JP2009096782A - New fluorene compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound which is excellent in heat resistance and the like and is useful as an additive for resins and the like. <P>SOLUTION: Provided is a new fluorene compound represented by formula (1), wherein X is an alkylidene group or an alkylene group; Y is a hydroxy group, a hydroxymethyl group, a mercapto group, a mercaptomethyl group, a carboxy group or an amino group; the ring Z is an aromatic hydrocarbon ring; R<SP>1</SP>and R<SP>2</SP>are each a substituent such as an alkyl group, an alkoxy group, an alkylthio group, or a halogen atom. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel fluorene compound useful as a functional material and the like, and a method for producing the same.

  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. As a method for expressing the excellent function of such a fluorene skeleton in a resin and making it moldable, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), such as bisphenol fluorene (BPF), biscresol fluorene, etc. There is known a method in which (BCF), bisaminophenylfluorene (BAFL), bisphenoxyethanol fluorene (BPEF), or the like is used as a constituent component of a resin and a fluorene skeleton is introduced into a part of the skeleton structure of the resin. For example, as an example of using such a compound having a fluorene skeleton as a resin raw material, Japanese Patent Application Laid-Open No. 2002-284864 (Patent Document 1) includes a polyester resin having a 9,9-bisphenylfluorene skeleton. A molding material is disclosed. JP-A-2004-339499 (Patent Document 2) discloses a resin having a fluorene skeleton such as bisphenolfluorene, bisaminophenylfluorene, or bisphenoxyethanolfluorene as a polymerization component (polyester resin, polycarbonate resin, A urethane resin, an acrylic resin, a polyamide resin, a polyimide resin, an epoxy resin, a vinyl ester resin, a phenol resin, an aniline resin, and the like) and an additive are disclosed.

  However, in such a method, since it is necessary to introduce a fluorene skeleton into the resin skeleton, a complicated polymerization reaction is required, and it is difficult to apply to a wide range of resins.

  On the other hand, as an example in which a compound having a fluorene skeleton such as a 9,9-bisphenylfluorene skeleton is added as it is, JP-A-2005-162785 (Patent Document 3) discloses a fluorene skeleton represented by the following formula (1). The resin composition comprised by the compound which has this, and a thermoplastic resin is disclosed.

(In the formula, R ^{1 to} R ⁴ are the same or different and represent a non-reactive group or a reactive group. However, R ¹ and R ² are at least reactive groups. K1 and k2 are the same or different. An integer of 1 to 5 and m1 and m2 are the same or different and represent an integer of 0 or 1 to 4).
In this document, as specific compounds represented by the formula (1), C of 9,9-bis (mono to trihydroxyphenyl) fluorenes and 9,9-bis (mono to trihydroxyphenyl) fluorenes are used. _2-4 alkylene oxide adducts, 9,9-bis (mono to trihydroxyphenyl) fluorenes or glycidyl ethers of C _2-4 alkylene oxide adducts, 9,9-bis (mono to trihydroxyphenyl) fluorenes Or the (meth) acrylate of the _C2-4 alkylene oxide adduct, the 9,9-bis (aminophenyl) fluorene, etc. are illustrated. And in this document, by adding the above compound to a thermoplastic resin (especially an aromatic ring-containing resin such as a polycarbonate-based resin), an excellent function (high refractive index, etc.) of the fluorene skeleton can be easily obtained. In addition, since it can be efficiently applied to a thermoplastic resin and can be molded, and it is not necessary to replace the resin skeleton, a wide range of thermoplastic resins can be used regardless of the type of thermoplastic resin. It describes that it can be molded with the function of the skeleton.

  Japanese Patent Laying-Open No. 2004-137262 (Patent Document 4) discloses a fluorene derivative represented by the following formula (I).

(In the formula, J ¹ and J ² are linking groups, -X ¹ -Pro ¹ and -X ² -Pro ² are hydrophilic groups protected by a detachable protecting group Pro ¹ or Pro ² , respectively, R ^1- R ⁴ represents an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, an aryl group, a halogen atom or a hydroxyl group, m1 and m2 are 0 or 1, n1 and n2 are 0 or an integer of 1 to 4, p1, p2 , Q1 and q2 represent an integer of 0 to 4, provided that at least one of n1 and n2 is 1 to 4, and n1 + p1 and n2 + p2 are integers of 5 or less.)
And in this document, since the fluorene derivative can be hydrophilized by deprotection caused by light irradiation, it is added to the base resin in combination with a photosensitizer to form the photosensitive resin composition, It is described that the sensitivity and resolution of the base resin as a resist can be improved.

  In the above document, it is not necessary to introduce a fluorene skeleton into the resin skeleton, and characteristics derived from 9,9-bis (phenyl) fluorene skeleton can be easily provided. However, bisphenol fluorene and the like have excellent characteristics as described above, but also have characteristics such as low flexibility and high viscosity, and there are problems to be improved.

