-bis (alkoxycarbonylmethoxy)-1, 1'-binaphthalene represented by formula (4) and then performing an acid treatment, (iii) a step for obtaining the 2, 2 '-bis (carboxylmethoxy)-1, 1'-binaphthalene represented by formula (2) by crystallization.

Description

Technical Field

[0001] The present invention relates to a method for producing binaphthalene carboxylic acid. Specifically, it relates to a method for obtaining a 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene compound with good hue. Background Art

[0002] In recent years, polyester resins or polyester carbonate resins containing binaphthalene carboxylic acid as a polymer component have excellent optical properties such as high refractive index and low birefringence, and have high heat resistance, and thus are expected to be used as raw materials for optical components such as optical discs, transparent conductive substrates, and filters. Among them, resins produced using 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene (hereinafter referred to as "Compound A") represented by the following chemical formula as a polymer component have attracted particular attention due to their excellent optical properties (for example, Patent Documents 1 to 4, etc.).

[0003] [Chemical Formula 1]

[0004] As a method for producing Compound A represented by the above formula, as shown in the following reaction formula, a method is known in which 1,1'-binaphthalene-2,2'-diol is reacted with a haloacetate such as ethyl chloroacetate, and the resulting diester is hydrolyzed (for example, Patent Document 5, etc.). However, most of the Compound A obtained by this reaction is not refined but directly converted into an acyl chloride form using thionyl chloride or oxalyl chloride in the state of a crude product and used.

[0005] As a raw material for optical components, in addition to refractive index or transmittance, hue sometimes becomes a problem, and it is difficult to be applied to optical components due to coloring. To date, no method for producing binaphthalene carboxylic acid with good hue has been reported.

[0006] [Chemical Formula 2]

[0007] Patent Documents Patent Document 1: Japanese Patent Application Laid-Open No. 2001-072872 Patent Document 2: Japanese Patent Application Laid-Open No. 2018-002893 Patent Document 3: Japanese Patent Application Laid-Open No. 2018-002894 Patent Document 4: Japanese Patent Application Laid-Open No. 2018-002895 Patent Document 5: Japanese Patent Application Laid-Open No. 2008-024650 Summary of the Invention The present invention has been completed in view of the above circumstances, and an object thereof is to provide a method for producing binaphthalene carboxylic acid with good hue suitable as a raw material for a resin having excellent optical properties.

[0008] The present inventors conducted intensive research to solve the above problems, and as a result, found that a binaphthalene carboxylic acid with good hue can be obtained by carrying out an etherification reaction in an environment or under a gas stream with an oxygen concentration of 6% by volume or less, thereby completing the present invention.

[0009] The present invention is as follows.

[0010] 1. A method for producing a 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene compound represented by formula (2), characterized by using a 1,1'-binaphthalene-2,2'-diol compound represented by formula (1) as a starting material, and successively carrying out the following steps (i) to (iii): (i): A step of carrying out an etherification reaction between a 1,1'-binaphthalene-2,2'-diol compound represented by formula (1) and a haloacetate compound represented by formula (3) in an environment or under a gas stream with an oxygen concentration of 6% by volume or less to produce a 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthalene compound represented by formula (4); (ii): A step of hydrolyzing the 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthalene compound represented by formula (4) and then carrying out an acid treatment; (iii): A step of obtaining a 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene compound represented by formula (2) by crystallization. [Chemical formula 3]

[0011] In the formula, R 1 each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and m each independently represents 0 or an integer of 1 to 4. [Chemical formula 4]

[0012] In the formula, R 1 and m have the same definitions as in formula (1). [Chemical formula 5]

[0013] In the formula, X represents a halogen atom, and R 2 represents a linear or branched alkyl group having 1 to 10 carbon atoms. [Chemical formula 6]

[0014] In the formula, R 1 and m have the same definitions as in formula (1), and R 2Each is independently the same as defined in formula (3).

[0015] 2. The method for producing 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl according to 1., characterized in that crystallization in step (iii) is carried out twice.

