Method for producing dicarboxylic acids and their derivatives

Abstract

To produce a dicarboxylic acid that has high purity, resists being colored, and includes a 9,9-bis(fused polycyclic aryl) fluorene skeleton, with high handleability and high efficiency.SOLUTION: In the presence of a palladium (II) catalyst, a dicarboxylic acid having a fluorene skeleton or a derivative thereof is subjected to a coupling reaction with a compound having a fused polycyclic arene skeleton, producing a dicarboxylic acid represented by the following formula (1) or a derivative thereof (where, ring Z1 and ring Z2 each denote a fused polycyclic arene ring, R1 and R2 each denote a substituent, m1 and m2 each denote an integer of 0 or greater, A1 and A2 each denote a linear or branched alkylene group, R3 and R4 each denote a substituent, and n1 and n2 each denote an integer of 0-3).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a dicarboxylic acid having a bis(fused polycyclic aryl)fluorene skeleton and a derivative thereof. [Background technology]

[0002] Dicarboxylic acids or their derivatives (dicarboxylic acids) have high refractive indexes and heat resistance, and are therefore used as resin raw materials, additives (or resin additives) such as refractive index improvers and heat resistance improvers. In particular, dicarboxylic acids having a fluorene skeleton have high refractive indexes and heat resistance, and are therefore used as materials in the optical field.

[0003] As a method for producing such dicarboxylic acids having a fluorene skeleton, Patent Document 1 discloses a method in which a compound having a fluorene skeleton and a compound having an arene ring skeleton are subjected to a coupling reaction to introduce an aryl group corresponding to the compound having the arene ring skeleton into at least one substitution position selected from positions 2 to 8 of the fluorene skeleton. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2020 / 213470 issue Summary of the Invention [Problem to be solved by the invention]

[0005] However, in recent years, in the optical field, with the increasing performance of optical devices such as cameras and image display devices, advanced optical properties and heat resistance are required, and it has been difficult to efficiently produce the dicarboxylic acids with high purity and little coloration using the production method of Patent Document 1. Furthermore, in the examples of Patent Document 1, dimethoxyethane is used as the solvent and tetrakis(triphenylphosphine)palladium(0) is used as the catalyst, but it has been found that not only are the dicarboxylic acids not efficiently produced in this example, but the catalyst is easily deactivated and the operability is poor.

[0006] Therefore, an object of the present invention is to provide a method for efficiently producing dicarboxylic acids having a bis(fused polycyclic aryl)fluorene skeleton, which are highly pure, have reduced coloration, and are easy to handle (operate). [Means for solving the problem]

[0007] As a result of intensive research to achieve the above object, the present inventors have found that dicarboxylic acids having a bis(fused polycyclic aryl)fluorene skeleton can be efficiently produced with high purity, reduced coloration, and high handleability by subjecting a dicarboxylic acid having a fluorene skeleton or a derivative thereof to a coupling reaction with a compound having a fused polycyclic arene skeleton in the presence of a palladium (II) catalyst, and have completed the present invention.

[0008] That is, the production method according to embodiment [I] of the present invention comprises the steps of:

[0009] [ka]

[0010] (In the formula, Ring Z 1 and ring Z 2 each independently represents a fused polycyclic arene ring; R 1 and R 2 each independently represents a substituent, m1 and m2 independently represent an integer of 0 or more, A 1 and A 2 each independently represents a linear or branched alkylene group; R 3 and R 4 each independently represents a substituent, and n1 and n2 independently represent an integer of 0 to 3. A method for producing a dicarboxylic acid represented by the formula: In the presence of a palladium (II) catalyst,

[0011] [ka]

[0012] [where, X 1 and X 2 independently represent reactive groups capable of forming a carbon-carbon bond by a coupling reaction, and A 1 , A 2 , R 3 , R 4 , n1 and n2 are the same as in equation (1)] or a derivative thereof, and a dicarboxylic acid represented by the following formulas (3a) and (3b):

[0013] [ka]

[0014] [where, X 3 and X 4 independently represent reactive groups capable of forming a carbon-carbon bond by a coupling reaction, and ring Z 1 , ring Z 2 , R 1 , R 2 , m1 and m2 are the same as in equation (1)] and a fused polycyclic arene compound represented by the formula (1) to obtain a dicarboxylic acid represented by the formula (1) or a derivative thereof.

[0015] Aspect [II] of the present invention is an aspect in which the coupling reaction in the reaction step of aspect [I] is carried out in the presence of a reaction solvent containing an aprotic solvent.

[0016] Aspect [III] of the present invention is an aspect in which the aprotic solvent in aspect [II] contains a ketone.

[0017] Aspect [IV] of the present invention is an aspect in which the production method further comprises a purification step of crystallizing the dicarboxylic acid represented by formula (1) or its derivative obtained in the reaction step using a crystallization solvent containing an aprotic solvent and a protic solvent. Aspect [IV] is applicable to any of Aspects [I] to [III].

[0018] Aspect [V] of the present invention is an aspect in which, in the purification step of Aspect [IV], the dicarboxylic acid represented by the formula (1) or its derivative is treated with activated carbon and then crystallized. Aspect [V] is applicable to any of Aspects [I] to [IV].

[0019] The embodiment [VI] of the present invention is a compound in which, in the formula (1), ring Z 1 and Z 2 is a naphthalene ring, and A 1 and A 2 is a linear or branched chain C 2-6 In this embodiment, the alkylene group is an alkylene group. The embodiment [VI] is applicable to any of the embodiments [I] to [V].

[0020] The embodiment [VII] of the present invention is a compound in which, in the formula (1), ring Z 1 and Z 2 The substitution positions of A are the 2- and 7-positions of the fluorene ring. 1 and A 2 is a linear or branched chain C 2-4 It is an embodiment in which m1, m2, n1 and n2 are alkylene groups, and m1, m2, n1 and n2 are 0. The embodiment [VII] is applicable to any of the embodiments [I] to [VI].

[0021] In this specification and claims, the term "derivative" of a dicarboxylic acid is used to mean not only ester (or amide)-forming derivatives such as dicarboxylic acid esters, dicarboxylic acid halides, and dicarboxylic acid anhydrides, but also compounds that can be converted from dicarboxylic acids by conventional methods, such as dicarboxylic acid amides and dicarboxylic acid salts.

[0022] The dicarboxylic acid ester may be a dicarboxylic acid alkyl ester, particularly a lower alkyl ester, such as a C ester such as a methyl ester, an ethyl ester, or a t-butyl ester. 1-4 Examples of the dicarboxylic acid halide include dicarboxylic acid chloride and dicarboxylic acid bromide. Examples of the dicarboxylic acid salt include metal salts, specifically alkali metal salts such as sodium salts, and ammonium salts.

[0023] Furthermore, in the present specification and claims, the number of carbon atoms in a substituent may be C1, C6, C 10 For example, "C1 alkyl group" means an alkyl group with 1 carbon atom, and "C 6-10 The term "aryl group" refers to an aryl group having 6 to 10 carbon atoms. [Effects of the Invention]

[0024] According to the production method of the present invention, dicarboxylic acids having a bis(fused polycyclic aryl)fluorene skeleton can be produced efficiently with high purity, reduced coloration, and high ease of handling. DETAILED DESCRIPTION OF THE INVENTION

[0025] In the present invention, the dicarboxylic acid represented by the formula (2) or a derivative thereof [hereinafter also referred to as "dicarboxylic acid (2)] is subjected to a coupling reaction with the fused polycyclic arene compounds represented by the formulas (3a) and (3b) [hereinafter also referred to as "fused polycyclic arene compounds (3a) and (3b)] in the presence of a palladium (II) catalyst to obtain the dicarboxylic acid represented by the formula (1) or a derivative thereof [hereinafter also referred to as "dicarboxylic acid (1)], thereby producing the dicarboxylic acid (1).

