JP5324082B2 - Process for producing 9,9-bis (carboxyaryl) fluorenes and esters thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of preparing a 9,9-bis(carboxyaryl)fluorene and its ester at a high yield. <P>SOLUTION: The 9,9-bis(carboxyaryl)fluorene is prepared by causing a compound represented by formula (1) to react with carbon monoxide in the presence of a transition metal catalyst, and water and/or an alcohol (in the formula, Z represents an aromatic hydrocarbon ring; R<SP>1</SP>represents a cyano group, a halogen atom or an alkyl group; R<SP>2</SP>represents a hydrocarbon group, an alkoxy group or the like; R<SP>3</SP>represents a trifluoromethyl group or the like; k is a natural number of 0 to 4; m is a natural number of 0 or greater; and n is an integer of 1 or greater). <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a method for producing 9,9-bis (carboxyaryl) fluorenes and esters thereof, and novel 9,9-bis (carboxyaryl) fluorenes (9,9-bis ( Carboxynaphthyl) fluorenes and the like) and esters thereof.

  A compound having a fluorene skeleton such as a 9,9-bisphenylfluorene skeleton has an excellent function in terms of refractive index, heat resistance and the like, and is known to be used as a resin raw material or an additive. Among the compounds having such a fluorene skeleton, in particular, a compound having a fluorene skeleton having a carboxyl group such as fluorenedibenzoic acid [4,4 ′-(9-fluorenylidene) dibenzoic acid] is a resin raw material (polyimide, Polyester, acrylic resin raw materials, etc.) and curing agents (epoxy resin curing agents, etc.) can be expected.

  As a method for producing such fluorenedibenzoic acid, Japanese Patent Application Laid-Open No. 2005-82564 (Patent Document 1) includes reacting 9,9-bis (4-hydroxyphenyl) fluorene with triphenylphosphine dibromide. Discloses a method in which the hydroxyl group of the compound is brominated and then reacted with butyllithium and dry ice.

However, in the method of this document, the yield is about 40%, which is not a sufficient value, the reaction conditions at low temperature are necessary, so it is not suitable for mass synthesis, and a large amount of metal-containing waste liquid comes out, so it is environmentally friendly. Therefore, the development of a more efficient and industrially usable production method is desired because it is not preferable.
JP 2005-82564 A (paragraph numbers [0015], [0018], [0019])

  Accordingly, an object of the present invention is to provide a method for producing 9,9-bis (carboxyaryl) fluorenes and esters thereof useful as a raw material for polymer materials in high yield.

  Another object of the present invention is to provide a production method suitable for mass synthesis, which can obtain 9,9-bis (carboxyaryl) fluorenes and esters thereof with high purity.

  Still another object of the present invention is to provide novel 9,9-bis (carboxyaryl) fluorenes and esters thereof having excellent heat resistance and the like.

  As a result of diligent studies to achieve the above-mentioned problems, the inventors of the present invention have used a compound obtained by sulfonated (for example, triflated) 9,9-bis (hydroxyaryl) fluorenes to form a carbonyl by carbon monoxide. When the reaction is carried out, the corresponding fluorene derivatives (9,9-bis (carboxyaryl) fluorenes and esters thereof) are obtained in high yield, and 9,9-bis (hydroxyaryl) fluorenes are obtained, It has been found that when a compound whose aryl group is a condensed polycyclic hydrocarbon group (such as a naphthyl group) is used, a novel fluorene derivative excellent in heat resistance and the like can be obtained, and the present invention has been completed.

  That is, the method of the present invention is a method for producing a fluorene derivative selected from 9,9-bis (carboxyaryl) fluorenes and esters thereof, which comprises a compound represented by the following formula (1) and carbon monoxide. It is a manufacturing method of the said fluorene derivative which includes at least the carbonylation process made to react.

(In the formula, ring Z represents an aromatic hydrocarbon ring, R ¹ is a cyano group, a halogen atom or an alkyl group, R ² is 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, wherein R ³ represents a hydrocarbon group optionally substituted by a halogen atom, k is an integer of 0 to 4, and m is an integer of 0 or more. , N is an integer of 1 or more.)
Prior to the carbonylation step, the method comprises reacting a compound represented by the following formula (1A) with a sulfonic acid corresponding to the group R ³ SO ₃ — (for example, trifluoromethanesulfonic acid) to form the above formula ( A sulfonic acid esterification step (for example, a triflation step) for obtaining the compound represented by 1) may be included.

(In the formula, Z, R ¹ , R ² , k, m, and n are the same as described above.)
In the formula (1) (or the formula (1A)), typically, the ring Z is a benzene ring or a naphthalene ring, R ¹ is an alkyl group, k is 0 to 1, and R ² is It is an alkyl group or an aryl group, m may be 0-2, and n may be 1-3.

In the carbonylation step, the compound represented by the formula (1) may be reacted with carbon monoxide in the presence of a transition metal catalyst (such as a palladium compound). In such a method, the ratio of the transition metal catalyst is, for example, about 0.1 per mol of the group R ³ SO ₃ — (for example, trifluoromethanesulfonyloxy group) of the compound represented by the formula (1). It may be about 00001 to 0.1 mol.

  In the carbonylation step, the compound represented by the formula (1) and carbon monoxide may be reacted in the presence of water and / or alcohols. When reacted in the presence of water, the corresponding carboxylic acid (9,9-bis (carboxyaryl) fluorenes) is efficiently obtained, and when reacted in the presence of alcohols, the corresponding ester is efficiently obtained. .

  The present invention also includes a fluorene derivative selected from a compound represented by the following formula (A1) and an ester thereof.

(In the formula, ring Z ¹ represents a condensed polycyclic aromatic hydrocarbon ring, and R ¹ , R ² , k, m, and n are the same as described above.)
In the formula (A1), the ring Z ¹ may be, for example, a naphthalene ring.

  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, 9,9-bis (carboxyaryl) fluorenes and esters useful as raw materials for polymer materials can be produced in high yield. Moreover, the method of the present invention can obtain 9,9-bis (carboxyaryl) fluorenes and esters thereof with high purity, and is suitable for mass synthesis. Therefore, the method of the present invention is extremely advantageous industrially. Furthermore, the present invention can provide novel 9,9-bis (carboxyaryl) fluorenes and esters thereof that are excellent in heat resistance and the like.

<Method for producing fluorene derivative>
The method of the present invention is a method for producing a fluorene derivative selected from 9,9-bis (carboxyaryl) fluorenes (compound represented by the following formula (A)) and esters thereof, It includes at least a carbonylation step of reacting the compound represented by 1) with carbon monoxide.

