JP2009234997A - Compound containing fluorene skeleton - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new nonfunctional fluorene-containing compound that is unreactive. <P>SOLUTION: The compound is represented by formula (1) [in the formula, Z may be the same or different and represents an aromatic hydrocarbon ring; R<SP>1</SP>may be the same or different and represents a hydrocarbon group, a halogen atom, or a cyano group; R<SP>2</SP>may be the same or different and represents a hydrocarbon group, an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, an -XR<SP>3</SP>group (in the formula, R<SP>3</SP>represents a hydrocarbon group and X represents an oxygen atom or a sulfur atom) or an -N(R<SP>4</SP>)<SB>2</SB>group (in the formula, R<SP>4</SP>may be the same or different and represents a hydrocarbon group); m may be the same or different and is a natural number of 0 to 4; and n may be the same or different and is a natural number of 0 to 4]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel compound containing a fluorene skeleton and a method for producing the same. Specifically, the present invention relates to a novel fluorene-containing compound having a high refractive index, excellent transparency and heat resistance, and useful for various uses such as a resin additive, and a method for producing the same.

  With the recent development of information technology (Information Technology, IT) industry, various information devices [for example, images such as flat panel display (FPD), display devices, etc.] are becoming lighter and smaller. As information devices become lighter and smaller, it is necessary to improve the performance of optical members used (for example, optical sheets and optical films). Excellent heat resistance and optical characteristics (for example, transparency, refractive index, etc.) ) Is strongly demanded.

  Such optical members are often composed of general-purpose resins (thermoplastic resins, thermosetting resins, etc.), and at the same time, impart various properties (for example, moldability, etc.) and adjust the reactivity. In general, a resin additive (for example, a diluent) is used. However, for the resin additive, the low reactivity of the additive itself, the compatibility with the resin, and the like are important, and it is essential that the original characteristics of the resin are not deteriorated.

  On the other hand, it is known that 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. 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 A general method is to use phenoxyethanol fluorene (BPEF) or the like as a constituent component of a resin and introduce a fluorene skeleton into a part of the skeleton structure of the resin. For example, as an example using such a resin having a fluorene skeleton, JP-A No. 2002-284864 (Patent Document 1) discloses a molding material composed of a polyester resin having a 9,9-bisphenylfluorene skeleton. It is disclosed. JP-A-2004-339499 (Patent Document 2) discloses bisphenolfluorene [9,9-bis (4-hydroxyphenyl) fluorene], bisaminophenylfluorene [9,9-bis (4-aminophenyl). Fluorene], bisphenoxyethanol fluorene [9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene] and other resins having a fluorene skeleton as a polymerization component (polyester resin, polycarbonate resin, urethane resin) , Acrylic resins, polyamide resins, polyimide resins, epoxy resins, vinyl ester resins, phenol resins, aniline resins, and the like) and additives.

Thus, polyfunctional (especially bifunctional) fluorene compounds such as BPF, BCF, and BPEF are known as resin monomers, but are not known for use as resin additives.
JP 2002-284864 A (Claims) JP 2004-339499 A (claims, paragraph number [0032])

  Accordingly, an object of the present invention is to provide a novel fluorene skeleton-containing compound that can be used as a resin additive or the like and a method for producing the same.

  Another object of the present invention is to provide a novel fluorene skeleton-containing compound having excellent compatibility with resins (particularly resins containing aromatic rings) and excellent handleability even when used as a resin additive. Is to provide.

  Still another object of the present invention is to provide a novel fluorene skeleton-containing compound that is excellent in heat resistance and optical properties (for example, refractive index, transparency, etc.) and that can maintain (or improve) the original properties of the resin, and a method for producing the same. There is to do.

  By using the fluorene compound described in the above-mentioned patent documents as a resin additive, it can be expected to give a high refractive index to the resin, and to improve the heat resistance. However, since such a fluorene compound is a polyfunctional compound having a reactive group such as a hydroxyl group, there is a possibility that it may have some influence on the resin, such as a reaction with the resin, and the original characteristics of the resin may be deteriorated. There is sex. Moreover, since it is a polyfunctional compound, when using it as a diluent etc., a viscosity is large and handling property may be scarce.

  Therefore, as a result of intensive studies to achieve the above-mentioned problems, the present inventors can apply a compound containing a specific fluorene skeleton substituted with an unsubstituted or non-reactive substituent as a resin additive or the like. Furthermore, it is found that the resin has excellent compatibility and handling properties, and even when used as a resin additive (diluent, etc.), it can improve or improve heat resistance and optical characteristics while maintaining the original characteristics of the resin. The present invention has been completed.

  That is, the compound having a fluorene skeleton of the present invention is represented by the following formula (1).

Wherein Z is the same or different and represents an aromatic hydrocarbon ring, R ¹ is the same or different and represents a hydrocarbon group, a halogen atom or a cyano group, R ² is the same or different and represents a hydrocarbon group, An acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a —XR ³ group (wherein R ³ represents a hydrocarbon group, X represents an oxygen atom or a sulfur atom) or —N (R ⁴ ) ₂ group ( In the formula, R ⁴ is the same or different and represents a hydrocarbon group). m is the same or different and is an integer of 0 to 4, and n is the same or different and is an integer of 0 or more. ]
In the formula (1), the ring Z may be a benzene ring or a naphthalene ring.