[0026] [Dicarboxylic acids (1)] In the formula (1), ring Z 1 and ring Z 2 Examples of the fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring) represented by the formula (I) include fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. Examples of the fused bicyclic arene ring include fused bicyclic C rings such as naphthalene rings and indene rings. 9-16 Examples of the fused tricyclic arene ring include an anthracene ring and a phenanthrene ring.

[0027] These fused polycyclic arene rings can be used alone or in combination of two or more. 1 The type of ring Z 2 Among these, fused polycyclic C rings such as naphthalene ring and anthracene ring are preferred. 10-16 An arene ring is preferred, and a fused polycyclic C 10-14 An arene ring is more preferred, and a naphthalene ring is most preferred. 1 and ring Z 2 The substitution positions are not particularly limited and may be, for example, the 1st and 8th positions, the 2nd and 7th positions, the 3rd and 6th positions, or the 4th and 5th positions of the fluorene ring, with the 2nd and 7th positions being preferred.

[0028] R 1 and R 2Examples of the substituent represented by the formula (I) include a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, a cyano group, and a substituted amino group.

[0029] Representative examples of these substituents include halogen atoms, hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. 1 and group R 2 Examples of the alkyl group include an alkyl group, a cycloalkyl group, an aryl group, and an alkoxy group. The alkyl group may be a straight-chain or branched C 1-6 Examples of the cycloalkyl group include C alkyl groups such as cyclohexyl groups. 5-8 Examples of the aryl group include C aryl groups such as phenyl groups. 6-14 The alkoxy group includes a linear or branched C 1-4 Alkoxy groups and the like are included. Group R 1 The type of group is R 2 Among these, alkyl groups are preferred, and straight-chain or branched C groups such as methyl groups are preferred. 1-4 Alkyl groups are particularly preferred.

[0030] base R 1 and group R 2 The numbers of substitutions m1 and m2 may be integers of 0 or more, and the ring Z 1 and ring Z 2 The numbers m1 and m2 can be selected appropriately depending on the type of group, and may each be, for example, an integer of 0 to 8. Preferred numbers of substitutions m1 and m2 are, in the following order, integers of 0 to 4, integers of 0 to 3, integers of 0 to 2, 0 or 1, with 0 being the most preferred. The numbers of substitutions m1 and m2 may be different, but are preferably the same. When the numbers of substitutions m1 and m2 are 2 or more, two or more groups R 1 or group R 2The types may be the same or different.

[0031] A 1 and A 2 Examples of the linear or branched alkylene group represented by the formula (I) include linear or branched C alkylene groups such as methylene, ethylene, trimethylene, propylene, 1,2-butanediyl, and 2-methylpropane-1,3-diyl. 1-8 These alkylene groups can be used alone or in combination of two or more. 1 The type of group A 2 Among these, linear or branched C groups such as ethylene groups and propylene groups are preferred. 2-3 Alkylene groups are preferred, with ethylene groups being particularly preferred.

[0032] R 3 and R 4 Examples of the substituent represented by the formula (I) include a hydrocarbon group, a cyano group, and a halogen atom. Examples of the hydrocarbon group include an alkyl group and an aryl group. Examples of the alkyl group include a linear or branched C alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. 1-6 Examples of aryl groups include C alkyl groups such as phenyl groups. 6-10 Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. These substituents can be used alone or in combination. The group R 3 The type of group is R 4 Among these, alkyl groups, cyano groups, and halogen atoms are preferred, alkyl groups are more preferred, and straight-chain or branched C groups such as methyl groups are also preferred. 1-4 Alkyl groups are more preferred, and C 1-2 Alkyl groups are most preferred.

[0033] base R 3 and R 4The numbers of substitutions n1 and n2 are integers of 0 to 3, preferably integers of 0 to 2, more preferably 0 or 1, and most preferably 0. The number of substitutions n1 may be different from the number of substitutions n2, but is preferably the same. When n1 and n2 are each 2 or more, two or more groups R substituted on the same or different benzene rings are 3 or R 4 The types may be the same or different from each other.

[0034] Examples of the dicarboxylic acids (1) include 9,9-bis(carboxy C) compounds such as 9,9-bis(2-carboxyethyl)-1,8-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-3,6-di(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-4,5-di(2-naphthyl)fluorene, 9,9-bis(2-carboxypropyl)-2,7-di(2-naphthyl)fluorene, and 9,9-bis(2-carboxyethyl)-2,7-di(1-naphthyl)fluorene. 2-6 alkyl)-dinaphthylfluorene and its derivatives.

[0035] The dicarboxylic acids (1) obtained by the production method of the present invention described below have high purity, and the purity (HPLC purity) measured by HPLC (high performance liquid chromatography) can be selected from a range of, for example, about 95% or more, with preferred ranges being 96% or more, 97% or more, 97.5% or more, 98% or more, and 98.5% or more, and most preferably 99% or more. The HPLC purity can usually be selected from a range of about 96 to 100%, preferably 98 to 99.99%, and more preferably 99 to 99.9%.

[0036] In this specification and claims, purity can be measured by the method described in the Examples below (method using HPLC), for example.

[0037] [Reaction process] In the reaction step, dicarboxylic acid (2) is subjected to a coupling reaction (or cross-coupling reaction) with fused polycyclic arene compounds (3a) and (3b) in the presence of a palladium (II) catalyst to introduce the aryl groups of the fused polycyclic arene compounds (3a) and (3b) into at least one substitution position selected from the 2- to 8-positions of the fluorene skeleton of the dicarboxylic acid (2), thereby obtaining dicarboxylic acid (1).

[0038] The coupling reaction is not particularly limited, and examples thereof include conventional coupling reactions, such as coupling reactions using a palladium catalyst, such as the Suzuki-Miyaura coupling reaction, the Migita-Kosugi-Stille coupling reaction, the Negishi coupling reaction, and the Hiyama coupling reaction. Among these coupling reactions, the Suzuki-Miyaura coupling reaction is preferred.

[0039] (Dicarboxylic acids (2)) In the formula (2), the reactive group X 1 and X 2 may be a halogen atom or a fluorinated alkanesulfonyloxy group, or may be a boronic acid group (dihydroxyboryl group or group [—B(OH) 2 ]) or a boronate ester group.

[0040] Examples of halogen atoms include iodine atoms, bromine atoms, and chlorine atoms. Examples of fluorinated alkanesulfonyloxy groups include fluorinated C groups such as trifluoromethanesulfonyloxy groups (or groups [-OTf]). 1-4 These halogen atoms and fluorinated alkanesulfonyloxy groups can be used alone or in combination of two or more.

[0041] Examples of the boronate ester group include dialkoxyboryl groups such as dimethoxyboryl, diisopropoxyboryl, and dibutoxyboryl; and cyclic boronate ester groups such as pinacolatoboryl (or group [-Bpin]), 1,3,2-dioxaborinan-2-yl, and 5,5-dimethyl-1,3,2-dioxaborinan-2-yl. These boronate ester groups and boronic acid groups can be used alone or in combination. Reactive group X 1 The type of reactive group X 2 may be different from, but are preferably the same.

[0042] Among these, the reactive group X 1 and X 2 As the aryl group, a halogen atom is preferred, an iodine atom or a bromine atom is more preferred, and a bromine atom is particularly preferred.

[0043] In the formula (2), A 1 , A 2 , R 3 , R 4 , n1 and n2 are the same as those in the formula (1), including preferred embodiments.

[0044] Preferred dicarboxylic acids (2) include 9,9-bis(C ) such as 9,9-bis(2-methoxycarbonylethyl)-2,7-dibromofluorene, 9,9-bis(2-ethoxycarbonylethyl)-2,7-dibromofluorene, and 9,9-bis(2-methoxycarbonylpropyl)-2,7-dibromofluorene. 1-4 Alkoxy-carbonyl-C 2-6 alkyl)-dihalofluorene.