There is a need for further development of materials having such a fluorene skeleton.
JP 2002-284864 A (Claims) JP 2004-339499 A (claims, paragraph number [0032]) JP 2005-162785 A (claims, paragraph number [0015]) Japanese Unexamined Patent Application Publication No. 2004-137262 (claims, column of effect of invention)

  Accordingly, an object of the present invention is to provide a compound having a novel fluorene skeleton that can be used as a functional material, and a method for producing the same.

  Another object of the present invention is to provide a compound having a novel fluorene skeleton that has properties such as a high refractive index and can realize improvement in flexibility, reduction in melt viscosity, improvement in carbon density, and the like, and a method for producing the same. It is to provide.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that an aromatic hydrocarbon ring skeleton (benzene skeleton, naphthalene skeleton, etc.) is inserted into the 9-position of a fluorene (fluorene, etc.) via an alkylidene group or an alkylene group. ) Having a novel fluorene skeleton in which two are bonded, [9,9-bis (arylalkyl) fluorenes] have properties such as a high refractive index and are useful as functional materials, Improved flexibility compared to conventional compounds having a fluorene skeleton (such as compounds in which two aromatic hydrocarbon ring skeletons are directly bonded to the 9-position of fluorenes) while having excellent properties such as a high refractive index. The present inventors have found that the melt viscosity can be reduced and the carbon density can be improved.

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

Wherein X represents an alkylidene group or an alkylene group, Y represents a hydroxyl group, a hydroxymethyl group, a mercapto group, a mercaptomethyl group, a carboxyl group or an amino group, a ring Z represents an aromatic hydrocarbon ring, and R ¹ represents a halogen atom, a cyano group or an alkyl group, and R ² represents a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, An acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group or a substituted amino group, k is an integer of 0 to 4, m is an integer of 0 or 1 or more, n is an integer of 0 or 1 or more, k, when m or n is respectively 2 or ^more, R 1, ^{R 2} or Y, respectively, be the same or different groups Good.)
In the formula (1), X may in particular be a methylene group. In the formula (1), typically, n may be 0 to 1 (particularly 0). In the formula (1), typically, Z may be a benzene ring or a naphthalene ring. Further, in the formula (1), typically, R ² is an alkyl group (eg, a C _1-4 alkyl group such as a methyl group) or an alkoxy group (eg, a C _1-4 alkoxy group such as a methoxy group). ), An alkylthio group (for example, a C _1-4 alkylthio group such as a methylthio group), or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), and m is 0-2. Good.

Representative compounds represented by the formula (1) include 9,9-bis (arylC _1-4 alkyl) fluorene [for example, 9,9-bis (9,9-bis (benzyl) fluorene, etc. C _6-10 aryl C _1-4 alkyl) fluorene], 9,9-bis (alkylaryl C _1-4 alkyl) fluorene [eg, 9,9-bis (such as 9,9-bis (alkylbenzyl) fluorene, Alkyl C _6-10 aryl C _1-4 alkyl) fluorene], 9,9-bis (alkoxyaryl C _1-4 alkyl) fluorene [eg, 9,9-bis such as 9,9-bis (alkoxybenzyl) fluorene (Alkoxy C _6-10 aryl C _1-4 alkyl) fluorene], 9,9-bis (alkylthioaryl C _1-4 alkyl) fluorene [eg, 9,9-bis (alkylthio C _6-10 arylC _1-4 alkyl) fluorene such as 9,9-bis (alkylthiobenzyl) fluorene], and 9,9-bis (haloarylC _1-4 alkyl) fluorene [eg 9,9-bis (halo C _6-10 aryl C _1-4 alkyl) fluorene] such as 9,9-bis (halobenzyl) fluorene.

  In the present invention, in the presence of a base catalyst, a compound represented by the following formula (2) and a compound represented by the following formula (3) are reacted to form the compound (represented by the above formula (1)). Also included is a method of producing the compound.

(In the formula, R ³ represents a halogen atom, and X, Z, R ¹ , R ² , k, and m are the same as above.)
In the present invention, in the presence of a base catalyst, the compound represented by the following formula (2) and (i) the compound represented by the following formula (3), or (ii) represented by the following formula (3). The method of manufacturing the said compound (compound represented by said Formula (1)) by making a compound and the compound represented by following formula (4) react is also contained.

(Wherein R ³ represents a halogen atom, Y ¹ represents a group capable of producing Y or Y, n 1 represents an integer of 1 or more, and X, Z, R ¹ , R ² , k, m are Same as above).

  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.

  The compound having a novel fluorene skeleton of the present invention has high heat resistance, high refractive index and the like and can be used as a functional material. Such a compound of the present invention has excellent properties (for example, high refractive index, etc.) possessed by a compound having a conventional fluorene skeleton, while improving flexibility and melting compared to such a conventional compound. Reduction of viscosity and improvement of carbon density can be realized. Therefore, taking advantage of such characteristics, for example, by improving the carbon density, it is possible to improve the etching resistance when used for resist applications. In addition, the compound of the present invention has few functional groups [hydroxyl group (phenolic hydroxyl group) and the like] contained in the molecule, and is excellent in conductivity and the like as compared with conventional compounds.