(In the formula, ring Z represents an aromatic hydrocarbon ring, R ¹ and R ² are the same or different and represent a substituent, and R ³ represents a hydrocarbon group which may be substituted with a halogen atom. An integer of 0 to 4, m is an integer of 0 or more, and n is an integer of 1 or more.)
[Compound represented by Formula (1)]
In the formula (1), 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 a phenyl group)] and the like], etc., and is often a cyano group or an alkyl group (particularly an alkyl group). 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 (1), examples of the aromatic hydrocarbon ring represented by the ring Z include a benzene ring and a condensed polycyclic aromatic hydrocarbon ring (specifically, a condensed polycyclic carbon ring including at least a benzene ring). Hydrogen ring). Examples of the condensed polycyclic aromatic hydrocarbon corresponding to the condensed polycyclic aromatic hydrocarbon ring include condensed bicyclic hydrocarbons (for example, C _8-20 condensed bicyclic hydrocarbons such as indene and naphthalene, preferably C _10-16 condensed bicyclic hydrocarbons) and condensed tricyclic hydrocarbons (for example, anthracene, phenanthrene, etc.) and the like, and the like. Preferable condensed polycyclic aromatic hydrocarbons include naphthalene and anthracene, and naphthalene is particularly preferable. The two rings Z substituted at the 9-position of fluorene may be the same or different rings, and may usually be the same ring.

  Preferred ring Z includes a benzene ring and a naphthalene ring (particularly a benzene ring). In addition, when the ring Z is a condensed polycyclic aromatic hydrocarbon ring, the substitution position of the ring Z substituted at the 9th position of fluorene is not particularly limited. For example, the naphthyl group substituted at the 9th position of fluorene is , 1-naphthyl group, 2-naphthyl group and the like.

In the formula (1), 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 ring Z, when m is plural (two or more), the groups R ² may be different from each other or the same. In the two rings Z, the groups R ² may be the same or different. The preferred substitution number m may be 0 to 8, preferably 0 to 6 (for example, 1 to 5), more preferably 0 to 4, particularly 0 to 2 (for example, 0 to 1). In the two rings Z, the number of substitutions m may be the same or different from each other.

In the formula (1), examples of the hydrocarbon group optionally substituted by the halogen atom represented by the group R 3 include a hydrocarbon group [an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group). A C 1-6 alkyl group such as a group, preferably a C 1-4 alkyl group, more preferably a C 1-2 alkyl group), an alkenyl group (for example, a C 2-6 alkenyl group such as an allyl group), an aryl group (For example, a C 6-14 aryl group such as a phenyl group, a tolyl group (p-tolyl group, etc.), a xylyl group, preferably a C 6-10 aryl group, more preferably a C 6-8 aryl group], a halogen atom A substituted hydrocarbon group (having a halogen atom) [a compound for the hydrocarbon group, for example, a halo group such as a halomethyl group (for example, a trifluoromethyl group, etc.) Kill group], and the like. Among these, preferred examples of the group R 3, a C 1-4 alkyl group (such as a methyl group), (tolyl group) C 6-8 aryl group, halo C 1-4 alkyl group (E.g., a trifluoromethyl group) is preferred, particularly a trifluoromethyl group, and when n is plural (2 or more), the groups R 3 may be different from each other or the same. In the two rings Z, the radicals R 3 may be the same or different.

In the formula (1), the substitution number n of the group R ³ SO ₃ — (for example, trifluoromethanesulfonyloxy group or trifluoromethylsulfonyloxy group) may be 1 or more, for example, 1 to 4, preferably It may be 1 to 3, more preferably 1 to 2 (particularly 1). In the two rings Z, the number of substitutions n may be the same or different from each other.

In the formula (1), as a typical combination, the ring Z is a benzene ring or a naphthalene ring, R ¹ is an alkyl group (for example, a C _1-4 alkyl group such as a methyl group), and k is 0 to 1 (particularly 0), R ² is an alkyl group (for example, a C _1-4 alkyl group such as a methyl group) or an aryl group (for example, a C _6-10 aryl group such as a phenyl group); A combination in which m is 0 to 2 and n is 1 to 3 is included.

Specific examples of the compound represented by the formula (1) include a sulfonate ester (formula (1A) corresponding to the compound [9,9-bis (hydroxyaryl) fluorenes] represented by the formula (1A) described later. ), For example, 9,9-bis (trifluoromethanesulfonyloxyphenyl) fluorene [9,9-bis (4-trifluoromethanesulfonyloxyphenyl) fluorene, etc.], 9,9- 9,9-bis (C _1-4 alkyl-trifluoromethanesulfonyloxyphenyl) such as bis (alkyl-trifluoromethanesulfonyloxyphenyl) fluorene [9,9-bis (4-trifluoromethanesulfonyloxy-3-methylphenyl) fluorene ) Fluorene, 9,9-bis (4-trifluoromethanesulfo) 9,9-bis (diC _1-4 alkyl-trifluoromethanesulfonyloxyphenyl) fluorene such as nyloxy-2,6-dimethylphenyl) fluorene], 9,9-bis (aryl-trifluoromethanesulfonyloxyphenyl) fluorene [For example, 9,9-bis (C _6-8 aryl-trifluoromethanesulfonyloxyphenyl) fluorene such as 9,9-bis (4-trifluoromethanesulfonyloxy-3-phenylphenyl) fluorene], 9,9- 9,9-bis (trifluoromethanesulfonyloxyphenyl) fluorenes such as bis (ditrifluoromethanesulfonyloxyphenyl) fluorene [9,9-bis (3,4-ditrifluoromethanesulfonyloxyphenyl) fluorene and the like]; 9 , -Bis (trifluoromethanesulfonyloxynaphthyl) fluorene [eg 9,9-bis [6- (2-trifluoromethanesulfonyloxynaphthyl)] fluorene (or 9,9-bis [2- (6-trifluoromethanesulfonyloxynaphthyl) )] Fluorene), 9,9-bis [1- (6-trifluoromethanesulfonyloxynaphthyl)] fluorene, 9,9-bis [1- (5-trifluoromethanesulfonyloxynaphthyl)] fluorene, etc. Triflates corresponding to 9,9-bis (hydroxyaryl) fluorenes such as 9-bis (trifluoromethanesulfonyloxynaphthyl) fluorenes (triflates of the compound represented by the formula (1A)) are included.

[Production method and sulfonate esterification step of compound represented by formula (1)]
In addition, the compound represented by the formula (1) is not particularly limited, but usually, a compound represented by the following formula (1A) and a sulfonic acid corresponding to the group R ³ SO ₃ — (for example, trifluoromethanesulfone). It is obtained by reacting with acids). Therefore, in the production method of the present invention, prior to the carbonylation step, the compound represented by the following formula (1A) is reacted with a sulfonic acid (for example, trifluoromethanesulfonic acid) corresponding to the group R ³ SO ₃ —. Then, a sulfonic acid esterification step (for example, a triflate step) for obtaining a compound represented by the formula (1) may be included. That is, the sulfonic acid esterification step is a step of converting a hydroxyl group of a compound represented by the following formula (1A) into a group R ³ SO ₃ — (such as a trifluoromethanesulfonyloxy group).