[0016] 3. The method for producing 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl according to 1., characterized in that steps (ii) to (iii) are all carried out in an inert gas environment or under an inert gas stream.

[0017] According to the present invention, a binaphthalene carboxylic acid with good hue can be obtained.

[0018] The production method of the present invention is very useful for industrial applications such as resin raw materials. Detailed Description of the Invention

[0019] The present invention will be described in detail below.

[0020] In the reaction of the production method of the present invention, as shown in the following reaction formula, using 1,1'-binaphthalene-2,2'-diol represented by formula (1) as a starting material, it is subjected to an etherification reaction with a haloacetate represented by formula (3) to produce 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyl represented by formula (4). After hydrolyzing the obtained 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyl and performing an acid treatment, 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by formula (2) can be obtained.

[0021] [Chemical Formula 7]

[0022] (In the formula, R 1 , m is the same as defined in formula (1), and R 2 Each is independently the same as defined in formula (3).) R in formulas (1), (2), and (4) 1Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. Among them, a linear or branched alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 or 10 carbon atoms is preferred. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferred, and an alkyl group having 1 to 2 carbon atoms is more preferred. Specific examples of the alkyl group include, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, 2-methylpentyl, cyclohexyl, etc. As the aromatic hydrocarbon group having 6 to 10 carbon atoms, it may be substituted with an alkyl group having 1 to 4 carbon atoms, and the number of carbon atoms also includes the carbon atoms of the substituted alkyl group. Specifically, examples include: 4-methylphenyl, 4-isopropylphenyl, phenyl, naphthyl, etc.

[0023] In formulas (1), (2), and (4), m each independently represents an integer of 0 or 1 to 4. Among them, an integer of 0 or 1, 2 is preferred.

[0024] In formula (3), X represents a halogen atom. Specifically, for example, it is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Among them, a chlorine atom and a bromine atom are preferred, and a chlorine atom is more preferred.

[0025] R in formulas (3) and (4) 2 Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms. Among them, the carbon atom bonded to the oxygen atom is preferably a linear or branched alkyl group of primary or secondary carbon, more preferably a linear or branched alkyl group of primary carbon. Among them, a linear alkyl group is further preferred. As the alkyl group, an alkyl group having 1 to 8 carbon atoms is preferred, an alkyl group having 1 to 4 carbon atoms is more preferred, and an alkyl group having 1 to 2 carbon atoms is further preferred. Specifically, examples include: methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, etc.

[0026] In the production method of the present invention, specific examples of the 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene compound represented by formula (2) as the final target product include: 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene ("Compound A"), 2,2'-bis(carboxymethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(carboxymethoxy)-3,3'-dimethyl-1,1'-binaphthalene, 2,2'-bis(carboxymethoxy)-4,4'-dimethyl-1,1'-binaphthalene, etc.

[0027] In the production method of the present invention, specific examples of the haloacetate compound represented by formula (3) include, for example: methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, propyl bromoacetate, methyl iodoacetate, ethyl iodoacetate, propyl iodoacetate, etc. R in formula (3) may also be used in combination. 2Two or more different haloacetate bodies, but in order to simplify step (ii), it is preferable to use one haloacetate body.

[0028] <Step (i)> (Oxygen concentration) In step (i) of the production method of the present invention, an etherification reaction is carried out between a 1,1'-binaphthalene-2,2'-diol body represented by formula (1) and a haloacetate body represented by formula (3) in an environment or gas stream with an oxygen concentration of 6% by volume or less to produce a 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthalene body represented by formula (4). The oxygen concentration is preferably 5% by volume or less, more preferably 4.5% by volume or less, and further preferably 4% by volume or less.

[0029] In step (i), in an environment or gas stream with an oxygen concentration of 6% by volume or less, specifically, it is possible to cite the use of inert gases such as nitrogen, argon, and helium, or the use of a mixture of an inert gas such as nitrogen in air to make the oxygen concentration 6% or less. From the perspective of economy, it is preferable to mix air and an inert gas, more preferably to mix air and nitrogen. As the lower limit value of the oxygen concentration, it is preferably 1% by volume or more, more preferably 2% by volume or more.

