JP2015221771A - Benzothienofluorene compound and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an organic EL element with high hole transport capability, high glass transformation temperature, low driving voltage, high luminous efficacy, and excellent durability; and a compound used for the same.SOLUTION: The present invention provides a benzothienofluorene compound represented by the general formula (1), and use thereof.

Description

  The present invention relates to a novel benzothienofluorene compound and an organic EL device using the same.

  An organic EL element is a surface-emitting element in which an organic thin film is held between a pair of electrodes, and has features such as a thin and light weight, a high viewing angle, and a high-speed response, and is expected to be applied to various display elements. . Recently, some practical applications such as mobile phone displays have begun. An organic EL element is an element that utilizes light emitted when holes injected from an anode and electrons injected from a cathode are recombined in a light emitting layer, and has a structure of a hole transport layer, a light emitting layer The mainstream is a multilayer stack type in which an electron transport layer and the like are stacked. Here, the charge transport layer such as the hole transport layer and the electron transport layer does not emit light by itself, but facilitates the injection of charges into the light emitting layer, and the charge injected into the light emitting layer or the light emitting layer. It plays the role of confining the energy of the generated excitons. Therefore, the charge transport layer is very important for lowering the driving voltage and improving the light emission efficiency of the organic EL element.

  As the hole transport material, an arylamine compound having an appropriate ionization potential and hole transport ability is used. As a typical hole transport material, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as NPD) is known. However, NPD has a low glass transition temperature, and has a big problem in the lifetime when the element is driven at a high temperature. Further, the driving voltage and luminous efficiency of the device using NPD for the hole transport layer were not sufficient.

  Against this background, development of arylamine compounds in which a condensed ring that can ensure a high glass transition temperature and has excellent hole transportability has been introduced.

  An example of a condensed ring that can ensure a high glass transition temperature is a benzothienofluorene ring in which a benzothiophene ring is condensed to a fluorene ring. A hole transport material in which an arylamino group is introduced into a benzothienofluorene ring has also been reported (see, for example, Patent Documents 1 to 3). However, these compounds tend to have a small energy gap, effectively confining the energy of electrons injected into the light-emitting layer and excitons generated in the light-emitting layer, and obtaining high luminous efficiency. There was room for improvement in terms of voltage.

WO2010 / 083872 EP2450975 WO2013 / 100467

  An object of the present invention is to provide a benzothienofluorene compound that is superior in light emission efficiency or low driving voltage as compared with a conventionally known compound, and further to provide an organic EL device having high light emission efficiency using the benzothienofluorene compound. And

  As a result of intensive studies, the present inventors have found that a benzothienofluorene compound represented by the following general formula (1) has characteristics suitable for a hole transport material. Furthermore, the present inventors have found that an organic EL device using the benzothienofluorene compound for the hole transport layer is excellent in luminous efficiency and durability, and completed the present invention.

（式中、
Ａｒ^１〜Ａｒ^３は、各々独立して、炭素数６〜２０の芳香族炭化水素基、又は炭素数３〜２０のヘテロ芳香族基［これらの基は、各々独立して、メチル基、エチル基、炭素数３〜１８の直鎖、分岐、又は環状のアルキル基、メトキシ基、エトキシ基、炭素数３〜１８の直鎖、分岐、又は環状のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、炭素数６〜２０のアリール基、炭素数６〜１８のアリールオキシ基、炭素数３〜２０のヘテロアリール基、炭素数３〜１８のトリアルキルシリル基、炭素数１８〜４０のトリアリールシリル基、シアノ基、ハロゲン原子、及び重水素原子からなる群より選ばれる置換基を１種以上有していてもよい］を表す。
Ｍは、炭素数６〜２０の２価の芳香族炭化水素基、又は炭素数３〜２０の２価のヘテロ芳香族基［これらの基は、各々独立して、メチル基、エチル基、炭素数３〜１８の直鎖、分岐、又は環状のアルキル基、メトキシ基、エトキシ基、炭素数３〜１８の直鎖、分岐、又は環状のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、炭素数６〜１２のアリール基、炭素数６〜１８のアリールオキシ基、炭素数３〜２０のヘテロアリール基、炭素数３〜１８のトリアルキルシリル基、炭素数１８〜４０のトリアリールシリル基、シアノ基、ハロゲン原子、及び重水素原子からなる群より選ばれる置換基を１種以上有していてもよい］を表す。
Ｒ^１〜Ｒ^１０は、各々独立して、炭素数６〜２０の芳香族炭化水素基、若しくは炭素数３〜２０のヘテロ芳香族基［これらの基は、各々独立して、メチル基、エチル基、炭素数３〜１８の直鎖、分岐、又は環状のアルキル基、メトキシ基、エトキシ基、炭素数３〜１８の直鎖、分岐、又は環状のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、炭素数６〜２０のアリール基、炭素数６〜１８のアリールオキシ基、炭素数３〜２０のヘテロアリール基、炭素数３〜１８のトリアルキルシリル基、炭素数１８〜４０のトリアリールシリル基、シアノ基、ハロゲン原子、及び重水素原子からなる群より選ばれる置換基を１種以上有していてもよい］、メチル基、エチル基、炭素数３〜１８の直鎖、分岐、若しくは環状のアルキル基、メトキシ基、エトキシ基、炭素数３〜１８の直鎖、分岐、若しくは環状のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数６〜１８のアリールオキシ基、炭素数３〜１８のトリアルキルシリル基、炭素数１８〜４０のトリアリールシリル基、シアノ基、ハロゲン原子、重水素原子、又は水素原子を表す。
Ａｒ^１とＡｒ^２は直接又は−Ｏ−、−ＮＨ−、−ＣＨ_２−、若しくは−Ｓ−を介して連結し、含窒素５員環又は６員環を形成してもよい。）
即ち本発明は、上記の一般式（１）で表されるベンゾチエノフルオレン化合物、及びその用途に関するものである。

