Method for producing binaphthyl carboxylic acids

Abstract

The present invention addresses the problem of providing a production method by which high purity 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl can be obtained. A solution to this problem is a method for producing 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by formula (2), the method being characterized by using a 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyl compound represented by formula (1) as a starting material and carrying out steps (i) to (iv) in the stated order. (i) A hydrolysis step; (ii) a step for distilling off a generated alcohol represented by formula (3) from the reaction system; (iii) a step for rendering the reaction liquid acidic; and (iv) a step for precipitating 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl in the presence of an organic solvent.

Description

[Technical field]

[0001] The present invention relates to a method for producing binaphthyl carboxylic acids. [Background technology]

[0002] In recent years, polyester resins and polyester carbonate resins, which use a dicarboxylic acid component having a binaphthalene skeleton as a polymerization component, have excellent optical properties such as a high refractive index and low birefringence, and are equipped with high heat resistance, and therefore are expected to be used as raw materials for optical components such as optical disks, transparent conductive substrates, and optical filters. Among them, resins produced using 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, which has a chemical structure represented by the following chemical formula, as a polymerization component have been attracting attention as being particularly excellent in optical properties (e.g., Patent Documents 1 to 3, etc.). [ka] Known methods for producing 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by the above chemical formula include a method of reacting 1,1'-binaphthalene-2,2'-diol with a halogenated acetate ester as shown in the following reaction formula, and a method of hydrolyzing the diester obtained by the above method. [ka] The present inventors have noticed for the first time that when the reaction solution is acidified after the above-mentioned hydrolysis reaction, if the reaction solution contains an alcohol, the carboxylic acid of 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl reacts with the alcohol to produce an ester, resulting in a decrease in the yield and purity of 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2018-002893 A [Patent Document 2] JP 2018-002894 A [Patent Document 3] JP 2018-002895 A Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a production method capable of obtaining highly pure 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl. [Means for solving the problem]

[0005] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that high-purity 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl can be obtained by distilling off the alcohol derived from the ester from the reaction system after the hydrolysis reaction, then acidifying the reaction solution, and precipitating 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl in the presence of an organic solvent, and have thus completed the present invention.

[0006] The present invention is as follows. 1. A method for producing 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by the following formula (2), which comprises using 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyl represented by the following formula (1) as a starting material and carrying out the following steps (i) to (iv) in order. (i) a hydrolysis reaction step, (ii) The resulting alcohol represented by the following formula (3) is distilled off from the reaction system: A process of (iii) acidifying the reaction solution; (iv) 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl in the presence of an organic solvent. [ka] (In the formula, each R is independently an alkyl group having 1 to 8 carbon atoms.) [ka] [ka] (In the formula, each R is independently an alkyl group having 1 to 8 carbon atoms.) 2. A method for producing 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl according to 1., comprising a reaction step of reacting 1,1'-binaphthalene-2,2'-diol with a halogenated acetate ester represented by the following formula (4) to obtain 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyl represented by the formula (1): [ka] (In the formula, X represents a halogen atom, and R represents an alkyl group having 1 to 8 carbon atoms.) Effect of the Invention

[0007] According to the present invention, the problem of the conventional hydrolysis reaction in which an ester-derived alcohol reacts with 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl to produce an ester and reduce the purity is eliminated, and high-purity 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl can be obtained. INDUSTRIAL APPLICABILITY The production method of the present invention is extremely useful in the industrial production of resin raw materials and the like, since it allows the production of high-purity 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The present invention will be described in detail below. The production method of the present invention is a method represented by the following reaction formula, and is characterized in that the above steps (i) to (iv) are carried out in the same reaction vessel in this order. Hereinafter, 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyls represented by the following formula (1) will be referred to as "diesters (1)", 2,2'-bis(carboxymethoxy)-1,1'-binaphthyls represented by the following formula (2) will be referred to as "target product A", and alcohols represented by the following formula (3) will be referred to as "alcohols". [ka] (In the formula, each R is independently an alkyl group having 1 to 8 carbon atoms.)

[0009] <Reaction process for obtaining diester (1)> The "diesters (1)" in the present invention can be obtained by a method of reacting 1,1'-binaphthalene-2,2'-diol with a halogenated acetate ester represented by the following formula (4) (hereinafter referred to as "esters (4)"), as shown in the following reaction formula: [ka] (In the formula, each R is independently an alkyl group having 1 to 8 carbon atoms.)