[Compound represented by Formula (1)]
The compound of the present invention is represented by the following formula (1).

Wherein X represents an alkylidene group or an alkylene group, Y represents a hydroxyl group, a hydroxymethyl group, a mercapto group, a mercaptomethyl group, a carboxyl group or an amino group, a ring Z represents an aromatic hydrocarbon ring, and R ¹ and R ² represent the same or different substituents, k is an integer of 0 to 4, m is an integer of 0 or 1 or more, n is 0 or an integer of 1 or more, and k, m, or n is 2 When it is above, R ¹ , R ² or Y may be the same or different groups, respectively.
In X of the above formula (1), examples of the alkylidene group include C _1-10 alkylidene groups such as a methylene group, an ethylidene group, a propylidene group, and a propane-2,2-diyl group, preferably a C _1-6 alkylidene group. More preferable examples include a C _1-4 alkylidene group. In X, the alkylene group is, for example, a C _2-10 alkylene group such as an ethylene group, a propylene group, a trimethylene group, or a tetramethylene group, preferably a C _2-6 alkylene group, more preferably a C _2-4 alkylene. Groups and the like. Preferred X is a direct bond or a C _1-4 alkylidene group (particularly a methylene group). In addition, the two groups X connecting the 9-position of the fluorene (or fluorene skeleton) and the ring Z may be the same or different. Usually, two Xs are often the same.

  In the formula (1), Y is a hydroxyl group, a hydroxymethyl group, a mercapto group, a mercaptomethyl group, a carboxyl group, or an amino group as described above. Of these, Y is preferably a hydroxyl group, mercapto group, carboxyl group or amino group.

  The number n of the groups Y substituted on the ring Z may be 0 or 1 or more, for example, 0 to 4, preferably 0 to 3, more preferably 0 to 2 (for example, 0 to 1), particularly 0. There may be. When n is 2 or more, Y may be the same or different groups.

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 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 with X is not particularly limited. For example, the naphthyl group substituted at the 9-position of fluorene is 1- A naphthyl group, a 2-naphthyl group, and the like may be used.

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 [eg, an alkyl group, an aryl group (a phenyl group, etc. Non-reactive substituents such as _6-10 aryl group, etc.], particularly a halogen atom, 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), the substituent represented by the group R ² may be a non-reactive substituent such as an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, s- C _1-20 alkyl group such as butyl group and t-butyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group, etc., cycloalkyl group (cyclopentyl group, cyclohexyl group etc.) C _5-10 cycloalkyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group, etc., aryl group [eg, phenyl group, alkylphenyl group (methylphenyl group (or tolyl group) , 2-methylphenyl group, 3-methylphenyl group), a dimethylphenyl group (xylyl)), _{C 6-10} aryl group such as a naphthyl group Alkoxy group (methoxy group; preferably _{C 6-8} aryl group, especially a phenyl group, a hydrocarbon group such as an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group) , An ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a t-butoxy group, etc., a C _1-20 alkoxy group, preferably a C _1-8 alkoxy group, more preferably a C _1-6 alkoxy group), cyclo Alkoxy groups (C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups), aryloxy groups (C _6-10 aryloxy groups such as phenoxy groups), aralkyloxy groups (for example, C ₆ such as benzyloxy groups) _-10 aryl _{-C 1-4} alkyloxy group) ether group such as (substituted hydroxyl group); alkyl Thio (methylthio, ethylthio, propylthio, n- butylthio group, _{C 1-20} alkylthio group such as t- butylthio group, preferably a _{C 1-8} alkylthio group, more preferably a _{C 1-6} alkylthio group) (such as _{C 5-10} cycloalkylthio groups such as cyclohexylthio group to cycloalkyl) cycloalkylthio group, _{(C 6-10} arylthio group such as thiophenoxy group) an arylthio group, aralkylthio group (eg, _C, such as benzylthio _6- Thioether groups (substituted mercapto groups) such as ₁₀ aryl-C _1-4 alkylthio groups); acyl groups (such as C _1-6 acyl groups such as acetyl groups); alkoxycarbonyl groups (C _1-4 alkoxy such as methoxycarbonyl groups) Ester groups (substituted carboxyl groups) such as carbonyl groups; A rogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom and the like); nitro group; cyano group; substituted amino group (dialkylamino group and the like) and the like.

Among these, the group R ² is a hydrocarbon group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, acyl group, alkoxycarbonyl group, halogen. An atom, a nitro group, a cyano group, and a substituted amino group are preferred. Particularly preferred groups R ² include an alkyl group (eg, a C _1-6 alkyl group), an alkoxy group (eg, a C _1-4 alkoxy group), Examples thereof include an alkylthio group (such as a C _1-4 alkylthio group) and a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).

