JP2014073986A - Anthracene derivative, method for producing the same, compound, composition, cured product, and fluorescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel anthracene derivative having a high refractive index and excellent heat resistance, a method for producing the same, a compound obtained from the anthracene derivative, a composition, a cured product, and a fluorescent element.SOLUTION: The anthracene derivative is represented by formula (1), and the compound is obtained by using the anthracene derivative as an intermediate. The composition contains the anthracene derivative or the compound. The cured product is obtained by curing the composition. The fluorescent element comprises the cured product. The method for producing the anthracene derivative includes a step of reacting anthracene-9-carbaldehyde with an indole in the presence of an acid catalyst or in the absence of a catalyst in an organic solvent. (In the formula (1), X is a residue of an indole, and Y is a residue of an indole or a hydroxyl group.)

Description

  The present invention relates to an anthracene derivative and a method for producing the same, a compound, a composition, a cured product, and a fluorescent element.

  Conventionally, anthracene is used in various applications such as wood insecticides, storage stabilizers, paints, epoxy resin and carbon black production raw materials, and anthraquinone dye synthetic raw materials. Moreover, since this anthracene is a condensed polycyclic aromatic compound in which three benzene rings are condensed, in addition to the characteristics such as structural hardness, high carbon density, high melting point, high refractive index, etc. It has useful properties such as the fact that π electrons act to emit fluorescence. Various application developments of anthracene have been attempted in order to further utilize such characteristics as added value. Various anthracene derivatives have been developed as high value-added materials in various technical fields.

  For example, a photo-curing polymer that acts as a sensitizer for radical photopolymerization by introducing a (meth) acrylate group at the 9th and 10th positions of anthracene to form a polymerizable monomer (see Japanese Patent Application Laid-Open No. 2007-99637) In addition, a polymer having ultraviolet absorbing ability and flame retardancy (see JP 2008-1637 A) can be obtained. Also in the field of photoresist, a radiation-sensitive resin composition containing anthracene and having advantages such as high sensitivity, high resolution, high etching resistance, and low sublimation (see JP-A-2005-346024) An antireflection film (see JP-A-7-82221) for preventing intermixing with a resist resin has been developed. Furthermore, it is expected that anthracene is used as an electron transporting material or a light emitting material and applied to an organic photoreceptor (OPC), an organic electroluminescence element, an organic solar cell, an organic light emitting diode, and the like (Japanese Patent Laid-Open No. 2009-40765). No. publication). Furthermore, taking advantage of the feature that anthracene has a high refractive index, in addition to being used as an optical material, a hologram recording material that is mixed with a high refractive index material, a low refractive index material, a sensitizing dye, etc., and records interference fringes by exposure (See JP-A-6-295151).

  On the other hand, cyclic compounds (heterocyclic compounds) containing heteroatoms such as nitrogen, oxygen, sulfur and the like exist in great numbers both in natural products and synthetic compounds, and play an important role as active ingredients such as pharmaceuticals and agricultural chemicals. Since many heterocyclic compounds are used in the fields of functional materials and electronic materials, which have been actively developed in recent years, the compounds required for the development of these products must be industrially efficiently produced at high quality and at low cost. Is desired.

  Focusing on indoles having aromatic heterocycles, for example, various novel polymers produced by utilizing the reactivity of the aromatic ring itself, such as epoxy resins, are applied to applications such as electronic materials as high heat resistant resins. (See Japanese Patent No. 4813201). An indole compound having an aromatic heterocycle is a basic skeleton of many physiologically active compounds and is important as a pharmaceutical raw material and an intermediate. For example, it is known that a bisindole derivative has an anti-inflammatory action (see JP-T-2002-520315). Furthermore, organic photoreceptors (OPC), organic electroluminescence elements, organic solar cells, organic light emitting diodes, etc., in which indole compounds are used in hole injection transport layers, light emitting layers, electron injection transport layers, etc. have been developed ( (See Japanese Patent No. 3229654 and Japanese Patent Laid-Open No. 2008-133225).

  Under these circumstances, development of a novel compound having an anthracene skeleton and an indole skeleton and capable of providing high functionality and imparting new properties is awaited. However, a compound having both an anthracene skeleton and an indole skeleton is not generally known, and there is no description regarding its physical and photochemical performance.

JP 2007-99637 A JP 2008-1637 A JP 2005-346024 A JP-A-7-82221 JP 2009-40765 A JP-A-6-295151 Japanese Patent No. 4813201 Japanese translation of PCT publication No. 2002-520315 Japanese Patent No. 3229654 JP 2008-133225 A

  The present invention has been made based on the above-described circumstances, and has a novel anthracene derivative having a high refractive index and excellent heat resistance, a method for producing the same, a compound obtained from the anthracene derivative, a composition, and a cured product. An object is to provide a fluorescent element.

（式（１）中、Ｘは、インドール類の残基である。Ｙは、インドール類の残基又は水酸基である。） The invention made to solve the above problems is
It is an anthracene derivative represented by the following general formula (1).

(In formula (1), X is a residue of an indole. Y is a residue or a hydroxyl group of an indole.)

