Dicarboxylic acids and their production method

Abstract

To provide novel dicarboxylic acids excellent in heat resistance and optical characteristics.SOLUTION: A novel dicarboxylic acid represented by the following formula (I) or a derivative thereof is produced by a coupling reaction between a compound having a fluorene skeleton and a compound having a condensed tetra- to hexacyclic arene ring skeleton. (In the formula, ring Z1a and ring Z1b each represent a tetra- to hexacyclic arene ring; R1a, R1b, R2a and R2b each represent a substituent; k1 and k2 each represent an integer of 0 or more; A1a and A1b are the same as or different from each other and each represent a linear or branched alkylene group; and n1 and n2 each represent an integer of 0-3.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel dicarboxylic acid having a fluorene skeleton or a derivative thereof, and a method for producing the same. [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] Patent Document 1 discloses that dicarboxylic acids having a specific chemical structure in which aryl groups are bonded to the 1-8 positions of a fluorene skeleton have excellent optical properties and heat resistance, and that when used as a polymerization component, a resin with remarkably excellent properties can be formed, despite the absence of an aryl group at the 9,9-position that is likely to improve the refractive index and glass transition temperature. In the examples of this document, naphthyl groups are described as the aryl groups bonded to the 1-8 positions 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 properties are required in terms of heat resistance and optical characteristics, and even the dicarboxylic acids of Patent Document 1 may not be sufficient.

[0006] Therefore, an object of the present invention is to provide novel dicarboxylic acids having excellent heat resistance and optical properties, and a method for producing the same. [Means for solving the problem]

[0007] As a result of extensive research to achieve the above object, the present inventors have discovered that novel dicarboxylic acids having a specific chemical structure in which fused tetracyclic to hexacyclic aryl groups are bonded to positions 1 to 8 of a fluorene skeleton have excellent heat resistance and optical properties, and have completed the present invention.

[0008] That is, the dicarboxylic acid or derivative thereof of the present invention is a dicarboxylic acid or derivative thereof represented by the following formula (I):

[0009] [ka]

[0010] (In the formula, Ring Z 1a and ring Z 1b are the same or different and represent a fused tetracyclic to hexacyclic arene ring, R 1a and R 1b are the same or different and represent substituents, k1 and k2 are the same or different and represent an integer of 0 or more, A 1a and A 1b are the same or different and represent a linear or branched alkylene group, R 2a and R 2b are the same or different and represent substituents, n1 and n2 may be the same or different and represent an integer of 0 to 3.

[0011] In the formula (I), Z 1a and Z 1b is a pyrene ring, and A 1a and A 1b is linear or branched chain C2-6 It may be an alkylene group. 1a and Z 1b The substitution positions of are the 2,7-positions of the fluorene ring, and A 1a and A 1b is linear or branched C 2-4 It is an alkylene group, and k1, k2, n1 and n2 may be 0.

[0012] The present invention provides a compound having a fluorene skeleton and a compound represented by the formula (I) in which the ring Z 1a and Z 1b and a compound having a fused tetra- to hexacyclic arene ring skeleton corresponding to the formula (I).

[0013] 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.

[0014] The dicarboxylic acid ester may be a dicarboxylic acid component 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.

[0015] 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]

[0016] In the present invention, a novel dicarboxylic acid or a derivative thereof having a specific chemical structure in which a fused tetracyclic to hexacyclic aryl group is bonded to positions 1 to 8 of a fluorene skeleton has excellent heat resistance and optical properties. DETAILED DESCRIPTION OF THE INVENTION

[0017] [Dicarboxylic acid or its derivatives] The novel dicarboxylic acid or derivative thereof (dicarboxylic acids) of the present disclosure is a dicarboxylic acid or derivative thereof represented by the above formula (I).