[0045] Dicarboxylic acids (2) may be prepared, for example, according to the method described in JP-A-2005-89422, specifically, by reacting a 9H-fluorene unsubstituted at the 9-position, such as 2,7-dibromofluorene, with an acrylic acid ester, such as methyl acrylate, or a haloacetic acid ester, such as methyl bromoacetate, in the presence of a base catalyst, such as trimethylbenzylammonium hydroxide.

[0046] (Fused polycyclic arene compounds (3a) and (3b)) In the formulas (3a) and (3b), the reactive group X 3 and X 4 is the reactive group X of the dicarboxylic acid (2). 1 and X 2 Any reactive group capable of coupling reaction with the reactive group X 1 and X 2 is a halogen atom or a fluorinated alkanesulfonyloxy group, the reactive group X 3 and X 4 is a boronic acid group or a boronic ester group, and the reactive group X 1 and X 2 is a boronic acid group or a boronic ester group, the reactive group X 3 and X 4 is a halogen atom or a fluorinated alkanesulfonyloxy group.

[0047] That is, in the formulas (3a) and (3b), the reactive group X 3 and X 4 may be a halogen atom or a fluorinated alkanesulfonyloxy group, or may be a boronic acid group (dihydroxyboryl group or group [—B(OH)2]) or a boronate ester group. 3 and X 4 As the alkyl group, a boronic acid ester group and / or a boronic acid group is preferred, and a boronic acid group is particularly preferred.

[0048] The fused polycyclic arene compounds (3a) and (3b) include 1-naphthylboronic acid and 2-naphthylboronic acid, with 2-naphthylboronic acid being preferred. The fused polycyclic arene compounds (3a) and (3b) are preferably the same compound. The fused polycyclic arene compounds (3a) and (3b) can also be commercially available products.

[0049] The ratio of the dicarboxylic acid (2) to the total amount of the fused polycyclic arene compounds (3a) and (3b) may be, for example, the former / latter (molar ratio) = about 1 / 2 to 1 / 10, and preferred ranges are 1 / 2.2 to 1 / 8, 1 / 2.5 to 1 / 5, and 1 / 2.7 to 1 / 3.3 in the following stepwise order.

[0050] (catalyst) The catalyst used in the reaction step contains a palladium (II) catalyst. In the production method of the present invention, since the catalyst contains a palladium (II) catalyst, deactivation of the catalyst can be suppressed, handling and operability can be improved, and dicarboxylic acids (1) with high purity and suppressed coloration can be efficiently produced.

[0051] Palladium(II) catalysts include palladium(II) acetate [or Pd(OAc)2], palladium(II) alkanoates such as palladium(II) propionate, and palladium(II)-phosphine complexes such as [1,2-bis(diphenylphosphino)ethane]palladium(II) dichloride [or Pd(dppe)Cl2], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride [or Pd(dppp)Cl2], [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride [or Pd(dppf)Cl2], bis(triphenylphosphine)palladium(II) dichloride [or Pd(PPh3)2Cl2], and bis(tri-o-tolylphosphine)palladium(II) dichloride [or Pd(P(o-tolyl)3)2Cl2]. The palladium (II) catalyst is reduced to a zero-valent complex by a reducing compound in the reaction system, such as a phosphine, amine, or organometallic reagent, which will be described later, and the reaction begins.

[0052] These palladium (II) catalysts can be used alone or in combination. 1-4 Palladium(II) alkanoates, such as Pd(dppe)Cl2, Pd(dppf)Cl2, and Pd(PPh3)2Cl2, are preferred, as are palladium(II)-phosphine complexes such as Pd(OAc)2. 1-2 Palladium(II) alkanoates are particularly preferred.

[0053] The proportion of the palladium (II) catalyst can be selected from a range of, for example, about 0.01 to 10 moles in terms of palladium relative to 100 moles of the dicarboxylic acid (2), with preferred ranges being 0.01 to 5 moles, 0.01 to 1 mole, 0.01 to 0.1 mole, 0.02 to 0.08 mole, 0.03 to 0.07 mole, and most preferably 0.04 to 0.06 mole. If the proportion of the palladium (II) catalyst is too low, the reaction conversion rate may decrease, while if it is too high, the dicarboxylic acid (1) may become discolored.

[0054] The palladium(II) catalyst may be combined with a ligand, and a combination of palladium(II) alkanoate and a ligand is particularly preferred. Ligands include phosphines, carbenes, and the like. Examples of phosphines include trialkylphosphines such as trimethylphosphine and tributylphosphine; tricycloalkylphosphines such as tricyclohexylphosphine; and triarylphosphines such as triphenylphosphine. Examples of carbenes include nitrogen-containing heterocyclic carbenes. These ligands can be used alone or in combination. Among these, phosphines are preferred, and triarylphosphines are particularly preferred.

[0055] The proportion of the ligand relative to 100 moles of the palladium (II) catalyst is, for example, 10 to 1,000 moles, preferably 50 to 500 moles, more preferably 100 to 300 moles, and most preferably 150 to 250 moles. If the proportion of the ligand is too small, the reaction-accelerating effect may not be exerted, whereas if it is too large, the purity of the dicarboxylic acid (1) may decrease.

[0056] In addition to the palladium(II) catalyst, the catalyst may further contain other catalysts such as a palladium(0) catalyst or a copper catalyst. The other catalyst is preferably a palladium(0) catalyst. Examples of the palladium(0) catalyst include palladium(0)-phosphine complexes such as tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)4] and bis(tri-t-butylphosphine)palladium(0) [or Pd(P(t-Bu)3)2].

[0057] The proportion of the other catalysts is 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on the total amount of catalysts. If the proportion of the other catalysts is too high, it may be difficult to produce the dicarboxylic acid (1) with high operability.

[0058] The proportion of the palladium (II) catalyst in the total catalyst is 50% by mass or more, preferably 70% by mass or more, further preferably 90% by mass or more, even more preferably 95% by mass or more, and most preferably 100% by mass. If the proportion of the palladium (II) catalyst is too low, it may be difficult to produce the dicarboxylic acid (1) with high operability.

[0059] The proportion of the catalyst can be selected, for example, from a range of about 0.01 to 10 moles in terms of metal relative to 100 moles of the dicarboxylic acid (2), with preferred ranges being 0.01 to 5 moles, 0.01 to 1 mole, 0.01 to 0.1 mole, 0.02 to 0.08 mole, 0.03 to 0.07 mole, and most preferably 0.04 to 0.06 mole. If the proportion of the catalyst is too small, the reaction conversion rate may decrease, whereas if it is too large, the dicarboxylic acid (1) may become discolored.

[0060] (base) In the reaction step, a base may be added to promote the coupling reaction. Examples of the base include metal carbonates or metal hydrogen carbonates, metal hydroxides, metal fluorides, metal phosphates, metal organic acid salts, and metal alkoxides.

[0061] Examples of metal carbonates include alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; and thallium(I) carbonate.

[0062] Examples of metal hydrogen carbonates include alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and cesium hydrogen carbonate.

[0063] Examples of metal hydroxides include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as barium hydroxide; and thallium(I) hydroxide.

[0064] Examples of metal fluorides include alkali metal fluorides such as potassium fluoride and cesium fluoride.

[0065] Examples of metal phosphates include alkali metal phosphates such as tripotassium phosphate.

[0066] Examples of metal organic acid salts include alkali metal acetates such as potassium acetate.

[0067] Examples of metal alkoxides include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[0068] These bases can be used alone or in combination. Among these bases, metal carbonates and / or metal hydrogen carbonates are preferred, alkali metal carbonates and / or alkali metal hydrogen carbonates are more preferred, and alkali metal carbonates such as sodium carbonate are most preferred.

[0069] The proportion of the base relative to 1 mole of the dicarboxylic acid (2) is, for example, 0.1 to 50 moles, preferably 0.5 to 30 moles, further preferably 1 to 10 moles, even more preferably 1.5 to 5 moles, and most preferably 2 to 3 moles. If the proportion of the base is too small, the reaction conversion rate may decrease, whereas if it is too large, the dicarboxylic acid (1) may become discolored.