The compound represented by the formula (1) particularly preferably has a group containing a hetero atom as a substituent. For example, in the formula (1), the total of n is at least 1 or more, and at least one of R ² is an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, —XR ³ group, or —N (R ⁴ ) _Two groups may be sufficient. Such a compound is often superior to an unsubstituted compound in terms of compatibility with a resin.

  The compound represented by the formula (1) is typically represented by the following formula (6).

(In the formula, R ^2a represents a hydrocarbon group, n1 is an integer of 0 or more, n2 is an integer of 1 or more, and n3 is an integer of 0 or more. R ¹ , R ³ , X, and m are the same as above. )
The compound represented by these may be sufficient. In the above formula (6), n1 may be about 0 to 2, n2 may be about 1 to 2, and n3 may be about 1 to 2.

Representative compounds of the invention include 9-phenyl-9-C _1-4 alkoxyphenylfluorene, 9,9-bis (C _1-4 alkoxyphenyl) fluorene, 9,9-bis (C _1-4 alkylthio). And compounds selected from phenyl) fluorene, 9,9-bis (N, N-diC _1-4 alkylaminophenyl) fluorene, and 9,9-bis (C _1-4 alkoxynaphthyl) fluorene.

  The novel fluorene skeleton-containing compound of the present invention is non-reactive (or has low reactivity) and can be used as a resin additive. Moreover, the novel compound of the present invention is excellent in compatibility with a resin (particularly, a resin containing an aromatic ring), and is excellent in handling properties even when used as a resin additive. Furthermore, the compound of the present invention is excellent in heat resistance and optical properties (for example, refractive index, transparency, etc.), and can maintain (or improve) the original properties of the resin.

  The compound of the present invention is represented by the following formula (1).

[In the formula, Z is the same or different and represents an aromatic hydrocarbon ring, R ¹ is the same or different and represents a non-reactive substituent, and R ² is the same or different and represents a non-reactive substituent. m is the same or different and is an integer of 0 to 4, and n is the same or different and is an integer of 0 or more. ]
In the ring Z of the formula (1), examples of the aromatic hydrocarbon ring include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, C such as naphthalene, indene ring, etc. _8-20 condensed bicyclic hydrocarbon rings (preferably C _10-16 condensed bicyclic hydrocarbon rings), etc .; condensed tricyclic hydrocarbon rings (eg anthracene, phenanthrene, etc.) Examples thereof include cyclic hydrocarbon rings. Preferred aromatic hydrocarbon rings include benzene and naphthalene rings. The two rings Z bonded to the fluorene ring may be the same or different rings, but are usually the same ring in many cases.

In the formula (1), the substituent R ¹ is not particularly limited as long as it is a non-reactive group (or a group that does not contain an active hydrogen atom), and examples thereof include a hydrocarbon group [for example, an alkyl group (for example, a methyl group). Group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group and the like C _1-6 alkyl group (for example, C _1-4 alkyl group, especially methyl group), etc., cycloalkyl group (for example, cyclohexyl) A C _5-10 cycloalkyl group (eg, a cyclo C _5-8 alkyl group, particularly a cyclohexyl group), an aryl group (eg, a C _6-10 aryl group such as a phenyl group or a naphthyl group), an aralkyl, etc. group (e.g., _{C 6-12} and aryl _{-C 1-4} alkyl group such as a benzyl group), etc.]; a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom It may be a cyano group; iodine, etc. atom). R ¹ is preferably a hydrocarbon group, and particularly preferably an alkyl group (the alkyl group exemplified above). In addition, when m is 2 or more, R ¹ may be the same or different from each other. Further, the substituents R ¹ substituted on the two benzene rings contained in the fluorene ring may be the same or different substituents, but are usually the same substituents in many cases. Furthermore, the bonding position of the substituent R ¹ is not particularly limited.

The number m of the substituent R ¹ is an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1 (particularly 0). In the two benzene rings included in the fluorene ring, the number m of the substituent R ¹ may be different from each other or the same.

In the formula (1), the substituent R ² of the ring Z is not particularly limited as long as it is a non-reactive substituent (a group that is not a reactive group such as a hydroxyl group, an amino group, or a carboxyl group). hydrogen group [e.g., an alkyl group (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, s- butyl group, _{C 1-20} alkyl group such as t- butyl group, preferably a _{C 1-8} alkyl Group, more preferably C _1-6 alkyl group, etc., cycloalkyl group (C _5-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group, etc., preferably C _5-8 cycloalkyl group, more preferably C _{5 -6} cycloalkyl group and the like), an aryl group (e.g., phenyl group, _{C 6-10} aryl group such as a naphthyl group, preferably a _{C 6-8} aryl group, especially Etc. Eniru group), an aralkyl group (benzyl group, _{C 6-10} and aryl _{-C 1-4} alkyl group), etc.], such as phenethyl group; a _{C 1-6} acyl group such as an acyl group (acetyl group); alkoxycarbonyl Groups (C _1-4 alkoxycarbonyl groups such as methoxycarbonyl groups); halogen atoms (fluorine atoms, chlorine atoms, etc.); non-reactive groups (or groups not containing active hydrogen atoms) such as cyano groups. Further, as the substituent R ² ring Z, (groups that do not contain or active hydrogen atom) other non-reactive groups, e.g., groups -XR 3 represented by the following formula (4) ⁽⁴⁾
(Wherein R ³ represents a hydrocarbon group, X represents an oxygen atom or a sulfur atom), and a group represented by the following formula (5) —N (R ⁴ ) ₂ (5)
(Wherein R ⁴ is the same or different and each represents a hydrocarbon group).