[0018] In the formula (I), Z 1a and Z 1b Examples of the fused tetracyclic to hexacyclic arene rings represented by the formula (I) include fused tetracyclic C rings such as a fluoranthene ring, an acephenanthrylene ring, an aceanthrylene ring, a triphenylene ring, a pyrene ring, a chrysene ring, a tetraphene ring, and a tetracene ring (a naphthacene ring). 16-18 Arene ring; fused pentacyclic rings such as picene ring, perylene ring, pentaphene ring, and pentacene ring 20-22 Arene rings; fused hexacyclic rings such as hexahelicene rings, hexaphene rings, and hexacene rings 24-28 Among these, fused tetracyclic arene rings are preferred from the viewpoint of excellent heat resistance and optical properties, and fused tetracyclic C 16-18 An arene ring is more preferred, and a pyrene ring is most preferred. 1a Types of ring Z 1b The types may be different from each other, but are preferably the same.

[0019] Ring Z 1a and Z 1b may be substituted at any of the 1- to 4-positions and the 5- to 8-positions of the fluorene skeleton, but are preferably symmetrically positioned on the paper in formula (I), such as the 1,8-positions, 2,7-positions, 3,6-positions, or 4,5-positions, and are particularly preferably 2,7-positions. 1a and Z 1bWhen is a pyrene ring, the 1st or 2nd position of the pyrene ring is preferably bonded to the fluorene ring, and the 1st position of the pyrene ring is particularly preferably bonded to the fluorene ring.

[0020] R 1a and R 1b Examples of the substituent (non-reactive substituent or non-polymerizable substituent) represented by the formula (I) include a halogen atom, a hydrocarbon group (or a group [-R A ]), the group [-OR A ](wherein, R A represents the hydrocarbon group), the group [—SR A ](wherein, R A represents the above hydrocarbon group), an acyl group, a nitro group, a cyano group, and a mono- or di-substituted amino group.

[0021] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0022] R A Examples of the hydrocarbon group represented by the formula include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0023] Examples of the alkyl group include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. 1-10 alkyl groups, preferably straight-chain or branched-chain C 1-6 Alkyl groups, more preferably linear or branched C 1-4 It is an alkyl group.

[0024] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are exemplified.

[0025] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl). 1-4 Examples include alkyl-phenyl groups.

[0026] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples of suitable alkyl groups include:

[0027] The group [-OR A ] includes, for example, an alkoxy group, a cycloalkyloxy group, an aryloxy group, and an aralkyloxy group. A Examples of the alkoxy group include a linear or branched C alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. 1-10 Examples of the cycloalkyloxy group include a C alkoxy group such as a cyclohexyloxy group. 5-10 Examples of the aryloxy group include a C aryloxy group such as a phenoxy group. 6-10 Examples of the aralkyloxy group include C aryloxy groups such as benzyloxy groups. 6-10 Aryl-C 1-4 An example is an alkyloxy group.

[0028] The group [—SR A ] includes, for example, an alkylthio group, a cycloalkylthio group, an arylthio group, and an aralkylthio group. A Examples of the alkylthio group include groups corresponding to the following: C methylthio group, ethylthio group, propylthio group, n-butylthio group, t-butylthio group, etc. 1-10 Examples of the cycloalkylthio group include a C alkylthio group such as a cyclohexylthio group. 5-10Examples of the arylthio group include a C thiophenoxy group. 6-10 Examples of the aralkylthio group include a C arylthio group such as a benzylthio group. 6-10 Aryl-C 1-4 Examples include alkylthio groups.

[0029] Acyl groups include C groups such as acetyl groups. 1-6 Examples include alkyl-carbonyl groups.

[0030] Examples of the mono- or di-substituted amino group include a dialkylamino group and a bis(alkylcarbonyl)amino group. Examples of the dialkylamino group include a di-C group such as a dimethylamino group. 1-4 Examples of the bis(alkylcarbonyl)amino group include bis(C 1-4 alkyl-carbonyl)amino groups.