[0010] (Esters (4)) "R" in the formula of ester (4) used in the synthesis of diester (1) is an alkyl group having 1 to 8 carbon atoms, and specific examples thereof include linear alkyl groups such as methyl, ethyl, and n-propyl groups, and branched alkyl groups in which the carbon bonded to the oxygen atom is a primary or secondary carbon, such as i-propyl and i-butyl groups. Among these, alkyl groups having 1 to 3 carbon atoms are preferred, and linear alkyl groups are more preferred. Similarly, "X" in the formula is a halogen atom, and is preferably a chlorine atom, a bromine atom, or an iodine atom. In the synthesis of the diester (1), two or more kinds of esters (4) having different alkyl ester moieties may be used in combination, but it is preferable to use one kind of ester (4) in order to simplify purification. The amount of the ester (4) used is not particularly limited as long as it is equal to or greater than the theoretical value (2.0) as a molar ratio relative to 1,1'-binaphthalene-2,2'-diol, but is usually 2 moles or more, preferably 2.1 to 3.0 moles, and more preferably 2.2 to 2.8 moles.

[0011] (Reaction Solvent) The synthesis of the diester (1) does not require the use of a reaction solvent, but it is preferable to use one for reasons such as improved operability and reaction rate during industrial production. The reaction solvent is not particularly limited as long as it is not distilled from the reaction vessel at the reaction temperature and is inactive in the reaction, and examples thereof include chain or cyclic ketone solvents having 5 to 8 carbon atoms, such as diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, 2-octanone, cyclopentanone, and cyclohexanone, and chain nitrile solvents having 2 to 6 carbon atoms, such as acetonitrile and propanenitrile. Each of these reaction solvents may be used alone, or two or more of them may be used in combination as appropriate to adjust the polarity. Among them, methyl isobutyl ketone and acetonitrile are preferable. The amount of the reaction solvent used is preferably within a range from 150 to 500 parts by weight, and more preferably from 200 to 300 parts by weight, per 100 parts by weight of 1,1'-binaphthalene-2,2'-diol.

[0012] (base) The synthesis of the diester (1) is preferably carried out by forming a salt from 1,1'-binaphthalene-2,2'-diol with a base, and then reacting it with the ester (4). Such a base is not particularly limited, but for example, alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, etc., alkali metal hydrogen carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate, etc., alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc., as well as organic bases such as triethylamine and pyridine, etc. may be suitably used. These may be used alone or in combination of two or more. Among them, sodium carbonate and potassium carbonate are preferred. The amount of the base used is preferably 2.0 to 2.5 mol, more preferably 2.05 to 2.15 mol, per 1 mol of 1,1'-binaphthalene-2,2'-diol. (alkali metal iodides) In the synthesis of the diester (1), the reaction can be carried out in the presence of an alkali metal iodide. Specific examples of the alkali metal iodide include potassium iodide, sodium iodide, cesium iodide, and lithium iodide. These may be used alone or in combination of two or more. The amount of the alkali metal iodide used 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 %, relative to 1 mol of 1,1'-binaphthalene-2,2'-diol.

[0013] (Reaction temperature, pressure) The reaction temperature is usually 50 to 150°C, preferably 70 to 130°C, more preferably 90 to 110°C. If the reaction temperature is high, the yield decreases due to hydrolysis of the diester (1) produced, and if the reaction temperature is low, the reaction rate decreases, which is undesirable. The reaction is usually carried out under normal pressure, but depending on the boiling point of the organic solvent used, the reaction may be carried out under increased or reduced pressure so that the reaction temperature falls within the above range. (End point of reaction) The end point of the reaction can be confirmed by liquid chromatography or gas chromatography analysis. The end point of the reaction is preferably the time when the unreacted 1,1'-binaphthalene-2,2'-diol disappears and the increase in the diester (1) is no longer observed. The reaction time varies depending on the reaction conditions such as the reaction temperature, but is usually completed within about 1 to 30 hours. After the reaction is completed, water is added to the reaction solution, the mixture is stirred, and the mixture is left to stand to separate the aqueous layer. This washing operation is carried out two or more times to remove inorganic salts in the reaction solution. The amount of water used in each washing operation is preferably in the range of 150 to 600 parts by weight, more preferably in the range of 200 to 400 parts by weight, relative to 100 parts by weight of the 1,1'-binaphthalene-2,2'-diol used, and the temperature is preferably in the range of 60 to 100°C, more preferably in the range of 70 to 90°C. As for the stirring, it is sufficient that the oil layer is in sufficient contact with the aqueous layer, and the required time varies depending on the apparatus, but usually about 30 minutes is sufficient.