In the formula (4), the substituent R ³ may be the hydrocarbon group exemplified above. X may be a heteroatom such as an oxygen atom or a sulfur atom. Specifically, the group represented by the formula (4) includes a group represented by —OR ³ [a group in which a hydrogen atom of a hydroxyl group is substituted with R ³ (the hydrocarbon group), for example, an alkoxy group. (For example, C _1-4 alkoxy group such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy group, etc.)]; a group represented by —SR ³ [hydrogen of thiol group A group in which an atom is substituted with R ³ (the hydrocarbon group), for example, an alkylthio group (for example, a C _1-4 alkylthio group such as a methylthio group or an ethylthio group) and the like.

In the formula (5), the substituent R ⁴ may also be the exemplified hydrocarbon group. Specifically, the group represented by the formula (5) includes an N, N-disubstituted amino group [for example, dialkylamino group (for example, di-C such as dimethylamino group, diethylamino group, ethylmethylamino group, etc.). _1-4 alkylamino group, etc.)] and the like. The two substituents R ⁴ substituted with the nitrogen atom may be the same or different.

Preferred examples of the substituent R ² include a hydrocarbon group, —XR ³ group, —N (R ⁴ ) ₂ group and the like, and in particular, an acyl group, an alkoxycarbonyl group, —XR ³ group, —N (R ⁴ ). _A group containing a hetero atom such as _two groups (hetero atom-containing group) is preferred. The compound represented by the above formula (1) having such a substituent is often superior to an unsubstituted compound in terms of compatibility with a resin and can be suitably used. The substituent R ² may be substituted on one ring Z alone or in combination of two or more. Further, the substituents R ² substituted on different rings Z may be the same or different from each other. Note that the substitution position of the substituent R ² is not particularly limited.

The number n of the substituent R ² can be appropriately selected according to the type of the ring Z, and is, for example, 0 to 8 (for example, 0 to 6), preferably 0 to 4 (for example, 0 to 3), and more preferably. 1-3, especially 1-2 (especially 1). The total of n in the two rings Z may be, for example, 0 to 12, preferably 0 to 8, more preferably 1 to 6, particularly 1 to 4 (for example, 1 to 2). In the two rings Z, the number n of the substituents R ² may be different from each other or the same.

The representative compound represented by the formula (1) includes a compound having at least one hetero atom-containing group in the substituent R ² in the formula (1), for example, the following formula (6):

(In the formula, R ^2a represents a substituent other than the —XR ³ group in the exemplified substituent R ² , n1 is an integer of 0 or more, n2 is an integer of 1 or more, and n3 is an integer of 0 or more. R ¹ , R ³ , X and m are the same as above)
And the like. That is, in the compound represented by the formula (6), the substituent R ² has at least one substituent selected from —OR ³ group and —SR ³ group (in the case of plural types, It may be a compound containing at least one).

Among these, in particular, in the formula (1), the substituent R ^{2 includes} at least one —OR ³ group (R ³ is the same as above), for example, the following formula (7)

(Wherein R ¹ , R ^2a , R ³ , X, m, n1, n2, and n3 are the same as above)
A compound represented by the formula is preferably used.

In the formulas (6) and (7), R ^2a is a substituent other than —XR ³ group (for example, —OR ³ group) among the exemplified substituents R ² , and usually a hydrocarbon group ( For example, it is often the exemplified hydrocarbon group (for example, the alkyl group etc.). The substitution number n1 of R ^2a may be, for example, 0 to 4, preferably 0 to 2, more preferably 0 to 1, particularly 0. In addition, the number of substitutions n2 of —XR ³ groups (for example, —OR ³ groups) may be 1 or more (for example, about 1 to 4), preferably 1 to 2, and more preferably 1. Further, the number of substitutions n3 of the —XR ³ group (eg, —OR ³ group) may be 0 or more, for example, 0 to 4, preferably 0 to 2, particularly 1 or more (eg, 1 ~ 2, preferably 1).

Specific examples of the fluorene compound include compounds in which at least one of n in the formula (1) is 0 (for example, n such as 9,9-bis (phenyl) fluorene, 9,9-bis (naphthyl) fluorene). A compound in which all are 0; 9-phenyl-9- (alkoxyphenyl) fluorene [for example, 9-phenyl-9-C _1-4 alkoxyphenylfluorene such as 9-phenyl-9- (4-methoxyphenyl) fluorene , 9-phenyl-9- (alkylthiophenyl) fluorene [eg, 9-phenyl-9-C _1-4 alkylthiophenyl such as 9-phenyl-9- (4-methylthiophenyl) fluorene] The other of 0 and n is 1 or more, and has at least a heteroatom-containing substituent such as an alkoxy group Such compounds}, said compound n is any one or more, (1) [9,9-bis (phenyl) fluorenes, 9,9-bis (naphthyl) fluorenes] and the like.