[0031] These groups R 1a and R 1b Among these, representative examples include hydrocarbon groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. When k1 or k2 is 1 or more, preferred groups R 1a and R 1b The alkyl group and the alkoxy group are linear or branched C groups such as methyl groups. 1-6 Linear or branched C such as alkyl group or methoxy group 1-4 Alkoxy groups are exemplified, among which alkyl groups, particularly straight or branched C groups such as methyl groups, are preferred. 1-4 An alkyl group is preferred. 1a or R 1b is an aryl group, the group R 1a or R 1b are rings Z 1a or Z 1b may form the ring assembly arene ring together with

[0032] The substitution numbers k1 and k2 are 1a and Z 1b For example, it can be selected from integers of about 0 to 12, and preferred ranges are the following stepwise integers of 0 to 6, 0 to 5, 0 to 4, 0 to 3, and 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0033] base R 1a and R 1b The numbers of substitutions k1 and k2 may be different from each other, but are usually the same. When the number of substitutions k1 or k2 is 2 or more, the number of substitutions k1 and k2 may be the same as the number of substitutions k2 on the same ring Z 1a or Z 1b Two or more groups R 1a or R 1b The types of rings Z may be the same or different. 1a and Z 1b The group R to be substituted 1a and R 1b The types of groups R may be different from each other, but are usually the same. 1a and R 1b The substitution position of ring Z is not particularly limited. 1a and Z 1b The selection may be made depending on the type of

[0034] R 2a and R 2b The substituent represented by the formula (non-reactive or non-polymerizable substituent) is a group [-Z 1a -(R 1a ) k1 ] and the group [-Z 1b -(R 1b ) k2 ] (Hereafter, these are referred to as Z 1 The substituent may be any other substituent than a group containing the alkyl group, and representative examples thereof include hydrocarbon groups such as alkyl groups (excluding aryl groups), halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, and cyano groups. Examples of the alkyl group include linear or branched C groups such as methyl groups, ethyl groups, and t-butyl groups. 1-6 When the number of substitutions n1 or n2 is 1 or more, preferred R2a and R 2b As the alkyl group, linear or branched C 1-4 It is an alkyl group.

[0035] R 2a and R 2b The substitution numbers n1 and n2 are, for example, integers of about 0 to 3, preferably integers of 0 to 2, more preferably 0 or 1, and particularly preferably 0. n1 and n2 may be different from each other, but are usually the same in many cases. Note that when n1 or n2 is 2 or more, the number of R substituted on the same benzene ring among the two benzene rings forming the fluorene skeleton is 2 or more. 2a or R 2b The types of R may be the same or different. In addition, of the two benzene rings forming the fluorene skeleton, R substituted on different benzene rings may be 2a and R 2b The types of R may be the same or different from each other, but are usually the same. 2a and R 2b The substitution position of Z is not particularly limited. 1 It is sufficient that the substituent is at a position other than the substitution position of the containing group.

[0036] Base A 1a and A 1b 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 Preferred alkylene groups include linear or branched C alkylene groups such as methylene, ethylene, trimethylene, propylene, and 2-methylpropane-1,3-diyl. 1-6 alkylene groups, more preferably linear or branched C 1-4 alkylene group, more preferably a linear or branched C 2-4 Alkylene groups, especially linear or branched C groups such as ethylene and propylene groups. 2-3An alkylene group is preferred, and an ethylene group is particularly preferred.

[0037] Examples of the dicarboxylic acid represented by the formula (I) include 9,9-bis(carboxy C) compounds such as 9,9-bis(2-carboxyethyl)-1,8-di(1-pyrenyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-di(1-pyrenyl)fluorene, 9,9-bis(2-carboxyethyl)-3,6-di(1-pyrenyl)fluorene, 9,9-bis(2-carboxyethyl)-4,5-di(1-pyrenyl)fluorene, 9,9-bis(2-carboxypropyl)-2,7-di(1-pyrenyl)fluorene, and 9,9-bis(2-carboxyethyl)-2,7-di(2-pyrenyl)fluorene. 2-6 Among these, 9,9-bis(2-carboxyethyl)-2,7-di(1-pyrenyl)fluorene is preferred.