(Where
Ar ^{1 to} Ar ³ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, ethyl group, Group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and a halogenated group having 1 to 3 carbon atoms An alkyl group, a C 1-3 halogenated alkoxy group, a C 6-20 aryl group, a C 6-18 aryloxy group, a C 3-20 heteroaryl group, a C 3-18 tri It may have one or more substituents selected from the group consisting of an alkylsilyl group, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a halogen atom, and a deuterium atom].
M is a bivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, ethyl group, carbon A linear, branched, or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, C1-C3 halogenated alkoxy group, C6-C12 aryl group, C6-C18 aryloxy group, C3-C20 heteroaryl group, C3-C18 trialkylsilyl group And may have one or more substituents selected from the group consisting of a C18-C40 triarylsilyl group, cyano group, halogen atom, and deuterium atom].
R ^{1 to} R ¹⁰ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, ethyl group, Group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and a halogenated group having 1 to 3 carbon atoms An alkyl group, a C 1-3 halogenated alkoxy group, a C 6-20 aryl group, a C 6-18 aryloxy group, a C 3-20 heteroaryl group, a C 3-18 tri An alkylsilyl group, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a halogen atom, and one or more substituents selected from the group consisting of deuterium atoms may be present], a methyl group, an ethyl group , A straight chain having 3 to 18 carbon atoms, Bi- or cyclic alkyl group, methoxy group, ethoxy group, linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, aryloxy having 6 to 18 carbon atoms Group, a trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a halogen atom, a deuterium atom, or a hydrogen atom.
Ar ¹ and Ar ² may be linked directly or via —O—, —NH—, —CH ₂ —, or —S— to form a nitrogen-containing 5-membered ring or 6-membered ring. )
That is, the present invention relates to a benzothienofluorene compound represented by the above general formula (1) and its use.

  The organic EL device using the benzothienofluorene compound of the present invention has a high light emission efficiency (current efficiency) and a low driving voltage as compared with an organic EL device using a conventionally known material, and further has excellent durability. Showed the effect.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide an organic EL element with a high brightness | luminance and efficiency and a long lifetime.

  Hereinafter, the present invention will be described in detail.

  General formula (1) of the present invention

で表されるベンゾチエノフルオレン化合物において、Ａｒ^１〜Ａｒ^３は、各々独立して、炭素数６〜２０の芳香族炭化水素基、又は炭素数３〜２０のヘテロ芳香族基（これらの基は、各々独立して、メチル基、エチル基、炭素数３〜１８の直鎖、分岐、又は環状のアルキル基、メトキシ基、エトキシ基、炭素数３〜１８の直鎖、分岐、又は環状のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、炭素数６〜２０のアリール基、炭素数６〜１８のアリールオキシ基、炭素数３〜２０のヘテロアリール基、炭素数３〜１８のトリアルキルシリル基、炭素数１８〜４０のトリアリールシリル基、シアノ基、ハロゲン原子、及び重水素原子からなる群より選ばれる置換基を１種以上有していてもよい）を表す。

In the benzothienofluorene compound represented by: Ar ^{1 to} Ar ³ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms (these groups are Each independently, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms. Group, C 1-3 halogenated alkyl group, C 1-3 halogenated alkoxy group, C 6-20 aryl group, C 6-18 aryloxy group, C 3-20 hetero It has at least one substituent selected from the group consisting of an aryl group, a trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a halogen atom, and a deuterium atom. May A representative.

The aromatic hydrocarbon group having 6 to 20 carbon atoms in Ar ^{1 to} Ar ³ can be expressed as a condensed hydrocarbon or optionally bonded aromatic hydrocarbon group having 6 to 20 carbon atoms, and is particularly limited. However, for example, phenyl group, biphenyl group, terphenyl group, naphthyl group, fluorenyl group, benzofluorenyl group, dibenzofluorenyl group, phenanthryl group, fluoranthenyl group, anthryl group, chrysenyl group, pyrenyl group , Triphenylene group, or perylenyl group.

As a C3-C20 heteroaromatic group in Ar < ¹ > -Ar < ³ >, it can represent with a C3-C20 aromatic group which has at least 1 hetero atom which may be condensed or connected, Although it does not specifically limit, For example, the C3-C20 heteroaromatic group containing the at least 1 oxygen atom, nitrogen atom, or sulfur atom which may be condensed or connected can be mentioned, Although it does not specifically limit, the C3-C20 heteroaromatic group containing the at least 1 sort (s) of hetero atom chosen from the group which consists of an oxygen atom, a nitrogen atom, and a sulfur atom which may be condensed or connected. For example, pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, pyridyl, Group, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzoimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothia Diazolyl group, benzoxazolyl group, benzisoxazolyl group, 2,1,3-benzooxadiazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, carbazolyl group, dibenzothienyl group, dibenzofura Examples include a nyl group, a phenoxazinyl group, a phenothiazinyl group, a phenazine group, and a thiantenyl group.

Linear 3 to 18 carbon atoms in Ar ¹ to Ar ^3, branched, or the alkyl group of cyclic, is not particularly limited, for example, propyl group, isopropyl group, n- butyl group, sec- butyl group Tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, cyclopropyl group, cyclohexyl group and the like.

