JP2009227603A - Method of manufacturing polycarboxylic acid having fluorene skeleton - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for simply and efficiently manufacturing a polycarboxylic acid having a fluorene skeleton [for example, 9,9-bis(carboxy 1-4C alkoxyphenyl)fluorene and the like]. <P>SOLUTION: The manufacturing method comprises reacting a compound represented by formula (2) with a carboxylic acid represented by formula (3) or a derivative thereof (for example, an ester, or an alkali or alkaline earth metal salt) in the presence of a basic compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a polycarboxylic acid having a fluorene skeleton (specifically, a 9,9-bis (phenyl) fluorene skeleton) and a novel polycarboxylic acid obtained by this method.

  A compound having a fluorene skeleton such as a 9,9-bisphenylfluorene skeleton has an excellent function in terms of refractive index and heat resistance, and is known to be used as a resin raw material. As a method for expressing such an excellent function of the fluorene skeleton in a resin, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), for example, bisphenol fluorene (BPF), biscresol fluorene (BCF), bis In general, aminophenylfluorene (BAFL), bisphenoxyethanol fluorene (BPEF) or the like is used as a constituent component of the resin, and a fluorene skeleton is introduced into a part of the skeleton structure of the resin. For example, as a polyester resin having such a fluorene skeleton, JP 2002-284864 A (Patent Document 1) discloses a molding material composed of a polyester resin having a 9,9-bisphenylfluorene skeleton. Yes. JP-A-2004-339499 (Patent Document 2) discloses resins containing bisphenol fluorene, bisaminophenyl fluorene, bisphenoxyethanol fluorene, or the like as polymerization components (polyester resin, polycarbonate resin, urethane resin, acrylic resin). A resin, a polyamide resin, a polyimide resin, an epoxy resin, a vinyl ester resin, a phenol resin, an aniline resin, and the like) and an additive are disclosed.

  Thus, conventionally, as a compound having a fluorene skeleton used for a resin raw material or the like, a compound having a hydroxyl group (including a phenolic hydroxyl group) or an amino group as a reactive substituent has been generally used. In developing a resin having a fluorene skeleton having functions and properties, a fluorene skeleton-containing compound having a carboxyl group is being demanded.

  Examples of the fluorene skeleton-containing compound having a carboxyl group as a reactive substituent include aliphatic dicarboxylic acids (aromatics) in addition to aromatic dicarboxylic acids such as 9,9-bis (4-carboxyphenyl) fluorene. Development of aliphatic dicarboxylic acids) is demanded. An aliphatic dicarboxylic acid having such a fluorene skeleton is still under development, but Chem. Lett, 1998, 27, 1055-1056 (Non-patent Document 1) discloses 9,9-bis [4- ( Along with 2-hydroxyethoxy) phenyl] fluorene and the like, 9,9-bis [4- (2-carboxyethoxy) phenyl] fluorene is disclosed as one compound thereof. In this document, as a typical synthesis method of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 0.25 mol of fluorenone, 1.00 mol of phenoxyethanol, 0. 3-mercaptopropionic acid. It was described that the reaction was performed by adding 0.22 mol of concentrated sulfuric acid to the mixture with 0015 mol (yield 73.8%), and 9,9-bis [4- (2-carboxyethoxy) The yield of phenyl] fluorene is 70.5%.

However, in the synthesis method of this document, it is necessary to use a large amount of phenoxy compound (phenoxypropionic acid) of about twice the theoretical amount, and the yield is not sufficient. In addition, since concentrated sulfuric acid is used as a catalyst, sulfuric acid removal and subsequent treatment are required, which is not an industrially advantageous method. It is also necessary to use mercaptopropionic acid having a strong odor in addition to sulfuric acid as a catalyst. Furthermore, in the method of this document, the reaction system tends to become viscous, and the reaction control becomes difficult. Furthermore, when sulfuric acid remains, there is a possibility that the quality may deteriorate.
JP 2002-284864 A (Claims) JP 2004-339499 A (claims, paragraph number [0032]) Chem. Lett, 1998, 27, 1055-1056

  Therefore, an object of the present invention is to easily produce a polycarboxylic acid having a fluorene skeleton [specifically, an aliphatic polycarboxylic acid having a fluorene skeleton such as 9,9-bis (4-carboxymethoxyphenyl) fluorene]. It is another object of the present invention to provide a method for producing efficiently and a polycarboxylic acid having a novel fluorene skeleton obtained by this method.

  Another object of the present invention is to provide a method for producing a polycarboxylic acid having a fluorene skeleton in a high yield even when the reaction is carried out in a proportion close to the theoretical amount, and a novel polycarboxylic acid having a fluorene skeleton obtained by this method. To provide acid.

  Still another object of the present invention is to provide a method for conveniently and industrially advantageously producing a polycarboxylic acid having a fluorene skeleton and a novel carboxylic acid having a fluorene skeleton obtained by this method. .

In order to achieve the above object, the present inventors have conducted extensive studies on a method for producing a polycarboxylic acid having a fluorene skeleton. As a result, 9,9-bis (hydroxyphenyl) fluorenes and halo fatty acids (for example, haloacetic acid, etc.) Haloalkanoic acid) or a derivative thereof (for example, C _1-4 alkyl ester, alkali metal salt such as sodium salt) is reacted with a corresponding polycarboxylic acid [for example, 9,9-bis (carboxy It was found that 9,9-bis (carboxy C _1-4 alkoxyphenyl) fluorene such as methoxyphenyl) fluorene] can be efficiently obtained in high yield, and the present invention was completed.

  That is, the present invention provides the following formula (1) in the presence of a basic compound.

(Wherein R ¹ is a cyano group, halogen atom or alkyl group, R ² is a hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, halogen atom, nitro group, cyano A group or a substituted amino group, R ³ represents an aliphatic hydrocarbon group, k is an integer of 0 to 4, m is an integer of 0 to 4, and n is an integer of 1 to 5. However, the total of m and n Is an integer of 5 or less.)
A carboxylic acid represented by the following formula (2):

(In the formula, R ¹ , R ² , k, m, and n are the same as described above.)
And a compound represented by the following formula (3)

(In the formula, X represents a halogen atom, and R ³ is the same as described above.)
It is a manufacturing method including the process with which the carboxylic acid represented by these, or its derivative (s) is made to react.