  The anthracene derivative has both an anthracene skeleton and an indole skeleton, has a high refractive index due to the anthracene skeleton, heat resistance (high melting point), fluorescence properties with respect to ultraviolet rays, and the reactivity due to the indole skeleton. It also has.

（式（２）中、Ｚは、炭素数１〜２０の有機基、水酸基又はハロゲン原子である。ｎは、０〜５の整数である。但し、ｎが２以上の場合、複数のＺは、同一でも異なっていてもよい。） X and / or Y in the above formula (1) may be represented by the following general formula (2).

(In Formula (2), Z is a C1-C20 organic group, a hydroxyl group, or a halogen atom. N is an integer of 0-5. However, when n is two or more, several Z are as follows. May be the same or different.)

  An anthracene derivative having such a structure can be efficiently produced from anthracene-9-carbaldehyde and indoles.

  A compound obtained by using the anthracene derivative as an intermediate, a composition containing the anthracene derivative or the compound, and a cured product obtained by curing the composition are also included in the present invention. These compounds, compositions and cured products can also exhibit high refractive index properties, high heat resistance, fluorescent properties, and the like. Moreover, the fluorescent element provided with the cured product is useful as a novel element having fluorescence.

（式（１）中、Ｘは、インドール類の残基である。Ｙは、インドール類の残基又は水酸基である。） Another invention made to solve the above problems is as follows:
This is a method for producing an anthracene derivative represented by the following general formula (1), which comprises a step of reacting an anthracene-9-carbaldehyde with an indole in an organic solvent in the presence of an acid catalyst or without a catalyst.

(In formula (1), X is a residue of an indole. Y is a residue or a hydroxyl group of an indole.)

  According to the production method, a novel anthracene derivative having a high refractive index and excellent heat resistance can be produced efficiently.

（式（３）中、Ｚは、炭素数１〜２０の有機基、水酸基又はハロゲン原子である。ｎは、０〜５の整数である。但し、ｎが２以上の場合、複数のＺは、同一でも異なっていてもよい。） The indole is preferably represented by the following formula (3).

(In Formula (3), Z is a C1-C20 organic group, a hydroxyl group, or a halogen atom. N is an integer of 0-5. However, when n is two or more, several Z are May be the same or different.)

  As described above, the anthracene derivative of the present invention has a high refractive index and excellent heat resistance. Furthermore, the anthracene derivative has fluorescence characteristics and high carbon density attributed to the anthracene skeleton, and can have reactivity and the like attributed to the indole skeleton. Moreover, the compound derived from the said anthracene derivative, the composition containing these, and hardened | cured material can also exhibit the said effect. Therefore, the anthracene derivatives, etc. are epoxy resin raw materials, polycarbonate raw materials, photoresist materials, coating materials, optical materials, recording materials, pigments, dyes, pharmaceutical raw materials, pharmaceutical intermediates, other antireflection films, semiconductor encapsulating materials, laminated layers As materials such as materials, paints, organic photoreceptors, organic solar cells, and organic EL elements, it can be used in a wide variety of fields.

HPLC chart of reaction end point in Example 1 1H-NMR chart of anthracene derivative obtained in Example 1 13C-NMR chart of anthracene derivative obtained in Example 1 Absorption spectrum of the anthracene derivative obtained in Example 1 Fluorescence spectrum of anthracene derivative obtained in Example 1 HPLC chart of reaction end point in Example 2 HPLC chart of reaction end point in Example 3 1H-NMR chart of anthracene derivative obtained in Example 3 13C-NMR chart of anthracene derivative obtained in Example 3 Absorption spectrum of the anthracene derivative obtained in Example 3 Fluorescence spectrum of anthracene derivative obtained in Example 3 EL spectrum of the organic EL device obtained in Example 5 The figure which shows the voltage change of the brightness | luminance of the organic EL element obtained in Example 5 The figure which shows the voltage change of the resistance of the organic EL element obtained in Example 5 The figure which shows the voltage change of the current efficiency of the organic EL element obtained in Example 5. EL spectrum of the organic EL device obtained in Example 6 The figure which shows the voltage change of the brightness | luminance of the organic EL element obtained in Example 6. The figure which shows the voltage change of the resistance of the organic EL element obtained in Example 6. The figure which shows the voltage change of the current efficiency of the organic EL element obtained in Example 6. EL spectrum of the organic EL device obtained in Example 7 The figure which shows the voltage change of the brightness | luminance of the organic EL element obtained in Example 7 The figure which shows the voltage change of the resistance of the organic EL element obtained in Example 7 The figure which shows the voltage change of the current efficiency of the organic EL element obtained in Example 7.

  Hereinafter, embodiments of the anthracene derivative of the present invention and its production method, compound, composition, cured product, and fluorescent element will be described in detail.

<Anthracene derivative>
The anthracene derivative is represented by the general formula (1).

  In formula (1), X is a residue of indoles. Y is a residue or a hydroxyl group of indoles.

  The indoles are compounds having an indole skeleton and are compounds in which part or all of the hydrogen atoms of indole and indole are substituted with substituents.

  Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a group in which these groups are linked to -O-, an organic group having 1 to 20 carbon atoms such as a nitro group and a cyano group, an amino group, and a mercapto group. Groups, hydroxyl groups, halogen atoms and the like. Here, the organic group means a group having one or more carbon atoms.

  Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups. Specific examples of these alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl and isobutyl. , Isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group , Boronyl group, 4-decylcyclohexyl group and the like.

  Examples of the aryl group include groups in which one hydrogen is removed from an aromatic ring which may have a substituent, and specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 1-anthryl group. , 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 2-fluorenyl group 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p-cumenyl group, p- Dodecylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, , 4,5-trimethoxyphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, An o-mercaptophenyl group, a p-cyanophenyl group, an m-nitrophenyl group, an m-azidophenyl group, and the like can be given.

  Examples of the aralkyl group include groups in which a hydrogen atom of an alkyl group such as a linear, branched, monocyclic or condensed polycyclic alkyl group is substituted with an aryl group, and examples include a benzyl group and a phenethyl group. Can do.

  Examples of the alkenyl group include straight chain, branched chain, monocyclic or condensed polycyclic alkenyl groups, and these may have a plurality of carbon-carbon double bonds in the structure. Specific examples As, vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group Groups and the like.

  Examples of the group in which the alkyl group, aryl group, aralkyl group and alkenyl group are linked to -O- include alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and naphthyloxy group, and benzyloxy group Examples include alkenyloxy groups such as aralkyloxy groups and vinyloxy groups.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

  Specific examples of the indoles include indole, 1-methylindole, 2-methylindole, 4-methylindole, 5-methylindole, 6-methylindole, 7-methylindole, 4-nitroindole, 5 -Nitroindole, 6-nitroindole, 7-nitroindole, 4-fluoroindole, 5-fluoroindole, 6-fluoroindole, 7-fluoroindole, 4-chloroindole, 5-chloroindole, 6-chloroindole, 7 -Chloroindole, 4-bromoindole, 5-bromoindole, 6-bromoindole, 7-bromoindole, 4-iodoindole, 5-iodoindole, 6-iodoindole, 7-iodoindole, 4-indolol, 5 -Indro 6-indole, 7-indole, 4-methoxyindole, 5-methoxyindole, 6-methoxyindole, 7-methoxyindole, 4-benzyloxyindole, 5-benzyloxyindole, 6-benzyloxyindole, Examples thereof include 7-benzyloxyindole, indole-4-carbonitrile, indole-5-carbonitrile, indole-6-carbonitrile, indole-7-carbonitrile and the like.

  The term “indole residue” refers to a group obtained by removing one hydrogen atom involved in bonding from the indole as a compound. The indole residue is preferably a group in which one hydrogen atom on the aromatic ring is removed from the indole, and more preferably a group in which the 3-position hydrogen atom is removed.

  As X and / or Y in the above formula (1), those represented by the above general formula (2) are more preferable. Furthermore, it is more preferable that X and Y are represented by the general formula (2). In formula (2), Z is a C1-C20 organic group, a hydroxyl group, or a halogen atom. n is an integer of 0-5. However, when n is 2 or more, the plurality of Z may be the same or different. An anthracene derivative having such a structure can be efficiently produced from anthracene-9-carbaldehyde and indoles.

  Examples of the organic group having 1 to 20 carbon atoms include alkyl groups, aryl groups, aralkyl groups, alkenyl groups, groups in which these groups are linked to -O-, nitro groups, cyano groups, and the like. Specific examples include those mentioned above as substituents of indole.

  As said Z, a C1-C5 organic group, a hydroxyl group, or a halogen atom is preferable, a halogen atom is more preferable, and a bromine atom is further more preferable. Thus, when a substituent is comparatively small, the carbon density of the said anthracene derivative increases more and a refractive index etc. can be raised. In addition, by having a halogen atom as a substituent, reactivity derived from a halogen atom can be imparted to the anthracene derivative.

  As said n, 0-4 are preferable, 0 or 1 is more preferable, and 0 is further more preferable. Thus, when the number of substituents is reduced, the carbon density of the anthracene derivative is further increased, and the refractive index and the like can be increased.

  Since the anthracene derivative has an anthracene skeleton, it has various characteristics peculiar to anthracene, such as a high carbon density, a high refractive index, and fluorescence performance with respect to ultraviolet rays, and has a melting point higher than that of anthracene.

  Since the anthracene derivative has one or more, preferably two reactive active indole groups, the anthracene derivative has various characteristics unique to anthracene, and also has various reactivity that indole compounds have. For example, the anthracene derivative can be allylated, glycidylated, acrylated, methylolated, and the like.

  The anthracene derivative has an anthracene skeleton and has a high melting point and a high refractive index equal to or higher than those of an anthracene compound such as bisphenolanthracene. Specifically, the melting point of the anthracene derivative can be 230 ° C. or higher, preferably 260 ° C. or higher and 300 ° C. or lower, and the refractive index can be 1.65 or higher and 2.0 or lower. The melting point and refractive index of the anthracene derivative can be adjusted by selecting the indole residues represented by X and Y.