[0038] The dicarboxylic acid represented by the formula (I) or its derivative has a high refractive index and high heat resistance.

[0039] The 5% mass loss temperature of the dicarboxylic acid represented by the formula (I) or its derivative may be, for example, about 350 to 500°C, and preferred ranges are 370 to 480°C, 390 to 470°C, 400 to 460°C, 410 to 450°C, 420 to 440°C, and 430 to 435°C, in the following stepwise order.

[0040] In this specification and claims, the 5% mass loss temperature of the dicarboxylic acid represented by the formula (I) or its derivative can be measured by the method described in the examples below.

[0041] [Method of producing dicarboxylic acid or its derivative] The method for producing the dicarboxylic acid or its derivative (dicarboxylic acid) of the present disclosure is not particularly limited, and may be a conventional method, for example, a method for producing a compound having a fluorene skeleton and a compound having the ring Z in the formula (I). 1a and Z 1band a compound having a fused tetra- to hexacyclic arene ring skeleton corresponding to the formula (II), to introduce a fused tetra- to hexacyclic aryl group corresponding to the compound having the fused tetra- to hexacyclic arene ring skeleton into at least one substitution position selected from positions 2 to 8 of the fluorene skeleton. More specifically, the compound may be produced by coupling reaction (or cross-coupling reaction) of a dicarboxylic acid represented by formula (II) below or a derivative thereof with compounds represented by formulas (IIIa) and (IIIb) below according to the following reaction scheme (hereinafter also referred to as the first production method).

[0042] [ka]

[0043] (In the formula, X 1a and X 1b each independently represents a reactive group capable of forming a carbon-carbon bond (or a direct bond) by a coupling reaction; X 2a is the reactive group X 1a and X 2b is the reactive group X 1b and each represents a reactive group capable of forming a carbon-carbon bond by a coupling reaction; Z 1a , Z 1b , R 1a , R 1b , k1, k2, R 2a , R 2b , n1, n2, A 1a , A 1b are the same as those in the formula (I) above, including preferred embodiments.

[0044] The coupling reaction is not particularly limited and includes conventional coupling reactions, such as palladium-catalyzed (or palladium(0)-catalyzed) coupling reactions such as the Suzuki-Miyaura coupling reaction, the Migita-Kosugi-Stille coupling reaction, the Negishi coupling reaction, and the Hiyama coupling reaction, and nickel-catalyzed (or nickel(0)-catalyzed) coupling reactions such as the Kumada-Tamao-Corriu coupling reaction. Of these coupling reactions, the Suzuki-Miyaura coupling reaction is frequently used.

[0045] Reactive Group X 1a and X 1b and X 2a and X 2b can be appropriately selected depending on the type of the coupling reaction. When synthesis is carried out by Suzuki-Miyaura coupling reaction, one reactive group, for example, group X 1a and X 1b Examples of the fluorinated alkanesulfonyloxy group include a halogen atom or a fluorinated alkanesulfonyloxy group. Examples of the halogen atom include an iodine atom, a bromine atom, and a chlorine atom. Examples of the fluorinated alkanesulfonyloxy group include a fluorinated alkanesulfonyloxy group such as a trifluoromethanesulfonyloxy group (or a group [-OTf]). 1-4 An example is an alkanesulfonyloxy group.

[0046] These one-reactive groups may be used alone or in combination of two or more. Among these one-reactive groups, a halogen atom is preferred, an iodine atom and a bromine atom are more preferred, and a bromine atom is usually used most often.