[0030] (Reaction conditions) In step (i) of the production method of the present invention, relative to 1 mole of the 1,1'-binaphthalene-2,2'-diol body represented by formula (1), it is preferable to use 2.1 to 3.0 moles of the haloacetate body represented by formula (3), and more preferably 2.2 to 2.8 moles.

[0031] In step (i), it is preferable to form a salt of the 1,1'-binaphthalene-2,2'-diol body represented by formula (1) with a base and then react it with the haloacetate body represented by formula (3). As such a base, there is no particular limitation. In addition to alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, it is also suitable to use organic bases such as triethylamine and pyridine. Among them, sodium carbonate or potassium carbonate is preferred. The usage amount of this base is preferably 2.0 to 2.5 molar times, more preferably 2.05 to 2.15 molar times, relative to 1 mole of the 1,1'-binaphthalene-2,2'-diol body represented by formula (1).

[0032] As a method for salifying 1,1'-binaphthalene-2,2'-diol represented by formula (1) with a base, it is preferable to charge the 1,1'-binaphthalene-2,2'-diol represented by formula (1), the aforementioned base, and a reaction solvent described later into a reaction vessel, heat it with stirring, and maintain it for about 10 minutes to 1 hour to form a salt. In this salification method, it is more preferable to add a metal iodide described later to the reaction vessel to form a salt.

[0033] In step (i), it is preferable to use a linear or cyclic ketone solvent having 5 to 8 carbon atoms or a linear nitrile solvent having 2 to 6 carbon atoms. Specifically, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, 2-octanone, cyclopentanone, cyclohexanone, etc., and acetonitrile, propionitrile, etc. can be mentioned. Among them, methyl isobutyl ketone and acetonitrile are preferable. The usage amount of the solvent is preferably in the range of 150 to 500 parts by weight, more preferably in the range of 200 to 300 parts by weight, based on 100 parts by weight of the 1,1'-binaphthalene-2,2'-diol represented by formula (1).

[0034] The reaction temperature in step (i) is preferably in the range of 50 to 130 °C, more preferably in the range of 70 to 120 °C, and further preferably in the range of 90 to 110 °C. The reaction pressure is usually carried out at normal pressure, but it can also be carried out under pressure or reduced pressure in such a way that the reaction temperature is within the aforementioned range according to the boiling point of the solvent used. It is preferable to carry out the reaction at normal pressure.

[0035] As a method for reacting the salt formed by salifying 1,1'-binaphthalene-2,2'-diol represented by formula (1) with a base in step (i) of the production method of the present invention with a haloacetate represented by formula (3), it is preferable to add dropwise the haloacetate represented by formula (3) thereto with stirring at the aforementioned reaction temperature after salifying to carry out the reaction. In this method, it is more preferable when salifying is carried out by the aforementioned method. If the dropping time is too long, the corresponding reaction time will also become long. In addition, if the dropping time is too short due to the reaction scale or equipment, etc., it will be difficult to control the temperature due to heat generation. Therefore, the preferable dropping time is about 5 minutes to 2 hours, more preferably 10 minutes to 1 hour. In addition, when using a metal carbonate or / and a metal hydrogencarbonate as the base, since carbon dioxide is generated, when it is difficult to discharge carbon dioxide in a reaction vessel or situation, etc., from the viewpoint of the reaction rate, the dropping time is further preferably 20 minutes to 40 minutes, and particularly preferably about 30 minutes.

[0036] (Metal iodide) The etherification reaction in step (i) of the manufacturing method of the present invention is preferably carried out in the presence of an alkali metal iodide. Specific examples of the alkali metal iodide include potassium iodide, sodium iodide, cesium iodide, lithium iodide, etc. These can be used alone or in combination of two or more. Among them, potassium iodide and sodium iodide are preferred.