  Therefore, according to the anthracene derivative, high versatility such as being usable for various resin raw materials can be exhibited. In particular, the anthracene derivative preferably has two indole skeletons connected by a methylene chain and is arranged so that the anthracene ring hangs, so that the symmetry is high and the polymer side chain is used when used as a resin raw material. This makes it possible to develop excellent applications such as being able to be introduced into the network. In particular, since the anthracene derivative has an indole skeleton, it is expected that when introduced into the polymer skeleton, the polymer has a very high carbon density or a specific function such as high crystallinity. The

  In addition, an anthracene derivative having an indole group having a substituent as a residue of the indole can be further added or adjusted while maintaining the characteristics of the anthracene derivative.

  For example, according to the anthracene derivative having a residue of an indole having a halogen atom as a substituent, the anthracene derivative has the refractive index and fluorescence characteristics, and the reactivity of the conventional indole skeleton is Polymerization reactions in different forms are possible, and further application development is possible.

  Since the anthracene derivative of the present invention has the above-described structure, it can be used directly or as a reaction intermediate, and as various synthetic resin raw materials such as an epoxy resin raw material, a polycarbonate resin raw material, and an acrylic resin raw material. In addition to the synthetic resin raw material, it can be used as, for example, a fluorescent material, an agrochemical intermediate, a pharmaceutical intermediate, or a pharmaceutical raw material.

<Method for producing anthracene derivative>
The anthracene derivative of the present invention is produced by a method comprising a step of reacting an anthracene-9-carbaldehyde with an indole in an organic solvent in the presence of an acid catalyst or without a catalyst. The reaction mechanism of the reaction is not clear, but is presumed to be due to the π-excess aromaticity of the indoles.

  Examples of the indoles used in the production method include those described above, and these are appropriately selected depending on the desired structure of the anthracene derivative. For example, by selecting an indole as the indole, an anthracene derivative in which X and Y in the above formula (1) are indole residues can be produced. In addition, you may use these individually or in combination of 2 or more types.

  Moreover, as a minimum of the compounding quantity of this indole, 2 mol is preferable with respect to 1 mol of anthracene-9-carbaldehyde, and 2.5 mol is more preferable. The upper limit of the amount of the phenols is preferably 100 mol, more preferably 50 mol, and particularly preferably 20 mol with respect to 1 mol of anthracene-9-carbaldehyde. If the amount of indole is less than the above lower limit, a high-order condensate of the raw material is produced, so that enormous energy is required for purification. Conversely, if the above upper limit is exceeded, enormous energy is required to remove unreacted indole. Both are uneconomical. An anthracene derivative in which Y is a hydroxyl group (one introduction of an indole ring) can be obtained by reducing the amount of indole compounded.

  The organic solvent used in this production method may be any one that does not react with indoles, anthracene-9-carbaldehyde, and synthesized anthracene derivatives. For example, alcohols, polyhydric alcohol ethers, cyclic ethers, polyvalent ethers, Alcohol esters, esters, sulfoxides, carboxylic acids and the like can be used.

  Examples of alcohols include monohydric alcohols such as methanol, ethanol, propanol, and butanol, butanediol, pentanediol, hexanediol, ethylene glycol, propylene glycol, trimethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, Examples thereof include dihydric alcohols such as propylene glycol and polyethylene glycol, and trihydric alcohols such as glycerin.

  Examples of the polyhydric alcohol ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol mono Examples include glycol ethers such as phenyl ether.

  In addition, examples of the cyclic ethers include 1,3-dioxane, 1,4-dioxane, tetrahydrofuran and the like. Examples of the polyhydric alcohol ester include glycol esters such as ethylene glycol acetate. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate and the like. Examples of the sulfoxides include dimethyl sulfoxide and diethyl sulfoxide. Examples of carboxylic acids include acetic acid and acetic anhydride.

  Among these, alcohols and polyhydric alcohol ethers are preferable, and methanol, ethylene glycol, and ethylene glycol monomethyl ether are particularly preferable.

  An organic solvent is not limited to the above-mentioned illustration, Moreover, you may use each individually or in mixture of 2 or more types. The lower limit of the amount of the organic solvent is preferably 1 part by mass, more preferably 5 parts by mass, and particularly preferably 10 parts by mass with respect to 100 parts by mass of the indoles. Moreover, as an upper limit of the compounding quantity of an organic solvent, 1000 mass parts is preferable with respect to 100 mass parts of indoles, 500 mass parts is still more preferable, 300 mass parts is especially preferable. If the blending amount of the organic solvent is less than the above lower limit, there is a risk that the inside of the reaction system will solidify, and the equipment may be damaged. On the contrary, when the compounding amount of the organic solvent exceeds the above upper limit, the reaction rate is lowered and the productivity may be lowered.

  Examples of the acid catalyst in the present invention include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and perchloric acid, organic acids such as oxalic acid, paratoluenesulfonic acid, methanesulfonic acid and phenolsulfonic acid, and resins such as strongly acidic ion exchange resins. Strong acids such as acids can be mentioned. These catalysts may be used alone, or may be used in combination of two or more kinds, or a reaction promoter such as mercaptoacetic acid may be used in combination. The amount of the acid catalyst used may be set within a range in which the reaction is not extreme and dangerous and is not too small for promoting the reaction. 20% by mass.