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.

Typical compounds represented by the formula (1) [ie, 9,9-bis (arylalkyl) fluorenes] include 9,9-bis (benzyl) fluorenes {for example, 9,9-bis ( Benzyl) fluorene; 9,9-bis (alkylbenzyl) fluorene [9,9-bis (C _1-4 alkylbenzyl) fluorene such as 9,9-bis (4-methylbenzyl) fluorene], 9,9- Bis (alkoxybenzyl) fluorene [9,9-bis (C _1-4 alkoxybenzyl) fluorene such as 9,9-bis (4-methoxybenzyl) fluorene], 9,9-bis (alkylthiobenzyl) fluorene [9 , 9- bis (4-methylthiobenzyl) fluorene such as 9,9-bis _{(C 1-4} alkyl thio benzyl) fluorene, etc.], such as 9,9-bis (benzyl) fluorene, etc., wherein m is 1 or more in the formula (1)}, 9,9-bis (naphthylmethyl) fluorenes {corresponding to these 9,9-bis (benzyl) fluorenes For example, 9,9-bis (naphthylmethyl) fluorene such as 9,9-bis (1-naphthylmethyl) fluorene, 9,9-bis (2-naphthylmethyl) fluorene}, 9,9-bis ( 9,9-bis (arylC _1-4 alkyl) fluorene such as phenethyl) fluorenes [compounds corresponding to the 9,9-bis (benzyl) fluorenes, such as 9,9-bis (phenethyl) fluorene, etc.] [For example, 9,9-bis (C _6-10 arylC _1-4 alkyl) fluorenes] and the like.

  The compound of the present invention (the compound represented by the formula (1)) is not particularly limited. For example, the compound in which n is 0 in the formula (1) and n is 1 or more in the formula (1). It can be roughly classified into production methods with compounds.

  In the formula (1), the compound in which n is 0 is obtained by, for example, reacting a compound represented by the following formula (2) with a compound represented by the following formula (3) in the presence of a base catalyst. Can be manufactured. In addition, the compound in which n is 1 or more in the formula (1) includes a compound represented by the following formula (2), a compound represented by the following formula (3), and a compound represented by the following formula (4): Can be obtained by reacting.

  In such a method, a fluorene anion is generated by reacting the compound (fluorenes) represented by the formula (2) with a base catalyst, and the generated fluorene anion is used as a nucleophile to formula (3) A compound represented by the formula (1) is obtained by a nucleophilic substitution reaction with the compound represented by the formula (and the compound represented by the formula (4)).

(Wherein R ³ represents a halogen atom, Y ¹ represents a group capable of producing Y or Y, n 1 represents an integer of 1 or more, and X, Z, R ¹ , R ² , k, m are Same as above.)
In the above method, examples of the compound represented by the formula (2) include fluorenes (for example, fluorene). In addition, the purity of the compound (fluorenes) represented by the formula (2) is usually 95% by weight or more, preferably 99% by weight or more.

In the formula (3) and the formula (4), examples of X include the same alkylidene group and alkylene group as described above. Preferred X is a methylene group as described above. In the formula (3) and the formula (4), examples of the halogen atom represented by R ³ include a chlorine atom, a bromine atom, and an iodine atom. Preferred halogen atoms are a chlorine atom and a bromine atom.

Moreover, the compound represented by the said Formula (4) may replace with the compound whose Y < ¹ > is Y in the said Formula (4), and may use the compound which can produce | generate Y. In Y ¹ of the formula (4), the group capable of generating Y is (A) a group in which Y is protected by a protecting group (removable protecting group), and (B) Y can be generated by a substitution reaction. Group [for example, a halogen atom (a chlorine atom, a bromine atom, an iodine atom, etc.), etc.].

In the above (A), the target compound can be obtained by deprotection after the reaction with the compound represented by the formula (2). For example, when Y is a hydroxyl group or a mercapto group, a compound in which Y is protected by a protecting group such as an alkyl group (for example, a C _1-4 alkyl group such as a methyl group, an ethyl group, or a t-butyl group) In the case where Y is a carboxyl group, a compound in which Y is protected by a protecting group such as an alkyl group (for example, a C _1-4 alkyl group such as a methyl group, an ethyl group, or a t-butyl group) may be used. It may be used. Deprotection can be performed by a conventional method using an acid or a base.

In (B) above, using a known reaction at an appropriate stage before the reaction with the compound represented by formula (2) or after the reaction with the compound represented by formula (2), Substituent Y ¹ capable of generating Y depending on the type of Y is substituted with Y (for example, substitution with a hydroxyl group using a hydroxide, substitution with an amino group using an amide compound (such as potassium amide)) By doing so, the target compound can be obtained.

  In the formula (4), n1 corresponds to n (except for the case of n = 0) in the formula (1), and may be 1 or more, for example, 1 to 4, preferably It may be 1 to 3, more preferably 1 to 2 (for example, 1).