[0037] The usage amount of the alkali metal iodide is preferably in the range of 1 to 25 mol%, more preferably in the range of 2 to 15 mol%, further preferably in the range of 2.5 to 10 mol%, and particularly preferably in the range of 3 to 5 mol% based on the 1,1'-binaphthalene-2,2'-diol represented by formula (1).

[0038] <Step (ii)> Step (ii) in the manufacturing method of the present invention is a step of hydrolyzing the 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthalene represented by formula (4 obtained in step (i), and then performing acid treatment. As the 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthalene represented by formula (4) used in the hydrolysis reaction of step (ii), the reaction solution obtained from the etherification reaction of step (i) can be directly used, or the oil layer obtained by performing a water washing operation on the reaction solution can also be used. In addition, substances extracted in solid or crystalline form from the oil layer or the reaction solution by crystallization or the like can also be used.

[0039] (Hydrolysis) In the hydrolysis of the 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthalene represented by formula (4), an alkali is preferably used. Specific examples of the alkali used include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide. By using these, an alkali metal salt of the 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene represented by formula (2) can be obtained. Regarding the alkali used, it can be directly added to the reaction vessel in a solid state or in an aqueous solution state. When the alkali is used in an aqueous solution form, the concentration is preferably 10 to 60% by weight, more preferably 20 to 50% by weight. The usage amount of these alkalis is preferably 2.0 to 6.0 moles, more preferably 2.5 to 4.0 moles based on 1 mole of the 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthalene represented by formula (4).

[0040] Including the water contained in the aqueous solution of the added alkali, the amount of water used in the hydrolysis is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight based on 100 parts by weight of the 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthalene represented by formula (4).

[0041] The reaction temperature is usually in the range of 30 to 100 °C, preferably in the range of 50 to 90 °C, more preferably in the range of 60 to 80 °C. It is preferred to add or dropwise add the above-mentioned base or its aqueous solution while maintaining this temperature.

[0042] In the hydrolysis, a reaction solvent may not be used, but from the reasons such as the operability during industrial production or the improvement of the reaction rate, it is preferred to use a reaction solvent. As the reaction solvent, there is no particular limitation as long as it does not distill out of the reaction vessel at the reaction temperature and is inactive for the reaction. For example, it can be cited: chain or cyclic ketone solvents having 5 to 8 carbon atoms such as diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, 2-octanone, cyclopentanone, cyclohexanone; chain nitrile solvents having 2 to 6 carbon atoms such as acetonitrile, propionitrile. The amount of the solvent used is preferably 100 to 600 parts by weight, more preferably 130 to 400 parts by weight, relative to 100 parts by weight of the 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyl compound of formula (4).

[0043] (Acid treatment) In order to obtain the 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl compound by acid-treating the alkali metal salt of the 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl compound represented by formula (2) generated by the hydrolysis reaction, an acid can be added to the reaction solution containing the alkali metal salt. In addition, the alkali metal salt can be taken out in solid form by crystallization, dissolved in a solvent and then acid-treated. When using the reaction solution, the generated alcohol can be removed by distillation as needed.

[0044] Specific examples of the acid used include: inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid; or organic acids such as p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid. Hydrogen chloride is preferably used as concentrated hydrochloric acid. The amount of these acids used is preferably 2.2 to 4.0 moles, more preferably 2.5 to 3.0 moles, relative to 1 mole of the 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyl compound represented by formula (4) which is the raw material for the above hydrolysis reaction.

[0045] In addition, when using the reaction solution obtained from the hydrolysis reaction, when the number of moles of the unreacted base remaining due to the excessive use of the base is larger than the number of moles of the alkali metal salt, it is preferred to neutralize it and then use the above amount of acid.