[0047] In the Suzuki-Miyaura coupling reaction, the one reactive group can be coupled with another reactive group, such as a group X 2a and X 2bExamples of the boronic acid group include a boronic acid group (dihydroxyboryl group or group [-B(OH)2]) and a boronate ester group. Examples of the boronate ester group include dialkoxyboryl groups such as a dimethoxyboryl group, a diisopropoxyboryl group, and a dibutoxyboryl group; and cyclic boronate ester groups such as a pinacolatoboryl group (or group [-Bpin]), a 1,3,2-dioxaborinan-2-yl group, and a 5,5-dimethyl-1,3,2-dioxaborinan-2-yl group.

[0048] These other reactive groups may be used alone or in combination of two or more. Of the other reactive groups, the group [—B(OH) 2 ] is usually used frequently.

[0049] In addition, the group X 1a and X 1b and group X 2a and X 2b The groups X may be any reactive groups as long as they are a pair of reactive groups capable of coupling reaction with each other. 1a and X 1b is the other reactive group such as a boronic acid group, and group X 2a and X 2b may be one of the reactive groups such as a halogen atom, but is usually a group X 1a and X 1b is one of the reactive groups such as a halogen atom, and the group X 2 is often the other reactive group such as a boronic acid group.

[0050] The dicarboxylic acid represented by the formula (II) or its derivatives are usually the dicarboxylic acid esters exemplified as the ester-forming derivatives. Specific dicarboxylic acids represented by the formula (II) or its derivatives include compounds corresponding to the preferred embodiments of the dicarboxylic acid represented by the formula (I), such as 9,9-bis(C fluorene)s 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)-dihalofluorenes.

[0051] The dicarboxylic acid represented by the formula (II) or a derivative thereof may be prepared, for example, in accordance with the method described in JP-A-2005-89422. Specifically, it may be prepared by a method in which a 9H-fluorene unsubstituted at the 9-position, such as 2,7-dibromofluorene, is reacted 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.

[0052] The compounds represented by the formulas (IIIa) and (IIIb) include compounds corresponding to preferred embodiments of the dicarboxylic acid represented by the formula (I), such as 1-pyrenylboronic acid and 2-pyrenylboronic acid, with 1-pyrenylboronic acid being preferred. The compounds represented by the formulas (IIIa) and (IIIb) are preferably the same compound. The compounds represented by the formulas (IIIa) and (IIIb) are commercially available products.

[0053] The ratio of the dicarboxylic acid represented by the formula (II) or its derivative to the total amount of the compounds represented by the formulas (IIIa) and (IIIb) 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 manner.

[0054] When synthesis is carried out by the Suzuki-Miyaura coupling reaction, the reaction is usually carried out in the presence of a palladium catalyst, such as a conventional coupling catalyst, for example, a palladium(0) catalyst or a palladium(II) catalyst.

[0055] Examples of palladium(0) catalysts 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].

[0056] Examples of palladium(II) catalysts include palladium(II)-phosphine complexes such as [1,2-bis(diphenylphosphino)ethane]palladium(II) dichloride (or PdCl(dppe)], [1,3-bis(diphenylphosphino)propane]palladium(II) dichloride (or PdCl(dppp)], [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (or PdCl(dppf)], bis(triphenylphosphine)palladium(II) dichloride (or PdCl(PPh)), and bis(tri-o-tolylphosphine)palladium(II) dichloride (or PdCl(P(o-tolyl))). When a palladium(II) catalyst is used, the reaction begins by reduction to a zero-valent complex with a reducing compound in the reaction system, such as a phosphine, amine, or organometallic reagent.

[0057] The palladium catalyst may be prepared in situ by adding a catalyst precursor such as tris(dibenzylideneacetone)dipalladium(0) chloroform complex [or Pd2(dba)3·CHCl3] to a ligand such as a phosphine or carbene.