  In the production method, the reaction proceeds without using a catalyst. Therefore, in this case, it is not necessary to remove the catalyst after the catalyst-free reaction, which is economical.

  The anthracene derivative is produced by adding the above indole, anthracene-9-carbaldehyde, and organic solvent into a reaction vessel and dissolving it, adding a catalyst if necessary, and stirring for a predetermined time.

  The reaction temperature in the reaction step of the production method is usually 0 to 100 ° C, preferably 25 to 60 ° C. If the reaction temperature is too low, the reaction time may be long. On the other hand, if the reaction temperature is too high, formation of reaction byproducts such as higher-order condensates and isomers is promoted, and the purity of the anthracene derivative is reduced. May be reduced.

  The pressure in the reaction vessel in the reaction step of the production method is usually normal pressure, but may be increased or reduced, and specifically, the internal pressure (gauge pressure) is -0.02 to 0.00. The range is preferably 2 MPa.

  The reaction time in the reaction step of the production method depends on the indole to be used, the type and amount of the organic solvent, the molar ratio, the reaction temperature, the pressure, etc., and cannot be generally defined, but generally 1 to 48 A time range is preferred.

  After completion of the reaction of the production method, the acid catalyst is removed. As a method for removing the catalyst, generally, the product is dissolved in a water-insoluble organic solvent such as methyl ethyl ketone and methyl isobutyl ketone, and is removed by washing with water. There are no particular restrictions, such as a method of filtering out a salt, a method of directly removing a resin acid such as an ion exchange resin, or a method of passing a reaction solution through a column packed with an anionic packing material. Further, when no catalyst is used, the step of removing the catalyst can be omitted.

  In the production method, after removal of the catalyst, the anthracene derivative is taken out by purification. In general, an organic solvent that acts as a poor solvent for the target product, and acts as a good solvent for other by-products and unreacted raw materials, is precipitated, filtered, and dried. The anthracene derivative which is a product can be obtained.

<Compound obtained using anthracene derivative as an intermediate>
A compound obtained using the anthracene derivative as an intermediate can be obtained by performing allylation, glycidylation, epoxidation, acrylation, methylolation or the like of the anthracene derivative. Each said reaction can be performed by a well-known method. These compounds can be used as resin raw materials such as epoxy resin raw materials and acrylic resin raw materials.

  These compounds obtained using the anthracene derivative as an intermediate also have anthracene skeleton, and thus have anthracene-specific properties such as a high melting point, a high refractive index, and fluorescence performance. Therefore, the resin obtained from the compound can have further added value such as having functions such as a high refractive index and fluorescence performance.

<Composition>
The composition containing the anthracene derivative or a compound obtained by using the anthracene derivative as an intermediate can be used for resin raw materials such as epoxy resin raw materials, polycarbonate resin raw materials, acrylic resin raw materials, adhesives, paints, and the like. As another component in the said composition, the well-known thing used when manufacturing each resin is mentioned. Examples of other components include a solvent, an inorganic filler, a pigment, a thixotropic agent, a fluidity improver, and other monomers.

  The solvent varies depending on the composition of the composition. For example, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether pro Pionates, aromatic hydrocarbons, ketones, esters and the like can be mentioned.

  Examples of the inorganic filler include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like. Includes organic or inorganic extender pigments, scaly pigments, and the like. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite. Examples of the fluidity improver include phenyl glycidyl ether, naphthyl glycidyl ether, and the like. be able to.

  Examples of the composition also include a composition for forming a light emitting layer containing the anthracene derivative or a compound obtained using the anthracene derivative as an intermediate as a light emitting dopant (guest material). This composition for forming a light-emitting layer usually contains a host material responsible for charge transport of electrons and holes together with the light-emitting dopant. Examples of the host material include 2-tert-butyl-9,10-bis (2-naphthyl) anthracene (TBADN), 2-methyl-9,10-bis (2-naphthyl) anthracene (MADN), 9,10- A compound having a 9,10-bis (2-naphthyl) anthracene skeleton such as bis (2-naphthyl) anthracene (ADN) can be preferably used. The content (doping amount) of the compound obtained by using the anthracene derivative or the anthracene derivative as an intermediate in the composition for forming a light emitting layer can be, for example, 1 to 20% by mass.

  The anthracene derivative or a composition containing the anthracene derivative as an intermediate can also be used as a material for forming other layers in the fluorescent element, such as a hole transport layer and an electron transport layer.

<Hardened product>
The cured product of the present invention is obtained by curing the above composition and can be used as various resins. These hardened | cured material can be used for various uses as a highly versatile material which provides various characteristics, such as a high melting point derived from the anthracene skeleton, a high refractive index, and fluorescence performance. In addition, the said hardened | cured material can be obtained by using the well-known method corresponding to each composition, such as light irradiation and a heating, said composition.

  These cured products can be used as various synthetic resins such as epoxy resins, polycarbonate resins, and acrylic resins. Furthermore, taking advantage of functionality, optical materials such as lenses and optical sheets, recording materials such as hologram recording materials, organic photoreceptors ( For example, it can be used as a highly functional material such as a light emitting layer of a fluorescent element), a photoresist material, an antireflection film, a semiconductor sealing material, or the like.