Although it does not specifically limit as a C3-C18 linear, branched, or cyclic alkoxy group in Ar < ¹ > -Ar < ³ >, For example, a propoxy group, an isopropoxy group, n-butoxy group, sec-butoxy Group, tert-butoxy group, pentyloxy group, hexyloxy group, stearyloxy group and the like.

Although it does not specifically limit as a C1-C3 halogenated alkyl group in Ar < ¹ > -Ar < ³ >, For example, a trifluoromethyl group, a trichloromethyl group, or 2-fluoroethyl group etc. are mentioned.

Examples of the halogenated alkoxy group having 1 to 3 carbon atoms in Ar ¹ to Ar ^3, although not particularly limited, for example, a trifluoromethoxy group, trichloromethoxy group, or a 2-fluoroethoxy group and the like.

The aryl group having 6 to 20 carbon atoms in Ar ^{1 to} Ar ³ can be represented as an aromatic hydrocarbon group having a total carbon number of 6 to 20 which may have a substituent. Although not particularly limited, for example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, Examples include 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 3,4-dimethylphenyl group, 2,6-dimethylphenyl group, biphenyl group, or naphthyl group.

The aryloxy group having 6 to 18 carbon atoms in Ar ^{1 to} Ar ³ can be represented as an aromatic hydrocarbon oxy group having 6 to 18 carbon atoms which may have a substituent. Although not particularly limited, for example, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2-methoxyphenoxy group, 3-methoxyphenoxy group, 4-methoxyphenoxy group Group, 2-cyanophenoxy group, 3-cyanophenoxy group, 4-cyanophenoxy group, 3,4-dimethylphenoxy group, 2,6-dimethylphenoxy group, biphenyloxy group, or naphthyloxy group.

About the C3-C20 heteroaryl group in Ar < ¹ > -Ar < ³ >, although it can represent with the C6-C20 heteroaromatic group which may have a substituent, as said substituent, Although not particularly limited, for example, pyrrolyl group, 1-methylpyrrolyl group, 1-phenylpyrrolyl group, thienyl group, 2-methylthienyl group, 2-cyanothienyl group, 2-phenylthienyl group, furyl group, 2-phenylfuryl group, imidazolyl group, 1-methylimidazolyl group, 2-methylimidazolyl group, 1-phenylimidazolyl group, 2-phenyl-imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl Group, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 2,4-diphenyl-1 3,5-triazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzoimidazolyl group, 2-methylbenzoimidazolyl group, 2-phenylbenzoimidazolyl group, 1-methylbenzimidazolyl group, 1-phenylbenzimidazolyl group, 1,2-diphenylbenzimidazolyl Group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group, benzoisoxazolyl group, 2,1,3-benzooxadiazolyl group Quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, carbazolyl group, 9-methylcarbazolyl group, 9-ethylcarbazolyl group, 9-phenylcarbazolyl group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group Group Nochiajiniru group, acridinyl group, phenanthroline group, phenazine group, or thianthrenyl group.

Although it does not specifically limit as a C3-C18 trialkylsilyl group in Ar < ¹ > -Ar < ³ >, For example, a trimethylsilyl group, a triethylsilyl group, or a tributylsilyl group etc. are mentioned.

The triarylsilyl group having 18 to 40 carbon atoms in Ar ^{1 to} Ar ³ is not particularly limited, and examples thereof include a triphenylsilyl group, a tri (2-methylphenyl) silyl group, and tri (3-methylphenyl). ) Silyl group, tri (4-methylphenyl) silyl group, or tri (4-biphenylyl) silyl group.

Examples of the halogen atom in Ar ^{1 to} Ar ³ include fluorine, chlorine, bromine, or iodine.