[0014] <(i) Hydrolysis reaction step> (Reaction Solvent) The "(i) hydrolysis reaction step" in the present invention can be carried out, for example, using a solution obtained after completion of the synthesis reaction of the diester (1) and completion of the water washing operation. When the "(i) hydrolysis reaction step" of the present invention is carried out using purified diester (1), it is preferable to use a mixed solvent of an organic solvent and water as the reaction solvent. Specific examples of the organic solvent to be used include chain or cyclic ketone solvents having 5 to 8 carbon atoms, such as diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, 2-octanone, cyclopentanone, and cyclohexanone, and chain nitrile solvents having 2 to 6 carbon atoms, such as acetonitrile and propanenitrile. The amount of the organic solvent to be 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 diester (1). The amount of water to be used is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight, relative to 100 parts by weight of the diester (1).

[0015] (base) A base is used to hydrolyze the diester (1). Specific examples of the base used include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and the use of these bases makes it possible to obtain an alkali metal salt as the metal salt (2). The base used may be used as a solid or in the form of an aqueous solution. When the base is used as an aqueous solution, the concentration is preferably 10 to 60% by weight, and more preferably 20 to 50% by weight. The amount of the base used is preferably 2.0 to 6.0 mol, more preferably 2.5 to 4.0 mol, per mol of the diester (1). (Reaction temperature) The reaction temperature is usually in the range of 30 to 100° C., preferably 50 to 90° C., more preferably 60 to 80° C., and it is preferable to add or dropwise add the above-mentioned base or an aqueous solution thereof while maintaining this temperature. The reaction usually completes in about 1 to 10 hours.

[0016] <(ii) Step of distilling off the produced alcohol represented by formula (3) from the reaction system> The production method of the present invention is characterized by having a step of distilling off the "alcohol" produced by the hydrolysis reaction from the reaction system after the above-mentioned (i) hydrolysis reaction step. (temperature) The temperature at which the "alcohol" is distilled off from the reaction system is preferably in the range of 40 to 130°C, more preferably in the range of 60 to 100°C, and even more preferably in the range of 70 to 90°C. (pressure) The pressure for distilling off the "alcohol" from the reaction system may be normal pressure or reduced pressure, but in the case of industrial implementation, it is preferable to carry out the reaction under reduced pressure since the solvent can be distilled off more efficiently. (solvent) When the "alcohol" is distilled off from the reaction system, an organic solvent may be added to the reaction system as necessary. Examples of the solvent to be added include chain ketone solvents having a total carbon number of 5 to 8, such as diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl hexyl ketone, and 2-octanone. (Distillate amount) When the "alcohol" is distilled off from the reaction system, the amount of the distilled off portion, including the "alcohol" to be distilled off and the organic solvent added to the reaction system as necessary, is preferably in the range of 150 to 450 parts by weight, more preferably 200 to 300 parts by weight, per 100 parts by weight of the diester (1).

[0017] <(iii) Step of making the reaction solution acidic> The production method of the present invention is characterized by having a step of acidifying the reaction solution after the step (ii) of distilling off the generated alcohol represented by formula (3) from the reaction system. Specific examples of the acid used in the step of acidifying the reaction solution include inorganic acids such as hydrogen chloride, hydrogen bromide, and sulfuric acid, and organic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. The amount of these acids used is preferably 2.2 to 4.0 mol, more preferably 2.5 to 3.0 mol, per mol of the diester (1). When concentrated hydrochloric acid is used as the acid, the amount used is preferably 2.2 to 4.0 mol, more preferably 2.5 to 3.0 mol, calculated as hydrogen chloride, per 1 mol of the diester (1). Specific examples of the reaction solvent in the step of acidifying the reaction solution include linear or cyclic ketone solvents having 5 to 8 carbon atoms, such as diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, 2-octanone, cyclopentanone, cyclohexanone, etc. The amount of the reaction solvent used is preferably 250 to 1050 parts by weight, more preferably 350 to 900 parts by weight, based on 100 parts by weight of the diester (1).