[0046] When performing acid treatment, the solvent is preferably a chain or cyclic ketone solvent, more preferably a chain or cyclic ketone solvent having 5 to 8 carbon atoms, and even more preferably a chain ketone solvent having 5 to 8 carbon atoms. Specifically, for example, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, 2-octanone, cyclopentanone, and cyclohexanone can be mentioned. As the amount of the solvent used, relative to 100 parts by weight of the 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyl represented by the formula (4) or 100 parts by weight of the alkali metal salt of the 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by the formula (2) which is the raw material for the above hydrolysis reaction, it is preferably 250 to 1050 parts by weight, and more preferably 350 to 900 parts by weight.

[0047] The temperature of the acid treatment is generally in the range of 30 to 100 °C, preferably in the range of 50 to 90 °C, and more preferably in the range of 75 to 85 °C.

[0048] Preferably, after the acid treatment, a solvent separated from water or water is added as needed to separate the aqueous layer, and then water is added to the obtained oil layer, followed by stirring and standing, and a water washing operation of removing the aqueous layer one or more times is performed to reduce or remove the generated salt or acid from the oil layer.

[0049] <Step (iii)> (Crystallization) Step (iii) in the production method of the present invention is a step of crystallizing the 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by the formula (2) obtained in step (ii). The oil layer containing the 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by the formula (2) obtained in step (ii) can be crystallized to precipitate the 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, or the solvent can be removed from the oil layer by distillation or the like, a solvent is added to the obtained residual liquid and dissolved therein, or the solvent of the oil layer is replaced with another solvent for crystallization.

[0050] As the solvent used in crystallization, examples include: linear or cyclic ketone solvents, cyclic ether solvents, cyclic ester solvents. Preferred are linear or cyclic ketone solvents having 5 to 8 carbon atoms, cyclic ethers or cyclic esters having 4 to 8 carbon atoms, and more preferred are linear ketone solvents having 5 to 8 carbon atoms. Specifically, for example, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, 2-octanone, cyclopentanone, cyclohexanone, tetrahydrofuran, 1,4-dioxane, γ-butyrolactone, γ-valerolactone, etc. can be cited. Regarding the amount of the solvent used, in the case of a linear ketone having 5 to 8 carbon atoms, relative to 100 parts by weight of the 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by the formula (2) used in the step (iii), it is preferably 250 to 1000 parts by weight, more preferably 300 to 800 parts by weight, and further preferably 400 to 600 parts by weight. When the crystallization solvent is a cyclic ketone solvent, a cyclic ether solvent, or a cyclic ester solvent, as the amount thereof used, relative to 100 parts by weight of the 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by the formula (2) used in the step (iii), it is preferably 50 to 600 parts by weight, more preferably 50 to 400 parts by weight, and further preferably 100 to 200 parts by weight.

[0051] A solution obtained by dissolving the 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by the formula (2) in the above solvent or the like is prepared, and it is cooled or by a known method such as distilling off the solvent, whereby crystals of the 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by the formula (2) can be precipitated.

[0052] By performing crystallization under the above conditions and filtering out the precipitated crystals, a target product with good hue can be obtained. In terms of obtaining a target product with good hue, it is more preferred to further perform crystallization on the obtained target product, that is, to perform the crystallization in the step (iii) twice.

[0053] (Drying) The crystals obtained by the crystallization in the step (iii) are preferably dried. The drying method is not particularly limited, and air drying can be performed at room temperature. In order to prevent deterioration of purity or hue, it is preferably dried under reduced pressure or / and in an inert gas such as nitrogen. Industrially, it is preferably carried out at 70 to 110 °C.

[0054] In the production method of the present invention, it is preferred that all steps from step (ii) to step (iii) are carried out in an environment or air flow with an oxygen concentration of 6% by volume or less. The oxygen concentration is preferably 5% by volume or less, more preferably 4.5% by volume or less, and further preferably 4% by volume or less. It is particularly preferred to carry out in an inert gas environment or air flow such as nitrogen, argon, or helium, and a 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl with good hue can be obtained.

[0055] Examples Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0056] The analysis method is as follows.