(In the formula, Z, R ¹ , R ² , k, m, and n are the same as described above.)
(Compound represented by Formula (1A))
In the above formula (1A), Z, R ¹ , R ² , k, m, and n all correspond to the case in the above formula (1), and the preferred embodiments are the same as described above.

  As typical compounds [9,9-bis (hydroxyaryl) fluorenes] represented by the formula (1A), (1) 9,9-bis (hydroxyphenyl) fluorenes, (2) 9,9- Bis (hydroxynaphthyl) fluorenes and the like are included.

(1) 9,9-bis (hydroxyphenyl) fluorenes 9,9-bis (hydroxyphenyl) fluorenes include 9,9-bis (monohydroxyphenyl) fluorenes, 9,9-bis (dihydroxyphenyl) Fluorenes, 9,9-bis (trihydroxyphenyl) fluorenes [for example, 9,9-bis (2,3,4-trihydroxyphenyl) fluorene, 9,9-bis (2,4,6-trihydroxy 9,9-bis (trihydroxyphenyl) such as phenyl) fluorene, 9,9-bis (2,4,5-trihydroxyphenyl) fluorene, 9,9-bis (3,4,5-trihydroxyphenyl) fluorene ) Fluorene, etc.], usually 9,9-bis (monohydroxyphenyl) fluorenes or 9,9-bis (dihydroxy) Cyphenyl) fluorenes, particularly 9,9-bis (monohydroxyphenyl) fluorenes, can be preferably used.

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.

  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).

(2) 9,9-bis (hydroxynaphthyl) fluorenes As 9,9-bis (hydroxynaphthyl) fluorenes, for example, 9,9-bis (hydroxynaphthyl) fluorenes {for example, 9,9-bis ( Hydroxynaphthyl) fluorene [eg, 9,9-bis [6- (2-hydroxynaphthyl)] fluorene (or 6,6- (9-fluorenylidene) -di (2-naphthol) or 9,9-bis [2- (6-hydroxynaphthyl)] fluorene), 9,9-bis [1- (6-hydroxynaphthyl)] fluorene (or 5,5- (9-fluorenylidene) -di (2-naphthol)), 9,9- Having a substituent such as bis [1- (5-hydroxynaphthyl)] fluorene (or 5,5- (9-fluorenylidene) -di (1-naphthol)), etc.] 9,9-bis (monohydroxynaphthyl) fluorene}, and 9,9-bis (polyhydroxynaphthyl) fluorenes corresponding to these 9,9-bis (monohydroxynaphthyl) fluorenes (for example, 9 , 9-bis (di- or trihydroxynaphthyl) fluorenes).

  In addition, 9,9-bis (hydroxynaphthyl) fluorenes are hydroxynaphthalenes (for example, naphthols such as naphthol) instead of phenols in the method for producing 9,9-bis (monohydroxyphenyl) fluorenes. , Polyhydroxynaphthalenes such as dihydroxynaphthalene).

  These 9,9-bis (hydroxyaryl) fluorenes (compound represented by the formula (1A)) may be used alone or in combination of two or more.

In the sulfonic acid esterification step (or reaction with sulfonic acids corresponding to the group R ³ SO ₃ —), the purity of the compound represented by the formula (1A) used is not particularly limited. , 95% by weight or more, preferably 99% by weight or more.

Moreover, sulfonic acid esterification step _- in (or a group R ³ SO 3 reaction of the corresponding sulfonic acids in), based on R ³ SO 3 _- Examples of the sulfonic acids corresponding to, sulfonic acids and represented by the following formula Derivatives and the like are included.

R ₃ SO ₃ H
(In the formula, R ³ is the same as above.)
Representative sulfonic acids include sulfonic acids corresponding to the hydrocarbon groups exemplified in the above R ³ , such as alkane sulfonic acids (for example, C _1-4 alkane sulfonic acids such as methanesulfonic acid), arene sulfones, and the like. Acids (eg, C _6-10 arene sulfonic acids such as benzene sulfonic acid, toluene sulfonic acid (p-toluene sulfonic acid etc.)), haloalkane sulfonic acids (eg halo C _1-4 alkane sulfonic acid such as trifluoromethane sulfonic acid) Etc.), derivatives thereof (sulfonic acid anhydride, sulfonic acid halide, sulfonic acid imide, sulfonic acid amide, etc.). These sulfonic acids may be used alone or in combination of two or more.

Of these, particularly preferred sulfonic acids are trifluoromethanesulfonic acids (sulfonic acids whose group R ³ is a trifluoromethyl group). Examples of the trifluoromethanesulfonic acid (or triflating reagent) include trifluoromethanesulfonic acid, trifluoromethanesulfonic acid derivatives {eg, trifluoromethanesulfonic acid anhydride, trifluoromethanesulfonic acid halide (such as trifluoromethanesulfonic acid chloride), trifluoro L-methanesulfonic acid imide (for example, N-substituted trifluoromethanesulfonic acid imide such as N-phenyltrifluoromethanesulfonimide), trifluoromethanesulfonic acid ester [for example, trifluoromethanesulfonic acid (4-nitrophenyl), etc.], trifluoromethanesulfonic acid Amido [for example, 1- (trifluoromethanesulfonyl) imidazole etc.] etc. are mentioned. These trifluoromethanesulfonic acids may be used alone or in combination of two or more. Of these, trifluoromethanesulfonic anhydride is particularly preferably used.

In _- (reaction with the corresponding sulfonic acids or radical R ³ SO 3), radical R ³ SO 3 _- sulfonate esterification step proportion of the corresponding sulfonic acids (trifluoromethane sulfonic acid), for example, the For example, 1 to 3 mol, preferably 1.05 to 2 mol, more preferably 1.1 to 1.5 mol, per 1 mol of the hydroxyl group of the compound represented by the formula (1A) (fluorenephenol derivative) It may be a degree.

The sulfonic acid esterification step (or reaction with sulfonic acids corresponding to the group R ³ SO ₃ —) may be performed in the presence of a catalyst. As the catalyst, a base catalyst (basic catalyst) can be preferably used. Examples of the base catalyst include amines [eg, aliphatic amines (eg, triethylamine, tri-n-propylamine, tri-n-butylamine, triisopropylamine, diisopropylethylamine, dicyclohexylethylamine, diethylcyclohexylamine, tribenzylamine). N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropanediamine, 1-methylpiperidine, 1-ethylpiperidine, 1,2,2 ′, 6,6 '-Pentamethylpiperidine, 1-methylpyrrolidine, 1-ethylpyrrolidine, 4-methylmorpholine, 4-ethylmorpholine, aliphatic tertiary amines such as 2,6-dimethylpiperazine), aromatic amines (eg, N, N-dimethylaniline, N, N-diethylaniline, -Aromatic tertiary amines such as phenylpyrrolidine, N-phenylmorpholine, 1,8-bis (dimethylamino) naphthalene), heterocyclic amines (pyridine, lutidine, collidine, 4- (dimethylamino) pyridine, 4 -Pyrrolidinopyridine, imidazole, 1,5-diazabicyclo [4.3.0] nonene, 1,8-diazabicyclo [5.4.0] undecene, etc.)], metal alkoxides (for example, sodium methoxide, sodium ethoxy) Sodium tert-butoxide, potassium tert-butoxide, etc.), organometallic compounds (butyl lithium, phenyl lithium, isopropyl magnesium chloride, cyclohexyl magnesium bromide, phenyl magnesium bromide, sodium amide, lithium diisopropyl) Pyramide, lithium 1,1-bis (trimethylsilyl) amide, sodium 1,1-bis (trimethylsilyl) amide, potassium 1,1-bis (trimethylsilyl) amide), organic acid salts (for example, sodium acetate, potassium acetate, etc.) Organic bases such as organic acid metal salts; carbonates (eg, potassium carbonate, sodium carbonate, etc.), bicarbonates (eg, potassium bicarbonate, sodium bicarbonate, etc.), hydroxides (eg, potassium hydroxide, And inorganic bases such as hydride (sodium hydride, potassium hydride, etc.).