In the formula (2), R ² may be a group selected from a C _1-4 alkyl group and a C _6-10 aryl group, and m may be 0-2. In the formula (3), R ³ may be a C _1-4 alkylene group.

Typically, in the method of the present invention, the compound represented by the formula (2) and the ester of the carboxylic acid represented by the formula (3) (for example, an alkyl ester such as a C _1-4 alkyl ester). And a compound selected from a salt (for example, a metal salt such as an alkali metal salt) may be reacted.

  In the method of the present invention, the carboxylic acid represented by the formula (1) can be obtained with a high yield even at a usage rate relatively close to the theoretical amount. Therefore, in the method of the present invention, for example, about 1 to 1.5 mol of the carboxylic acid represented by the formula (3) or a derivative thereof is added to 1 mol of the hydroxyl group of the compound represented by the formula (2). May be used.

  In the method, the reaction between the compound represented by the formula (2) and the carboxylic acid represented by the formula (3) or a derivative thereof is particularly selected from polar organic solvents (for example, alcohols and sulfoxides). Or in the presence of at least one solvent).

  The present invention also includes a carboxylic acid represented by the following formula (1A). Such a carboxylic acid may be a carboxylic acid obtained by the above method or a carboxylic acid obtained by another method (for example, the method of Non-Patent Document 1).

(In the formula, R ¹ , R ² , R ³ , k, m, and n are the same as above. However, when m is 0 and n is 1, R ³ is not an ethylene group.)
In the above formula (1A), typically, R ² is a group selected from a C _1-4 alkyl group and a C _6-10 aryl group, m is 0 to 2, and R ³ is a methylene group. Yes, n may be 1 to 3. Such a carboxylic acid is superior in heat resistance and the like as compared with 9,9-bis [4- (2-carboxyethoxy) phenyl] fluorene.

  In the present specification, the “class” such as a compound name includes a case of “having no substituent” and a case of “having a substituent”, and “may have a substituent”. May mean.

  In the method of the present invention, a 9,9-bis (hydroxyphenyl) fluorene is reacted with a halo fatty acid or a derivative thereof to produce a polyene having a fluorene skeleton without requiring a catalyst such as concentrated sulfuric acid or mercaptopropionic acid. Carboxylic acid can be produced easily and efficiently. In particular, according to the method of the present invention, a polycarboxylic acid having a fluorene skeleton can be obtained in a high yield even when the reaction is performed at a ratio close to the theoretical amount by selecting the type of the solvent. Moreover, the starting carboxylic acid or its derivative is often obtained at low cost. Therefore, the method of the present invention is industrially advantageous and is a production process with extremely high practicality.

  The production method of the present invention comprises the following formula (1):

(In the formula, R ¹ is a substituent, R ² is a substituent, R ³ is an aliphatic hydrocarbon group, k is an integer of 0-4, m is an integer of 0-4, and n is an integer of 1-5. (However, the sum of m and n is an integer of 5 or less.)
A carboxylic acid represented by the following formula (2):

(In the formula, X represents a halogen atom, and R ¹ , R ² , R ³ , k, m, and n are the same as above.)
And a compound represented by the following formula (3)

(In the formula, X represents a halogen atom, and R ³ is the same as described above.)
Is a production method including at least a step of reacting the carboxylic acid (halocarboxylic acid, halofatty acid) represented by

[Compound represented by Formula (2)]
In the formula (2), examples of the substituent represented by the group R ¹ include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [for example, an alkyl group, an aryl group ( C _6-10 aryl group such as phenyl group)], etc.], and the like, in particular, are often cyano groups or alkyl groups (particularly alkyl groups). Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . In addition, when k is plural (two or more), the groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number k is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

In the formula (2), the substituent represented by R ² is a substituent other than a carboxyl group (particularly a non-reactive substituent), for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group). Group, isopropyl group, butyl group, s-butyl group, t-butyl group and the like, C _1-20 alkyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group, etc.), cycloalkyl group (C _5-10 cycloalkyl group such as cyclopentyl group and cyclohexyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group etc.), aryl group [for example, phenyl group, alkyl Phenyl group (methylphenyl group (or tolyl group, 2-methylphenyl group, 3-methylphenyl group, etc.), dimethylphenyl group (xylyl group), etc. ), A C _6-10 aryl group such as a naphthyl group, preferably a C _6-8 aryl group, particularly a phenyl group], an aralkyl group (a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group or a phenethyl group). Hydrocarbon groups such as etc .; C _1-20 alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy group, preferably C _1-8 alkoxy group, More preferably, a C _1-6 alkoxy group), a cycloalkoxy group (C _5-10 cycloalkyloxy group such as cyclohexyloxy group), an aryloxy group (C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (e.g., _{C 6-10} aryl _{-C 1-4} alkyl group such as a benzyl group), etc. Ether group (substituted hydroxyl group); an alkylthio group (methylthio group, ethylthio group, propylthio group, n- butylthio group, _{C 1-20} alkylthio group such as t- butylthio group, preferably a _{C 1-8} alkylthio group, more preferably C _1-6 alkylthio group), cycloalkylthio group (C _5-10 cycloalkylthio group such as cyclohexylthio group), arylthio group (C _6-10 arylthio group such as thiophenoxy group), aralkylthio group (for example, Thioether groups (substituted mercapto groups) such as C _6-10 aryl-C _1-4 alkylthio groups such as benzylthio groups; acyl groups (such as C _1-6 acyl groups such as acetyl groups); hydroxyl groups; halogen atoms ( Fluorine, chlorine, bromine, iodine, etc.); nitro ; And the like substituted amino group (such as dialkylamino group); a cyano group.

Of these, the group R ² is preferably a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a halogen atom, a nitro group, a cyano group, or a substituted amino group, The preferred group R ² is a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group)], alkoxy group (eg, C _1-4 alkoxy group), halogen atom (fluorine atom, chlorine atom, bromine). Atoms, iodine atoms, etc.).