[0018] <(iv) Step of Precipitating 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl in the Presence of an Organic Solvent> The production method of the present invention is characterized by comprising a step of precipitating the target product A in the presence of an organic solvent after the step (iii) of acidifying the reaction solution. After the step (iii) of acidifying the reaction solution and before the step (iv) of precipitating the target product A, it is preferable to wash the reaction solution with water, and more preferably to wash the reaction solution with water once or multiple times to such an extent that the aqueous layer after the washing operation is neutral to weakly acidic. In addition, in the production method of the present invention, the step (iv) is preferably an embodiment in which 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl is crystallized in the presence of an organic solvent. (solvent) The step of precipitating the target substance A is carried out at least in the presence of an organic solvent. It can be carried out not only in the presence of an organic solvent but also in the presence of a mixture of an organic solvent and water. Among them, it is preferable to precipitate the target substance A in the presence of any of the following solvents (a) to (e): (a) one or more selected from chain ketone solvents having a total carbon number of 5 to 8, (b) one or more selected from cyclic ketone solvents having a total carbon number of 5 to 8, (c) one or more selected from cyclic ether solvents having a total carbon number of 4 to 8, (d) one or more selected from cyclic ester solvents having a total carbon number of 4 to 8, or (e) a mixed solvent of water and one or more selected from chain ketone solvents having a total carbon number of 3 to 8. Among these, methyl isobutyl ketone, methyl amyl ketone, and 2-octanone, which have low solubility in water, are preferred, and the amount of the chain ketone solvent used to dissolve the target A is preferably 250 to 1000 parts by weight, more preferably 300 to 800 parts by weight, and even more preferably 400 to 600 parts by weight, relative to 100 parts by weight of the target A contained in the crystals or solution used. The amount of the cyclic ketone solvent, cyclic ether solvent, and cyclic ester solvent used to dissolve the target A is preferably 50 to 600 parts by weight, more preferably 50 to 400 parts by weight, and even more preferably 100 to 200 parts by weight, relative to 100 parts by weight of the target A contained in the crystals or solution used. (temperature) The temperature for precipitating the target substance A is preferably 90 to 130°C, more preferably 95 to 105°C, when, for example, methyl isobutyl ketone, methyl amyl ketone, 2-octanone or the like is used. The target substance A may be precipitated by dissolving the target substance A in an organic solvent and cooling the solution as it is, or the crystals may be precipitated while distilling off the organic solvent from the solution by distillation. The time required for distilling off the solvent is preferably 2 to 15 hours, more preferably 4 to 10 hours, and even more preferably 6 to 8 hours. In the step of precipitating the target product A, it is preferable to cool after or while precipitating the crystals, and the cooling rate is preferably 5 to 15°C per hour, more preferably 7 to 12°C. In addition, when precipitating the crystals, it is not necessary to use seed crystals, but it is preferable to use seed crystals, and crystals precipitated without seed crystals may be used as seed crystals. The final cooling temperature is preferably 20 to 60°C, more preferably 25 to 35°C. After cooling to the above temperature, the precipitated crystals are separated by a filtration operation.

[0019] <Drying> In the production method of the present invention, it is preferable to dry the crystals obtained after the step (iv) of precipitating the target product A. By drying, the solvent used in the step (iv) of precipitating the target product A can be removed. This drying can be performed on the crystals obtained by crystallization under reduced pressure, preferably at 60 to 120°C, more preferably at 70 to 110°C under reduced pressure. Drying can be performed under normal pressure or reduced pressure, but when carried out industrially, it is preferable to perform drying under reduced pressure, because the solvent used in the step (iv) of precipitating the target product A can be removed more efficiently. EXAMPLES