  These catalysts (base catalysts) may be used alone or in combination of two or more.

  Among these, triethylamine, tri-n-propylamine, tri-n-butylamine, triisopropylamine, diisopropylethylamine, 1-methylpiperidine, 1-ethylpiperidine, 1,2,2 ′, 6,6′-pentamethyl Tertiary amines such as piperidine, 1-methylpyrrolidine, 1-ethylpyrrolidine, 4-methylmorpholine, 4-ethylmorpholine, 2,6-dimethylpiperazine, pyridine, lutidine, collidine, 4- (dimethylamino) pyridine, 4- Preferred are heterocyclic amines such as pyrrolidinopyridine, inorganic bases such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium hydride, etc., especially triethylamine, diisopropylethylamine, pyridine, lutidine, collidine Preferably used.

  The ratio of the catalyst (base catalyst) to be used is, for example, 1 to 50 molar equivalents, preferably 1.05 to 1 mol of the hydroxyl group of the compound represented by the formula (1A) (fluorene phenol derivative). It may be about 20 molar equivalents (for example, 1.1 to 10 molar equivalents), more preferably about 1.2 to 2 molar equivalents.

The sulfonic acid esterification step (or reaction with sulfonic acids corresponding to the group R ³ SO ₃ —) may be performed in the absence of a solvent or in a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, hydrocarbon solvents (for example, aromatic hydrocarbons such as toluene and xylene), halogen solvents (haloalkanes such as dichloromethane and chloroform), and the like. Etc.), ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and 1,4-dioxane), amides (such as dimethylformamide), sulfoxides (such as dimethyl sulfoxide), nitriles (acetonitrile) Etc.). The amines (such as pyridine) may be used as a solvent. These solvents may be used alone or in combination of two or more.

The amount of the solvent used is, for example, from 0.3 to 1 part by weight with respect to 1 part by weight of the total amount of the sulfonic acid (such as trifluoromethanesulfonic acid) corresponding to the compound represented by the formula (1A) and the group R ³ SO ₃ —. It may be about 100 parts by weight, preferably 0.5 to 50 parts by weight, and more preferably about 1 to 30 parts by weight.

  In addition, reaction temperature can be selected from the range of -100-200 degreeC, Preferably it is -10-100 degreeC, More preferably, about 0-30 degreeC may be sufficient. Moreover, reaction time is not specifically limited, Although it can select suitably according to reaction temperature, Usually, 1 to 12 hours, Preferably about 2 to 8 hours may be sufficient. The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (such as nitrogen or a rare gas), and 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.

[Carbonylation step]
In the carbonylation step, a compound represented by the following formula (1) is reacted with carbon monoxide. Carbon monoxide is usually used in a gaseous state in the reaction system. The pressure of carbon monoxide may be, for example, about 1 to 100 kgf / cm ² , preferably about 5 to 70 kgf / cm ² , and more preferably about 15 to 50 kgf / cm ² .

  The carbonylation step may be usually performed in the presence of a transition metal catalyst (or a transition metal compound). Examples of the transition metal catalyst include palladium compounds [eg, palladium oxide; palladium salts such as palladium halide (palladium chloride, palladium bromide, palladium iodide, etc.), palladium nitrate, palladium organic acid salts (palladium acetate, etc.); Complexes (for example, dichlorobis (triphenylphosphine) palladium, [1,4-bis (diphenylphosphino) butane] dichloropalladium, tetrakistriphenylphosphinepalladium, etc.), nitrile complexes (dichlorobisbenzonitrilepalladium, dichlorobisacetonitrilepalladium, etc.) )) And other transition metal compounds corresponding to these palladium compounds (for example, ruthenium compounds, rhodium compounds, nickel compounds, platinum compounds, etc.) Is mentioned. These transition metal catalysts may be used alone or in combination of two or more. A preferred transition metal catalyst is a palladium compound.

The ratio of the transition metal catalyst used is, for example, 0.00001 mol or more with respect to 1 mol of the group R ³ SO ₃ — (for example, trifluoromethanesulfonyloxy group) of the compound represented by the formula (1) ( For example, about 0.00005 to 1 mol), preferably 0.0001 to 0.5 mol, more preferably 0.0003 to 0.1 mol, particularly about 0.0005 to 0.05 mol, Usually, it may be about 0.0001 to 0.1 mol.

  In addition, you may perform a carbonylation process in presence of a coordination compound as needed. Such a coordinating compound can enhance the catalytic activity in combination or combination with the transition metal catalyst (for example, complexed with the transition metal catalyst). Such a coordinating compound may be used together with the transition metal complex (for example, palladium phosphine complex) as described above, but usually complex formation of palladium oxide, palladium halide, palladium organic acid salt, etc. Often used together with a transition metal compound.

  The coordination compound is not particularly limited, and phosphines [for example, tri-t-butylphosphine, tricyclohexylphosphine, triphenylphosphine, trio-tolylphosphine, 1,2-bis (diphenylphosphino) ethane, 1 , 3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, etc.], nitriles (acetonitrile, benzonitrile, etc.) and the like. These coordination compounds may be used alone or in combination of two or more.

The ratio of the coordination compound used is, for example, 0.00001 to 0 with respect to 1 mol of the group R ³ SO ₃ — (for example, trifluoromethanesulfonyloxy group) of the compound represented by the formula (1). It may be about 0.5 mol, preferably about 0.0001 to 0.3 mol, more preferably about 0.001 to 0.05 mol.

  Moreover, the usage-amount of a coordination compound is 0.1-10 mol with respect to 1 mol of transition metal catalysts, Preferably it is 0.5-8 mol, More preferably, it is 1-5 mol, Especially 1.5. About 4 mol may be sufficient.