In the same benzene ring, when m is plural (2 or more), the groups R ² may be different from each other or the same. In the two benzene rings, the groups R ² may be the same or different. The substitution position of the group R ² is not particularly limited, and for example, it may be substituted at an appropriate position (for example, the 3rd position, the 3rd, 5th position, etc.) of the 2-6 position of the phenyl group. Further, the preferred substitution number m may be 0 to 4, preferably 0 to 3, and more preferably 0 to 2. In the two benzene rings, the number of substitutions m may be the same or different from each other.

  Moreover, in the said Formula (2), the substitution number n of a hydroxyl group should just be 1-5, for example, 1-4, Preferably 1-3, More preferably, 1-2 may be sufficient. The number of substitutions n may be the same or different in each benzene ring and is usually the same in many cases. The substitution position of the hydroxyl group is not particularly limited, as long as it is substituted at an appropriate substitution position of the benzene ring (for example, the 3-position, 4-position, etc. of the phenyl group), preferably at least the 4-position. (When n is 1, the 4th position; when n is 2, the 3rd and 4th positions, the 2nd and 4th positions, etc.).

  As typical compounds [9,9-bis (hydroxyphenyl) fluorenes] represented by the formula (2), for example, 9,9-bis (monohydroxyphenyl) fluorenes, 9,9-bis (dihydroxy) Phenyl) fluorenes, 9,9-bis (trihydroxyphenyl) fluorenes [for example, 9,9-bis (2,3,4-trihydroxyphenyl) fluorene, 9,9-bis (2,4,6- 9,9-bis (tri) such as trihydroxyphenyl) fluorene, 9,9-bis (2,4,5-trihydroxyphenyl) fluorene, 9,9-bis (3,4,5-trihydroxyphenyl) fluorene Hydroxyphenyl) fluorene, etc.], usually 9,9-bis (monohydroxyphenyl) fluorenes or 9,9-bis (dihydroxyphenyl) Yl) fluorenes, can be suitably used especially 9,9-bis (mono-hydroxyphenyl) fluorenes.

Examples of 9,9-bis (monohydroxyphenyl) fluorenes include 9,9-bis (hydroxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene (bisphenolfluorene or 4,4 ′-( 9-fluorenylidene) diphenol), etc.], 9,9-bis (hydroxyphenyl) fluorene having a substituent {for example, 9,9-bis (alkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy- 3-methylphenyl) fluorene (biscresol fluorene), 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-butylphenyl) fluorene, 9,9- 9,9-bis (C, such as bis (3-hydroxy-2-methylphenyl) fluorene _1-4 alkyl-hydroxyphenyl) fluorene, 9,9-bis (diC _1-4 alkyl-hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-2,6-dimethylphenyl) fluorene], 9,9-bis (C _5-8 cycloalkyl-monohydroxyphenyl) fluorene such as 9,9-bis (cycloalkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene Etc.], 9,9-bis (aryl-hydroxyphenyl) fluorene [for example, 9,9-bis (C _6-8 aryl-hydroxyphenyl) such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene ) Fluorene etc.], 9,9-bis (aralkyl-hydroxyphenyl) fluore [For example, 9,9-bis (C _6-8 arylC _1-2 alkyl-hydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-benzylphenyl) fluorene] and the like} and the like. It is done.

As 9,9-bis (dihydroxyphenyl) fluorenes, fluorenes corresponding to the 9,9-bis (monohydroxyphenyl) fluorenes, for example, 9,9-bis (dihydroxyphenyl) fluorene [9,9- Bis (3,4-dihydroxyphenyl) fluorene (biscatecholfluorene), 9,9-bis (3,5-dihydroxyphenyl) fluorene, etc.], substituted 9,9-bis (dihydroxyphenyl) fluorene {e.g. 9,9-bis (alkyl-dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxy-5-methylphenyl) fluorene, 9,9-bis (3,4-dihydroxy-6-methylphenyl) fluorene 9,9-bis (C _1-4 alkyl-dihydroxyphenyl) fluoro Ren, 9,9-bis (2,4-dihydroxy-3,6-dimethylphenyl) fluorene such as 9,9-bis _{(di-C 1-4} alkyl - dihydroxyphenyl) fluorene, etc.], 9,9-bis ( Aryl-dihydroxyphenyl) fluorene [for example, 9,9-bis (C _6-8 aryl-dihydroxyphenyl) fluorene such as 9,9-bis (3,4-dihydroxy-5-phenylphenyl) fluorene, etc.] etc. Can be illustrated.

  The compounds represented by formula (2) may be used alone or in combination of two or more.

  As bis (monohydroxyphenyl) fluorenes, commercially available products may be used, and various synthesis methods such as (a) fluorenones and phenols in the presence of hydrogen chloride gas and mercaptocarboxylic acid are used. Method of reacting (document [J. Appl. Polym. Sci., 27 (9), 3289, 1982], JP-A-6-145087, JP-A-8-217713), (b) acid catalyst (and alkyl A method of reacting 9-fluorenone with alkylphenols in the presence of mercaptan (Japanese Patent Laid-Open No. 2000-26349), (c) fluorenones and phenols in the presence of hydrochloric acid and thiols (such as mercaptocarboxylic acid) (D) in the presence of sulfuric acid and thiols (such as mercaptocarboxylic acid), A method of producing bisphenolfluorene by reacting with a diol and crystallizing with a crystallization solvent composed of a hydrocarbon and a polar solvent (Japanese Patent Laid-Open No. 2003-221352). May be used.

  In addition, as 9,9-bis (di or trihydroxyphenyl) fluorenes, commercially available products may be used, and in the method for producing 9,9-bis (monohydroxyphenyl) fluorenes, instead of phenols. Moreover, you may use what was manufactured by using corresponding polyhydric alcohol (dihydroxyphenols, trihydroxyphenols).

[Carboxylic acid represented by formula (3) or a derivative thereof]
In the formula (3), examples of the halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom.