[0070] (Reaction solvent) In the reaction step, a highly pure dicarboxylic acid (1) can be efficiently produced by coupling reaction of dicarboxylic acid (2) with fused polycyclic arene compounds (3a) and (3b) using a reaction solvent containing an aprotic solvent as a reaction solvent inert to the reaction.

[0071] The aprotic solvent may be an aprotic nonpolar solvent or an aprotic polar solvent.

[0072] Aprotic nonpolar solvents include aliphatic hydrocarbons such as hexane, heptane, octane, decane, and dodecane; alicyclic hydrocarbons such as cyclohexane; and aromatic hydrocarbons such as benzene and alkylbenzenes. Examples of alkylbenzenes include mono- and tetra-C alkylbenzenes such as toluene, xylene, ethylbenzene, trimethylbenzene, ethyltoluene, propylbenzene, and cumene. 1-4 These hydrocarbons can be used alone or in combination. Among these, aromatic hydrocarbons are preferred, and mono- or di-C hydrocarbons such as toluene, xylene, and ethylbenzene are also preferred. 1-2 Alkyl-benzenes are more preferred, with toluene being especially preferred.

[0073] Aprotic polar solvents include chain ethers such as diethyl ether and diisopropyl ether; glycol ethers such as methyl cellosolve, methyl carbitol, and dimethoxyethane; cyclic ethers such as propylene oxide, dioxolane, dioxole, trioxane, furan, tetrahydrofuran (THF), 1,3-dioxane, 1,4-dioxane, dioxene, 2-methylfuran, pyran, and tetrahydropyran; acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK). ketones such as methyl acetate and ethyl acetate; nitriles such as acetonitrile and benzonitrile; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide (DMSO), methyl ethyl sulfoxide, and diethyl sulfoxide; and halogenated hydrocarbons such as methylene chloride, methylene dichloride, and chloroform. These aprotic polar solvents can be used alone or in combination.

[0074] Among these aprotic polar solvents, C 1,4-dioxane and the like are preferred because they can efficiently produce dicarboxylic acids (1) with high purity. 3-10 Preferred are cyclic ethers; ketones such as MEK, MIBK, and cyclohexanone; alkyl amides such as DMF; and alkyl sulfoxides such as DMSO. 3-5 Cyclic ethers, aliphatic or alicyclic ketones, N,N-diC 1-4 Alkylamides, DiC 1-4 Alkyl sulfoxides are more preferred, aliphatic ketones, C 3-5 Cyclic ethers are particularly preferred, and aliphatic ketones having 4 or more carbon atoms are most preferred.

[0075] The reaction solvent may further contain a protic solvent in addition to the aprotic solvent. The protic solvent may be a protic polar solvent. Examples of the protic polar solvent include C 10 solvents such as methanol, ethanol, propanol, isopropanol, hexanol, heptanol, octanol, decanol, and lauryl alcohol. 1-12 Alkanols; aliphatic polyhydric alcohols such as ethylene glycol and propylene glycol. These protic polar solvents can be used alone or in combination. Among these, C solvents such as ethanol and isopropanol are preferred. 1-6 Alkanols are preferred, C 3-5 Alkanols are particularly preferred.

[0076] The reaction solvent may contain an aprotic solvent, and is preferably a combination of an aprotic nonpolar solvent and an aprotic polar solvent, a combination of an aprotic nonpolar solvent and a protic polar solvent, or an aprotic polar solvent alone; more preferably a combination of an aromatic hydrocarbon and an aprotic polar solvent, a combination of an aromatic hydrocarbon and a protic polar solvent, or a ketone alone; more preferably a combination of an aromatic hydrocarbon and a ketone, or a ketone alone; and most preferably a ketone having 4 or more carbon atoms alone.

[0077] The reaction solvent is an aromatic hydrocarbon and a C 3-10 When combined with an aprotic polar solvent selected from cyclic ethers, alkylamides, and alkyl sulfoxides, the ratio of the aprotic polar solvent relative to 100 parts by volume of the aromatic hydrocarbons is, for example, 5 to 200 parts by volume, preferably 10 to 100 parts by volume, more preferably 30 to 70 parts by volume, and most preferably 40 to 60 parts by volume.

[0078] When the reaction solvent is a combination of aromatic hydrocarbons and ketones, the proportion of the ketones is, for example, 5 to 300 parts by volume, preferably 10 to 200 parts by volume, and more preferably 50 to 150 parts by volume, per 100 parts by volume of the aromatic hydrocarbons.

[0079] When the reaction solvent is a combination of aromatic hydrocarbons and a protic polar solvent, the ratio of the protic polar solvent relative to 100 parts by volume of aromatic hydrocarbons is, for example, 5 to 200 parts by volume, preferably 10 to 100 parts by volume, more preferably 30 to 70 parts by volume, and most preferably 40 to 60 parts by volume.

[0080] In particular, in the present invention, when the reaction solvent contains an aliphatic ketone having 4 or more carbon atoms, the production of binaphthalene, a by-product, during the reaction can be suppressed, and the selectivity and yield can be improved. Therefore, the proportion of the aliphatic ketone having 4 or more carbon atoms in the reaction solvent may be 10% by mass or more, for example, 30% by mass or more, preferably 50% by mass or more, further preferably 80% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass. The aliphatic ketone having 4 or more carbon atoms is preferably an aliphatic ketone having 4 to 8 carbon atoms, and particularly preferably an aliphatic ketone having 5 to 7 carbon atoms.

[0081] In the present specification and claims, the volume ratios are those at 25° C. and atmospheric pressure.

[0082] The reaction solvent may further contain water in addition to the aprotic solvent and the protic polar solvent. The proportion of water is, for example, 1 to 100 parts by mass, preferably 3 to 50 parts by mass, and more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the aprotic solvent and the protic polar solvent combined.

[0083] The reaction solvent may further contain other solvents in addition to the above solvents.

[0084] The proportion of the other solvent in the total reaction solvent is 50% by mass or less, preferably 30% by mass or less, further preferably 20% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less. If the proportion of the other solvent is too high, there is a risk that highly pure dicarboxylic acids (1) cannot be efficiently produced.

[0085] The total proportion of the aprotic solvent and the protic polar solvent in the total reaction solvent is 50% by mass or more, preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, and most preferably 100% by mass. If the total proportion is too small, there is a risk that highly pure dicarboxylic acids (1) cannot be efficiently produced.

[0086] The proportion of the solvent is, for example, 10 to 10,000 parts by mass, preferably 50 to 8,000 parts by mass, further preferably 100 to 5,000 parts by mass, even more preferably 500 to 4,000 parts by mass, and most preferably 1,000 to 3,000 parts by mass relative to 100 parts by mass of the dicarboxylic acid (2).

[0087] (Other additives) In the reaction step, conventional additives used in reactions may be further used. Examples of conventional additives include a co-catalyst (phase transfer catalyst). Examples of the co-catalyst include tetraalkylammonium halides such as tetrabutylammonium bromide (TBAB) and trioctylmethylammonium chloride. These co-catalysts can be used alone or in combination. Among these co-catalysts, TBAB is often used.

[0088] The proportion of the co-catalyst is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 8 parts by mass, more preferably 1 to 5 parts by mass, and even more preferably 2 to 4 parts by mass, relative to 100 parts by mass of the dicarboxylic acids (2).

[0089] (Reaction conditions) The reaction temperature is not particularly limited, but can be selected from the range of about 50 to 200° C., for example, 55 to 150° C., preferably 60 to 100° C., further preferably 70 to 98° C., more preferably 75 to 96° C., particularly preferably 80 to 95° C., and most preferably 85 to 93° C. The reaction time is not particularly limited, but can be selected from the range of about 30 minutes to 24 hours, for example, 0.5 to 12 hours, preferably 1 to 10 hours, and further preferably 2 to 8 hours.