Specific examples of Ar ^{1 to} Ar ³ include phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butylphenyl group, 4-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-neopentylphenyl group, 4-n-hexylphenyl group, 4-n-octylphenyl group, 4-n-decylphenyl group, 4-n- Dodecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4-tritylphenyl group, 3-trityl group Enyl group, 4-triphenylsilylphenyl group, 3-triphenylsilylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group 2,6-dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group 2-methoxyphenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 2- Isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphe Group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxy Phenyl group, 2- (2-ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n-decyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 4-phenoxyphenyl group, 3-phenoxyphenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl -4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 3-ethyl 5-methoxyphenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl Group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2 -Methoxy-6-ethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 3-cyanophenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-di Fluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 4-biphenyl group, 3-biphenyl group, 2-biphenyl group, 2-methyl-1,1′-biphenyl-4-yl group, 3-methyl-1,1′-biphenyl-4-yl group, 2′-methyl-1,1′-biphenyl-4-yl group, 3′-methyl-1,1′-biphenyl-4-yl group, 4'-methyl-1,1'-biphenyl-4-yl group, 2,6-dimethyl-1,1'-biphenyl-4-yl group, 2,2'-dimethyl-1,1'-biphenyl-4 -Yl group, 2,3'-dimethyl-1,1'-biphenyl-4-yl group, 2,4'-dimethyl-1,1'-biphenyl-4-yl group, 3,2'-dimethyl-1 , 1′-biphenyl-4-yl group, 2 ′, 3′-dimethyl-1,1′-biphenyl-4-yl group, 2 ′, 4′-dimethyl-1,1′-biphenyl-4-yl group, 2 ′, 5′-dimethyl-1,1′-biphenyl-4-yl group, 2 ′, 6′-dimethyl-1, 1′-biphenyl-4-yl group, p-terphenyl group, m-terphenyl group, o-terphenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 4- Methylnaphthalen-1-yl group, 6-methylnaphthalen-2-yl group, 4- (1-naphthyl) phenyl group, 4- (2-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group, 3- (2-naphthyl) phenyl group, 3-methyl-4- (1-naphthyl) phenyl group, 3-methyl-4- (2-naphthyl) phenyl group, 4- (2-methylnaphthalen-1-yl) phenyl group , 3- (2-methylnaphthalen-1-yl) phenyl group, -Phenylnaphthalen-1-yl group, 4- (2-methylphenyl) naphthalen-1-yl group, 4- (3-methylphenyl) naphthalen-1-yl group, 4- (4-methylphenyl) naphthalene-1 -Yl group, 6-phenylnaphthalen-2-yl group, 4- (2-methylphenyl) naphthalen-2-yl group, 4- (3-methylphenyl) naphthalen-2-yl group, 4- (4-methyl) Phenyl) naphthalen-2-yl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9-diethyl-2-fluorenyl group, 9,9-di-n-propyl-2-fluorenyl group 9,9-di-n-octyl-2-fluorenyl group, 9,9-diphenyl-2-fluorenyl group, 9,9′-spirobifluorenyl group, 9-phenanthryl group, 2-phenane Ryl group, 11,11′-dimethylbenzo [a] fluoren-9-yl group, 11,11′-dimethylbenzo [a] fluoren-3-yl group, 11,11′-dimethylbenzo [b] fluorene-9 -Yl group, 11,11'-dimethylbenzo [b] fluoren-3-yl group, 11,11'-dimethylbenzo [c] fluoren-9-yl group, 11,11'-dimethylbenzo [c] fluorene- 2-yl group, 3-fluoranthenyl group, 8-fluoranthenyl group, 1-pyrenyl group, 2-pyrenyl group, 9-anthryl group, 2-anthryl group, 2-triphenylene group, 3-chrysenyl group, 6 -Chrysenyl group, 3-perylenyl group, 1-imidazolyl group, 2-phenyl-1-imidazolyl group, 2-phenyl-3,4-dimethyl-1-imidazolyl group, 2,3,4-trif Nyl-1-imidazolyl group, 2- (2-naphthyl) -3,4-dimethyl-1-imidazolyl group, 2- (2-naphthyl) -3,4-diphenyl-1-imidazolyl group, 1-methyl-2 -Imidazolyl group, 1-ethyl-2-imidazolyl group, 1-phenyl-2-imidazolyl group, 1-methyl-4-phenyl-2-imidazolyl group, 1-methyl-4,5-dimethyl-2-imidazolyl group, 1-methyl-4,5-diphenyl-2-imidazolyl group, 1-phenyl-4,5-dimethyl-2-imidazolyl group, 1-phenyl-4,5-diphenyl-2-imidazolyl group, 1-phenyl-4 , 5-Dibiphenylyl-2-imidazolyl group, 1-methyl-3-pyrazolyl group, 1-phenyl-3-pyrazolyl group, 1-methyl-4-pyrazolyl group, 1-phenyl-4 -Pyrazolyl group, 1-methyl-5-pyrazolyl group, 1-phenyl-5-pyrazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group Group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 2-pyridyl group, 3-methyl-2-pyridyl group, 4-methyl- 2-pyridyl group, 5-methyl-2-pyridyl group, 6-methyl-2-pyridyl group, 3-pyridyl group, 4-methyl-3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 2,2 '-Bipyridin-3-yl group, 2,2'-bipyridin-4-yl group, 2,2'-bipyridin-5-yl group, 2,3'-bipyridin-3-yl group, 2,3′-bipyridin-4-yl group, 2,3′-bipyridin-5-yl group, 5-pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 4,6-diphenyl-1,3 , 5-triazin-2-yl group, 1-benzimidazolyl group, 2-methyl-1-benzimidazolyl group, 2-phenyl-1-benzimidazolyl group, 1-methyl-2-benzoimidazolyl group, 1-phenyl-2-benzoimidazolyl group 1-methyl-5-benzimidazolyl group, 1,2-dimethyl-5-benzimidazolyl group, 1-methyl-2-phenyl-5-benzimidazolyl group, 1-phenyl-5-benzimidazolyl group, 1,2-diphenyl-5 -Benzoimidazolyl group, 1-methyl-6-benzimidazolyl group, 1,2-dimethyl-6-benzimidazolyl group, 1- Tyl-2-phenyl-6-benzimidazolyl group, 1-phenyl-6-benzimidazolyl group, 1,2-diphenyl-6-benzimidazolyl group, 1-methyl-3-indazolyl group, 1-phenyl-3-indazolyl group, 2 -Benzothiazolyl group, 4-benzothiazolyl group, 5-benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, 3-benzoisothiazolyl group, 4-benzoisothiazolyl group, 5-benzoisothiazolyl group, 6- Benzoisothiazolyl group, 7-benzisothiazolyl group, 2,1,3-benzothiadiazol-4-yl group, 2,1,3-benzothiadiazol-5-yl group, 2-benzoxazolyl group, 4-benzoxazolyl group, 5-benzoxazolyl group, 6-benzoxazolyl group, 7-benzoo Xazolyl group, 3-benzisoxazolyl group, 4-benzisoxazolyl group, 5-benzoisoxazolyl group, 6-benzoisoxazolyl group, 7-benzisoxazolyl group, 2, 1,3-benzooxadiazolyl-4-yl group, 2,1,3-benzooxadiazolyl-5-yl group, 2-quinolyl group, 3-quinolyl group, 5-quinolyl group, 6-quinolyl group, 1-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 2-quinoxalyl group, 3-phenyl-2-quinoxalyl group, 6-quinoxalyl group, 2,3-dimethyl-6-quinoxalyl group, 2,3-diphenyl -6-quinoxalyl group, 2-quinazolyl group, 4-quinazolyl group, 2-acridinyl group, 9-acridinyl group, 1,10-phenanthrolin-3-yl group, 1,10-phe Introlin-5-yl group, 2-thienyl group, 3-thienyl group, 2-benzothienyl group, 3-benzothienyl group, 2-dibenzothienyl group, 4-dibenzothienyl group, 2-furanyl group, 3-furanyl group 2-benzofuranyl group, 3-benzofuranyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, 9-methylcarbazol-2-yl group, 9-methylcarbazol-3-yl group, 9-methylcarbazole- 4-yl group, 9-phenylcarbazol-2-yl group, 9-phenylcarbazol-3-yl group, 9-phenylcarbazol-4-yl group, 9-biphenylcarbazol-2-yl group, 9-biphenylcarbazole- 3-yl group, 9-biphenylcarbazol-4-yl group, 2-thianthryl group, 10-phenylphenothiazine- -Yl group, 10-phenylphenothiazin-2-yl group, 10-phenylphenoxazin-3-yl group, 10-phenylphenoxazin-2-yl group, 1-methylindol-2-yl group, 1-phenylindole 2-yl group, 9-phenylcarbazol-4-yl group, 1-methylindol-2-yl group, 1-phenylindol-2-yl group, 4- (2-pyridyl) phenyl group, 4- (3 -Pyridyl) phenyl group, 4- (4-pyridyl) phenyl group, 3- (2-pyridyl) phenyl group, 3- (3-pyridyl) phenyl group, 3- (4-pyridyl) phenyl group, 4- (2 -Phenylimidazol-1-yl) phenyl group, 4- (1-phenylimidazol-2-yl) phenyl group, 4- (2,3,4-triphenylimidazol-1-yl) ) Phenyl group, 4- (1-methyl-4,5-diphenylimidazol-2-yl) phenyl group, 4- (2-methylbenzimidazol-1-yl) phenyl group, 4- (2-phenylbenzimidazole-) 1-yl) phenyl group, 4- (1-methylbenzimidazol-2-yl) phenyl group, 4- (2-phenylbenzimidazol-1-yl) phenyl group, 3- (2-methylbenzimidazole-1- Yl) phenyl group, 3- (2-phenylbenzimidazol-1-yl) phenyl group, 3- (1-methylbenzimidazol-2-yl) phenyl group, 3- (2-phenylbenzimidazol-1-yl) Phenyl group, 4- (3,5-diphenyltriazin-1-yl) phenyl group, 4- (2-thienyl) phenyl group, 4- (2-furanyl) Phenyl group, 5-phenylthiophen-2-yl group, 5-phenylfuran-2-yl group, 4- (5-phenylthiophen-2-yl) phenyl group, 4- (5-phenylfuran-2-yl) Phenyl group, 3- (5-phenylthiophen-2-yl) phenyl group, 3- (5-phenylfuran-2-yl) phenyl group, 4- (2-benzothienyl) phenyl group, 4- (3-benzo Thienyl) phenyl group, 3- (2-benzothienyl) phenyl group, 3- (3-benzothienyl) phenyl group, 4- (2-dibenzothienyl) phenyl group, 4- (4-dibenzothienyl) phenyl group, 3 -(2-dibenzothienyl) phenyl group, 3- (4-dibenzothienyl) phenyl group, 4- (2-dibenzofuranyl) phenyl group, 4- (4-dibenzofuranyl) phene Group, 3- (2-dibenzofuranyl) phenyl group, 3- (4-dibenzofuranyl) phenyl group, 5-phenylpyridin-2-yl group, 4-phenylpyridin-2-yl group, 5-phenyl Examples thereof include, but are not limited to, a pyridin-3-yl group, a 4- (9-carbazolyl) phenyl group, or a 3- (9-carbazolyl) phenyl group.