In the formula (3), the aliphatic hydrocarbon group represented by the group R ³ includes a saturated aliphatic hydrocarbon group [for example, an alkylene group (including an alkylidene group. For example, a methylene group, an ethylene group, an ethylidene group). Group, trimethylene group, propylene group, propylidene group, tetramethylene group, pentamethylene group, hexamethylene group, etc., C _1-10 alkylene group, preferably C _1-6 alkylene group, more preferably C _1-4 alkylene group) Chain saturated aliphatic hydrocarbon groups such as alicyclic saturated hydrocarbon groups such as cycloalkylene groups (for example, C _5-10 cycloalkylene groups such as cyclohexylene group), unsaturated aliphatic hydrocarbon groups [ for example, such alkenylene groups (e.g., a vinylene group, _{C 2-6} alkenylene group such as propen-1,3-diyl group) Jo unsaturated aliphatic hydrocarbon group; cycloalkenylene group (e.g., C _5-10 cycloalkenylene group such as cyclohexene-1,4-diyl group) such as alicyclic unsaturated hydrocarbon group such as], and the like.

Further, the group R ³ includes a group represented by the following formula (3A).

-R ^3a -R ^3b- (3A)
(In the formula, R ^3a represents an aliphatic hydrocarbon group bonded to a carboxyl group, and R ^3b represents an aliphatic hydrocarbon group different from R ^3a or an aromatic hydrocarbon group.)
In the above formula (3A), R ^3a is an aliphatic hydrocarbon group bonded to or adjacent to the carboxyl group of the compound represented by formula (2), and examples of the aliphatic hydrocarbon group include the groups exemplified above (for example, And alkylene groups). In the group R ^3b , examples of the aliphatic hydrocarbon group include the above-mentioned exemplified aliphatic hydrocarbon groups different from the group R ^3a . In the group R ^3b , examples of the aromatic hydrocarbon group include an arylene group [for example, a C _6-10 arylene group such as a phenylene group (1,4-phenylene group, etc.), a naphthylene group] and the like. Typical combinations of R ^3a and R ^3b include, for example, (1) a combination in which R ^3a is an alkylene group, and R ^3b is an aliphatic hydrocarbon group that is not an alkylene group (for example, a cycloalkylene group); 2) A combination in which R ^3a is an alkylene group and R ^3b is an arylene group is included.

Incidentally, aliphatic hydrocarbon groups represented by the radicals R ³ are as long as it does not inhibit the reaction of a carboxylic acid represented by the formula the compound represented by the formula (2) (3), substituents ( For example, it may have a nitro group, a cyano group, a substituted amino group, etc.), and the aliphatic hydrocarbon group includes a group having such a substituent.

A preferred group R ³ is a chain aliphatic hydrocarbon group (for example, a C _1-10 alkylene group), and particularly an alkylene group [for example, a lower alkylene group such as a methylene group, an ethylene group (for example, C _1-4). Alkylene group) and the like. Among these, in particular, a carboxylic acid (or a derivative thereof) in which R ³ is a methylene group does not cause a side reaction (eg, generation of hydrogen halide), and is expected to improve the heat resistance of the resulting polycarboxylic acid. This is preferable because it is possible.

Representative carboxylic acids represented by formula (3) include halo fatty acids such as halo saturated fatty acids [for example, haloalkanoic acids such as chloroacetic acid, 2-chloropropionic acid, 3-chloropropionic acid, α-chloro. Halo C _2-10 alkanoic acids such as butyric acid, β-chlorobutyric acid, γ-chlorobutyric acid, bromoalkanoic acids corresponding to these chloroalkanoic acids, preferably halo C _2-6 alkanoic acids, more preferably halo C _{2- 4} alkanoic acid) etc.], halo unsaturated fatty acids [e.g., haloalkene acid (e.g., 3-chloro acrylic acid, 3-chloro crotonate, halo C _3-10 alkene such as bromo alkenoic acid corresponding to these chloro alkenoic acids Acid, preferably halo C _3-6 alkenoic acid) and the like.

The compound represented by the formula (3) may be a fatty acid (free fatty acid) as described above, and the reaction (dehydrohalogenation reaction) with the compound represented by the formula (2) is more efficiently performed. It may be derivatized for progress. Such a carboxylic acid derivative (or reactive derivative) is not particularly limited as long as it is a compound that protects (caps) the carboxyl group of the fatty acid and does not inhibit the reaction with the compound represented by formula (2). not, for example, esters of carboxylic acids [e.g., alkyl esters (e.g., methyl ester, ethyl ester, n- propyl ester, isopropyl ester, n- butyl ester, s- butyl ester, _{C 1-10,} such as t- butyl ester Alkyl ester, preferably C _1-6 alkyl ester, more preferably C _1-4 alkyl ester), cycloalkyl ester (eg C _5-10 cycloalkyl ester such as cyclohexyl ester), aryl ester (eg phenyl ester etc.) _{C 6-10} aryl ester of Etc.], salts of carboxylic acids {eg, metal salts [eg, alkali metal salts (eg, lithium salts, sodium salts, potassium salts, etc.), alkaline earth metal salts (eg, calcium salts, etc.)], amine salts ( Examples thereof include mono to trialkylamine salts such as dimethylamine salts, trimethylamine salts, and triethylamine salts, pyridine salts, ammonium salts, and the like}.

Preferred derivatives include esters of carboxylic acids {eg, alkyl esters [eg, lower alkyl esters (C _1-4 alkyl esters) such as methyl esters, ethyl esters, etc.], etc.}], salts of carboxylic acids [especially metal salts. (Alkali metal salts, alkaline earth metal salts, etc.)] and the like.

  The carboxylic acid represented by formula (3) or a derivative thereof may be used alone or in combination of two or more.

  In the reaction, the ratio (use ratio) of the compound represented by the formula (2) and the carboxylic acid represented by the formula (3) or a derivative thereof is, for example, the hydroxyl group of the compound represented by the formula (2). 1 mol or more (for example, 1 to 10 mol), preferably 1 to 8 mol (for example, 1.01 to 7 mol) of the carboxylic acid represented by the formula (3) or a derivative thereof with respect to 1 mol, more preferably 1.05-5 mol (for example, 1.1-3 mol) may be sufficient. In particular, in the present invention, the ratio near the theoretical amount, for example, 1 mol of the carboxylic acid or its derivative represented by the formula (3) with respect to 1 mol of the hydroxyl group of the compound represented by the formula (2) ( For example, even if it is about 1 to 1.5 mol, preferably 1 to 1.3 mol, more preferably about 1 to 1.2 mol), the target product can be efficiently obtained in a high yield.