[0090] The reaction may be carried out with stirring, in an inert atmosphere such as nitrogen or a rare gas such as helium or argon, under normal pressure or under pressure, or while dehydrating.

[0091] [Refining process] In the production method of the present disclosure, the purity of the dicarboxylic acid compound (1) can be further improved by subjecting the dicarboxylic acid compound (1) obtained in the reaction step to a purification step.

[0092] In the purification step, the dicarboxylic acid (1) is preferably crystallized using a crystallization solvent containing an aromatic hydrocarbon and / or a polar solvent.

[0093] Examples of aromatic hydrocarbons include the aromatic hydrocarbons exemplified as reaction solvents. The aromatic hydrocarbons can be used alone or in combination of two or more. Among the aromatic hydrocarbons, mono- or di-C hydrocarbons such as toluene, xylene, and ethylbenzene are preferred. 1-2 Alkyl-benzenes are preferred, with toluene being especially preferred.

[0094] The polar solvent may be any of the polar solvents exemplified as the reaction solvent. The polar solvents may be used alone or in combination of two or more. Among the polar solvents, C 10 solvents such as ethanol and isopropanol are preferred. 1-4 Alkanols: Aliphatic ketones having 4 or more carbon atoms, such as MIBK, are preferred. 2-3 Alkanols; aliphatic ketones having 4 to 8 carbon atoms are particularly preferred.

[0095] Among the crystallization solvents, good solvents include aromatic hydrocarbons and aliphatic ketones having 4 or more carbon atoms. 1-4 Alkanols and the like.

[0096] The proportion of the poor solvent may be 1 part by volume or more relative to 100 parts by volume of the good solvent, for example, 1 to 200 parts by volume, preferably 10 to 100 parts by volume, and from the viewpoint of efficient production of dicarboxylic acids (1), is more preferably 20 to 80 parts by volume, more preferably 20 to 50 parts by volume, most preferably 20 to 40 parts by volume, and particularly preferably 30 to 40 parts by volume. If the proportion of the poor solvent is too low, there is a risk that highly pure dicarboxylic acids (1) cannot be efficiently produced, and conversely, if the proportion is too high, there is a risk that the purity cannot be improved.

[0097] The crystallization solvent may further contain other solvents in addition to aromatic hydrocarbons and polar solvents. Examples of other solvents include the other solvents exemplified as reaction solvents. The other solvents can be used alone or in combination of two or more.

[0098] The proportion of the other solvent is 50% by mass or less, preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, and most preferably 5% by mass or less, based on the total crystallization solvent. If the proportion of the other solvent is too high, there is a risk that highly pure dicarboxylic acids (1) cannot be efficiently produced.

[0099] The proportion of the crystallization solvent is, for example, 10 to 2000 parts by mass, preferably 50 to 1500 parts by mass, more preferably 100 to 1000 parts by mass, and most preferably 200 to 500 parts by mass, relative to 100 parts by mass of the dicarboxylic acid (1).

[0100] In the crystallization treatment, dicarboxylic acids (1) can be dissolved in the crystallization solvent and cooled to precipitate or crystallize dicarboxylic acids (1) with higher purity. After dissolution, if necessary, a predetermined amount of the solvent may be distilled off under reduced pressure to adjust the amount of the crystallization solvent to fall within the above-mentioned ratio range. The crystallization solvent may be added (or mixed) in its entirety before heating, or may be added stepwise, e.g., a portion of the solvent is added, the temperature is raised to a predetermined temperature, and then the remaining solvent is added.

[0101] The temperature at which the dicarboxylic acid (1) is dissolved in the crystallization solvent is a temperature below the boiling point of the solvent, for example, 30 to 200°C, and preferred ranges are 50 to 150°C, 60 to 140°C, 80 to 130°C, and 100 to 120°C in the following stepwise order.

[0102] The solution obtained by dissolving dicarboxylic acids (1) in a crystallization solvent is cooled to crystallize dicarboxylic acids (1) with higher purity. Crystallization can be performed by rapid cooling, natural cooling, or slow cooling. Rapid cooling appears to be relatively easy to obtain dicarboxylic acids (1) with higher purity. Typical cooling rates can be selected, for example, from a range of about 0.1 to 100°C / min. Preferred ranges are the following stepwise rates: 1°C / min or more, 1 to 50°C / min, 3 to 30°C / min, 5 to 20°C / min, 7 to 15°C / min, 8 to 12°C / min, and 9 to 11°C / min. The precipitation temperature (the temperature at which precipitation or crystallization begins) may be 80°C or lower, for example, 30 to 80°C, preferably 40 to 75°C, more preferably 50 to 70°C, and even more preferably 55 to 65°C. The ultimate cooling temperature is, for example, −10° C. to 30° C., preferably −5° C. to 20° C., and more preferably 0 to 10° C. The retention time at the ultimate cooling temperature is not particularly limited and may be, for example, about 1 minute to 12 hours, preferably 0.5 to 6 hours, and more preferably 1 to 3 hours.

[0103] In the crystallization procedure, seed crystals may be added if necessary, and the crystallization procedure may be carried out once or repeatedly. The crystals produced by the crystallization are usually filtered by a separation means such as filtration (e.g., suction filtration) or centrifugation, and then dried to obtain dicarboxylic acids (1) with high purity.

[0104] Drying after crystallization may be performed under reduced pressure, and the drying temperature may be, for example, about 50 to 200°C, with preferred ranges being 60 to 150°C, 70 to 120°C, 80 to 100°C, and 85 to 95°C in the following stepwise manner. Drying may be performed by raising the temperature all at once or by raising the temperature stepwise. Drying time may be, for example, about 1 hour to 1 week, and is preferably 1 to 3 days.

[0105] In the purification step, the reaction liquid before being subjected to crystallization may be neutralized and washed as necessary, and then subjected to a preliminary removal treatment to remove impurities from the reaction liquid mixture, after which the resulting residue may be crystallized.

[0106] In the preliminary removal treatment, washing may be carried out by a conventional method, but by treating the dicarboxylic acid (1) with activated carbon after washing, metal components derived from the catalyst, such as palladium, can be effectively removed, and coloration of the dicarboxylic acid (1) can be suppressed.

[0107] In the preliminary removal treatment, it is preferable to wash the reaction solution containing the dicarboxylic acids (1) obtained in the reaction step with a washing solvent such as water, and then treat the washed reaction solution with activated carbon. It is particularly preferable to add granular activated carbon to the reaction solution, stir it, and then filter it.

[0108] Activated carbon has a BET specific surface area of ​​100 to 5000 cm, calculated by the nitrogen adsorption method. 2 / cm 3 can be selected from a range of about 500 to 4000 cm 2 / cm 3 , preferably 1000 to 3500 cm 2 / cm 3 , and more preferably 2000 to 3000 cm 2 / cm 3 is.

[0109] The shape of the activated carbon is not particularly limited and may be granular (or powdery), fibrous, irregular, etc., but granular or fibrous shapes are preferred, with granular shapes being particularly preferred. The median primary particle size (D50) of the granular activated carbon is, for example, 1 to 100 μm, preferably 10 to 50 μm, and more preferably 30 to 40 μm.

[0110] The proportion of activated carbon can be selected from the range of about 1 to 100 parts by mass per 100 parts by mass of the dicarboxylic acids (1), for example, 3 to 100 parts by mass, preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and most preferably 15 to 25 parts by mass. If the proportion of activated carbon is too low, the effect of inhibiting coloration may be reduced, whereas if it is too high, the work of washing the activated carbon may become complicated, reducing operability. [Example]

[0111] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0112] Comparative Example 1 9,9-bis(2-methoxycarbonylethyl)-2,7-dibromofluorene (DBrFDP-m) was synthesized in the same manner as in Example 1 of JP 2005-89422 A, except that methyl acrylate [37.9 g (0.44 mol)] was used instead of t-butyl acrylate and 2,7-dibromo-9H-fluorene [54.7 g (0.17 mol)] was used instead of fluorene.