  Further, the carbonylation step may be performed in the presence of a base catalyst. The base catalyst is not particularly limited and includes, for example, organic bases [eg, amines (eg, triethylamine, tributylamine, etc.), organic acid salts (eg, sodium acetate, potassium acetate, etc.)], inorganic bases [eg, Illustrated in the triflating step of hydroxide (eg, sodium hydroxide, potassium hydroxide, etc.), carbonate (eg, sodium carbonate, potassium carbonate, etc.), bicarbonate (eg, sodium bicarbonate, etc.), etc. And the base catalyst. These base catalysts may be used alone or in combination of two or more.

The use ratio of the base catalyst is, for example, 0.5 to 10 mol, preferably 1 mol with respect to 1 mol of the group R ³ SO ₃ — (for example, trifluoromethanesulfonyloxy group) of the compound represented by the formula (1). It may be about 0.8 to 8 mol, more preferably about 1 to 5 mol.

  The carbonylation step can usually be performed in the presence of water and / or alcohols. When water is present in the reaction system, 9,9-bis (carboxyaryl) fluorenes (that is, a compound represented by the following formula (A)) and alcohols are present as products as the product. , 9-bis (carboxyaryl) fluorene esters (that is, esters of compounds represented by the formula (A) described later) can be obtained efficiently. From the viewpoint of improving the addition rate, alcohols are preferably used. Therefore, even in the case of obtaining the 9,9-bis (carboxyaryl) fluorenes, as will be described later, an alcohol is used to obtain an ester, followed by a hydrolysis treatment to obtain 9,9-bis. (Carboxyaryl) fluorenes may be obtained. Water and / or alcohols are usually present in the reaction system, but may be added after the reaction.

Examples of alcohols include aliphatic alcohols [eg, alkanols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, n-pentanol, n-hexanol, n-heptanol, C _1-20 alkanols such as n-octanol and 2-ethylhexanol, preferably C _1-15 alkanols), cycloalkanols (C _5-10 cycloalkanols such as cyclopentanol, cyclohexanol, cycloheptanol) and the like], aromatic alcohols (e.g., phenol, etc. _{C 6-15} aryl alcohols such as naphthol), araliphatic alcohols (e.g., benzyl alcohol, _{C 6-10} aryl _{-C 1-4} aralkyl, such as phenethyl alcohol Etc. alcohol) and the like. These alcohols may be used alone or in combination of two or more.
Preferable alcohols include primary alcohols [for example, primary aliphatic alcohols such as methanol and ethanol (for example, primary C _1-4 alkanol, etc.)] and the like.
Moreover, you may combine water and alcohol.

The ratio of water and / or alcohol used is, for example, 0.8 with respect to 1 mol of the group R ³ SO ₃ — (for example, trifluoromethanesulfonyloxy group) of the compound represented by the formula (1). It may be about 10 to 10 mol, preferably 1 to 8 mol (eg 1 to 6 mol), more preferably about 1.1 to 5 mol.

  The carbonylation step may be performed in the absence of a solvent or in a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, hydrocarbon solvents (for example, aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as toluene and xylene, etc.) ), Ether solvents (eg, cyclic ethers such as tetrahydrofuran and 1,4-dioxane), amides (eg, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), sulfoxides (eg, dimethyl sulfoxide, etc.) , Sulfones (for example, sulfolane, dimethyl sulfone, etc.). Moreover, you may use the said alcohols and water for a solvent. These solvents may be used alone or in combination of two or more.

  The amount of the solvent used is, for example, 0.3 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 1 part by weight of the compound represented by the formula (1). It may be about a part.

  Reaction temperature can be selected from the range of 50-250 degreeC, Preferably it is 70-200 degreeC, More preferably, about 90-150 degreeC may be sufficient. The reaction time is not particularly limited and can be appropriately selected depending on the reaction temperature and reaction scale. However, it can usually be selected from a range of about 1 to 48 hours, preferably about 2 to 24 hours. Moreover, you may perform reaction, stirring. Furthermore, the reaction may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed under normal pressure or under 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. Typically, after completion of the reaction, it may be purified by recrystallization or the like by appropriately adding a crystallization solvent.

  As described above, selected from 9,9-bis (carboxyaryl) fluorenes (that is, a compound represented by the following formula (A)) and esters thereof (specifically, esters corresponding to the alcohols). The obtained fluorene derivative is obtained. As described above, when the alcohol is present in the carbonylation reaction system (or added after the carbonylation reaction), the ester is obtained, and water is present in the carbonylation reaction system (or added after the carbonylation reaction). ) And carboxylic acid. Therefore, when the ester is obtained using alcohols, the carboxylic acid may be obtained by performing a hydrolysis treatment as necessary.

[Hydrolysis step]
That is, in the production method of the present invention, in the carbonylation step, the reaction between the compound represented by the formula (1) and carbon monoxide is performed in the presence of alcohols, and 9,9-bis (carboxyaryl) After obtaining an ester of a fluorene (compound represented by the formula (A)) and the alcohol, the ester is hydrolyzed, and 9,9-bis (carboxyaryl) fluorene (expressed by the formula (A)). The hydrolysis step to obtain a compound to be obtained may be further included.

  In the hydrolysis step, an ester of 9,9-bis (carboxyaryl) fluorene and the alcohol is hydrolyzed to obtain 9,9-bis (carboxyaryl) fluorene. Such a hydrolysis step can be usually carried out by mixing the ester with a base or an acid for hydrolysis. The base is not particularly limited as long as it can be hydrolyzed, and for example, an inorganic base such as a hydroxide (for example, potassium hydroxide, sodium hydroxide) can be preferably used. The bases may be used alone or in combination of two or more. Moreover, it does not specifically limit as an acid, For example, inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, etc. can be used conveniently. The acids may be used alone or in combination of two or more. In addition, these bases or acids may be dissolved in an appropriate solvent (such as water) and used for hydrolysis.

  The amount of the base or acid used is, for example, about 1 to 10 molar equivalents, preferably 1.2 to 8 molar equivalents, more preferably about 1.5 to 5 molar equivalents with respect to 1 mol of the ester group of the ester. May be.

  The hydrolysis temperature can be selected according to the type of base or acid, and may be, for example, 20 to 200 ° C, preferably 30 to 180 ° C, and more preferably about 50 to 150 ° C. In addition, you may perform a hydrolysis under reflux using a suitable solvent. The hydrolysis time can be selected according to the type of acid or base, the hydrolysis temperature, etc., and may be, for example, 2 to 120 hours, preferably about 5 to 72 hours.

  After hydrolysis, the resulting compound may be separated and purified by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. Typically, after completion of the reaction, an extraction operation may be performed, and then a crystallization solvent may be added as appropriate, and purification may be performed by recrystallization or the like.

  In the method of the present invention, a fluorene derivative can be obtained with high yield. In addition, the method of the present invention can obtain a fluorene derivative with high purity, and can be synthesized in large quantities. For example, the yield of fluorene derivatives (9,9-bis (carboxyaryl) fluorenes and esters thereof) obtained by the method of the present invention is 50 mol% or more based on the compound represented by the formula (1) ( For example, 55 to 100 mol%), preferably 60 mol% or more (for example, 63 to 99.99 mol%), more preferably 65 mol% or more (for example, 65 to 99.95 mol%) may be used. .