  The reaction may usually be performed in the presence of a basic compound (basic catalyst, basic catalyst). Examples of basic compounds include inorganic bases {e.g., metal hydroxides [e.g., alkali metal hydroxides (e.g., lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxides (e.g. For example, calcium hydroxide, etc.], metal hydrides (eg, alkali or alkaline earth metal hydrides such as sodium hydride, potassium hydride), metal carbonates (eg, lithium carbonate, potassium carbonate, sodium carbonate, etc.) Alkali metal or alkaline earth metal carbonate), metal hydrogen carbonate (eg, potassium hydrogen carbonate, sodium hydrogen carbonate, etc.)}, organic base {eg, aliphatic amine [primary to tertiary aliphatic amine, eg, Trialkylamine (triethylamine, diethylmethylamine, diisopropylethylamine, tri-n-pro An aliphatic tertiary amine such as methyldicyclohexylamine], an aromatic amine (a primary to tertiary aromatic amine such as N, N- Aromatic tertiary amines such as dimethylaniline), heterocyclic amines (primary to tertiary heterocyclic amines such as picoline, pyridine, pyrazine, pyrimidine, pyridazine, 1-methylimidazole, triethylenediamine, N, N Amines such as dimethylaminopyridine, heterocyclic tertiary amines such as 1,8-diazabicyclo [5.4.0] unde-7-cene, and heterocyclic secondary amines such as piperidine. Carboxylate metal salts (alkali metal acetates such as sodium acetate and calcium acetate or alkaline earth gold) Quaternary ammonium salts (tetraalkylammonium halides such as tetraethylammonium chloride; benzyltrialkylammonium halides such as benzyltrimethylammonium chloride); quaternary phosphonium salts (such as benzyltriphenylphosphonium chloride)}, etc. Can be illustrated.

  Of these, metal hydroxides [for example, alkali metal hydroxides (for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxides (for example, calcium hydroxide, etc.) Etc.] are preferred.

  These basic compounds may be used alone or in combination of two or more.

  Although the usage-amount of a basic compound is based also on the kind etc., for example with respect to 1 mol of hydroxyl groups of the compound represented by the said Formula (2), for example, 0.1-10 molar equivalent, Preferably it is 0. 0.5-7 molar equivalents, more preferably 1-6 molar equivalents (eg, 1.2-5 molar equivalents), especially 1.3-4 molar equivalents (eg, 1.5-3 molar equivalents) Also good.

The reaction between the compound represented by the formula (2) and the carboxylic acid represented by the formula (3) or a derivative thereof may be performed in the absence of a solvent or in the presence (or in a solvent) of a solvent. May be. The solvent is not limited as long as it does not inhibit the reaction. For example, alcohols {for example, C _1-6 such as alkanol (eg, methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, etc.) Alkanols, preferably C _1-4 alkanols, more preferably C _1-3 alkanols, alkylene glycol monoalkyl ethers (C _1-4 alkoxy-C _2-4 alkanols such as 2-methoxyethanol), cycloalkanols (cyclohexanols) Etc.], glycerin etc.}, amides (eg, N-mono or diC _1-4 alkylformamide such as N-methylformamide, N, N-dimethylformamide; N-methylacetamide, N, N-dimethylacetamide Such as - such as mono- or di-C _1-4 alkyl acetamide), nitriles (e.g., acetonitrile, propionitrile and the like), sulfur compounds [sulfoxides (e.g., dimethyl sulfoxide), sulfones (e.g., cyclic sulphones such as sulfolane) Etc.], ethers (eg, dialkyl ethers such as diethyl ether; (poly) alkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether; cyclic ethers such as tetrahydrofuran, 1,4-dioxane, etc.), hydrocarbons (eg, Organic solvents such as aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane; aromatic hydrocarbons such as toluene and xylene); and inorganic solvents such as water. Moreover, you may use the said amines as a solvent. These solvents may be used alone or in combination of two or more.

Preferable solvents include polar organic solvents (for example, alcohols, amides, sulfoxides and the like), especially alcohols [alkanol (for example, C _1-4 alkanol) and the like], sulfoxides (dimethylsulfoxide and the like). Etc. are preferable. Among these, alkanols such as isopropanol are extremely useful because they can produce the target product in a high yield despite being inexpensive.

  The ratio of the solvent is, for example, 0.3 to 100 parts by weight, preferably 1 part by weight based on the total amount of the compound represented by the formula (2) and the carboxylic acid represented by the formula (3) or a derivative thereof, It may be about 0.5 to 50 parts by weight, more preferably about 1 to 30 parts by weight.

  The reaction temperature is, for example, about 0 to 250 ° C. (for example, 20 to 220 ° C.), preferably about 30 to 200 ° C. (for example, 50 to 180 ° C.), more preferably about 60 to 150 ° C. (for example, 70 to 130 ° C.). It may be. The reaction may be performed while refluxing the solvent.

  The reaction time is not particularly limited and can be appropriately selected depending on the reaction temperature and the like, but is usually 1 to 72 hours, preferably 2 to 48 hours, and more preferably about 5 to 36 hours. The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (such as nitrogen or a rare gas), or may be performed under reduced pressure, normal pressure, or increased pressure.

  The produced compound may be separated and purified by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.

  As described above, the carboxylic acid (or a derivative thereof) represented by the formula (1) is obtained. When the compound represented by the formula (2) is reacted with the carboxylic acid derivative represented by the formula (3), a corresponding derivative of the compound represented by the formula (2) is obtained. For example, when the ester of the carboxylic acid represented by the formula (3) is used, the ester of the carboxylic acid represented by the formula (1) is obtained, and when the metal salt of the carboxylic acid represented by the formula (3) is used. A metal salt of a carboxylic acid represented by the formula (1) is obtained. In addition, the derivative | guide_body of such carboxylic acid is also contained in this invention. In such a case, by subjecting the reaction product of the compound represented by the formula (2) and the derivative of the carboxylic acid represented by the formula (3) to a hydrolysis treatment or a neutralization treatment, The target product (carboxylic acid represented by formula (1)) can be obtained.