[0020] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The analysis method is as follows. <Analysis method> 1. Confirmation of the concentration of target substance A in the reaction solution, reaction yield, and reaction end point After measurement under the conditions below, the purity (%) of the target compound A obtained in the examples and comparative examples was calculated using the liquid chromatography calibration curve of the target compound. Measurement equipment: High-performance liquid chromatography analyzer (manufactured by Shimadzu Corporation) Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A Column: HALO-C18 Oven temperature: 50℃ Flow rate: 0.7ml / min Mobile phase: (A) acetonitrile, (B) 0.1 vol% phosphoric acid water Gradient conditions: (A) Volume % (time from start of analysis) 30%(0min)→100%(12min)→100%(15min) Detection wavelength: 280nm

[0021] <Example 1> The manufacturing method of the present invention 300g of 1,1'-binaphthalene-2,2'-diol, 750g of methyl isobutyl ketone, 304.1g of potassium carbonate, and 6.0g of potassium iodide were charged into a four-neck flask, heated to 100°C, and stirred at the same temperature for 2 hours. After stirring, 300g of methyl isobutyl ketone was distilled under reduced pressure, and then a mixed solution of 282.5g of ethyl chloroacetate and 2.5g of N-methylpyrrolidone was prepared, and this mixed solution was added dropwise while keeping the temperature of the reaction liquid at 90-100°C. After stirring for 10 hours, 2400g of water was added and the temperature was raised to 80°C, and then the mixture was left to stand and the water layer was removed. 900g of methyl isobutyl ketone was added to the obtained oil layer, and 261.9g of 48% aqueous sodium hydroxide solution was added dropwise while keeping the temperature of the reaction liquid at 80-85°C (step (i)). After stirring for 2 hours, 1200 g of methyl isobutyl ketone was added to the reaction solution, and 1200 g of methyl isobutyl ketone, ethanol and water were distilled off under reduced pressure (final reduced pressure: 65 kPa) while maintaining the temperature of the reaction solution at 70 to 85°C (step (ii)). 900 g of water and 1,590 g of methyl isobutyl were added, and 327.8 g of concentrated hydrochloric acid was added dropwise while maintaining at 80 to 85°C, followed by stirring at the same temperature for 30 minutes (step (iii)). After standing, the aqueous layer was removed, and water was added to the resulting oil layer and stirred. This water washing operation of separating and removing the aqueous layer was repeated several times until the pH of the aqueous layer reached 4. Next, 1954 g of water and methyl isobutyl ketone were distilled from the oil layer obtained under normal pressure. During the distillation, seed crystals obtained by a conventionally known manufacturing method were added at 95°C, and crystal precipitation was confirmed (step (iv)). The mixture was cooled to 30°C at a cooling rate of 10°C per hour, filtered, and then dried to obtain 385.3 g of the first crystallized product A (yield: 91.4%, purity: 99.7%, monoethyl ester (one of the carboxylic acids of the product A reacted with alcohol): 0.2%). (Crystallization of target product A) 30.0g of the obtained crystals of target A, 183.9g of methyl isobutyl ketone, and 9.8g of water were charged into a four-neck flask, and the temperature was raised to 85°C to dissolve. Then, 119.6g of water and methyl isobutyl ketone were distilled under normal pressure. During the distillation, at 95°C, seed crystals obtained by a conventionally known manufacturing method were added to confirm the precipitation of crystals. After this, the crystallization solution was cooled to 25°C at a cooling rate of 10°C per hour, filtered, and then dried under reduced pressure to obtain 24.8g of the second crystallization of target A (yield: 86.7%, purity: 99.9%, monoethyl ester: 0.08%).