[Fluorene derivative]
As described above, a fluorene derivative selected from 9,9-bis (carboxyaryl) fluorenes [ie, a compound represented by the following formula (A)] and esters thereof is obtained.

(In the formula, Z, R ¹ , R ² , k, m, and n are the same as described above.)
Representative compounds represented by the above formula (A) include a carboxylic acid (9,9-bis) corresponding to the compound [9,9-bis (hydroxyaryl) fluorenes] represented by the above formula (1A). (Hydroxyaryl) a compound in which the hydroxy group of fluorene is substituted with a carboxy group), for example, 9,9-bis (carboxyphenyl) fluorene [9,9-bis (4-carboxyphenyl) fluorene and the like], 9,9- 9,9-bis (C _1-4 alkyl-carboxyphenyl) fluorene, such as bis (alkyl-carboxyphenyl) fluorene [9,9-bis (4-carboxy-3-methylphenyl) fluorene, 9,9-bis ( 4-carboxy-2,6-dimethylphenyl) fluorene such as 9,9-bis _{(di-C 1-4} alkyl - carboxyphenyl) full Ren, etc.], 9,9-bis (aryl - carboxyphenyl) fluorene [e.g., 9,9-bis (4-carboxy-3-phenylphenyl) fluorene such as 9,9-bis _{(C 6-8} aryl - carboxy 9,9-bis (carboxyphenyl) fluorenes such as 9,9-bis (dicarboxyphenyl) fluorene [9,9-bis (3,4-dicarboxyphenyl) fluorene, etc.]; 9 , 9-bis (carboxynaphthyl) fluorene [for example, 9,9-bis [6- (2-carboxynaphthyl)] fluorene (or 9,9-bis [2- (6-carboxynaphthyl)] fluorene), 9, 9-bis [1- (6-carboxynaphthyl)] fluorene, 9,9-bis [1- (5-carboxynaphthyl)] fluore Etc.] and the like 9,9-bis (carboxymethyl naphthyl) fluorene such as.

As typical esters, esters corresponding to the alcohols, for example, 9,9- such as 9,9-bis (alkoxycarbonylphenyl) fluorene [9,9-bis (4-methoxycarbonylphenyl) fluorene, etc. bis _{(C 1-4} alkoxycarbonyl phenyl) fluorene, 9,9-bis (alkyl - alkoxycarbonyl phenyl) fluorene [9,9-bis (4-methoxycarbonyl-3-methylphenyl) fluorene, 9,9-bis 9,9-bis (C _1-4 alkyl-mono or diC _1-4 alkoxycarbonylphenyl) fluorene such as (4-methoxycarbonyl-2,6-dimethylphenyl) fluorene], 9,9-bis (aryl -Alkoxycarbonylphenyl) fluorene [eg 9,9-bis (4 9,9-bis such methoxycarbonyl-3-phenylphenyl) fluorene _{(C 6-8} aryl _{-C 1-4} alkoxycarbonyl phenyl) fluorene, etc.], 9,9-bis (di-alkoxycarbonyl phenyl) fluorene [9, 9,9-bis (alkoxycarbonylphenyl) fluorenes such as 9-bis (3,4-dimethoxycarbonylphenyl) fluorene]; 9,9-bis (alkoxycarbonylnaphthyl) fluorene [eg, 9,9-bis [ 6- (2-methoxycarbonylnaphthyl)] fluorene (or 9,9-bis [2- (6-methoxycarbonylnaphthyl)] fluorene), 9,9-bis [1- (6-methoxycarbonylnaphthyl)] fluorene, 9,9-bis [1- (5-methoxycarbonylnaphthyl)] fluoro Alkyl esters (eg, C _1-4 alkyl esters) such as 9,9-bis (alkoxycarbonylnaphthyl) fluorenes such as len etc., and cycloalkyl esters corresponding to these alkyl esters. .

  In particular, in the present invention, among the compounds represented by the formula (A) and esters thereof, novel compounds excellent in various properties such as heat resistance (compounds represented by the following formula (A1) and esters thereof) are provided. can get. Therefore, the present invention also includes a specific fluorene derivative selected from a compound represented by the following formula (A1) and an ester thereof.

(In the formula, ring Z ¹ represents a condensed polycyclic aromatic hydrocarbon ring, and R ¹ , R ² , k, m, and n are the same as described above.)
In the above formula (A1), examples of the condensed polycyclic aromatic hydrocarbon ring represented by the ring Z ¹ include the rings exemplified above, for example, a naphthalene ring. In the formula (A1), the preferred embodiment and substitution position of the condensed polycyclic hydrocarbon ring are the same as described above.

  Such a compound represented by the formula (A1) includes the 9,9-bis (carboxynaphthyl) fluorenes. Examples of the ester of the compound represented by the formula (A1) include alkyl esters such as the 9,9-bis (alkoxycarbonylnaphthyl) fluorenes, cycloalkyl esters corresponding to the alkyl esters, and the like. It is done.

  In the method of the present invention, fluorene derivatives [9,9-bis (carboxyaryl) fluorenes and esters thereof] can be obtained with high yield. Further, the purity of the fluorene derivative obtained by the method of the present invention is high, and the method of the present invention is industrially extremely advantageous as a method for obtaining a fluorene derivative.

Such a fluorene derivative is a resin raw material {eg, a polyester resin [eg, polyalkylene terephthalate (poly C _2-4 alkylene terephthalate such as polyethylene terephthalate, polybutylene terephthalate), polyalkylene arylate resin such as polyethylene naphthalate; Polyarylate etc.], liquid crystalline polymer, polyamide resin, polyimide resin, polybenzimidazole, polycarboxylic acid raw material of resin having a polymerization component such as polycarboxylic acid or derivative thereof (such as lower alkyl ester)} It is useful as a functional material [for example, an additive (resist additive, etc.), a reagent (medicine, agrochemical, etc.) or an intermediate, etc.]. In particular, among fluorene derivatives, specific fluorene derivatives such as 9,9-bis (carboxynaphthyl) fluorenes and esters thereof are more difficult than conventional fluorene derivatives (such as 9,9-bis (carboxyphenyl) fluorenes). It has excellent properties such as high heat resistance, high refractive index, low linear expansion, high transparency, and high carbon density, and is useful as a compound for imparting or improving these properties.

Such a fluorene derivative 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.