<Fluorescent element>
The fluorescent element of the present invention includes the cured product. As the said fluorescent element, the layer structure (organic EL element) provided with the hardened | cured material of the said composition for light emitting layers as a light emitting layer can be mentioned. As the layer structure of the fluorescent element, similarly to the known organic EL element, it consists of a three-layer structure consisting of (transparent) anode-light-emitting layer-cathode, transparent anode-hole transport layer-light-emitting layer-electron transport layer-cathode. Examples thereof include a five-layer structure, and a multilayer structure composed of a transparent anode-hole injection layer-hole transport layer-light emitting layer-hole blocking layer-electron transport layer-electron injection layer-cathode. However, it is not limited to these layer structures.

  The manufacturing method of the fluorescent element and the material of each layer other than the light emitting layer are not particularly limited, and a known manufacturing method and a known material can be used. Further, the fluorescent element of the present invention has a layer (cured product) formed from the anthracene derivative or a composition containing the anthracene derivative as an intermediate as another layer such as a hole transport layer or an electron transport layer. Also included. In addition, the said layer structure can also be functioned as an organic solar cell.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In addition, the measurement of the obtained anthracene derivative was performed with the following measuring apparatus and measuring method.

<GPC purity>
The GPC purity was measured by using Tosoh HLC-8220 GPC, RI detector, TSK-Gel SuperHZ2000 + HZ1000 + HZ1000 (4.6 mmφ × 150 mm) column, and tetrahydrofuran as a developing solvent at 0.35 ml / min. Determined by area ratio.

<HPLC purity>
HPLC purity and reaction end point confirmation were performed using HPLC Promince series manufactured by Shimadzu Corporation, UV detector SPD-20A (246 nm), ODS-3 (4.6 mmφ × 250 mm) column manufactured by GL Science, and water / acetonitrile = developing solvent = 40/60 was fed at 1.0 ml / min, and the area ratio of the target product peak was determined.

<Melting point>
The melting point was determined by a peak top method with a temperature rising rate of 5 ° C./min under a nitrogen atmosphere with a DSC8230 differential scanning calorimeter manufactured by Rigaku.

<1H-NMR and 13C-NMR>
1H-NMR was measured with DMSO-d6 solvent using TUN as a reference substance, using UNITY-INOVA 400 MHz manufactured by Varian. 13C-NMR was measured with a heavy acetone solvent using UNITY-INOVA 400 MHz manufactured by Varian and TMS as a reference substance.

<Refractive index>
The refractive index is measured by dissolving in propylene glycol monomethyl ether acetate (PGMEA) at concentrations of 1, 5 and 10% by mass at 25 ° C. using a RA-520N refractometer manufactured by Kyoto Electronics Industry. And the converted refractive index at 100% by mass was determined.

<Absorption / fluorescence spectrum>
The absorption spectrum is measured by dissolving in THF at a concentration of 1 × 10 −5 mol / L using a spectrophotometer V-570 manufactured by JASCO, and the fluorescence spectrum is a fluorescence spectrophotometer F-7000 manufactured by Hitachi High-Technologies Corporation. And dissolved in DMSO at a concentration of 1 × 10 −6 mol / L and excited at the maximum wavelength for measurement. Moreover, the presence or absence of light emission was observed by irradiating 365 nm ultraviolet rays using a handy UV lamp SLUV-4 manufactured by ASONE.

[Example 1] Synthesis of bisindole anthracene In a 3 L reactor equipped with a reflux tube, indole (292.9 g, 2.50 mol), anthracene-9-carbaldehyde (103.1 g, 0.5 mol) and methanol (292.9 g) were used. ) And dissolved at 40 ° C. 35% hydrochloric acid (29.3 g) was added, and the reaction was carried out at 40 ° C. for 24 hours. It was confirmed by HPLC that the anthracene-9-carbaldehyde peak disappeared and that the desired product was mainly produced. The HPLC chart of the reaction end point is shown in FIG. Next, the reaction solution was dissolved in methyl isobutyl ketone (1077 g), neutralized with 48% aqueous NaOH (19.0 g), and adjusted to pH 6 in the system. Subsequently, it was washed with distilled water (292.9 g) twice to remove the salt. After distilling off methyl isobutyl ketone under reduced pressure, toluene (1422 g) was added and stirred at 10 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 140.4 g of white crystals (yield 66.5%).

  The obtained crystal had a GPC purity of 99.9%, an HPLC purity of 99.6%, a melting point of 265 ° C., a converted refractive index of 1.716 (25 ° C.), and 1H-NMR (400 MHz, DMSO-d6, δ, ppm). /10.8, 2H, -NH / 7.4, 1H, -CH- / 6.7, 6.9, 7.3, 10H, Indole-H / 7.0, 7.3, 8.0, 8.5, 8.7, 9H, Anthryl-H) and 13C-NMR (400 MHz, heavy acetone, δ, ppm / 35.8, -CH- / 112.1, 112.1, 119.0, 119. 3, 120.2, 122.0, 125.5, 137.9, -Indole / 124.7, 124.8, 127.8, 128.2, 129.9, 131.3, 132.9, 136 .9, -Anthryl), 3,3 ′-(9-anthrace Nilmethylene) bisindole was confirmed. FIG. 2 shows a 1H-NMR chart, and FIG. 3 shows a 13C-NMR chart. Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. FIG. 4 shows an absorption spectrum, and FIG. 5 shows a fluorescence spectrum (excitation wavelength: 375 nm).