In the benzothienofluorene compound represented by the general formula (1), Ar ^{1 to} Ar ³ are each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl from the viewpoint of excellent hole transport properties. Group, fluorenyl group, benzofluorenyl group, dibenzothienyl group, dibenzofuranyl group, or carbazolyl group (these groups are each independently a methyl group, an ethyl group, a straight chain having 3 to 18 carbon atoms, branched Or a cyclic alkyl group, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 20 carbon atoms, C6-C18 aryloxy group, C3-C20 heteroaryl group, C3-C18 trialkylsilyl group, C18-C40 triaryl Lil group, a cyano group, it is preferably a halogen atom, and may have a substituent having 1 or more selected from the group consisting of deuterium atoms).

  Among these, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, a dibenzothienyl group, a dibenzofuranyl group, or a carbazolyl group (these groups are each independently a methyl group, an ethyl group, Group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and a halogenated group having 1 to 3 carbon atoms Alkyl group, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 18 carbon atoms, heteroaryl group having 3 to 20 carbon atoms, trialkylsilyl group having 3 to 18 carbon atoms, tria having 18 to 40 carbon atoms More preferably, it may have one or more substituents selected from the group consisting of a reel silyl group, a cyano group, a halogen atom, and a deuterium atom.

  Among these, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, a dibenzothienyl group, a dibenzofuranyl group, or a carbazolyl group (these groups are each independently a methyl group A substituent selected from the group consisting of methoxy, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, naphthyl, carbazolyl, 9-phenylcarbazolyl, and fluorine It is more preferable that one or more may be present.