[0113] A reactor was charged with 192.3 g (0.39 mol) of DBrFDP-m, 200 g (1.2 mol) of 2-naphthylboronic acid, 4.3 L of dimethoxyethane, and 1 L of 2 M aqueous sodium carbonate. Under a nitrogen stream, 22.4 g (19.4 mmol) of tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)4] was added and the mixture was heated to reflux at an internal temperature of 71–78°C for 5 hours. After cooling to room temperature, 2.0 L of toluene and 500 mL of ion-exchanged water were added, followed by five separate extractions and washings. The organic layer changed color from deep orange to brown. The insoluble matter was filtered and concentrated to yield 305 g of brown crude crystals. The resulting crude crystals were dissolved in a mixture of 1.5 kg of ethyl acetate and 300 g of isopropyl alcohol (IPA) by heating, then cooled to below 10°C with ice water and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain 130 g of gray-brown crystals. The obtained gray-brown crystals were purified by column chromatography (silica gel carrier, developing solvent chloroform:ethyl acetate (volume ratio) = 4:1), then recrystallized from methanol and dried under reduced pressure to obtain 116 g of 9,9-bis(2-methoxycarbonylethyl)-2,7-di(2-naphthyl)fluorene (2,7-DNFDP-m) (white crystals, yield 54.9%) represented by the following formula.

[0114] [ka]

[0115] Comparative Examples 2 to 4 2,7-DNFDP-m was obtained in the same manner as in Comparative Example 1, except that the reaction conditions were changed to those shown in Table 1 and the grayish brown crystals obtained in the purification step were not purified by column chromatography.

[0116] Comparative Example 5 DBrFDP-m was synthesized in the same manner as in Comparative Example 1.

[0117] A reactor was charged with 193.5 g (0.39 mol) of DBrFDP-m, 147.6 g (0.86 mol) of 2-naphthylboronic acid, 4.3 L of dimethoxyethane, and 0.5 L of 2 M aqueous sodium carbonate solution. Under a nitrogen stream, 40.225 g (0.195 mmol) of Pd(PPh3) was added, and the mixture was heated to reflux at an internal temperature of 75-80 °C for 5 hours to react. After cooling to room temperature, 2.0 L of toluene and 500 mL of ion-exchanged water were added, and the mixture was washed by extraction five times. After draining, the organic layer was washed with 20 parts by weight of powdered activated carbon ("Special Shirasagi FP-6" manufactured by Osaka Gas Chemicals Co., Ltd., specific surface area 2504.3 cm) per 100 parts by weight of DBrFDP-m. 2 / cm 3 The palladium was removed by adding 2,7-DNFDP-m (average particle size 49.9 μm, high purity product) and stirring at 80°C for 60 minutes, followed by filtration to remove insoluble matter. The organic layer was concentrated, and the resulting crude crystals were dissolved by heating in a mixture of 1.5 kg of ethyl acetate and 300 g of isopropyl alcohol (IPA). The mixture was then cooled to below 10°C with ice water and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain 153.7 g of 2,7-DNFDP-m (white crystals, yield 66.7%, HPLC purity 99.4 area%).

[0118] Comparative Example 6 DBrFDP-m was synthesized in the same manner as in Comparative Example 1.

[0119] A reactor was charged with 193.5 g (0.39 mol) of DBrFDP-m, 147.6 g (0.86 mol) of 2-naphthylboronic acid, 4.3 L of dimethoxyethane, and 0.5 L of 2 M aqueous sodium carbonate solution. Under a nitrogen stream, 40.225 g (0.195 mmol) of Pd(PPh3) was added, and the mixture was heated to reflux at an internal temperature of 75-80 °C for 5 hours. After the reaction, the mixture was drained, and 100 mL of ion-exchanged water was added. The mixture was washed by extraction five times. After draining, 20 parts by weight of powdered activated carbon (Osaka Gas Chemicals Co., Ltd., "Special Shirasagi FP-6") was added to 100 parts by weight of DBrFDP-m to the organic layer. The mixture was stirred at 80 °C for 60 minutes to remove palladium, and then insoluble matter was removed by filtration. The organic layer was concentrated, and 132.6 mL of toluene was removed. 18 mL of IPA was added, and the mixture was cooled to 25°C or below and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain white crystals. 30.8 g of 2,7-DNFDP-m (white crystals, yield 86.8%, HPLC purity 99.1% area) was obtained.

[0120] Comparative Example 7 DBrFDP-m was synthesized in the same manner as in Comparative Example 1.

[0121] A reactor was charged with 29.8 g (0.06 mol) of DBrFDP-m, 22.7 g (0.13 mol) of 2-naphthylboronic acid, 318.5 mL of toluene, and 0.08 L of 2 M aqueous sodium carbonate. Under a nitrogen stream, 434.5 mg (0.03 mmol) of Pd(PPh3) was added, and the mixture was heated to reflux at an internal temperature of 83-90 °C for 6 hours. After the reaction, the mixture was drained, and 100 mL of ion-exchanged water was added. The mixture was washed by extraction five times. After draining, 20 parts by weight of powdered activated carbon (Osaka Gas Chemicals Co., Ltd., "Special Shirasagi FP-6") was added to 100 parts by weight of DBrFDP-m to the organic layer. The mixture was stirred at 80 °C for 60 minutes to remove palladium, and then insoluble matter was removed by filtration. The organic layer was concentrated to remove 238.7 mL of toluene, then heated to reflux at 110 °C to dissolve. After cooling, 18 mL of IPA was added at 80 °C, cooled to below 25 °C, and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain white crystals. 29.8 g of 2,7-DNFDP-m (white crystals, yield 84.1%, HPLC purity 99.4 area%) was obtained.

[0122] Comparative Example 8 2,7-DNFDP-m was obtained in the same manner as in Comparative Example 7, except that the reaction conditions were changed to those shown in Table 1.

[0123] Comparative Example 9 The powdered activated carbon (Osaka Gas Chemicals Co., Ltd. "Special Shirasagi FP-6") in the purification process was replaced with powdered activated carbon (Osaka Gas Chemicals Co., Ltd. "Carborafine", specific surface area 2504.3 cm 2 / cm 3 2,7-DNFDP-m was obtained in the same manner as in Comparative Example 7, except that the average particle size was changed to 49.9 μm.

[0124] Comparative Example 10 DBrFDP-m was synthesized in the same manner as in Comparative Example 1.

[0125] A reactor was charged with 29.8 g (0.06 mol) of DBrFDP-m, 22.7 g (0.13 mol) of 2-naphthylboronic acid, 212.3 mL of toluene, 106.2 mL of isopropyl alcohol (IPA), and 0.08 L of 2 M aqueous sodium carbonate. Under a nitrogen stream, 40.034 mg (0.03 mmol) of Pd(PPh3) was added, and the mixture was heated to reflux at an internal temperature of 75-82 °C for 6 hours. After the reaction, the mixture was drained, and 100 mL of ion-exchanged water was added, followed by five separate extractions and washings. After draining, 20 parts by weight of powdered activated carbon (Osaka Gas Chemicals Co., Ltd., "Special Shirasagi FP-6") was added to 100 parts by weight of DBrFDP-m to the organic layer. The mixture was stirred at 80 °C for 60 minutes to remove palladium, and then insoluble matter was removed by filtration. The organic layer was concentrated to remove 162.5 mL of toluene, then heated to reflux at 110 °C to dissolve. After cooling, 18 mL of IPA was added at 80 °C, cooled to below 25 °C, and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain white crystals. 31.2 g of 2,7-DNFDP-m (white crystals, yield 88.0%, HPLC purity 99.5 area%) was obtained.

[0126] Comparative Example 11 2,7-DNFDP-m was obtained in the same manner as in Comparative Example 10, except that the reaction conditions were changed to those shown in Table 1 (the same volume of ethanol was used instead of the IPA reaction solvent, and the reaction temperature was changed).