[0058] These catalysts can be used alone or in combination of two or more. Among these catalysts, palladium(0)-phosphine complexes such as Pd(PPh3)4 are usually used. The proportion of the catalyst, calculated as metal, may be, for example, about 0.01 to 0.1 moles, preferably 0.03 to 0.07 moles, per mole of the dicarboxylic acid represented by the formula (II) or its derivative.

[0059] The Suzuki-Miyaura coupling reaction may be carried out in the presence of a base, such as a metal carbonate or hydrogen carbonate, a metal hydroxide, a metal fluoride, a metal phosphate, a metal organic acid salt, or a metal alkoxide.

[0060] Examples of metal carbonates or hydrogen carbonates include alkali metal carbonates or hydrogen carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, and sodium hydrogen carbonate, and thallium (I) carbonate.

[0061] Examples of metal hydroxides include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, and thallium(I) hydroxide.

[0062] Examples of metal fluorides include alkali metal fluorides such as potassium fluoride and cesium fluoride.

[0063] Examples of metal phosphates include alkali metal phosphates such as tripotassium phosphate.

[0064] Examples of metal organic acid salts include alkali metal acetates such as potassium acetate.

[0065] Examples of metal alkoxides include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[0066] These bases can be used alone or in combination of two or more. Usually, metal carbonates such as potassium carbonate are frequently used. The ratio of the base may be, for example, about 0.1 to 50 moles, preferably 1 to 25 moles, per mole of the dicarboxylic acid represented by the formula (II) or its derivative.

[0067] The coupling reaction may be carried out in the presence or absence of a phase transfer catalyst. Examples of the phase transfer catalyst include tetraalkylammonium halides such as tetrabutylammonium bromide (TBAB) and trioctylmethylammonium chloride. These phase transfer catalysts can be used alone or in combination. Among these phase transfer catalysts, TBAB is commonly used.

[0068] The coupling reaction may be carried out in the absence or presence of an inert solvent. Examples of the solvent include water; alcohols such as methanol and ethanol; ethers such as cyclic ethers and chain ethers; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; nitriles such as acetonitrile and benzonitrile; amides such as N,N-dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide; and hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0069] Examples of cyclic ethers include dioxane and tetrahydrofuran. Examples of chain ethers include dialkyl ethers such as diethyl ether and diisopropyl ether, and glycol ethers. Examples of glycol ethers include (poly)alkylene glycol monoalkyl ethers such as methyl cellosolve and methyl carbitol, and (poly)alkylene glycol dialkyl ethers such as dimethoxyethane.

[0070] Examples of aliphatic hydrocarbons include hexane and dodecane. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include toluene and xylene.

[0071] These solvents can be used alone or in combination of two or more. Among these solvents, a mixed solvent of water and a chain ether such as dimethoxyethane is usually used.

[0072] The coupling reaction may be carried out under an inert gas atmosphere, for example, under an atmosphere of nitrogen or a rare gas such as helium or argon. The reaction temperature is, for example, 50 to 200° C., preferably 60 to 100° C. The reaction time is not particularly limited and may be, for example, about 1 to 10 hours.

[0073] After completion of the reaction, the reaction mixture may be separated and purified, if necessary, by a conventional separation and purification method, such as washing, extraction, filtration, dehydration, concentration, decantation, recrystallization, reprecipitation, chromatography, or a combination thereof.

[0074] Furthermore, the dicarboxylic acid represented by the formula (I) or its derivative may be produced into a compound represented by the formula (I) by a second production method shown in the following reaction scheme.

[0075] [ka]

[0076] (In the formula, X 1a , X 1b , X 2a and X 2b is the same as the formulas (II), (IIIa) and (IIIb) including preferred embodiments thereof, and Z 1a , Z 1b , R 1a , R 1b , k1, k2, R 2a , R 2b , n1, n2, A 1a , A 1b are the same as those in the formula (I) above, including preferred embodiments.