  Among these, phenyl group, 4-methylphenyl group, 3-methylphenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 4- (4-dibenzothienyl) phenyl group, 4- (4-dibenzo) Furanyl) phenyl group, 4- (9-carbazolyl) phenyl group, 4-biphenyl group, 3-biphenyl group, p-terphenyl group, m-terphenyl group, 1-naphthyl group, 2-naphthyl group, 9- Phenanthryl group, 4- (1-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group, 9,9-dimethyl-2-fluorenyl group, 2-dibenzothienyl group, 2-dibenzofuranyl group, 4- ( It is more preferably a 9-carbazolyl) phenyl group or a 9-phenylcarbazol-3-yl group.

  In the benzothienofluorene compound represented by the general formula (1), M is a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a divalent heteroaromatic group having 3 to 20 carbon atoms (these Each group is independently a methyl group, an ethyl group, a C3-C18 linear, branched, or cyclic alkyl group, a methoxy group, an ethoxy group, a C3-C18 linear, branched, or cyclic group. An alkoxy group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, and 3 to 20 carbon atoms. Having one or more substituents selected from the group consisting of a heteroaryl group having 3 to 18 carbon atoms, a trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a halogen atom, and a deuterium atom. May be) It is.

  The divalent aromatic hydrocarbon group having 6 to 20 carbon atoms in M can be represented by a condensed ring or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be linked, and is particularly limited. Phenylene group, biphenylene group, terphenylene group, naphthylene group, phenylnaphthalene-diyl group, binaphthylene group, fluorene-diyl group, benzofluorene-diyl group, dibenzofluorene-diyl group, phenanthrene-diyl group, Examples include fluoranthene-diyl group, anthracene-diyl group, chrysene-diyl group, pyrene-diyl group, triphenylene-diyl group, and perylene-diyl group.

  The divalent heteroaromatic group having 3 to 20 carbon atoms in M is represented by a divalent heteroaromatic group having 3 to 20 carbon atoms having at least one hetero atom that may be condensed or linked. Although not particularly limited, for example, a divalent heteroaromatic group having 3 to 20 carbon atoms containing at least one oxygen atom, nitrogen atom, or sulfur atom can be exemplified, and the method is particularly limited. A divalent heteroaromatic group having 3 to 20 carbon atoms containing at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, which may be condensed or linked, For example, pyrrole-diyl group, thiophene-diyl group, furan-diyl group, imidazole-diyl group, thiazole-diyl group, isothiazole-diyl group, oxazole-diyl Group, isoxazole-diyl group, pyridine-diyl group, pyrimidine-diyl group, pyrazine-diyl group, triazine-idyl group, indole-diyl group, benzothiophene-diyl group, benzofuran-diyl group, benzimidazole-diyl group Benzothiazole-diyl group, benzoisothiazole-diyl group, 2,1,3-benzothiadiazole-diyl group, benzoxazole-diyl group, benzisoxazole-diyl group, 2,1,3-benzooxadiazole- Diyl group, thienothiophene-diyl group, dithienothiophene-diyl group, benzodithiophene-diyl group, quinoline-diyl group, isoquinoline-diyl group, quinoxaline-diyl group, phenanthroline-diyl group, dibenzothiophene-diyl group, benzothienobe Zothiophene-diyl group, dibenzofuran-diyl group, carbazole-diyl group, phenoxazine-diyl group, phenothiazine-diyl group, thianthrene-diyl group, phenylthiophene-diyl group, diphenylthiophene-diyl group, phenylfuran-diyl group, diphenyl Examples include a furan-diyl group, a bithiophene-diyl group, a terthiophene-diyl group, a phenylpyridine-diyl group, or a bipyridine-diyl group.

A linear, branched or cyclic alkyl group having 3 to 18 carbon atoms in M, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, 1 carbon atom -3 halogenated alkoxy groups, C6-C18 aryloxy groups, C3-C20 heteroaryl groups, C3-C18 trialkylsilyl groups, C18-C40 triarylsilyl groups, and for a halogen atom, it can be exemplified the same substituents as the substituents indicated in Ar ¹ to Ar ³ of the.

  In addition, although it does not specifically limit as a C6-C12 aryl group in M, For example, a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl Group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 3,4-dimethylphenyl group, 2,6-dimethylphenyl group, biphenyl group Or a naphthyl group.