[0127] Comparative Example 12 2,7-DNFDP-m was obtained in the same manner as in Comparative Example 10, except that the conditions for the reaction and purification steps were changed to those shown in Tables 1 and 3 (the same volume of methanol was used instead of the reaction solvent IPA, the reaction temperature was changed, and the type of activated carbon was changed).

[0128] Example 1 DBrFDP-m was synthesized in the same manner as in Comparative Example 1.

[0129] A reactor was charged with 29.8 g (0.06 mol) of DBrFDP-m, 22.7 g (0.13 mol) of 2-naphthylboronic acid, 318.5 mL of toluene, and 0.08 L of 2 M aqueous sodium carbonate solution. Under a nitrogen stream, 21.1 mg (0.03 mmol) of bis(triphenylphosphine)palladium(II) dichloride [Pd(PPh3)2Cl2] and 15.7 mg (0.06 mmol) of triphenylphosphine were added, and the reaction was carried out by heating under reflux at an internal temperature of 83-90 °C for 6 hours. After the reaction, the solution was drained, and 100 mL of ion-exchanged water was added, followed by five separations and washing. After draining, 20 parts by weight of powdered activated carbon (Osaka Gas Chemicals Co., Ltd., "Special Shirasagi FP-6") was added to 100 parts by weight of DBrFDP-m to the organic layer, and the mixture was stirred at 80°C for 60 minutes to remove palladium. The insoluble material was then filtered off. The organic layer was concentrated to remove 132.6 mL of toluene, and the mixture was heated to reflux at 110°C to dissolve the toluene. After cooling, 18 mL of IPA was added at 80°C, cooled to below 25°C, and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain white crystals. 30.0 g of 2,7-DNFDP-m (white crystals, 84.6% yield, 99.8% area HPLC purity) was obtained.

[0130] Examples 2 and 3 2,7-DNFDP-m was obtained in the same manner as in Example 1, except that the reaction conditions were changed to those shown in Table 2 (the catalyst type was changed).

[0131] Example 4 DBrFDP-m was synthesized in the same manner as in Comparative Example 1.

[0132] A reactor was charged with 29.8 g (0.06 mol) of DBrFDP-m, 22.7 g (0.13 mol) of 2-naphthylboronic acid, 212.3 mL of toluene, 106.2 mL of isopropyl alcohol (IPA), and 0.08 L of 2 M aqueous sodium carbonate. Under a nitrogen stream, 26.7 mg (0.03 mmol) of palladium acetate (Pd(OAc)) and 15.7 mg (0.06 mmol) of triphenylphosphine were added, and the mixture was heated to reflux at an internal temperature of 75-82 °C for 6 hours. After the reaction, the mixture was drained, and 100 mL of ion-exchanged water was added, followed by five separate extractions and washings. After draining, 20 parts by weight of powdered activated carbon (Osaka Gas Chemicals Co., Ltd., "Special Shirasagi FP-6") was added to 100 parts by weight of DBrFDP-m to the organic layer. The mixture was stirred at 80 °C for 60 minutes to remove palladium, and then insoluble matter was removed by filtration. The organic layer was concentrated to remove 132.6 mL of toluene, then heated to reflux at 110 °C to dissolve. After cooling, 18 mL of IPA was added at 80 °C, cooled to below 25 °C, and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain white crystals. 30.2 g of 2,7-DNFDP-m (white crystals, yield 85.1%, HPLC purity 99.5 area%) was obtained.

[0133] Example 5 The target product (organic layer after five separate extractions) obtained in the same manner as in Example 4 was treated to remove palladium using powdered activated carbon ("Carborafine" manufactured by Osaka Gas Chemicals Co., Ltd.) in the same manner as in Example 4, followed by filtration to remove insoluble matter. The organic layer was concentrated to remove 162.5 mL of toluene, and then heated to reflux at 110 °C to dissolve the toluene. After cooling, 18 mL of IPA was added at 80 °C, cooled to below 25 °C, and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain white crystals. 32.0 g of 2,7-DNFDP-m (white crystals, yield 90.4%, HPLC purity 99.0 area%) was obtained.

[0134] Examples 6 to 10 2,7-DNFDP-m was obtained in the same manner as in Example 3, except that the conditions for the reaction step and purification step were changed to those shown in Tables 2 and 4.

[0135] Examples 11-12 2,7-DNFDP-m was obtained in the same manner as in Example 4, except that the conditions for the reaction step and purification step were changed to those shown in Tables 2 and 4.

[0136] Example 13 2,7-DNFDP-m was obtained in the same manner as in Example 3, except that the conditions for the reaction step and purification step were changed to those shown in Tables 2 and 4.

[0137] Examples 14 to 18 2,7-DNFDP-m was obtained in the same manner as in Example 4, except that the conditions for the reaction step and purification step were changed to those shown in Tables 2 and 4.

[0138] Example 19 DBrFDP-m was synthesized in the same manner as in Comparative Example 1.

[0139] A reactor was charged with 29.8 g (0.06 mol) of DBrFDP-m, 22.7 g (0.13 mol) of 2-naphthylboronic acid, 157.9 mL (137.4 g) of toluene, 170.4 mL (137.4 g) of methyl ethyl ketone (MEK), and 0.08 L of 2 M aqueous sodium carbonate solution. Under a nitrogen stream, 26.7 mg (0.03 mmol) of palladium acetate Pd(OAc) and 15.7 mg (0.06 mmol) of triphenylphosphine were added, and the mixture was heated to reflux at an internal temperature of 77-80 °C for 6 hours. After the reaction, the solution was drained, and 100 mL of ion-exchanged water was added. The mixture was washed by separation and extraction five times. After draining, 5 parts by weight of powdered activated carbon ("Carborafine" manufactured by Osaka Gas Chemicals Co., Ltd.) was added to 100 parts by weight of DBrFDP-m to the organic layer, and the mixture was stirred at 80°C for 60 minutes to remove palladium, followed by filtration to remove insoluble matter. The organic layer was concentrated to remove 216 mL of toluene and MEK, and then heated to reflux at 110°C to dissolve the residue. After cooling, 18 mL of IPA was added at 80°C, cooled to below 25°C, and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain white crystals. 30.7 g of 2,7-DNFDP-m (white crystals, yield 86.5%, HPLC purity 99.6% area%) was obtained.

[0140] Example 20 DBrFDP-m was synthesized in the same manner as in Comparative Example 1.

[0141] A reactor was charged with 29.8 g (0.06 mol) of DBrFDP-m, 22.7 g (0.13 mol) of 2-naphthylboronic acid, 431.9 mL of methyl isobutyl ketone (MIBK), and 0.08 L of 2 M aqueous sodium carbonate. Under a nitrogen stream, 26.7 mg (0.03 mmol) of palladium acetate (Pd(OAc)) and 15.7 mg (0.06 mmol) of triphenylphosphine were added, and the mixture was heated to reflux at an internal temperature of 88-92 °C for 6 hours. After the reaction, the mixture was drained, and 100 mL of ion-exchanged water was added and washed five times with separation. After draining, 5 parts by weight of powdered activated carbon ("Carborafine" manufactured by Osaka Gas Chemicals Co., Ltd.) was added to the organic layer (100 parts by weight of DBrFDP-m) and stirred at 80 °C for 60 minutes to remove palladium. Insoluble matter was then removed by filtration. The organic layer was concentrated to remove 352.2 mL of MIBK, then heated to reflux at 110 °C to dissolve. After cooling, 18 mL of IPA was added at 80 °C, cooled to below 25 °C, and stirred for 1 hour to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain white crystals. 32.6 g of 2,7-DNFDP-m (white crystals, yield 94.0%, HPLC purity 99.6 area%) was obtained.