[0057] <Analysis Method> 1. Confirmation of Purity Measuring apparatus: High performance liquid chromatography analyzer (manufactured by Shimadzu Corporation) Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A Chromatographic column: HALO-C18 Oven temperature: 50 °C Flow rate: 0.7 ml / min Detection wavelength: 280 nm Mobile phase: (A) Acetonitrile, (B) 0.1 vol% Aqueous phosphoric acid solution Gradient condition: (A) Volume % (time from the start of analysis) 30% (0 min) → 100% (12 min) → 100% (15 min) 2. Color phase (APHA) Dissolve the crystals in tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Corporation, purity 97% or more) to obtain a 30 wt% solution. After performing "standard calibration" of the following measuring instrument with tetrahydrofuran, measure the dissolved color of the 30 wt% solution.

[0058] Measuring instrument: TZ 6000 (manufactured by Nippon Denshoku Industries Co., Ltd.) <Example 1> Charge 60 g of 1,1'-binaphthalene-2,2'-diol, 150 g of methyl isobutyl ketone, 60.8 g of potassium carbonate, and 1.2 g of potassium iodide into a four-necked flask, perform nitrogen replacement, and confirm that the oxygen concentration is 0 vol% with an oxygen concentration meter. Heat up to 100 °C, distill 60 g of methyl isobutyl ketone under reduced pressure, and then repressurize with nitrogen, and confirm that the oxygen concentration is 0 vol%. After preparing a mixed solution of 56.9 g of ethyl chloroacetate and 0.5 g of N-methylpyrrolidone, add dropwise this mixed solution while maintaining the temperature of the reaction solution at 90 - 100 °C. After stirring for 10 hours, confirm that the oxygen concentration is 0 vol%, add 240 g of water, heat up to 80 °C, and then allow to stand to remove the aqueous layer (step i). The subsequent operations are also carried out in a nitrogen atmosphere.

[0059] After adding 180 g of methyl isobutyl ketone to the obtained oil layer, 52.3 g of 48% aqueous sodium hydroxide solution was added dropwise while maintaining the temperature of the reaction solution at 80 - 85°C. After stirring for 2 hours, 240 g of methyl isobutyl ketone was added to the reaction solution, and while maintaining the temperature of the reaction solution at 70 - 85°C, 240 g of methyl isobutyl ketone, ethanol, and water were distilled off under reduced pressure. 180 g of water and 318 g of methyl isobutyl ketone were added, 65.4 g of concentrated hydrochloric acid was added dropwise while maintaining the temperature at 80 - 85°C, and the mixture was stirred at the same temperature for 30 minutes. After standing, the aqueous layer was extracted, and the obtained oil layer was washed with water by adding water and stirring twice, and then the aqueous layer was separated and removed (step ii).

[0060] Next, water and 390 g of methyl isobutyl ketone were distilled off from the obtained oil layer under normal pressure. During the distillation, seeds obtained by a conventionally known production method were added at 95°C and the precipitation of crystals was confirmed. The mixture was cooled to 30°C at a cooling rate of 10°C per hour and filtered to obtain 75 g of 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene with APHA 60 (step iii).

[0061] (Recrystallization of the target product) 60 g of the crystals obtained from the above step (iii), 350 g of methyl isobutyl ketone, and 86 g of water were charged into a four-necked flask, purged with nitrogen, and the oxygen concentration was confirmed to be 0% with an oxygen concentration meter (subsequent operations were also carried out in a nitrogen atmosphere). Then, the temperature was raised to 85°C and stirred to dissolve it. After standing, the aqueous layer was extracted, and the obtained oil layer was washed with water by adding water and stirring once, and then the aqueous layer was separated and removed. Next, 200 g of water and methyl isobutyl ketone were distilled off from the obtained oil layer under normal pressure. During the distillation, seeds obtained by a conventionally known production method were added at 95°C and the precipitation of crystals was confirmed. Then, the crystallization solution was cooled to 25°C at a cooling rate of 10°C per hour and filtered, and then dried under reduced pressure to obtain 56.0 g of 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene with a purity of 99.9% and APHA 30.