Representative examples of the compound represented by the formula (3) include, for example, benzyl halides (for example, benzyl halide (for example, benzyl halide such as 4-chloromethylbenzene and 4-bromomethylbenzene), and alkylbenzyl halide. [For example, C _1-4 alkylbenzyl halide such as 4-methylbenzyl chloride and 4-methylbenzyl bromide], alkoxybenzyl halide [eg C _1-4 alkoxy such as 4-methoxybenzyl chloride, 4-methoxybenzyl bromide, etc. benzyl halides, alkyl thio benzyl halide [e.g., 4-methylthiobenzyl chloride, etc. C _1-4 alkyl thio benzyl halide such as 4-methylthiophenyl bromide, halo benzyl halide (e.g., 4-black Benzyl chloride, 4-bromobenzyl bromide, etc.)}, halomethylnaphthalenes {compounds corresponding to the benzyl halides such as halomethylnaphthalene [eg, benzyl halides such as chloromethylnaphthalene, bromomethylnaphthalene, etc.]} _{(C 6-10} aryl _{C 1-4} alkyl halides such as _{C 6-10} arylmethyl halides, etc.) arylalkyl halides such as and the like. These compounds may be used alone or in combination of two or more.

Representative examples of the compound represented by the formula (4) include hydroxybenzyl halides (for example, hydroxybenzyl halides such as 4-chloromethylphenol and 4-bromomethylphenol) and mercaptobenzyl halides. (For example, mercaptobenzyl halides such as 4-chloromethylthiophenol and 4-bromomethylthiophenol), carboxybenzyl halides (for example, carboxybenzyl halides such as 4-carboxybenzyl chloride and 4-carboxybenzyl bromide), aminobenzyl halides Benzyl halides such as 4-benzylmethylaniline, 4-chlorobromoaniline and the like; corresponding to these benzyl halides, Y (hydro Compounds in which a syl group, carboxyl group, etc.) are protected by a protecting group (alkyl ethers, alkyl esters, etc.); corresponding to these benzyl halides, compounds capable of producing Y (hydroxyl groups, carboxyl groups, etc.) (for example, 4-chlorobenzyl chloride, halobenzyl halides such as 4-bromobenzyl bromide, etc.); corresponding to these compounds, a compound in which the benzyl group is a naphthylmethyl group; corresponding to the aforementioned compounds (benzyl halides), in which the benzyl group is arylalkyl halides such as compounds phenethyl group _(such as a _{C 6-10} aryl _{C 1-4} alkyl halides such as _{C 6-10} arylmethyl halides) may be mentioned. These compounds may be used alone or in combination of two or more. Benzyl halides can also be synthesized by the method described in JP-A-2003-238458.

  The purity of the compound represented by the formula (3) and the compound represented by the formula (4) may be usually 95% by weight or more, preferably 99% by weight or more.

  In addition, when using the compound represented by the said Formula (3) and the compound represented by the said Formula (4), the compound represented by the said Formula (3) and the compound represented by the said Formula (4) are used. In order to increase the reaction selectivity, the compound represented by the above formula (2), the compound represented by the above formula (3) and the above may be used. You may make it react with the other component, after making it react with any one compound among the compounds represented by Formula (4).

  When obtaining a compound in which n is 0 in the formula (1), the ratio of the compound represented by the formula (2) and the compound represented by the formula (3) in the reaction is the former / the latter ( Molar ratio) = 1/10 to 1 / 0.8, preferably 1/8 to 1/1, and more preferably about 1/5 to 1 / 1.5.

  Moreover, when obtaining the compound whose n is 1 or more in the said Formula (1), in a reaction, the compound represented by the said Formula (2), the compound represented by the said Formula (3), and the said Formula (4) The ratio of the compound represented by the formula is the former / the latter (molar ratio) = 1/10 to 1 / 0.8, preferably 1/8 to 1/1, and more preferably 1/5 to 1 / 1.5. It may be a degree. The ratio of the compound represented by the formula (2) and the compound represented by the formula (3) or the compound represented by the formula (4) is the former / the latter (molar ratio) = 1 / It may be about 2 to 1 / 0.5, preferably 1 / 1.5 to 1 / 0.7, and more preferably about 1/1 to 1 / 0.8. Furthermore, the ratio of the compound represented by the formula (3) and the compound represented by the formula (4) is the former / the latter (molar ratio) = 1/3 to 1 / 0.3, preferably 1. It may be about 1/2 to 1 / 0.5, more preferably about 1 / 1.5 to 1 / 0.7.