[0077] In the second production method, instead of the dicarboxylic acid represented by formula (II) or its derivative in the first production method, 9H-fluorenes represented by formula (IV) are used to couple with compounds represented by formulas (IIIa) and (IIIb), and the resulting compound represented by formula (V) is used as a 9H fluorene unsubstituted at the 9-position in the method described in the above-mentioned JP-A-2005-89422 to produce a compound represented by formula (I). That is, in the second production method, A substituted at the 9-position of the fluorene skeleton is used. 1a or A 1b containing group and the Z 1 The order of introduction of the containing groups is different from that in the first production method.

[0078] The 9H-fluorenes represented by the formula (IV) include those having a coupling reactive group and unsubstituted at the 9-position, such as dihalofluorenes such as 2,7-dibromofluorene. The compound represented by the formula (IV) may be a commercially available product. [Example]

[0079] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0080] 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.

[0081] 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, 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.

[0082] [ka]

[0083] Example 1 Using the same method as in Comparative Example 1 except for using 1-pyrenylboronic acid instead of 2-naphthylboronic acid, 5.5 g of 9,9-bis(2-methoxycarbonylethyl)-2,7-di(1-pyrenyl)fluorene (2,7-DPyFDP-m) represented by the following formula (white crystals, yield 36.8%) was obtained.

[0084] [ka]

[0085] Comparative Example 2 Using the same method as in Comparative Example 1 except for using phenylboronic acid instead of 2-naphthylboronic acid, 119.7 g of 9,9-bis(2-methoxycarbonylethyl)-2,7-diphenylfluorene (2,7-DPFDP-m) represented by the following formula (white crystals, yield 80.1%) was obtained.

[0086] [ka]

[0087] The 5% mass loss temperatures of the dicarboxylic acids obtained in Comparative Examples 1 and 2 and Example 1 were measured by the following method. The results are shown in Table 1.

[0088] (5% mass reduction temperature) Using a thermogravimetry-differential thermal analyzer (TG-DTA) (TG / DTA6200 manufactured by SII NanoTechnology Inc.), the temperature at which the sample mass decreased by 5% by mass was measured under conditions of a nitrogen atmosphere and a heating rate of 10°C / min.

[0089] [Table 1]

[0090] As is clear from the results in Table 1, the dicarboxylic acids of the examples were superior in heat resistance to the dicarboxylic acids of the comparative examples. [Industrial Applicability]

[0091] 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 (I) 【Chemical 1】 (In the formula, Ring Z １ａ and ring Z １ｂ are the same or different and represent a fused tetra- to hexacyclic arene ring, R １ａ and R １ｂ are the same or different and represent substituents, k1 and k2 represent 0, A １ａ and A １ｂ are the same or different and represent a linear or branched alkylene group, R ２ａ and R ２ｂ are the same or different and represent substituents, n1 and n2 are the same or different and represent an integer of 0 to 3. or a derivative thereof, A dicarboxylic acid or a derivative thereof, wherein the derivative is a dicarboxylic acid ester, a dicarboxylic acid halide, a dicarboxylic acid anhydride, a dicarboxylic acid amide or a dicarboxylic acid salt.

2. In the formula (I), Z １ａ and Z １ｂ is a pyrene ring, and A １ａ and A １ｂ is linear or branched C ２－６ 2. The dicarboxylic acid or derivative thereof according to claim 1, wherein the dicarboxylic acid is an alkylene group.

3. Z １ａ and Z １ｂ is substituted at the 2,7-position of the fluorene ring, １ａ and A １ｂ is a linear or branched chain C ２－４ 3. The dicarboxylic acid or derivative thereof according to claim 1, wherein n1 and n2 are alkylene groups and n1 and n2 are 0.

4. A compound having a fluorene skeleton and a compound having the ring Z in the formula (I) １ａ and Z １ｂ 4. The method for producing the dicarboxylic acid or a derivative thereof according to claim 1, comprising a step of coupling reaction with a compound having a fused tetra- to hexacyclic arene ring skeleton corresponding to

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