As 9,9-bis (phenyl) fluorenes, for example, 9,9-bis (alkylphenyl) fluorene [for example, 9,9-bis (4-methylphenyl) fluorene, 9,9-bis (4-ethyl) 9,9-bis (C _1-6 alkylphenyl) fluorene such as phenyl) fluorene, 9,9-bis (3,4-dimethylphenyl) fluorene, preferably 9,9-bis (C _1-4 alkylphenyl) 9,9-bis (phenyl) fluorenes containing no heteroatom-containing group in the group R ² such as fluorene]; 9,9-bis (alkoxyphenyl) fluorene [eg, 9,9-bis (4-methoxyphenyl) 9,9-bi, such as fluorene, 9,9-bis (4-ethoxyphenyl) fluorene, 9,9-bis (3,4-dimethoxyphenyl) fluorene _{(C 1-6} alkoxyphenyl) fluorene, preferably 9,9-bis _{(C 1-4} alkoxyphenyl) fluorene], 9,9-bis (alkylthio phenyl) fluorene [e.g., 9,9-bis (4-methylthio phenyl) fluorene such as 9,9-bis _{(C 1-6} alkyl thio phenyl) fluorene, preferably 9,9-bis _{(C 1-4} alkyl thio phenyl) fluorene, 9,9-bis (N, N-dialkylamino 9,9-bis (N, N-diC _1-6 alkylaminophenyl) fluorene, such as phenyl) fluorene [e.g. 9,9-bis [4- (N, N-dimethylamino) phenyl] fluorene, preferably 9,9-bis (N, _{N-di-C 1-4} alkylamino phenyl) fluorene, 9-alkyl-phenyl-9-Arco Shi phenyl fluorene [e.g., 9- (4-methylphenyl) -9- (4-methoxyphenyl) fluorene, 9- (4-methylphenyl) -9-bis _{9-C 1} such as (4-ethoxyphenyl) fluorene _-6 alkylphenyl-9-C _1-6 alkoxyphenylfluorene, preferably at least one heterogeneous group R ² such as 9- (C _1-4 alkylphenyl) -9- (C _1-4 alkoxyphenyl) fluorene]. 9,9-bis (phenyl) fluorenes containing an atom-containing group are included.

In addition, the 9,9-bis (naphthyl) fluorenes correspond to the 9,9-bis (phenyl) fluorenes and are compounds in which a phenyl group is substituted with a naphthyl group, such as 9,9-bis (alkoxynaphthyl). ) fluorene [e.g., 9,9-bis (6-methoxy-2-naphthyl) fluorene such as 9,9-bis _{(C 1-6} alkoxy naphthyl) fluorene, preferably 9,9-bis _{(C 1-4} alkoxy Naphthyl) fluorene] and the like.

Of these, 9-phenyl-9-C _1-4 alkoxyphenylfluorene, 9,9-bis (C _1-4 alkoxyphenyl) fluorene, 9,9-bis (C _1-4 alkylthiophenyl) fluorene, At least one heteroatom in the group R ² in the above formula (1) such as 9-bis (N, N-diC _1-4 alkylaminophenyl) fluorene, 9,9-bis (C _1-4 alkoxynaphthyl) fluorene, etc. A compound containing a containing group (particularly, the aforementioned —XR ³ ) is preferred, and in particular, a group R ² for substituting two rings Z in the formula (1) such as 9,9-bis (C _1-4 alkoxyphenyl) fluorene. least one hetero atom-containing group both in (particularly, the -XR ³⁾ compounds containing preferred.

[Production method]
The method for producing the compound having a fluorene skeleton represented by the formula (1) is not particularly limited. For example, a fluorenone represented by the following formula (2) and a compound represented by the following formula (3) (Hereinafter, it may be referred to as a non-reactive aromatic compound) or a nucleophile (for example, Grignard reagent, lithiated product, etc.) corresponding to this compound can be obtained through a step of reacting.

(Wherein Z, R ¹ , R ² , m, and n are the same as above)
The fluorenones (9-fluorenones) represented by the formula (2) correspond to the fluorene ring (or skeleton) of the compound represented by the formula (1). In the formula (2), the substituents R ¹ and m are the same as described above. As the fluorenones, commercially available products may be used, or synthetic products utilizing or applying conventional techniques (for example, techniques described in JP-A-6-21729) may be used. The purity of the fluorenones to be used is, for example, 95% by weight or more, preferably 98% by weight or more, and more preferably 99% by weight or more. The fluorenones can be used alone or in combination of two or more.

As described in the section of the compound represented by the formula (1), the ring Z has other non-reactive substituents (for example, the substituents exemplified above) in addition to the substituent R ^1. May be.