  In the reaction, the base catalyst is not particularly limited as long as it can generate a fluorene anion (anion of the compound represented by the formula (2)), and a conventional inorganic base or organic base can be used. Examples of inorganic bases include metal hydroxides (alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide), and the like. It is done. Examples of the organic base include metal alkoxides (for example, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium butoxide, potassium t-butoxide), quaternary ammonium hydroxides (tetramethylammonium hydroxide, tetraethylammonium hydroxide, And tetraalkylammonium hydroxide such as tetra-n-butylammonium hydroxide and trimethylbenzylammonium hydroxide). The base catalysts may be used alone or in combination of two or more.

  The amount of the base catalyst to be used is 1 to 10 equivalents (molar equivalent), preferably 1.2 to 8 equivalents, more preferably 1. relative to 1 mol of the compound represented by the formula (2) (fluorenes). About 5-5 equivalent may be sufficient.

  The reaction may be performed in the presence of a solvent. The solvent is not particularly limited as long as it is non-reactive with the base catalyst and can dissolve fluorenes (and the compound represented by the formula (3) and the compound represented by the formula (4)). It can be used in a wide range. Typical solvents include, for example, ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and 1,4-dioxane), aromatic solvents (aromatics such as benzene, toluene, xylene, and the like). Hydrocarbons, anisole and the like), amides (dimethylformamide and the like), sulfoxides (dimethylsulfoxide and the like) and the like. The solvents may be used alone or in combination of two or more.

  If a protic solvent (water, alcohol, etc.) is present in the reaction system (in the solvent), the activity of the intermediate fluorene anion may be lost. May be used in the reaction.

  The amount of the solvent used is such that at least fluorenes can be dissolved, and for example, 0.5 to 100 parts by weight, preferably 1 to 1 part by weight with respect to 1 part by weight of fluorenes (compound represented by the formula (2)) It may be about 50 parts by weight, more preferably about 2 to 40 parts by weight.

  Although reaction temperature is not specifically limited, From a viewpoint of stability of a fluorene anion, you may carry out normally at -10 degreeC-120 degreeC, Preferably it is 0-100 degreeC, More preferably, it is about 20-70 degreeC. The reaction time can be adjusted according to the type of raw material, the reaction temperature, the concentration in the solvent, etc., for example, 30 minutes to 48 hours, preferably 1 to 36 hours, more preferably about 2 to 24 hours. Also good.

  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. In addition, although reaction is normally performed by mixing each component, you may perform mixing in steps.

  The produced compound 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.

[Uses of fluorene compounds]
The fluorene compound of the present invention (compound represented by the formula (1)) has a fluorene skeleton and an aromatic hydrocarbon skeleton (benzene skeleton, naphthalene skeleton, etc.), and has various properties ( Optical properties, heat resistance, water resistance, moisture resistance, chemical resistance, electrical properties, mechanical properties, dimensional stability, etc.) and are useful for improving or improving these properties in various applications. Moreover, it has a high refractive index due to the skeleton. In particular, the compounds of the present invention can realize improved flexibility, reduced melt viscosity, improved carbon density, etc., compared to conventional compounds having a fluorene skeleton (such as bisphenol fluorene), and further improved properties in various applications Can be expected. For example, by improving the carbon density, the etching resistance can be improved when used for resist applications. Furthermore, it has few functional groups and is advantageous in terms of imparting conductivity as compared with a conventional compound having a fluorene skeleton. Therefore, such a fluorene compound of the present invention can be suitably used as a functional material [for example, an additive (resist additive, etc.), a reagent (medicine, agrochemical, etc.) or an intermediate, etc.]. , And can be used as a compound for efficiently imparting the excellent characteristics as described above.

(Additive use and resin composition)
Examples of the additive include resin additives (or resin additives). When used as an additive, a resin composition containing a resin and the fluorene compound (for example, 9,9-bis (benzyl) fluorene, 9,9-bis (alkylbenzyl) fluorene, 9,9-bis (halobenzyl) fluorene, etc.) Product (thermoplastic resin composition, heat or photocurable resin composition). In such a resin composition, the resin is not particularly limited, and a wide range of resins (thermoplastic resin, heat or photocurable resin, etc.) can be used.

Examples of the thermoplastic resin include olefin resins, halogen-containing vinyl resins (polyvinyl chloride, fluororesins, etc.), acrylic resins, styrene resins, polycarbonate resins, polyester resins [for example, polyalkylene terephthalate ( Poly _C2-4 alkylene terephthalate such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, etc., polyalkylene arylate resin such as polyethylene naphthalate, polyarylate resin (for example, aromatic dicarboxylic acid ( Terephthalic acid) and aromatic diols (biphenol, bisphenol A, xylylene glycol, alkylene oxide adducts thereof) as polymerization components Arylate resins, etc.)], polyacetal resins, polyamide resins, polyphenylene ether resins, polysulfone resins, polyphenylene sulfide resins, polyimide resins, polyether ketone resins, thermoplastic elastomers, and the like. The thermoplastic resins may be used alone or in combination of two or more.