[Example 2]
Indole (100.0 g, 0.85 mol), anthracene-9-carbaldehyde (35.2 g, 0.17 mol) and methanol (100.0 g) were placed in a 1 L reaction vessel with a reflux tube and dissolved at 40 ° C. . The reaction was carried out at 40 ° C. for 24 hours, and it was confirmed by HPLC that the anthracene-9-carbaldehyde peak disappeared and that the desired product was mainly produced. The HPLC chart of the reaction end point is shown in FIG. Subsequently, toluene (200 g) was added and stirred at 10 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 30.3 g (yield 42.0%) of white crystals.

  The obtained crystals had a GPC purity of 96.5%, an HPLC purity of 98.2%, a melting point of 262 ° C., and blue light emission when irradiated with a UV lamp (365 nm) was visually confirmed.

  As shown in this example, the anthracene derivative according to the present invention synthesized in Examples 1 to 2 has a melting point higher than that of anthracene (melting point 218 ° C.) and a refractive index equivalent to or higher than that of anthracene. It was shown to have fluorescence with respect to ultraviolet rays. It was also shown that the anthracene derivative can be produced in an organic solvent under non-catalytic conditions (Example 2).

[Example 3] Synthesis of bis (5-bromoindole) anthracene In a 500 ml reaction vessel equipped with a reflux tube, 5-bromoindole (11.8 g, 0.06 mol) and anthracene-9-carbaldehyde (4.9 g, 0. 024 mol) and methanol (23.6 g) were added and dissolved at 45 ° C. 35% hydrochloric acid (1.2 g) was added as a catalyst, and the reaction was carried out at 45 ° C. for 24 hours. It was confirmed by HPLC that the anthracene-9-carbaldehyde peak disappeared and that the desired product was mainly produced. An HPLC chart of the reaction end point is shown in FIG. Next, the reaction solution was dissolved in methyl isobutyl ketone (35.5 g), washed 5 times with pure water (35.5 g), and adjusted to pH 6 in the system. Subsequently, after distilling off methyl isobutyl ketone under reduced pressure, methanol (23.7 g) was added and stirred at 10 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 10.0 g (yield 72.5%) of light brown crystals.

  The obtained crystal had a GPC purity of 99.6%, an HPLC purity of 99.7%, a melting point of 231 ° C., a converted refractive index of 1.6592 (25 ° C.), and 1H-NMR (400 MHz, DMSO-d6, δ, ppm). /11.0, 2H, -NH / 7.6, 1H, -CH- / 6.7, 7.0, 7.2, 7.4, 8H, Indole-H / 7.3, 7.4 8.1, 8.6, 8.7, 9H, Anthryl-H) and 13C-NMR (400 MHz, heavy acetone, δ, ppm / 35.4, -CH- / 112.3, 114.0, 114. 1,118.5,122.6,124.8,125.6,136.6, -Indole / 126.4,126.5,128.2,129.9,130.0,131.3,132 9, 135.8, -Anthryl), 3,3 ′-(9-a It was confirmed that the tiger Se sulfonyl-methylene) bis (5-bromo-indole). FIG. 8 shows a 1H-NMR chart, and FIG. 9 shows a 13C-NMR chart. Moreover, the blue light emission at the time of UV lamp (365 nm) irradiation was confirmed visually. FIG. 10 shows an absorption spectrum, and FIG. 11 shows a fluorescence spectrum (excitation wavelength: 375 nm).

[Example 4] Epoxidation of bisindole anthracene In a 500 ml reaction vessel with a reflux tube, the crystals obtained in Example 1 above (12.6 g, 0.30 mol) and epichlorohydrin (44.1 g, 0. 48 mol), tetrabutylammonium bromide (0.37 g), and dimethyl sulfoxide (12.6 g) were added and dissolved at 60 ° C. Sodium hydroxide (3.0 g, 0.08 mol) was added and reacted at 60 ° C. for 8 hours. Next, the reaction solution was dissolved in toluene (63.0 g), washed twice with 63.0 g of pure water, and then toluene was distilled off under reduced pressure. Then, methanol (150.1 g) was added. The mixture was stirred and crystallized at 10 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 14.8 g (yield 91.6%) of yellow crystals. The obtained crystal had a GPC purity of 92.7%, an HPLC purity of 96.6%, a melting point of 260 ° C., and blue light emission when irradiated with a UV lamp (365 nm) was visually confirmed.

[Example 5] Manufacture of organic EL element In the following examples, all mixing ratios indicate mass ratios unless otherwise specified. Vapor deposition (vacuum deposition) was performed at a rate of 1 to 2 cm / s in a vacuum of 1 to 2 × 10 ⁻⁴ Pa.
For evaluation of the light emission characteristics of the element, the characteristics of an organic EL element having an electrode area of 1.9 mm × 1.9 mm were measured. A current and voltage change was measured using 6241A made from ADMT as a current / voltage source, emission luminance was measured using BM-9 made by Topcon, and emission spectrum was measured using Specbos 1201 made by JETI.