[Example 1] Production of 4,4 '-(9-fluorenylidene) dibenzoic acid (1) Triflation A flask equipped with a DC (direct current) stirrer, thermometer and dropping funnel was purged with nitrogen, and 309 g of pyridine ( 3.9 mol), 1.4 L of acetonitrile, and 1.2 L of toluene, and while stirring, 525 g (1.5 mol) of 4,4 ′-(9-fluorenylidene) diphenol (Osaka Gas Chemical Co., Ltd.) was added little by little. In addition, it was completely dissolved. After cooling the internal temperature to 10 ° C. with an ice bath, 931 g (3.3 mol) of trifluoromethanesulfonic anhydride (manufactured by Showa Denko KK) was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 4 hours and left overnight. Water and toluene were added to the reaction solution, and the mixture was stirred and allowed to stand to separate the aqueous layer. The organic layer was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. Anhydrous sodium sulfate was removed by filtration, and the filtrate was concentrated under reduced pressure to about 1.5 L. The residue was heated to 65 ° C. in an oil bath, 1.5 L of n-hexane was added dropwise with stirring, and the mixture was gradually cooled over 1 hour. The precipitated crystals were filtered under reduced pressure, washed with a solvent (toluene: n-hexane = 1: 2), and then dried under reduced pressure. The corresponding triflate (melting point: 160.0-161.5 ° C.) was obtained with a yield of 763 g and a yield of 83%.

(2) Carbonylation 369 g (0.6 mol) of triflate obtained in a pressure vessel equipped with a gas introduction pipe, 600 ml of toluene, 243 g (2.4 mol) of triethylamine, 96 g (3 mol) of methanol, palladium acetate (Mitsuwa Chemical) 270 mg (1.2 mmol), 1,3-bis (diphenylphosphino) propane (manufactured by Amax Co.) 990 mg (2.4 mmol) were sealed and sealed, and the inside was twice with nitrogen. Substitution was performed 3 times with carbon oxide, and the pressure was increased to 2 MPa with carbon monoxide. The temperature was gradually raised to 100 ° C., and the mixture was reacted at 100 ° C. for 7 hours while appropriately pressurizing with carbon monoxide. After cooling to room temperature, after depressurization and replacement with nitrogen, the container was opened, water and toluene were added to the reaction solution, and the aqueous layer was separated after stirring. The organic layer was washed successively with aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous sodium sulfate. The organic layer was filtered through a funnel with celite and activated carbon, and the filtrate was dried under reduced pressure. Toluene was added to the residue, heated to 65 ° C. in an oil bath, n-hexane was added dropwise with stirring, and the mixture was gradually cooled over 1 hour. The precipitated crystals were filtered under reduced pressure, washed with a solvent (toluene: n-hexane = 1: 1), and then dried under reduced pressure. The corresponding methyl ester (melting point: 181.0-183.0 ° C.) was obtained with a yield of 224 g and a yield of 86%. The purity measured by liquid chromatography was 97.3%.

(3) Hydrolysis A flask equipped with a DC stirrer, thermometer, and reflux condenser was replaced with nitrogen, and 690 g (1.6 mol) of the obtained methyl ester and 1.5 L of tetrahydrofuran (THF) were added, and 10% with stirring. 1.7 L of aqueous sodium hydroxide was added. After stirring at reflux for 5 hours, THF was distilled off. After cooling to room temperature, water and toluene were added and stirred, and then allowed to stand to separate the organic layer. Toluene was added to the aqueous layer and stirred, and then allowed to stand to separate the organic layer. The aqueous layer was filtered through a funnel with celite and activated carbon. The filtrate was heated to 60 ° C., 470 g (4.5 mol) of concentrated hydrochloric acid was added dropwise, and the mixture was aged for 30 minutes, and then gradually cooled to room temperature. The precipitated crystals were filtered under reduced pressure, and the filtrate was washed 3 times with water. Hydrous crystals were dried by ventilation at 50 ° C., and 4,4 ′-(9-fluorenylidene) dibenzoic acid (or 9,9-bis (4-carboxyphenyl) fluorene, white powder, melting point: 300.0 ° C. <) Yield 651 g, 99% yield. The purity measured by liquid chromatography was 98.1%.

¹ H-NMR [DMSO-d ₆ / TMS, δ value (ppm)]
7.23-7.26 (d, 2H), 7.33-7.37 (t, 1H), 7.43-7.49 (m, 2H), 7.84-7.86 (d, 2H) ), 7.97-7.99 (d, 1H), 12.46 (s, 2H).

[Example 2] Production of 9,9-bis (3-methyl-4-carboxyphenyl) fluorene (1) Triflation To 9 ml of toluene and 6.17 g (78 mmol) of pyridine, 9,9-bis (3 -Methyl-4-hydroxyphenyl) fluorene (Osaka Gas Chemical Co., Ltd.) 11.36 g (30 mmol) was added little by little, the internal temperature was cooled to 10 ° C. in an ice bath, and trifluoromethanesulfonic anhydride (Showa Denko) 18.6 g (66 mmol) (manufactured by Co., Ltd.) was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 4 hours and left overnight. Water and ethyl acetate were added to the reaction solution, and the mixture was stirred and allowed to stand to separate the aqueous layer. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous sodium sulfate. The filtrate from which anhydrous sodium sulfate was removed by filtration was dried under reduced pressure. The residue was suspended in a solvent (n-hexane: ethyl acetate = 4: 1), filtered under reduced pressure, and dried to give the corresponding triflate (melting point: 162.0). −163.0 ° C.) was obtained in a yield of 17.8 g and a yield of 92%.

(2) Carbonylation 19.28 g (30 mmol) of triflate obtained in a pressure vessel equipped with a gas introduction pipe, 30 ml of toluene, 12.14 g (120 mmol) of triethylamine, 4.81 g (150 mmol) of methanol, palladium acetate (Mitsuwa) (Chemicals Co., Ltd.) 13 mg (0.06 mmol), 1,3-bis (diphenylphosphino) propane (Azumax Co., Ltd.) 50 mg (0.12 mmol) was added and sealed, and the inside was twice with nitrogen The carbon monoxide was substituted three times, and the pressure was increased to 0.2 MPa with carbon monoxide. The temperature was gradually raised to 100 ° C., and the mixture was reacted at 100 ° C. for 8 hours while appropriately pressurizing with carbon monoxide. After cooling to room temperature, after depressurization and replacement with nitrogen, the container was opened, water and ethyl acetate water were added to the reaction solution and stirred, and then the aqueous layer was separated. The organic layer was washed successively with aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous sodium sulfate. The organic layer was filtered through a funnel with celite and activated carbon, and the filtrate was dried under reduced pressure. The residue was purified by column chromatography on silica gel (developing solvent n-hexane: ethyl acetate = 4: 1), yield 9.46 g, yield 68%, corresponding methyl ester (melting point: 159.0-161.0 ° C. )

(3) Hydrolysis 6.94 g (15 mmol) of the obtained methyl ester was dissolved in 15 ml of THF, 16 ml of 10% aqueous sodium hydroxide solution was added with stirring, and the mixture was stirred at reflux for 48 hours. The reaction solution was cooled to room temperature, THF was distilled off with a rotary evaporator, water and toluene were added, and the mixture was stirred and allowed to stand to separate the organic layer. Toluene was added to the aqueous layer and stirred, and then allowed to stand to separate the organic layer. The aqueous layer was heated to 60 ° C., 4.38 g (42 mmol) of concentrated hydrochloric acid was added dropwise, and the mixture was slowly cooled to room temperature. The precipitated crystals were filtered under reduced pressure, and the filtrate was washed 3 times with water. The water-containing crystals were dried by ventilation at 50 ° C. to obtain 9,9-bis (3-methyl-4-carboxyphenyl) fluorene (melting point: 294.0-298.0 ° C.) in a yield of 6.39 g and a yield of 98%. It was.