  Among these thermoplastic resins, a thermoplastic resin containing an aromatic ring (such as a benzene ring), for example, an aromatic polycarbonate resin (such as bisphenol A polycarbonate), an aromatic polyester resin (such as the polyalkylene arylate resin) ), Polysulfone resins, polyphenylene ether resins, polyphenylene sulfide resins and the like are preferable. The fluorene compound is highly compatible with these aromatic ring-containing resins, and therefore has high dispersibility in the resin.

  Thermosetting resins (or photocurable resins) include phenolic resins, furan resins, amino resins (urea resins, melamine resins, etc.), unsaturated polyester resins, diallyl phthalate resins, epoxy resins, vinyl ester resins, polyurethanes. Resin, thermosetting polyimide resin, silicon resin (silicone resin, polysilane, etc.), photopolymerizable monomer or oligomer (for example, (meth) such as epoxy (meth) acrylate, polyurethane (meth) acrylate, polyester (meth) acrylate) Examples thereof include acrylate compounds). The thermosetting resin may be an initial condensate. Thermosetting resins may be used alone or in combination of two or more.

  The ratio of the fluorene compound is, for example, 1 to 700 parts by weight, preferably 50 to 600 parts by weight, and more preferably 100 parts by weight with respect to 100 parts by weight of the resin (particularly thermoplastic resin such as a thermoplastic resin having an aromatic ring). About 500 parts by weight (for example, 200 to 300 parts by weight) may be used.

  The resin composition has various additives depending on applications, for example, fillers, flame retardants, reinforcing agents, plasticizers, polymerization initiators, catalysts, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc. ), Mold release agent, antistatic agent, colorant (dye / pigment), antifoaming agent, leveling agent, dispersant, flow regulator, carbon material (carbon black, graphite, carbon fiber, activated carbon, fullerene, carbon nanotube, etc.) Etc. may be included. These additives may be used alone or in combination of two or more. The resin composition may be a composition containing a solvent (such as a coating composition) depending on the type of resin.

  The novel fluorene compound of the present invention has excellent properties such as high heat resistance and a high refractive index, and can be suitably used as a functional material such as a resin additive. In addition, the fluorene compound of the present invention is excellent in additive dispersibility and is also suitable as a molding material containing various additives. For example, the novel fluorene compound of the present invention (or a resin containing a fluorene compound as a polymerization component) can efficiently disperse an additive such as carbon. Therefore, when applied to a resin or the like, it is possible to efficiently obtain a molded body (including a film and a film) having the above-described excellent characteristics and high strength or high hardness. In addition, the compounds of the present invention can realize improved flexibility, reduced melt viscosity, improved carbon density, etc., compared to conventional compounds having a fluorene skeleton (such as bisphenol fluorene), and further improved properties in various applications Can be expected. For example, by improving the carbon density, the etching resistance can be improved when used for resist applications.

  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
In a 300 mL three-necked flask, 1.66 g (10.0 mmol) of fluorene (manufactured by Osaka Gas Chemical Co., Ltd.) and 3.36 g (30.0 mmol) of potassium butoxide (manufactured by Nacalai Tesque) are placed, and dimethyl sulfoxide (DMSO) as a solvent is added. ) (Manufactured by Nacalai Tesque) 70.0 mL was mixed and stirred at 50 ° C. for 10 minutes. While stirring, 6.00 g (24.0 mmol) of 4-bromobenzyl bromide (manufactured by Aldrich) was added in portions of 1.00 g in 6 portions and added every 10 minutes. Then, it stirred at 50 degreeC for 19 hours. After the reaction, the solution was quenched by pouring into ice, and 20.0 g of diethyl ether (manufactured by Nacalai Tesque) was added to the obtained solid and extracted three times. After drying with 10.0 g of sodium sulfate (manufactured by Nacalai Tesque), the solvent was distilled off with an evaporator to obtain 5.96 g of a sample. As a result of measuring HPLC of the obtained sample, the purity was 56%.

Furthermore, as a result of measuring ¹ H-NMR of the obtained sample, it was confirmed that it was the intended 9,9-bis (4-bromobenzyl) fluorene (the following formula).

¹ H-NMR (CDCl ₃ , δ): 3.31 ppm (s, 4H), 6.48 ppm (d, 4H), 7.00 ppm (d, 4H), 7.20-7.50 ppm (m, 8H)
(Example 2)
In a 300 mL three-necked flask, 1.66 g (10.0 mmol) of fluorene (manufactured by Osaka Gas Chemical Co., Ltd.) and 3.36 g (30.0 mmol) of potassium butoxide (manufactured by Nacalai Tesque) are placed, and dimethyl sulfoxide (DMSO) as a solvent is added. ) (Manufactured by Nacalai Tesque) 70.0 mL was mixed and stirred at 50 ° C. for 10 minutes. While stirring, 4.44 g (24.0 mmol) of 4-methylbenzyl bromide (manufactured by Aldrich) was added in portions of 0.74 g in 6 portions and added every 10 minutes. Then, it stirred at 50 degreeC for 19 hours. After the reaction, the solution was quenched by pouring into ice, and 20.0 g of diethyl ether (manufactured by Nacalai Tesque) was added to the obtained solid and extracted three times. After drying with 10.0 g of sodium sulfate (manufactured by Nacalai Tesque), the solvent was distilled off with an evaporator to obtain 5.96 g of a sample. As a result of measuring HPLC of the obtained sample, the purity was 67%.