The non-reactive aromatic compound represented by the formula (3) is an aromatic hydrocarbon group (aromatic optionally having a substituent) substituted at the 9-position of the fluorene ring in the formula (1). Group hydrocarbon group). In the formula (3), the substituents R ² and n are the same as described above.

Typical non-reactive aromatic compounds represented by the formula (3) include compounds in which n is 0 (C _6-10 arenes such as benzene and naphthalene), n is 1 or more, and the substituent R Compound (or arenes) in which ² is a hydrocarbon group [for example, alkylbenzenes (for example, C _1-4 alkylbenzene such as toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, xylene, etc.), alkylnaphthalenes (1-methyl Alkyl C _6-10 arenes such as naphthalene, C _1-4 alkylnaphthalene such as 2-methylnaphthalene), etc., a compound wherein n is 1 or more and the substituent R ² is at least one heteroatom-containing group [ For example, alkoxybenzenes (for example, anisole, ethoxybenzene, o-methylmethoxybenzene, o-ethylene) Le methoxybenzene, _{C 1-4} alkoxy benzene) such as o- ethyl ethoxy benzene, alkoxy naphthalenes (e.g., alkoxy _{C 6-10} arene such as _{C 1-4} alkoxy-naphthalene), etc.), such as methoxy naphthalene; alkylthio benzene Alkylthio C _6-10 arenes such as C _1-4 alkoxybenzenes such as thioanisole; N, N-dialkylaminobenzenes such as N, N-diC such as N, N-dimethylaniline N, N-dialkylamino C _6-10 arenes such as _1-4 alkylaminobenzene) and the like.

  As the non-reactive aromatic compound, a commercial product may be used, or a synthetic product using or applying a conventional technique may be used. The purity of the non-reactive aromatic compound used is, for example, 95% by weight or more, preferably 98% by weight or more, and more preferably 99% by weight or more.

In addition, among the compounds represented by the formula (1), in the two rings Z, compounds having different types of substituents R ² or the number of substitutions n include a plurality of corresponding compounds represented by the formula (3). In combination, it may be produced by reacting with the compound represented by the formula (2) as it is, but after reacting one compound (3) and further reacting with a different compound (3), a high yield is obtained. It is easy to obtain a compound represented by the formula (1) corresponding to

  Therefore, in the following, (A) a method of reacting the compound represented by the formula (2) and the compound represented by the formula (3) in one step, and (B) the formula (2) This method will be described in detail by dividing it into a method in which the compound represented by the formula (3) is reacted in two steps.

(Method (A))
In the method (A), the compound represented by the formula (2) is usually reacted with the compound represented by the formula (3). In such a method (A), the usage-amount of the said non-aromatic compound can be selected from the range of about 0.1-150 mol with respect to 1 mol of said fluorenones, for example, 2-100 mol (for example, 2 to 80 mol), preferably 2.5 to 75 mol (for example, 2.5 to 60 mol), more preferably 3 to 50 mol (for example, 3 to 30 mol), particularly about 3.5 to 20 mol. It may be about 2.5-20 mol normally.

  In the method (A), the reaction between the fluorenones and the non-reactive aromatic compound is usually performed in the presence of an acid catalyst in many cases. Examples of the acid catalyst include inorganic acids [eg, protonic acid (sulfuric acid, hydrogen chloride (or hydrochloric acid), phosphoric acid, etc.), Lewis acid (eg, boron trifluoride, aluminum chloride, zinc chloride, etc.)], organic Acids {eg, sulfonic acids (eg, alkanesulfonic acids such as methanesulfonic acid, arenesulfonic acids such as p-toluenesulfonic acid), carboxylic acids [eg, aliphatic carboxylic acids (eg, alkanes such as acetic acid, oxalic acid, etc.) Mono or dicarboxylic acid etc.)] and the like}. In addition, a solid acid (for example, an inorganic solid acid such as a metal oxide or an organic solid acid such as an ion exchange resin) may be used as the acid catalyst. These acid catalysts may be used alone or in combination of two or more.

Among these acid catalysts, inorganic acids are preferable, and among these, proton acids (particularly sulfuric acid) are preferably used from the viewpoint of catalytic activity. In particular, when sulfuric acid and thiols described below are combined, a high-purity fluorene compound having a small amount of residual sulfur can be obtained in a high yield simply and efficiently. Therefore, the combination of these compounds enables mass production of the compound of the present invention at an industrially low cost. Usually, as sulfuric acid, 80 to 99% by weight (for example, 85 to 98% by weight), preferably about 90 to 97.5% by weight sulfuric acid (concentrated sulfuric acid) may be used in terms of H ₂ SO ₄ .

  The amount of the acid catalyst to be used can be appropriately selected according to the type thereof, and is, for example, 0.01 to 100 parts by weight, preferably 0.05 to 80 parts by weight, more preferably 1 part by weight of the fluorenones. About 0.1-50 weight part may be sufficient.

  In the reaction between the fluorenones and the non-reactive aromatic compound, a combination of the acid catalyst and a thiol as a promoter may be used. By combining the acid catalyst and thiols, the reaction proceeds efficiently, so that the amount of raw material used can be reduced.