  In the method of the present invention, the carboxylic acid represented by the formula (1) (polycarboxylic acid having a fluorene skeleton) can be obtained easily and efficiently without using a catalyst such as concentrated sulfuric acid. In particular, according to the method of the present invention, a polycarboxylic acid having a fluorene skeleton can be obtained with high yield, and mass synthesis is also possible. For example, the yield of the carboxylic acid represented by the formula (1) obtained by the method of the present invention is 50 mol% or more (for example, 55 to 100 mol%) based on the compound represented by the formula (2). , Preferably 60 mol% or more (e.g. 65 to 99.99 mol%), more preferably 70 mol% or more (e.g. 75 to 99.95 mol%), 90 mol% or more [e.g. 93 mol% or more (for example, 94 to 100 mol%), preferably 95 mol% or more (for example, 96 to 99.99 mol%)].

[Carboxylic acid represented by formula (1)]
As described above, the carboxylic acid represented by the formula (1) (polycarboxylic acid having a fluorene skeleton) is obtained. In the above formula (1), R ¹ , R ² , R ³ , k, m, and n are the same as described above, and preferred embodiments are also the same as described above.

Representative carboxylic acids represented by the formula (1) include carboxylic acids corresponding to the compound [9,9-bis (hydroxyphenyl) fluorenes] represented by the formula (2), for example, 9, 9-bis (carboxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- (carboxymethoxy) phenyl] fluorene, 9,9-bis [4- (1-carboxyethoxy) phenyl] fluorene, 9,9- Bis [4- (2-carboxyethoxy) phenyl] fluorene, 9,9-bis [4- (1-carboxypropoxy) phenyl] fluorene, 9,9-bis [4- (2-carboxypropoxy) phenyl] fluorene, 9,9-bis (carboxy C _1-4 alkoxyphene such as 9,9-bis [4- (3-carboxypropoxy) phenyl] fluorene Nyl) fluorene and the like}, 9,9-bis (alkyl-carboxyalkoxyphenyl) fluorene {e.g., 9,9-bis [4- (carboxymethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- 9,9-bis (mono or diC _1-4 alkyl-carboxy C _1-4 alkoxyphenyl) fluorene such as (carboxymethoxy) -2,6-dimethylphenyl] fluorene}, 9,9-bis (aryl- Carboxyalkoxyphenyl) fluorene {eg, 9,9-bis (C _6-10 aryl-carboxy C _1-4 alkoxyphenyl) fluorene such as 9,9-bis [4- (carboxymethoxy) -3-phenylphenyl] fluorene }, 9,9-bis [di- or tri (carboxyalkoxy) phenyl] fluore 9,9-bis such as 9,9-bis [3,4-di (carboxymethoxy) phenyl] fluorene, 9,9-bis [3,4-di (2-carboxyethoxy) phenyl] fluorene 9,9-bis (carboxyalkoxyphenyl) fluorenes such as [di (carboxyC _1-4 alkoxy) phenyl] fluorene}, corresponding to these compounds, the alkoxy group is a group derived from another aliphatic hydrocarbon group (for example, , Cycloalkoxy groups) and the like.

  In particular, in the present invention, among the carboxylic acids represented by the formula (1), the compound described in Non-Patent Document 1, that is, 9,9-bis [4- (2-carboxyethoxy) phenyl] fluorene, etc. As compared with the above, a novel compound excellent in various properties such as heat resistance can be obtained.

  For this reason, the carboxylic acid represented by the following formula (1A) is also included in the present invention.

(In the formula, R ¹ , R ² , R ³ , k, m, and n are the same as above. However, when m is 0 and n is 1, R ³ is not an ethylene group.)
In the above formula (1A), R ¹ , R ² , R ³ , k, m, and n are the same as described above, and the preferred embodiments are also the same as described above.

In the formula (1A), particularly preferred R ³ is a methylene group. Such a carboxylic acid is superior in characteristics such as heat resistance as compared with a compound in which R ³ is an ethylene group.

Representative carboxylic acids represented by the formula (1A) include compounds in which R ³ is a methylene group in the formula (1), such as 9,9-bis (carboxymethoxyphenyl) fluorene {for example, 9,9 -Bis [4- (carboxymethoxy) phenyl] fluorene and the like}, 9,9-bis (alkyl-carboxymethoxyphenyl) fluorene {eg, 9,9-bis [4- (carboxymethoxy) -3-methylphenyl] fluorene 9,9-bis (mono- or di-C _1-4 alkyl-carboxymethoxyphenyl) fluorene such as 9,9-bis [4- (carboxymethoxy) -2,6-dimethylphenyl] fluorene}, 9,9 -Bis (aryl-carboxymethoxyphenyl) fluorene {e.g. 9,9-bis [4- (carboxymethoxy)- - phenyl phenyl] fluorene such as 9,9-bis _{(C 6-10} aryl - carboxymethoxy phenyl) fluorene} etc.. The present invention also includes derivatives of such carboxylic acids (esters, salts such as metal salts).

  In the method of the present invention, a polycarboxylic acid having a fluorene skeleton can be easily and efficiently produced. In particular, the method of the present invention is extremely industrially advantageous because a polycarboxylic acid having a fluorene skeleton can be obtained in a high yield even when the reaction is carried out in a proportion close to the theoretical amount.

  The polycarboxylic acid having such a fluorene skeleton has excellent properties such as high heat resistance, high refractive index, low linear expansion, and high transparency, and is a compound for imparting or improving these properties. For example, resin raw materials {for example, polycarboxylic acids such as polyester resins, liquid crystalline polymers, polyamide resins, polyimide resins, polybenzimidazoles, acrylic resins or derivatives thereof (lower alkyl esters, etc.) Polycarboxylic acid raw material for resin as a polymerization component}, functional materials [for example, additives (resist additives, etc.), reagents (pharmaceuticals, agricultural chemicals, etc.), intermediates, etc.], etc.