Furthermore, as a result of measuring ¹ H-NMR of the obtained sample, it was confirmed to be the intended 9,9-bis (4-methylbenzyl) fluorene (the following formula).

¹ H-NMR (CDCl ₃ , δ): 2.13 ppm (s, 6H), 3.30 ppm (s, 4H), 6.56 ppm (d, 4H), 6.73 ppm (d, 4H), 7.14 -7.44 ppm (m, 8H).

(Example 3)
A 300 mL three-necked flask was charged with 0.30 g (1.80 mmol) of fluorene (Osaka Gas Chemical Co., Ltd.) and 0.61 g (5.40 mmol) of potassium butoxide (Nacalai Tesque), and dimethyl sulfoxide (DMSO) as a solvent. ) (Manufactured by Nacalai Tesque) 13.0 mL was mixed and stirred at 50 ° C. for 10 minutes. While stirring, 0.96 g (4.4 mmol) of 4-methylthiobenzyl bromide (manufactured by Aldrich) was added in 0.16 g portions in 6 portions and added every 10 minutes. Then, it stirred at 50 degreeC for 19 hours. After the reaction, the solution was quenched by pouring into ice, and 10.0 g of diethyl ether (manufactured by Nacalai Tesque) was added to the obtained solid and extracted three times. After drying with 6.00 g of sodium sulfate (manufactured by Nacalai Tesque), the solvent was distilled off with an evaporator to obtain 0.84 g of a sample. As a result of measuring HPLC of the obtained sample, the purity was 80%.

Furthermore, as a result of measuring ¹ H-NMR of the obtained sample, it was confirmed to be the intended 9,9-bis (4-methylthiobenzyl) fluorene (the following formula).

¹ H-NMR (CDCl ₃ , δ): 2.33 ppm (s, 6H), 3.30 ppm (s, 4H), 6.57 ppm (d, 4H), 6.81 ppm (d, 4H), 7.19 −7.67 ppm (m, 8H).

Example 4
As a result of synthesis in the same manner as in Example 1 except that 4-bromobenzyl bromide (manufactured by Aldrich) was changed to 4-tertbutylbenzyl bromide (manufactured by Acros), the intended 9,9-bis (4-tertbutylbenzyl) was synthesized. It was confirmed that it was fluorene (the following formula).

(Example 5)
As a result of synthesis in the same manner as in Example 1 except that 4-bromobenzyl bromide (manufactured by Aldrich) was changed to 4-chlorobenzyl bromide (manufactured by Tokyo Chemical Industry), the desired 9,9-bis (4-chlorobenzyl) fluorene was synthesized. (The following formula) was confirmed.

Claims (7)

A compound represented by the following formula (1).

Wherein X represents an alkylidene group or an alkylene group, Y represents a hydroxyl group, a hydroxymethyl group, a mercapto group, a mercaptomethyl group, a carboxyl group or an amino group, a ring Z represents an aromatic hydrocarbon ring, and R ¹ represents a halogen atom, a cyano group or an alkyl group, and R ² represents a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, An acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group or a substituted amino group, k is an integer of 0 to 4, m is an integer of 0 or 1 or more, n is an integer of 0 or 1 or more, k, when m or n is respectively 2 or ^more, R 1, ^{R 2} or Y, respectively, be the same or different groups Good.)   The compound according to claim 1, wherein X is a methylene group.   The compound according to claim 1 or 2, wherein n is 0 to 1.   The compound according to any one of claims 1 to 3, wherein Z is a benzene ring or a naphthalene ring. The compound according to any one of claims 1 to 4, wherein R ² is an alkyl group, an alkoxy group, an alkylthio group, or a halogen atom, and m is 0 to 2.   The compound represented by the formula (1) is 9,9-bis (benzyl) fluorene, 9,9-bis (alkylbenzyl) fluorene, 9,9-bis (alkoxybenzyl) fluorene, 9,9-bis (alkylthio). The compound according to any one of claims 1 to 5, which is a compound selected from (benzyl) fluorene and 9,9-bis (halobenzyl) fluorene. In the presence of a base catalyst, a compound represented by the following formula (2) and (i) a compound represented by the following formula (3), or (ii) a compound represented by the following formula (3) and the following formula ( The method to manufacture the compound in any one of Claims 1-6 by making the compound represented by 4) react.

(Wherein R ³ represents a halogen atom, Y ¹ represents a group capable of producing Y or Y, n 1 represents an integer of 1 or more, and X, Z, R ¹ , R ² , k, m are Same as above.)