  The following materials were sequentially deposited on an ITO (film thickness 110 nm) anode on the substrate to produce an organic EL device having the following constitution. 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile (HAT-CN) (film thickness 60 nm) was deposited as a hole injection layer. N, N'-diphenyl-N, N'-bis (1-naphthyl) benzidine (NPD) (thickness 20 nm) was deposited as a hole transport layer. As a light emitting layer, 2-tert-butyl-9,10-bis (2-naphthyl) anthracene (TBADN) (film thickness 30 nm) in which 7% concentration of the compound obtained in Synthesis Example 1 as a light emitting dopant was mixed. ) Was deposited. Bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum (BAlq) (film thickness 10 nm) was deposited as a hole blocking layer. Tris- (8-quinolinolato) aluminum (Alq3) (film thickness 30 nm) was deposited as an electron transport layer. Next, LiF was vapor-deposited with a film thickness of 0.8 nm as an electron injection layer on the electron transport layer. Further, an aluminum (Al) film having a thickness of 150 nm was laminated thereon as a cathode to prepare an organic light emitting device sample.

When the optical surface of the obtained organic EL element was magnified and observed with a microscope, good light emission without dark spots was confirmed. FIG. 12 shows an EL spectrum in a state where a current of 0.5 mA is passed through this element. In addition, the current / voltage / luminance characteristics of the device were measured. FIG. 13, FIG. 14, and FIG. 15 show voltage changes in the luminance (cd / m ² ), resistance (kΩ), and current efficiency (cd / A) of the element, respectively.

[Example 6]
An element similar to that of Example 5 was prepared except that 2-methyl-9,10-bis (2-naphthyl) anthracene (MADN) was used instead of TBADN of Example 5.

When the optical surface of the obtained organic EL element was magnified and observed with a microscope, good light emission without dark spots was confirmed. FIG. 16 shows an EL spectrum in a state where a current of 0.5 mA is passed. In addition, the current / voltage / luminance characteristics of the device were measured. FIG. 17, FIG. 18, and FIG. 19 show voltage changes in the luminance (cd / m ² ), resistance (kΩ), and current efficiency (cd / A) of the element, respectively.

[Example 7]
An element similar to that of Example 5 was prepared except that 9,10-bis (2-naphthyl) anthracene (ADN) was used instead of TBADN of Example 5.

When the optical surface of the obtained organic EL element was magnified and observed with a microscope, good light emission without dark spots was confirmed. An EL spectrum in a state where a current of 0.5 mA is applied is shown in FIG. In addition, the current / voltage / luminance characteristics of the device were measured. FIG. 21, FIG. 22, and FIG. 23 show voltage changes in the luminance (cd / m ² ), resistance (kΩ), and current efficiency (cd / A) of the element, respectively.

The anthracene derivative of the present invention and a compound obtained using the anthracene derivative as an intermediate can provide a highly versatile material that imparts various properties such as a high carbon density, a high melting point, a high refractive index, and fluorescence performance. It can be used for resin raw materials such as resin raw materials, polycarbonate resin raw materials, and acrylic resin raw materials. These anthracene derivatives as raw materials include, for example, laminated materials, coating materials such as paints, optical materials such as lenses and optical sheets, recording materials such as hologram recording materials, organic photoreceptors, photoresist materials, and antireflections. It can be used for highly functional materials such as films and semiconductor encapsulants, magnetic materials such as molecular magnetic memory, etc., and these can be used as materials for organic solar cells, organic EL elements, liquid crystal display elements, etc. . The anthracene derivative of the present invention can be used not only as a resin raw material but also as, for example, a pharmaceutical intermediate or a dye intermediate.

Claims (8)

Anthracene derivatives represented by the following general formula (1).

(In formula (1), X is a residue of an indole. Y is a residue or a hydroxyl group of an indole.) The anthracene derivative according to claim 1, wherein X and / or Y in the formula (1) is represented by the following general formula (2).

(In Formula (2), Z is a C1-C20 organic group, a hydroxyl group, or a halogen atom. N is an integer of 0-5. However, when n is two or more, several Z are as follows. May be the same or different.)   A compound obtained by using the anthracene derivative according to claim 1 as an intermediate.   A composition comprising the anthracene derivative according to claim 1 or 2 or the compound according to claim 3.   Hardened | cured material obtained by hardening | curing the composition of Claim 4.   A fluorescent device comprising the cured product according to claim 5. A method for producing an anthracene derivative represented by the following general formula (1), which comprises a step of reacting an anthracene-9-carbaldehyde with an indole in an organic solvent in the presence of an acid catalyst or without a catalyst.

(In formula (1), X is a residue of an indole. Y is a residue or a hydroxyl group of an indole.) The method for producing an anthracene derivative according to claim 7, wherein the indole is represented by the following formula (3).

(In Formula (3), Z is a C1-C20 organic group, a hydroxyl group, or a halogen atom. N is an integer of 0-5. However, when n is two or more, several Z are May be the same or different.)

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