The polycarboxylic acid having such a fluorene skeleton can be used for various applications. Specifically, a photosensitive resin such as a resist, a printed wiring board, a liquid crystal alignment film, an ink material, a light emitting material (for example, a light emitting material for organic EL), an organic semiconductor, a graphitization precursor, a gas separation film (for example, CO ₂ gas separation membrane, etc.), coating agents (for example, optical overcoat agents such as coating agents for LED (light emitting diode) elements or hard coating agents), lenses [pickup lenses (eg, DVD (digital versatile tiles) Disc) pickup lens, etc.), micro lens (eg, micro lens for liquid crystal projector), spectacle lens, etc.], polarizing film (eg, polarizing film for liquid crystal display), optical film or optical sheet {eg, film for touch panel , Organic EL film, flexible substrate film, display Film [for example, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction electron-emitting device display), FED (field emission display), NED (nano-emissive display), Etc.}, antireflection film (or antireflection film, eg, antireflection film for display device), fuel cell membrane, optical fiber, optical waveguide, hologram It can use suitably as materials, such as.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

HPLC was measured with the following equipment and conditions.
Equipment used: HITACHI L-71 series Detector: HITACHI L-7405 λ = 254 nm
Column: Nacalai Tesque COSMOSIL 5C18-AR-11 150-4.6 mm Monf. No. K52820
Eluent: THF (tetrahydrofuran): Water = 50: 50
Flow rate: 1 mL / min.

Example 1
9,9-bis (4-hydroxyphenyl) fluorene (BPF, Osaka Gas Chemical Co., Ltd.) 10.00 g (0.02857 mol), sodium hydroxide 2.50 g (0.0625 mol) and dimethyl sulfoxide (DMSO) ) After adding 100 mL and heating at 100 ° C. for 1 hour, 13.30 g (0.144 mol) of sodium chloroacetate was added and reacted at a reaction temperature of 100 ° C. for 24 hours. The reaction solution after the reaction was poured into 350 mL of water, 8 mL of concentrated hydrochloric acid was added, the precipitate was collected by filtration, washed with water and dried to obtain the desired product in a yield of 12.9 g (yield 96.9%). . From the result measured by HPLC (High Performance Liquid Chromatography), the composition of the reaction product was 0.14% BPF, dicarboxylic acid represented by the following formula {9,9-bis [4- (carboxymethoxy) phenyl] Fluorene} was 99.86%, and the corresponding dicarboxylic acid was obtained in high yield and purity.

¹ H-NMR (270 MHz, DMSO-d6):
δ 4.61 (s, 4H, —O—CH ₂ —), δ 6.74-6.77 (4H, Ar—H), δ 7.10-7.14 (4H, Ar—H), δ 7.25— 7.36 (6H, Ar-H)
(Example 2)
Under argon atmosphere, 9,9-bis (4-hydroxyphenyl) fluorene (BPF, Osaka Gas Chemical Co., Ltd.) 10.00 g (0.02857 mol), sodium hydroxide 2.50 g (0.0625 mol) and After adding 150 mL of isopropyl alcohol and heating to reflux for 1 hour, 7.30 g (0.063 mol) of sodium chloroacetate was added and heating to reflux for 24 hours. The reaction solution after the reaction was poured into 350 mL of water, 8 mL of concentrated hydrochloric acid was added, the precipitate was collected by filtration, washed with water and dried to obtain the target product at a yield of 12.6 g (yield 94.5%). . From the results measured by HPLC (high performance liquid chromatography), the composition of the reaction product was 2.55% BPF and 97.45 dicarboxylic acid {9,9-bis [4- (carboxymethoxy) phenyl] fluorene}. % And other were 0.37%, and the corresponding dicarboxylic acid was obtained in high yield and purity.

(Example 3)
9,9-bis (4-hydroxyphenyl) fluorene (BPF, Osaka Gas Chemical Co., Ltd.) 20.00 g (0.0586 mol), sodium hydroxide 4.8 g (0.120 mol) and dimethyl sulfoxide 100 mL After addition and heating for 1 hour, 20 g (0.123 mol) of bromoacetic acid ethyl ester was added and heated for 24 hours. The reaction solution after the reaction was poured into ice water, the precipitate was collected by filtration, washed with water and dried to obtain a crude product with a yield of 95%. From the result of HPLC (high performance liquid chromatography), the composition of the crude product is 1.514% for BPF, 13.038% for monocarboxylic acid ester, 84.470% for dicarboxylic acid ester, and 0.978% for other. The ester corresponding to the dicarboxylic acid was obtained in high yield and purity.

  The crude product was hydrolyzed with an aqueous sodium hydroxide solution to obtain the desired product. From the results of HPLC (High Performance Liquid Chromatography), the composition of the reaction product was 83.406% of the corresponding dicarboxylic acid (the remainder was unhydrolyzed product and BPF).

Example 4
9,9-bis (4-hydroxyphenyl) fluorene (BPF, Osaka Gas Chemical Co., Ltd.) 10.00 g (0.02857 mol), sodium hydroxide 2.50 g (0.0625 mol) and 100 mL of water were added. After heating to reflux for 1 hour, 13.30 g (0.144 mol) of sodium chloroacetate was added and heated to reflux for 24 hours. The reaction solution after the reaction was poured into 350 mL of water, 8 mL of concentrated hydrochloric acid was added, the precipitate was collected by filtration, washed with water and dried to obtain the desired product in a yield of 7.09 g (yield 53.2%). . From the results measured by HPLC (High Performance Liquid Chromatography), the composition of the reaction product was 6.62% BPF, 38.23% corresponding monocarboxylic acid, 54.81% corresponding dicarboxylic acid, It was 0.35%.

(Example 5)
The target product was obtained in a yield of 6.84 g (yield: 51.3%) in the same manner as in Example 4 except that the reaction was performed in an argon atmosphere. From the results measured by HPLC (High Performance Liquid Chromatography), the composition of the reaction product was 811% for BPF, 38.59% for the corresponding monocarboxylic acid, 52.84% for the corresponding dicarboxylic acid, It was 0.46%.

(Example 6)
In Example 5, in place of 100 mL of water, 100 mL of dimethylformamide was used, and the target product was obtained in the same manner as in Example 5 except that the reaction was performed at 100 ° C. instead of heating to reflux. 66.9%). From the results measured by HPLC (high performance liquid chromatography), the composition of the reaction product was 2.82% for BPF, 28.24% for the corresponding monocarboxylic acid, and 68.94% for the corresponding dicarboxylic acid. .