Examples of thiols include mercaptocarboxylic acids (thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid, etc.), alkyl mercaptans (methyl mercaptan, ethyl). Mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, C _1-16 alkyl mercaptan (especially C _1-4 alkyl mercaptan) such as dodecyl mercaptan), aralkyl mercaptan (benzyl mercaptan, etc.) or a salt thereof. . Examples of the salt include alkali metal salts (for example, sodium salts such as methyl mercaptan sodium and ethyl mercaptan sodium). Among these thiols, mercapto C _2-6 carboxylic acid (for example, β-mercaptopropionic acid) is preferable. Thiols can be used alone or in combination of two or more.

  The amount of the thiols used can be selected from a range of about 0 to 5 parts by weight with respect to 1 part by weight of the fluorenones, for example, 0.001 to 1 part by weight, preferably 0.0015 to 0.5 parts by weight. More preferably, it may be about 0.002 to 0.1 parts by weight, particularly about 0.003 to 0.05 parts by weight.

  Moreover, the usage-amount of the said thiols can be selected from the range of about 0-5 weight part with respect to 1 weight part of said acid catalysts, for example, 0.001-1 weight part, Preferably it is 0.0015-0.5. It may be about 0.002 to 0.1 parts by weight, more preferably about 0.003 to 0.05 parts by weight.

  The reaction between the fluorenones and the non-reactive aromatic compound may be performed in the absence of a solvent or in the presence of a solvent. The solvent is not particularly limited as long as it can dissolve the fluorenones and non-reactive aromatic compounds, but the solvent is non-reactive with respect to the acid catalyst and thiols in order to suppress a decrease in reaction efficiency. Is preferred.

Examples of the solvent include alcohols (eg, C _1-6 alkanols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol), glycol ethers [eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, (poly) C _2-4 alkylene glycol mono or di C _1-4 alkyl ether], glycol monoalkyl ether acetate [For example, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, B propylene glycol monomethyl ether acetate, 3-methoxybutyl-1-acetate such as _{(poly) C 2-4} alkylene glycol mono _{C 1-4} alkyl ether acetates, etc.] ,, ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, Dialkyl ketones such as methyl amyl ketone and 4-hydroxy-4-methyl-2-pentanone; cycloalkanones such as cyclohexanone) and ethers (for example, chain ethers such as dimethyl ether and diethyl ether; cyclics such as dioxane and tetrahydrofuran) Ethers), esters [for example, carboxylic acid esters such as ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate; hydroxy esters such as ethyl hydroxyacetate and ethyl 2-hydroxypropionate; Dicarboxylic acid esters; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylbutanoate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3- Etc.] and the like.] And the like. An excess of the compound represented by the formula (2) 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 can be selected, for example, from the range of about 0 to 500 parts by weight, for example, 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, with respect to 1 part by weight of the fluorenones. Preferably it may be about 1 to 10 parts by weight.

  Although the said reaction can be suitably selected according to the raw material to be used, the kind of catalyst system, etc., for example, 0-250 degreeC, Preferably it is 20-150 degreeC, More preferably, it is 30-100 degreeC (for example, 40-80 degreeC). It may be done to the extent. The reaction time can also be appropriately selected according to the raw materials used, the type of catalyst system, the reaction conditions, and the like, for example, 30 minutes to 48 hours, preferably 1 to 24 hours, more preferably about 1 to 10 hours. May be.

  The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed at normal pressure or under pressure.

  The reaction mixture after completion of the reaction usually contains unreacted fluorenones, unreacted non-reactive aromatic compounds, catalyst (acid catalyst, thiols), in addition to the compound represented by the formula (1) produced. , Side reaction products and the like. Therefore, the reaction mixture 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.

(Method (B))
In the method (B), the compound represented by the formula (2) and the two compounds represented by the formula (3) are reacted in two stages. That is, in the method (B), one of the compound represented by the formula (2) and the compound represented by the formula (3) or a nucleophile corresponding to the compound (for example, Grignard reagent, lithiated product, etc.) To obtain a compound represented by the following formula (3A), and then react this compound with the other compound represented by the above formula (3). (It may be called the second stage reaction).

(Wherein Z, R ¹ , R ² , m, and n are the same as above)
In the first stage reaction of the method (B), the compound represented by the formula (2) is usually reacted with a nucleophile corresponding to the compound represented by the formula (3). After such a reaction, the obtained product (compound represented by the formula (3A)) is separated and subjected to a reaction with the compound represented by the formula (2) (second stage reaction). Alternatively, after the reaction, it may be reacted with the compound represented by the formula (2) as it is (second stage reaction).

  In the reaction of the compound represented by the formula (3A) and the compound represented by the formula (2) (second-stage reaction), these ratios are the former / the latter (molar ratio) = 1/0. It may be 3 to 0.8 / 1, preferably 1 / 0.35 to 0.9 / 1, and more preferably about 1 / 0.4 to 0.95 / 1.