[0062] <Example 2> 60 g of 1,1'-binaphthalene-2,2'-diol, 150 g of methyl isobutyl ketone, 60.8 g of potassium carbonate, and 1.2 g of potassium iodide were charged into a four-necked flask, and replaced with a mixed gas of air and nitrogen with an oxygen concentration of 3.5%. The oxygen concentration was confirmed to be 4 vol% in terms of oxygen concentration. After heating to 100 °C and distilling off 67 g of methyl isobutyl ketone under reduced pressure, the pressure was restored with the above mixed gas, and the oxygen concentration was confirmed to be 4 vol%. After preparing a mixed solution of 56.9 g of ethyl chloroacetate and 0.5 g of N-methylpyrrolidone, this mixed solution was added dropwise while maintaining the temperature of the reaction solution at 90 - 100 °C. After stirring for 10 hours, when the oxygen concentration was confirmed to be 4%, nitrogen replacement was carried out, and the oxygen concentration was confirmed to be 0%. The subsequent operations were carried out under a nitrogen atmosphere. 240 g of water was added to the reaction solution and heated to 80 °C, and then left to stand to remove the aqueous layer (step i).

[0063] To the obtained oil layer, 182 g of methyl isobutyl ketone was added, and 52.4 g of 48% aqueous sodium hydroxide solution was added dropwise while maintaining the temperature of the reaction solution at 80 - 85 °C. After stirring for 2 hours, 242 g of methyl isobutyl ketone was added to the reaction solution, and while maintaining the temperature of the reaction solution at 70 - 85 °C, 241 g of methyl isobutyl ketone, ethanol, and water were distilled off under reduced pressure. 180 g of water and 318 g of methyl isobutyl ketone were added, 65.2 g of concentrated hydrochloric acid was added dropwise while maintaining the temperature at 80 - 85 °C, and the mixture was stirred at the same temperature for 30 minutes. After standing, the aqueous layer was extracted, and a water washing operation of adding water to the obtained oil layer and stirring twice, and then separating and removing the aqueous layer was carried out (step ii).

[0064] Next, water and 408 g of methyl isobutyl ketone were distilled off from the obtained oil layer under normal pressure. During the distillation, seeds obtained by a conventionally known manufacturing method were added at 95 °C, and the precipitation of crystals was confirmed. The mixture was cooled to 30 °C at a cooling rate of 10 °C per hour, and filtered to obtain 79 g of 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene with an APHA of 70 (step iii).

[0065] (Recrystallization of the target product) 65 g of the crystals obtained from the above step (iii), 378 g of methyl isobutyl ketone, and 92 g of water were charged into a four-necked flask, and nitrogen replacement was carried out. The oxygen concentration was confirmed to be 0% with an oxygen concentration meter. Subsequent operations were also carried out in a nitrogen atmosphere. Then, the temperature was raised to 85 °C and stirred to dissolve it. After standing, the aqueous layer was extracted, and water was added to the obtained oil layer and stirred once, and the washing operation of separating and removing the aqueous layer was carried out. Next, 217 g of water and methyl isobutyl ketone were distilled off from the obtained oil layer under normal pressure. During the distillation, seeds obtained by a conventionally known production method were added at 95 °C and the precipitation of crystals was confirmed. Then, the crystallized liquid was cooled to 25 °C at a cooling rate of 10 °C per hour and filtered, and then dried under reduced pressure to obtain 61.7 g of 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene with a purity of 99.9% and APHA 30.

[0066] <Comparative Example 1> 60 g of 1,1'-binaphthalene-2,2'-diol, 150 g of methyl isobutyl ketone, 61.0 g of potassium carbonate, and 1.2 g of potassium iodide were charged into a four-necked flask, and replacement was carried out with instrument air. The temperature was raised to 100 °C, and after 63 g of methyl isobutyl ketone was distilled off under reduced pressure, the pressure was restored with air. After preparing a mixed solution of 56.9 g of ethyl chloroacetate and 0.5 g of N-methylpyrrolidone, this mixed solution was added dropwise while maintaining the temperature of the reaction solution at 90-100 °C. After stirring for 10 hours, nitrogen replacement was carried out, and the oxygen concentration was confirmed to be 0%. Subsequent operations were also carried out in a nitrogen atmosphere. 240 g of water was added and the temperature was raised to 80 °C, and then the aqueous layer was removed by standing.