Specific examples of M include 1,4-phenylene group, 2-methyl-1,4-phenylene group, 2-ethyl-1,4-phenylene group, 2-n-propyl-1,4-phenylene group, 2 -Isopropyl-1,4-phenylene group, 2-n-butyl-1,4-phenylene group, 2-n-hexyl-1,4-phenylene group, 2-n-octyl-1,4-phenylene group, 1 , 3-phenylene group, 5-methyl-1,3-phenylene group, 5-ethyl-1,3-phenylene group, 5-n-propyl-1,3-phenylene group, 5-isopropyl-1,3-phenylene Group, 5-n-butyl-1,3-phenylene group, 5-n-hexyl-1,3-phenylene group, 5-n-octyl-1,3-phenylene group, 2-methyl-1,3-phenylene Group, 2-ethyl-1,3-phenylene group, 4 Methyl-1,3-phenylene group, 4-ethyl-1,3-phenylene group, 1,2-phenylene group, 4-methyl-1,2-phenylene group, 4-ethyl-1,2-phenylene group, 4 -N-propyl-1,2-phenylene group, 4-isopropyl-1,2-phenylene group, 4-n-butyl-1,2-phenylene group, 4-n-hexyl-1,2-phenylene group, 4 -N-octyl-1,2-phenylene group, 3-methyl-1,2-phenylene group, 3-ethyl-1,2-phenylene group, 3,6-dimethyl-1,4-phenylene group, 3,6 -Diethyl-1,4-phenylene group, 3,6-di-n-butyl-1,4-phenylene group, 3,6-di-n-hexyl-1,4-phenylene group, 3,6-di- n-octyl-1,4-phenylene group, 2,3-dimethyl-1, -Phenylene group, 2,3-diethyl-1,4-phenylene group, 2-methoxy-1,4-phenylene group, 2-ethoxy-1,4-phenylene group, 2-n-propyloxy-1,4- Phenylene group, 2-isopropyloxy-1,4-phenylene group, 2-n-butoxy-1,4-phenylene group, 2-n-hexyloxy-1,4-phenylene group, 2-n-octyloxy-1 , 4-phenylene group, 5-methoxy-1,3-phenylene group, 5-ethoxy-1,3-phenylene group, 5-n-propyloxy-1,3-phenylene group, 5-isopropyloxy-1,3 -Phenylene group, 5-n-butoxy-1,3-phenylene group, 5-n-hexyloxy-1,3-phenylene group, 5-n-octyloxy-1,3-phenylene group, 2-methoxy-1 , 3-phenylene group, 2-ethoxy-1,3-phenylene group, 4-methoxy-1,3-phenylene group, 4-ethoxy-1,3-phenylene group, 4-methoxy-1,2-phenylene group, 4 -Ethoxy-1,2-phenylene group, 4-n-propyloxy-1,2-phenylene group, 4-isopropyloxy-1,2-phenylene group, 4-n-butoxy-1,2-phenylene group, 4 -N-hexyloxy-1,2-phenylene group, 4-n-octyloxy-1,2-phenylene group, 3-methoxy-1,2-phenylene group, 3-ethoxy-1,2-phenylene group, 3 , 6-Ditoxy-1,4-phenylene group, 3,6-diethoxy-1,4-phenylene group, 3,6-di-n-butoxy-1,4-phenylene group, 3,6-di-n- group Hexyloxy-1,4-fu Nylene group, 3,6-di-n-octyloxy-1,4-phenylene group, 2,3-dimethoxy-1,4-phenylene group, 2,3-diethoxy-1,4-phenylene group, 2-cyano -1,4-phenylene group, 5-cyano-1,3-phenylene group, 2-cyano-1,3-phenylene group, 4-cyano-1,3-phenylene group, 4-cyano-1,2-phenylene Group, 3-cyano-1,2-phenylene group, 3,6-dicyano-1,4-phenylene group, 2,3-dicyano-1,4-phenylene group, 2,5-dicyano-1,3-phenylene Group, 2,4-dicyano-1,3-phenylene group, 4,5-dicyano-1,3-phenylene group, 3,4-dicyano-1,2-phenylene group, 4,5-dicyano-1,2 -Phenylene group, 2-fluoro-1,4-phenylene 5-fluoro-1,3-phenylene group, 2-fluoro-1,3-phenylene group, 4-fluoro-1,3-phenylene group, 4-fluoro-1,2-phenylene group, 3-fluoro-1 , 2-phenylene group, 3,6-difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 2,5-difluoro-1,3-phenylene group, 2,4-difluoro -1,3-phenylene group, 4,5-difluoro-1,3-phenylene group, 3,4-difluoro-1,2-phenylene group, 4,5-difluoro-1,2-phenylene group, 4,4 '-Biphenylene group, 3,4'-biphenylene group, 2,4'-biphenylene group, 3,3'-biphenylene group, 3,2'-biphenylene group, 2,2'-biphenylene group, 2-methyl-4 , 4′-biphenylene group, 3- Tyl-4,4′-biphenylene group, 2,2′-dimethyl-4,4′-biphenylene group, 3,3′-dimethyl-4,4′-biphenylene group, 2,3′-dimethyl-4,4 '-Biphenylene group, 3,5-dimethyl-4,4'-biphenylene group, 3,6-dimethyl-4,4'-biphenylene group, 2,5-dimethyl-4,4'-biphenylene group, 2,6 -Dimethyl-4,4'-biphenylene group, 2,5,2 ', 5'-tetramethyl-4,4'-biphenylene group, 2,6,2', 6'-tetramethyl-4,4'- Biphenylene group, 3,5,3 ′, 5′-tetramethyl-4,4′-biphenylene group, 2-methoxy-4,4′-biphenylene group, 3-methoxy-4,4′-biphenylene group, 2, 2'-dimethoxy-4,4'-biphenylene group, 3,3'-dimethoxy-4,4'-biphenylene group 2,3′-dimethoxy-4,4′-biphenylene group, 3,5-dimethoxy-4,4′-biphenylene group, 3,6-dimethoxy-4,4′-biphenylene group, 2,5-dimethoxy-4 , 4′-biphenylene group, 2,6-dimethoxy-4,4′-biphenylene