  The second stage reaction may be carried out in the presence of an acid catalyst. The acid catalyst can be appropriately selected according to the type of raw material to be used. For example, proton acid {inorganic acid (sulfuric acid, hydrogen chloride, nitric acid, hydrochloric acid, phosphoric acid, etc.), organic acid [for example, sulfonic acid (for example, , Alkanesulfonic acids such as methanesulfonic acid, haloalkanesulfonic acids such as trifluoromethanesulfonic acid, etc.], Lewis acids [metal halides (aluminum chloride, iron (III) chloride, etc.), boron halides (boron fluoride, etc.) Etc.] etc.}. As the acid catalyst, a solid acid (for example, an inorganic solid acid such as a metal oxide or an organic solid acid such as an ion exchange resin) may be used.

  The acid catalysts may be used alone or in combination of two or more.

Among these, preferred acid catalysts include strong acids such as sulfuric acid, hydrochloric acid, and sulfonic acid, ion exchange resins, and the like. In particular, haloalkanesulfonic acids such as fluoroalkanesulfonic acids (for example, trifluoromethanesulfonic acid, Perfluoroalkanesulfonic acids such as fluoroethanesulfonic acid and perfluorobutanesulfonic acid, preferably perfluoroC _1-10 alkanesulfonic acid, more preferably perfluoroC _1-8 alkanesulfonic acid, especially perfluoroC _1-4 Alkanesulfonic acid) is preferred. In addition, in a case where the reaction is performed on a large scale (or an industrial scale), sulfuric acid, hydrochloric acid, an ion exchange resin, or the like may be suitably used.

  The ratio of the acid catalyst to be used is, for example, 0.01 to 10 mol, preferably 0.05 to 8 mol, more preferably 0.1 to 5 mol per 1 mol of the compound represented by the formula (3A). About mol (for example, 0.2-4 mol) may be sufficient.

The reaction may be performed in the absence of a solvent or in a solvent. The solvent (reaction solvent) may be non-reactive with respect to the compound represented by the formula (3A) and the compound represented by the formula (2), and further to the acid catalyst. Can be used in Typical solvents (organic solvents) include ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane), aromatic solvents (aromatic hydrocarbons such as benzene, toluene and xylene). Etc.), alcohols (C _1-4 alkanols such as methanol, ethanol and isopropanol), ketones (eg, alkanones such as acetone, methyl ethyl ketone and methyl isobutyl ketone) and the like. Moreover, you may use an excess raw material (For example, the compound etc. which are represented by said Formula (2)) as a solvent. The solvents may be used alone or in combination of two or more.

  The reaction varies depending on the type of raw material and acid catalyst used, but is usually 10 to 150 ° C., preferably 30 to 140 ° C., more preferably about 50 to 130 ° C. (for example, 60 to 120 ° C.). There are many cases. Moreover, reaction time can be adjusted according to the kind of raw material, reaction temperature, etc. For example, it is 30 minutes-48 hours, Usually, 1 to 24 hours, Preferably it is about 1 to 10 hours.

  The reaction may be performed with stirring, may be performed in air or in an inert gas atmosphere (nitrogen, rare gas, etc.), or may be performed at normal pressure or under pressure. The progress of the reaction can also be confirmed (or traced) by high performance liquid chromatography (HPLC) or the like.

  In many cases, the reaction mixture after completion of the reaction usually contains an unreacted raw material, an acid catalyst, a side reaction product and the like in addition to the generated compound represented by the formula (1). Therefore, it can 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.

  The novel non-functional fluorene-containing compound of the present invention has a fluorene skeleton and is non-reactive or inert, and has various properties [heat resistance, optical properties (transparency, high refractive index, etc.), etc. ]. The non-functional fluorene-containing compound is also excellent in compatibility with a resin (particularly a resin containing an aromatic ring). Furthermore, it does not cause an increase in viscosity and is excellent in handling properties. Therefore, the compound of the present invention is useful as a resin additive (for example, a resin diluent, a resin modifier, etc.).

  For example, since the non-functional fluorene-containing compound is non-reactive or inert, it does not react with the resin even when applied to various resins, and it is for diluting the resin with excellent handling properties. Useful as a diluent. In addition, when the non-functional fluorene-containing compound is applied to a heat (or light) curable resin (resin component), it can be diluted without reacting with the resin component, thus preventing rapid curing of the resin component. can do. That is, when the non-functional fluorene-containing compound is used, various reactions such as heat (or light) curing reaction can be effectively controlled.

  In addition, since the non-functional fluorene-containing compound is excellent in various properties [heat resistance, optical properties (transparency, high refractive index, etc.), etc.], resin modification that improves or improves these properties in various applications. It is also useful as an agent. Specifically, the non-functional fluorene-containing compound can be applied to various resins to improve or improve the heat resistance and optical properties of the resin and also improve the moldability. In addition, even when the non-functional fluorene-containing compound is a resin used for optical applications and is originally applied to a resin having excellent characteristics, the excellent characteristics are maintained (or improved) Formability can be improved. In addition, the compound of the present invention often liquefies at a high temperature and can be used as a high boiling point solvent.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, each evaluation method in an Example is as follows.