[0142] Example 21 2,7-DNFDP-m was obtained in the same manner as in Example 20, except that the purification step of DBrFDP-m described in Example 1 of JP 2005-89422 A was omitted in the synthesis of DBrFDP-m. The obtained 2,7-DNFDP-m was a white crystal with a yield of 78.3% and an HPLC purity of 99.5%. Note that the yield in Example 21 differs from the yields in other Examples and Comparative Examples and is the total yield from 2,7-dibromo-9H-fluorene.

[0143] The conversion rate and selectivity of the dicarboxylic acids (1a) obtained in the comparative examples and examples, the yield, purity, and Pd content of the dicarboxylic acids (1) were measured by the following methods (evaluation results), and the results are shown in Tables 3 and 4.

[0144] [Conversion and selectivity of 2,7-DNFDP-m] The HPLC (high performance liquid chromatograph) was performed using an "LC-2030C PlusPlus" manufactured by Shimadzu Corporation and an "ODS-80TM" manufactured by Tosoh Corporation. The sample after the reaction was dissolved in acetonitrile, and the conversion rate and selectivity of 2,7-DNFDP-m were calculated from the area percentage of each component according to the following formula.

[0145] Conversion rate = [100 - (area of ​​DBrFDP-m%)] x 100 (%) Selectivity = (area % of 2,7-DNFDP-m) / (total area % of 2,7-DNFDP-m and by-products) × 100 (%)

[0146] [Yield and purity of 2,7-DNFDP-m] Using the HPLC and the column, the purified sample was dissolved in acetonitrile and measured, and the HPLC yield and purity (area %) were calculated.

[0147] [Pd content of 2,7-DNFDP-m] ICP-MS: Measurement was performed using Agilent's "ICPMS8800".

[0148] [Table 1]

[0149] [Table 2]

[0150] [Table 3]

[0151] [Table 4]

[0152] Details of the abbreviations in the table are shown below.

[0153] (solvent) DME: Dimethoxyethane T. + IPA: toluene and isopropanol T. + MeOH: toluene and methanol T. + EtOH: Toluene and Ethanol T.+DO: Toluene and dioxane T. +DMF: Toluene and dimethylformamide T. + DMSO: Toluene and dimethyl sulfoxide T. + BuOH: Toluene and n-butanol T. + DME: Toluene and dimethoxyethane T.+MEK: Toluene and methyl ethyl ketone.

[0154] (catalyst species) (PPh3)4: Tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4] Cl2: Bis(triphenylphosphine)palladium(II) dichloride [Pd(PPh3)2Cl2] Dppf: [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride [Pd(dppf)Cl2] (OAc)2: Palladium(II) acetate [Pd(OAc)2].

[0155] (ligand) TPP: triphenylphosphine.

[0156] (base species) 2M, Na: 2M aqueous sodium carbonate solution 2M, K: 2M potassium carbonate solution.

[0157] (ratio) Catalyst amount [eq]: Molar ratio to 1 mole of DBrFDP-m Amount of base [eq]: Molar ratio to 1 mole of DBrFDP-m Amount of boronic acid [eq]: Molar ratio to 1 mole of DBrFDP-m.

[0158] (good solvent) EtOAc: ethyl acetate toluene * :Toluene is used in small amounts as a good solvent.

[0159] (Pd-free treatment) FP-6 20%: Powdered activated carbon ("Special Shirasagi FP-6" manufactured by Osaka Gas Chemicals Co., Ltd.) blended at a ratio of 20 parts by mass to 100 parts by mass of DBrFDP-m. Carbo 20%: Powdered activated carbon ("Carborafine" manufactured by Osaka Gas Chemicals Co., Ltd.) blended at a ratio of 20 parts by mass to 100 parts by mass of DBrFDP-m Carbo 10%: Powdered activated carbon ("Carborafine" manufactured by Osaka Gas Chemicals Co., Ltd.) blended at a ratio of 10 parts by mass to 100 parts by mass of DBrFDP-m Carbo 5%: Powdered activated carbon ("Carborafine" manufactured by Osaka Gas Chemicals Co., Ltd.) blended at a ratio of 5 parts by mass to 100 parts by mass of DBrFDP-m Carbo 2%: Powdered activated carbon ("Carborafine" manufactured by Osaka Gas Chemicals Co., Ltd.) blended at a ratio of 2 parts by mass to 100 parts by mass of DBrFDP-m.

[0160] (yield) As is clear from the results in Tables 3 and 4, the dicarboxylic acids (1) obtained in the examples had high yields and purities and were suppressed in coloration. In particular, selectivity and yield were improved in Examples 19 to 21, in which aliphatic ketones were used as the reaction solvent. The effect was remarkable in Examples 20 and 21, in which aliphatic ketones were used alone as the reaction solvent. In Example 21, selectivity and yield were improved even when the purification step of DBrFDP-m was omitted, and work efficiency was also improved.

[0161] Among the comparative examples, there are some examples in which the selectivity and yield were improved, but since the catalyst species was Pd(PPh3)4, it deteriorated in air and was difficult to handle, whereas in the examples, the catalyst was stable in air and was therefore easy to handle. [Industrial Applicability]

[0162] The dicarboxylic acids of the present invention exhibit high refractive index and heat resistance, and therefore can be effectively used as resin raw materials, or additives (or resin additives) such as refractive index improvers and heat resistance improvers.

Claims

1. The following formula (1) 【Chemistry 1】 (In the formula, Ring Z １ and ring Z ２ each independently represents a fused polycyclic arene ring; R １ and R ２ each independently represents a substituent; m1 and m2 each independently represents an integer of 0 or more; A １ and A ２ each independently represents a linear or branched alkylene group; R ３ and R ４ each independently represents a substituent, and n1 and n2 independently represent an integer of 0 to 3. A method for producing a dicarboxylic acid represented by the formula: A reaction solvent consisting of ketones and C １－２ In the presence of palladium(II) alkanoate, a compound represented by the following formula (2) 【Chemistry 2】 [In the formula, X １ and X ２ each independently represents a reactive group capable of forming a carbon-carbon bond by a coupling reaction; １ , A ２ , R ３ , R ４ , n1 and n2 are the same as in formula (1)] or a derivative thereof, and a dicarboxylic acid represented by the following formulas (3a) and (3b): 【Transformation 3】 [In the formula, X ３ and X ４ each independently represents a reactive group capable of forming a carbon-carbon bond by a coupling reaction; １ , ring Z ２ , R １ , R ２ , m1 and m2 are the same as in formula (1)]. a reaction step of coupling a fused polycyclic arene compound represented by the formula (1) with the dicarboxylic acid represented by the formula (1) or a derivative thereof, Said C １－２ The ratio of palladium (II) alkanoate is 0.01 to 5 moles per 100 moles of the dicarboxylic acid represented by the formula (2) or its derivative, and The method for producing a dicarboxylic acid derivative represented by the formulas (1) and (2) is a dicarboxylic acid ester, a dicarboxylic acid halide, a dicarboxylic acid anhydride, a dicarboxylic acid amide or a dicarboxylic acid salt.

2. The method according to claim 1, further comprising a purification step of crystallizing the dicarboxylic acid represented by formula (1) or a derivative thereof obtained in the reaction step using a crystallization solvent containing an aprotic solvent and a protic solvent.

3. 3. The method according to claim 2, wherein in the purification step, the dicarboxylic acid represented by formula (1) or a derivative thereof is treated with activated carbon and then crystallized.

4. In the formula (1), ring Z １ and Z ２ is a naphthalene ring, and A １ and A ２ is a linear or branched chain C ２－６ The method according to any one of claims 1 to 3, wherein the alkylene group is an alkylene group.

5. In the formula (1), ring Z １ and Z ２ The substitution positions are the 2 and 7 positions of the fluorene ring. , A １ and A ２ is a linear or branched chain C ２－４ The method according to any one of claims 1 to 3, wherein m1, m2, n1 and n2 are alkylene groups, and m1, m2, n1 and n2 are 0.

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