[0067] To the obtained oil layer, 181 g of methyl isobutyl ketone was added, and 52.4 g of 48% aqueous sodium hydroxide solution was added dropwise while maintaining the temperature of the reaction solution at 80-85 °C. After stirring for 2 hours, 240 g of methyl isobutyl ketone, ethanol, and water were distilled off under reduced pressure while maintaining the temperature of the reaction solution at 70-85 °C. 180 g of water and 319 g of methyl isobutyl ketone were added, 69.5 g of concentrated hydrochloric acid was added dropwise while maintaining the temperature at 80-85 °C, and the mixture was stirred at the same temperature for 30 minutes. After standing, the aqueous layer was extracted, and water was added to the obtained oil layer and stirred twice, and then the washing operation of separating and removing the aqueous layer was carried out.

[0068] Next, water and 400 g of methyl isobutyl ketone were distilled off from the obtained oil layer under normal pressure. During the distillation, seeds obtained by a conventionally known production method were added at 95 °C and the precipitation of crystals was confirmed. It was cooled to 30 °C at a cooling rate of 10 °C per hour and filtered to obtain 77 g of 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene with APHA 370.

[0069] (Recrystallization of the target product) 60 g of the crystals of the target substance A, 356 g of methyl isobutyl ketone, and 86 g of water were charged into a four-necked flask, and nitrogen substitution was performed. The oxygen concentration was confirmed to be 0% with an oxygen concentration meter. Subsequent operations were also carried out in a nitrogen atmosphere. Then, the temperature was raised to 85 °C and stirred to dissolve it. After standing, the aqueous layer was extracted, and a water washing operation of adding water to the obtained oil layer, stirring, and then separating and removing the aqueous layer was performed once. Next, water and 210 g of methyl isobutyl ketone were distilled off from the obtained oil layer under normal pressure. During the distillation, seeds obtained by a conventionally known production method were added at 95 °C, and the precipitation of crystals was confirmed. Then, the crystallized liquid was cooled to 25 °C at a cooling rate of 10 °C per hour and filtered, and then dried under reduced pressure to obtain 57.6 g of 2,2'-bis(carboxymethoxy)-1,1'-binaphthalene with a purity of 99.9% and APHA 100.

Claims

1. A method for producing a 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by formula (2), characterized in that, using a 1,1'-binaphthalene-2,2'-diol represented by formula (1) as a starting material, and successively performing the following steps (i) to (iii), (i): A step of subjecting the 1,1'-binaphthalene-2,2'-diol represented by formula (1) and a haloacetate represented by formula (3) to an etherification reaction in an environment or gas stream with an oxygen concentration of 6% by volume or less to produce a 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyl represented by formula (4); (ii): A step of hydrolyzing the 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyl represented by formula (4) and then performing an acid treatment; (iii): A step of obtaining the 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by formula (2) by crystallization, [Chemical formula 1] In the formula, R 1 each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and m each independently represents 0 or an integer of 1 to 4. [Chemical formula 2] wherein, R 1 , m are the same as defined in formula (1), [Chemical formula 3] In the formula, X represents a halogen atom, and R 2 represents a linear or branched alkyl group having 1 to 10 carbon atoms, [Chemical formula 4] wherein, R 1 , m are the same as defined in formula (1), and R 2 are each independently the same as defined in formula (3).

2. The method for producing a 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl according to claim 1, characterized in that, crystallization in step (iii) is carried out twice.

3. The method for producing a 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl according to claim 1, characterized in that, all of steps (ii) to (iii) are carried out in an environment or gas stream of an inert gas.

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