[Evaluation methods]
(purity)
Purity was determined by liquid chromatography analysis. A liquid chromatograph (manufactured by Hitachi, Ltd., “liquid chromatograph L-7000”), a reverse phase column (manufactured by Tosoh Corporation, TSKgel ODS-80TM) is used as a column, and a mobile phase: a mixed solvent of water and acetonitrile ( Development was performed for 60 minutes under the conditions of water / acetonitrile (weight ratio) = 40/60, flow rate of 1 mL / min, and purity was calculated from the obtained peak area under a measurement wavelength of 254 nm.

(Glass-transition temperature)
The glass transition temperature (Tg) was measured by increasing the temperature at a rate of 10 ° C./min with a differential scanning calorimeter (SDS, “DSC6220”).

(Molecular weight)
The molecular weight was measured using a field desorption (FD) mass spectrum (“JMS-700”, manufactured by JEOL Ltd.) at an acceleration voltage of 8 kV, a counter voltage of 2 kV, and an emitter current of 0 to 40 mA.

⁽¹ H-NMR)
¹ H-NMR analysis was performed using a JEOL GTX-400 spectrometer using tetramethylsilane as an internal standard and CDCl ₃ as a solvent.

Example 1
In a 300 mL separable flask, 18 parts by weight of 9-fluorenone (0.1 mol, manufactured by Osaka Gas Chemical), 64.8 parts by weight of anisole (0.6 mol, manufactured by Kishida Chemical), 20 parts by weight of sulfuric acid, β-mercapto The reaction was carried out by charging 0.1 parts by weight of propionic acid (βMPA) and stirring at 60 ° C. for 4 hours.

After adding 300 parts by weight of methyl isobutyl ketone to the obtained reaction liquid and further neutralizing by adding 28 parts by weight of a 48% by weight sodium hydroxide aqueous solution, the organic layer and the aqueous layer were separated, and the organic layer was separated. Washed repeatedly with 100 parts by weight of water until neutral. The washed organic layer was cooled to 10 ° C. to precipitate crystals, and 30 parts by weight of white crystals were obtained. The purity of the obtained crystal was 99.8%. Moreover, when the obtained crystal was analyzed by ¹ H-NMR, it was confirmed that it was 9,9-bis (4-methoxyphenyl) fluorene (a compound represented by the following formula), which was the target product. In addition, the production | generation of the regioisomer was not confirmed from < ¹ > H-NMR analysis. Furthermore, the molecular weight (m / z) of the produced | generated crystal | crystallization was 378, and the glass transition temperature was 140 degreeC.

The ¹ H-NMR spectrum data of the obtained 9,9-bisanisole fluorene is shown below.

¹ H-NMR (CDCl ₃ ) ppm: 3.7 (s, 6H), 6.8 (d, 4H), 7.2 (d, 4H), 7.3 to 7.6 (m, 6H), 7.8 (d, 2H).

(Example 2)
In Example 1, instead of 64.8 parts by weight of anisole, the reaction and purification were carried out in the same manner as in Example 1 except that 73.3 parts by weight of 2-methylanisole (0.6 mol, manufactured by Kishida Chemical Co., Ltd.) was used. went. As a result, 28 parts by weight of 9,9-bis (3-methyl-4-methoxyphenyl) fluorene (white crystals, a compound represented by the following formula), which was the target product, was obtained. The purity of the 9,9-bis (3-methyl-4-methoxyphenyl) fluorene obtained was 99.0%.

Claims (6)

A compound having a fluorene skeleton represented by the following formula (1).

Wherein Z is the same or different and represents an aromatic hydrocarbon ring, R ¹ is the same or different and represents a hydrocarbon group, a halogen atom or a cyano group, R ² is the same or different and represents a hydrocarbon group, An acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a —XR ³ group (wherein R ³ represents a hydrocarbon group, X represents an oxygen atom or a sulfur atom) or —N (R ⁴ ) ₂ group ( In the formula, R ⁴ is the same or different and represents a hydrocarbon group). m is the same or different and is an integer of 0 to 4, and n is the same or different and is an integer of 0 or more. ]   The compound according to claim 1, wherein in formula (1), ring Z is a benzene ring or a naphthalene ring. In formula (1), the total of n is at least 1 or more, and at least one of R ² is an acyl group, an alkoxycarbonyl group, a halogen atom, a cyano group, a —XR ³ group, or —N (R ⁴ ) _2. The compound according to claim 1 or 2, which is a group. Following formula (6)

(In the formula, R ^2a represents a hydrocarbon group, n1 is an integer of 0 or more, n2 is an integer of 1 or more, and n3 is an integer of 0 or more. R ¹ , R ³ , X, and m are the same as above. )
The compound according to any one of claims 1 to 3, which is a compound represented by the formula:   The compound according to claim 4, wherein in formula (6), n1 is 0 to 2, n2 is 1 to 2, and n3 is 1 to 2. 9-phenyl-9-C _1-4 alkoxyphenylfluorene, 9,9-bis (C _1-4 alkoxyphenyl) fluorene, 9,9-bis (C _1-4 alkylthiophenyl) fluorene, 9,9-bis ( The compound according to claim 1, which is a compound selected from N, N-diC _1-4 alkylaminophenyl) fluorene and 9,9-bis (C _1-4 alkoxynaphthyl) fluorene.