[0022] <Comparative Example 1> Production method 1 different from the production method of the present invention: No step (ii) 35g of 1,1'-binaphthalene-2,2'-diol, 52.5g of methyl isobutyl ketone, 35.5g of potassium carbonate, and 0.7g of potassium iodide were charged into a four-neck flask, heated to 100°C, and stirred at the same temperature for 2 hours. After preparing a mixed solution of 33.0g of ethyl chloroacetate and 0.3g 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, 140g of water was added and the temperature was raised to 80°C, and the water layer was removed. Next, 105.0g of methyl isobutyl ketone was added, and 30.6g of 48% aqueous sodium hydroxide solution was added dropwise while maintaining the reaction solution temperature at 80-85°C (step (i)). After 2 hours, 185.5 g of methyl isobutyl ketone and 105.0 g of water were added to the reaction liquid, and then 38.2 g of concentrated hydrochloric acid was added dropwise while maintaining the temperature at 80 to 85° C., followed by stirring at the same temperature for 30 minutes (step (iii)). After standing, the aqueous layer was removed, water was added to the obtained oil layer, and the mixture was stirred. The aqueous layer was separated and removed, and this water washing operation was repeated several times until the pH of the aqueous layer reached 4. Then, under normal pressure, 231.6 g of water and methyl isobutyl ketone were distilled from the obtained oil layer by distillation. During the distillation, seed crystals obtained by a conventionally known manufacturing method were added at 95°C to confirm the precipitation of crystals (step (iv)). After this, the solution from which the crystals were precipitated was cooled to 25°C at a cooling rate of 10°C per hour and filtered to obtain 51.5 g of the first crystallized product A (purity: 98.3%, monoethyl ester: 1.6%). (Crystallization of target product A) 30.0g of the obtained crystals of target A, 183.9g of methyl isobutyl ketone, and 9.8g of water were charged into a four-neck flask, and the temperature was raised to 85°C to dissolve. Then, 119.6g of water and methyl isobutyl ketone were distilled under normal pressure. During the distillation, at 95°C, seed crystals obtained by a conventionally known manufacturing method were added to confirm the precipitation of crystals. After this, the crystallization solution was cooled to 25°C at a cooling rate of 10°C per hour, filtered, and then dried under reduced pressure to obtain 24.8g of the second crystallization of target A (yield: 86.4%, purity: 99.2%, monoethyl ester: 0.7%).

[0023] The first crystallization of Example 1 has a purity of 99.7% and a monoethyl ester content of 0.2%. In contrast, the first crystallization of Comparative Example 1 has a purity of 98.3% and a monoethyl ester content of 1.6%, and the second crystallization also has a purity of 99.2% and a monoethyl ester content of 0.7%. From these results, it was confirmed that the production method of the present invention including step (ii) is an excellent production method capable of obtaining high-purity 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl.

[0024] <Comparative Example 2> Production method 2 different from the production method of the present invention: No step (iv) 1.0 g of 2,2'-bis(ethoxycarbonylmethoxy)-1,1'-binaphthyl was dissolved in 30 mL of a 20% aqueous solution of sodium hydroxide in ethanol (ethanol:water=80:20, volume ratio), and the solution was refluxed for 2 hours (step (i)). Ethanol was distilled off from the reaction mixture, and the mixture was cooled (step (ii)). Water was added to the obtained oil layer, and the pH was adjusted to 1 with concentrated hydrochloric acid (step (iii)). The precipitated crystals were filtered off, and the resulting solution was dried over sodium sulfate in ethyl acetate, after which the solvent was distilled off to obtain target product A. The obtained target product A had a purity of 99.6% and contained 0.2% of monoethyl ester, as calculated based on the peak area of ​​liquid chromatography. The first crystallization of target product A obtained in Example 1 had a purity of 99.95% and contained 0.02% of monoethyl ester, as calculated based on the peak area of ​​liquid chromatography.

Claims

1. A method for producing 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl represented by the following formula (2), which comprises using 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyl represented by the following formula (1) as a starting material and carrying out the following steps (i) to (iv) in order: (i) a hydrolysis reaction step using a base; (ii) removing the produced alcohol represented by the following formula (3) from the reaction system under reduced pressure; (iii) acidifying the reaction solution; (iv) A step of precipitating 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl in the presence of an organic solvent. 【Chemistry 1】 (In the formula, each R is independently an alkyl group having 1 to 8 carbon atoms.) 【Chemistry 2】 【Chemistry 3】 (In the formula, each R is independently an alkyl group having 1 to 8 carbon atoms.)

2. The method for producing 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl according to claim 1, comprising a reaction step of reacting 1,1'-binaphthalene-2,2'-diol with a halogenated acetate ester represented by the following formula (4) to obtain a 2,2'-bis(alkoxycarbonylmethoxy)-1,1'-binaphthyl represented by the formula (1): 【Chemistry 4】 (In the formula, X represents a halogen atom, and R represents an alkyl group having 1 to 8 carbon atoms.)

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