(Example 7)
In Example 5, instead of 2.50 g (0.0625 mol) of sodium hydroxide, 4.14 g (0.0738 mol) of potassium hydroxide was used. The yield was 7.00 g (52.5% yield). From the results measured by HPLC (High Performance Liquid Chromatography), the composition of the reaction product was 6.32% for BPF, 39.28% for the corresponding monocarboxylic acid, 54.16% for the corresponding dicarboxylic acid, It was 0.25%.

(Example 8)
In Example 1, in place of 13.30 g (0.144 mol) of sodium chloroacetate, 7.30 g (0.063 mol) of sodium chloroacetate was used. The yield was 7.44 g (55.8% yield). From the results measured by HPLC (High Performance Liquid Chromatography), the composition of the reaction product was 6.17% for BPF, 36.00% for the corresponding monocarboxylic acid, 57.54% for the corresponding dicarboxylic acid, It was 0.28%.

Example 9
In Example 7, the target product was obtained in a yield of 7.24 g (yield 54.3%) in the same manner as in Example 7 except that the reaction time was changed from 24 hours to 36 hours. From the results measured by HPLC (High Performance Liquid Chromatography), the composition of the reaction product was 5.90% for BPF, 5.90% for the corresponding monocarboxylic acid, 56.10% for the corresponding dicarboxylic acid, It was 0.27%.

(Example 10)
In Example 7, the target product was obtained in a yield of 7.28 g (yield 54.6%) in the same manner as in Example 7 except that the reaction time was changed from 24 hours to 48 hours. From the results measured by HPLC (High Performance Liquid Chromatography), the composition of the reaction product was 6.24% for BPF, 37.14% for the corresponding monocarboxylic acid, 56.31% for the corresponding dicarboxylic acid, It was 0.31%.

(Example 11)
In Example 1, in place of 13.30 g (0.144 mol) of sodium chloroacetate, 8.65 g (0.074 mol) of sodium chloroacetate was used. The yield was 6.72 g (yield 50.4%). From the results measured by HPLC (High Performance Liquid Chromatography), the composition of the reaction product was 7.29% for BPF, 40.38% for the corresponding monocarboxylic acid, 52.00% for the corresponding dicarboxylic acid, It was 0.32%.

Example 12
In Example 1, in place of 13.30 g (0.144 mol) of sodium chloroacetate, 10.00 g (0.086 mol) of sodium chloroacetate was used. The yield was 7.02 g (52.7% yield). From the results measured by HPLC (High Performance Liquid Chromatography), the composition of the reaction product was 6.61% BPF, 38.37% corresponding monocarboxylic acid, 54.34% corresponding dicarboxylic acid, and others. It was 0.32%.

(Example 13)
In Example 1, instead of using sodium chloroacetate (13.30 g, 0.144 mol), sodium chloroacetate (9.06 g, 0.078 mol) was used. The yield was 6.92 g (yield 51.9%). From the results measured by HPLC (High Performance Liquid Chromatography), the composition of the reaction product was 6.90% for BPF, 39.29% for the corresponding monocarboxylic acid, 53.50% for the corresponding dicarboxylic acid, It was 0.30%.

(Example 14)
In Example 1, in place of 13.30 g (0.144 mol) of sodium chloroacetate, 3.33 g (0.026 mol) of sodium chloroacetate was used. The yield was 1.55 g (yield 11.7%). From the results measured by HPLC (High Performance Liquid Chromatography), the composition of the reaction product is 40.19% BPF, 46.96% corresponding monocarboxylic acid, 12.02% corresponding dicarboxylic acid, 0.83%.

(Example 15)
9,9-bis (4-hydroxyphenyl) fluorene (BPF, Osaka Gas Chemical Co., Ltd.) 19.50 g (0.05714 mol), potassium hydroxide 7.2 g (0.1091 mol) and ethanol 200 mL were added. After heating for 1 hour, 20 g (0.123 mol) of bromoacetic acid ethyl ester was added and heated for 24 hours. The reaction solution after the reaction was poured into ice water, the precipitate was collected by filtration, washed with water and dried to obtain a crude product. From the result of HPLC (high performance liquid chromatography), the composition of the crude product was 29.899% for BPF, 47.066% for monocarboxylic acid ester, 19.590% for dicarboxylic acid ester, and 3.544% for the other. Met.

Claims (9)

In the presence of a basic compound, the following formula (1)

(Wherein R ¹ is a cyano group, halogen atom or alkyl group, R ² is a hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, halogen atom, nitro group, cyano A group or a substituted amino group, R ³ represents an aliphatic hydrocarbon group, k is an integer of 0 to 4, m is an integer of 0 to 4, and n is an integer of 1 to 5. However, the total of m and n Is an integer of 5 or less.)
A carboxylic acid represented by the following formula (2):

(In the formula, R ¹ , R ² , k, m, and n are the same as described above.)
And a compound represented by the following formula (3)

(In the formula, X represents a halogen atom, and R ³ is the same as described above.)
The manufacturing method including the process of making the carboxylic acid represented by these, or its derivative (s) react. In the formula (2), ^{R 2} _is a selected group from _{C 1-4} alkyl and _{C 6-10} aryl group, The process according to claim 1, wherein m is 0-2. The production method according to claim 1 or 2, wherein in formula (3), R ³ is a C _1-4 alkylene group.   The production method according to any one of claims 1 to 3, wherein the compound represented by the formula (2) is reacted with a compound selected from alkyl esters and salts of carboxylic acids represented by the formula (3).   The carboxylic acid represented by Formula (3) or its derivative 1-1.5 mol is used with respect to 1 mol of hydroxyl groups of the compound represented by Formula (2). Manufacturing method.   The production method according to claim 1, wherein the reaction is carried out in the presence of a polar organic solvent.   The production method according to any one of claims 1 to 6, wherein the reaction is carried out in the presence of at least one solvent selected from alcohols and sulfoxides. Carboxylic acid represented by the following formula (1A).

(In the formula, R ¹ , R ² , R ³ , k, m, and n are the same as above. However, when m is 0 and n is 1, R ³ is not an ethylene group.) In the formula (1A), R ² is a group selected from a C _1-4 alkyl group and a C _6-10 aryl group, m is 0 to 2, R ³ is a methylene group, and n is 1 to 1 The carboxylic acid according to claim 8, which is 3.