[Example 3]
Preparation of 9,9-bis (6-carboxy-2-naphthyl) fluorene (1) Triflation 9,9-bis (6-hydroxy-) with stirring in 150 ml of toluene, 20 ml of acetonitrile and 10.28 g (130 mmol) of pyridine 2-Naphtyl) fluorene (Osaka Gas Chemical Co., Ltd.) 27.64 g (50 mmol) was added little by little, the internal temperature was cooled to 10 ° C. in an ice bath, and trifluoromethanesulfonic anhydride (Showa Denko Co., Ltd.) was added. 31.0 g (110 mmol) was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 4 hours and left overnight. Water and ethyl acetate were added to the reaction solution, and the mixture was stirred and allowed to stand to separate the aqueous layer. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous sodium sulfate. The filtrate from which anhydrous sodium sulfate was removed by filtration was dried under reduced pressure. The residue was suspended in a solvent (n-hexane: ethyl acetate = 4: 1), filtered under reduced pressure, and dried to give the corresponding triflate (melting point: 144.0). -145.5 ° C.) was obtained in a yield of 27.6 g, a yield of 77%.

(2) Carbonylation In a pressure vessel equipped with a gas introduction tube, the obtained triflate 21.44 g (30 mmol), toluene 30 ml, triethylamine 12.14 g (120 mmol), methanol 4.81 g (150 mmol), palladium acetate (Mitsu) (Wa Chemicals Co., Ltd.) 13 mg (0.06 mmol), 1,3-bis (diphenylphosphino) propane (Azumax Co., Ltd.) 50 mg (0.12 mmol) was added and sealed, and the inside was filled with nitrogen. 1 time, and carbon monoxide was substituted 3 times, and the pressure was increased to 0.2 MPa with carbon monoxide. The temperature was gradually raised to 95 ° C., and the mixture was reacted at 95 ° C. for 6 hours while appropriately pressurizing with carbon monoxide. After cooling to room temperature, after depressurization and replacement with nitrogen, the container was opened, water and ethyl acetate water were added to the reaction solution and stirred, and then the aqueous layer was separated. The organic layer was washed successively with aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous sodium sulfate. The organic layer was filtered through a funnel covered with celite and activated carbon, the filtrate was concentrated under reduced pressure, and a solvent (hexane: ethyl acetate = 2: 1) was added and left standing. The precipitated crystals were filtered and washed with a solvent (hexane: ethyl acetate = 2: 1) to obtain the corresponding methyl ester (melting point: 254.0-255.0 ° C.) in a yield of 13.44 g and a yield of 84%.

(3) Hydrolysis 5.35 (10 mmol) of methyl ester was suspended in 20 ml of THF, 10 ml of 10% aqueous sodium hydroxide solution was added with stirring, and the mixture was stirred at reflux for 20 hours. The reaction solution was cooled to room temperature, THF was distilled off with a rotary evaporator, water and toluene were added, and the mixture was stirred and allowed to stand to separate the organic layer. Toluene was added to the aqueous layer and stirred, and then allowed to stand to separate the organic layer. The aqueous layer was heated to 60 ° C., 2.92 g (28 mmol) of concentrated hydrochloric acid was added dropwise, and the mixture was slowly cooled to room temperature. The precipitated crystals (amorphous) were filtered under reduced pressure, and the filtrate was washed with water three times. The hydrous crystal (amorphous) was dried by ventilation at 50 ° C., yielding 4.91 g of 9,9-bis (6-carboxy-2-naphthyl) fluorene [melting point: 232.0-255.0 ° C. (amorphous)]. The rate was 97%.

¹ H-NMR [DMSO-d ₆ / TMS, δ value (ppm)]
7.35-7.40 (m, 2H), 7.43-7.49 (m, 4H), 7.62-7.67 (m, 4H), 7.83 (d, 2H), 7. 90 (dd, 2H) 8.01-8.07 (m, 4H), 8.54 (s, 2H).

Claims (10)

  A fluorene derivative selected from a compound represented by the following formula (A1) and an ester thereof with a primary aliphatic alcohol.

(Wherein ring Z ¹ Represents a condensed polycyclic aromatic hydrocarbon ring, R ¹ Is a cyano group, a halogen atom or an alkyl group, R ² Represents a hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, halogen atom, nitro group, cyano group or substituted amino group. k is an integer of 0 to 4, m is an integer of 0 or more, and n is an integer of 1 or more. )   Ring Z ¹ The fluorene derivative according to claim 1, wherein is a naphthalene ring. A method for producing a fluorene derivative selected from a compound represented by the formula (A1) according to claim 1 and an ester thereof with a primary aliphatic alcohol, the compound represented by the following formula (1): A method for producing the fluorene derivative, comprising at least a carbonylation step of reacting with carbon monoxide.

(In the formula, ring Z represents a condensed polycyclic aromatic hydrocarbon ring, R ¹ represents a cyano group, a halogen atom or an alkyl group, R ² represents 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, R ³ represents a hydrocarbon group optionally substituted by a halogen atom, k is an integer of 0 to 4, and m is (An integer of 0 or more and n is an integer of 1 or more.) Prior to the carbonylation step, a compound represented by the following formula (1A) is reacted with a sulfonic acid corresponding to the group R ³ SO ₃ — to obtain a compound represented by the formula (1). The manufacturing method of Claim 3 including a process.

(In the formula, Z, R ¹ , R ² , k, m, and n are the same as described above.) A ring Z Gana Futaren ring, ^{R 1} is an alkyl group, k is 0 to 1, ^{R 2} is an alkyl or aryl group, m is 0 to 2, with n is 1 to 3 The manufacturing method according to claim 3 or 4 . The production method according to claim 3 , wherein the sulfonic acid is trifluoromethanesulfonic acid. The production method according to any one of claims 3 to 6 , wherein in the carbonylation step, the compound represented by the formula (1) and carbon monoxide are reacted in the presence of a transition metal catalyst. The production method according to claim 7 , wherein the transition metal catalyst is a palladium compound. The production method according to claim 7 or 8 , wherein the proportion of the transition metal catalyst is 0.00001 to 0.1 mol with respect to 1 mol of the group R ³ SO ₃ of the compound represented by the formula (1). The production method according to any one of claims 3 to 9 , wherein in the carbonylation step, the compound represented by the formula (1) and carbon monoxide are reacted in the presence of water and / or alcohols.