group, 2,5,2 ′, 5′-tetramethoxy-4,4′-biphenylene group, 2,6,2 ′, 6 '-Tetramethoxy-4,4'-biphenylene group, 2,2'-ditrifluoromethyl-4,4'-biphenylene group, 2-fluoro-4,4'-biphenylene group, 3-fluoro-4,4' -Biphenylene group, 2,2'-difluoro-4,4'-biphenylene group, 3,3'-difluoro-4,4'-biphenylene group, 2,3'-difluoro-4,4'-biphenylene group, 3 , 5-Difluoro-4,4′-biphenylene group, 3,6-diph Fluoro-4,4′-biphenylene group, 2,5-difluoro-4,4′-biphenylene group, 2,6-difluoro-4,4′-biphenylene group, 2,5,2 ′, 5′-tetrafluoro -4,4'-biphenylene group, 2,6,2 ', 6'-tetrafluoro-4,4'-biphenylene group, 2-cyano-4,4'-biphenylene group, 3-cyano-4,4' -Biphenylene group, 2,2'-dicyano-4,4'-biphenylene group, 3,3'-dicyano-4,4'-biphenylene group, 2,3'-dicyano-4,4'-biphenylene group, 3 , 5-dicyano-4,4′-biphenylene group, 3,6-dicyano-4,4′-biphenylene group, 2,5-dicyano-4,4′-biphenylene group, 2,6-dicyano-4,4 '-Biphenylene group, 2,5,2', 5'-tetracyano-4,4'-biphenylene group 2,6,2 ′, 6′-tetracyano-4,4′-biphenylene group, 2-phenyl-4,4′-biphenylene group, 3-phenyl-4,4′-biphenylene group, 2,2′-diphenyl -4,4'-biphenylene group, 3,3'-diphenyl-4,4'-biphenylene group, 2,3'-diphenyl-4,4'-biphenylene group, 3,5-diphenyl-4,4'- Biphenylene group, 3,6-diphenyl-4,4′-biphenylene group, 2,5-diphenyl-4,4′-biphenylene group, 2,6-diphenyl-4,4′-biphenylene group, 2,5,2 ', 5'-tetraphenyl-4,4'-biphenylene group, 2,6,2', 6'-tetraphenyl-4,4'-biphenylene group, 2-methyl-3,4'-biphenylene group, 4 -Methyl-3,4'-biphenylene group, 5-methyl-3,4'-biphe Len group, 6-methyl-3,4'-biphenylene group, 2'-methyl-3,4'-biphenylene group, 3'-methyl-3,4'-biphenylene group, 2,2'-dimethyl-3, 4'-biphenylene group, 4,2'-dimethyl-3,4'-biphenylene group, 5,2'-dimethyl-3,4'-biphenylene group, 6,2'-dimethyl-3,4'-biphenylene group 2,3′-dimethyl-3,4′-biphenylene group, 4,3′-dimethyl-3,4′-biphenylene group, 5,3′-dimethyl-3,4′-biphenylene group, 6,3 ′ -Dimethyl-3,4'-biphenylene group, 2-methoxy-3,4'-biphenylene group, 4-methoxy-3,4'-biphenylene group, 5-methoxy-3,4'-biphenylene group, 6-methoxy -3,4'-biphenylene group, 2'-methoxy-3,4'-biphenylene group, 3'- Toxi-3,4'-biphenylene group, 2,2'-dimethoxy-3,4'-biphenylene group, 4,2'-dimethoxy-3,4'-biphenylene group, 5,2'-dimethoxy-3,4 '-Biphenylene group, 6,2'-dimethoxy-3,4'-biphenylene group, 2,3'-dimethoxy-3,4'-biphenylene group, 4,3'-dimethoxy-3,4'-biphenylene group, 5,3′-dimethoxy-3,4′-biphenylene group, 6,3′-dimethoxy-3,4′-biphenylene group, 2-fluoro-3,4′-biphenylene group, 4-fluoro-3,4 ′ -Biphenylene group, 5-fluoro-3,4'-biphenylene group, 6-fluoro-3,4'-biphenylene group, 2'-fluoro-3,4'-biphenylene group, 3'-fluoro-3,4 ' -Biphenylene group, 2,2'-difluoro-3,4'-biphenyl Len group, 4,2′-difluoro-3,4′-biphenylene group, 5,2′-difluoro-3,4′-biphenylene group, 6,2′-difluoro-3,4′-biphenylene group, 2, 3'-difluoro-3,4'-biphenylene group, 4,3'-difluoro-3,4'-biphenylene group, 5,3'-difluoro-3,4'-biphenylene group, 6,3'-difluoro- 3,4′-biphenylene group, 2-cyano-3,4′-biphenylene group, 4-cyano-3,4′-biphenylene group, 5-cyano-3,4′-biphenylene group, 6-cyano-3, 4'-biphenylene group, 2'-cyano-3,4'-biphenylene group, 3'-cyano-3,4'-biphenylene group, 2,2'-dicyano-3,4'-biphenylene group, 4,2 '-Dicyano-3,4'-biphenylene group, 5,2'-dicyano-3,4'-biphe Nylene group, 6,2′-dicyano-3,4′-biphenylene group, 2,3′-dicyano-3,4′-biphenylene group, 4,3′-dicyano-3,4′-biphenylene group, 5, 3'-dicyano-3,4'-biphenylene group, 6,3'-dicyano-3,4'-biphenylene group, 2-phenyl-3,4'-biphenylene group, 4-phenyl-3,4'-biphenylene Group, 5-phenyl-3,4'-biphenylene group, 6-phenyl-3,4'-biphenylene group, 2'-phenyl-3,4'-biphenylene group, 3'-phenyl-3,4'-biphenylene Group, 2,2′-diphenyl-3,4′-biphenylene group, 4,2′-diphenyl-3,4′-biphenylene group, 5,2′-diphenyl-3,4′-biphenylene group, 6,2 '-Diphenyl-3,4'-biphenylene group, 2,3'-diphenyl-3, '-Biphenylene group, 4,3'-diphenyl-3,4'-biphenylene group, 5,3'-diphenyl-3,4'-biphenylene group, 6,3'-diphenyl-3,4'-biphenylene group, 2-methyl-3,3′-biphenylene group, 4-methyl-3,3′-biphenylene group, 5-methyl-3,3′-biphenylene group, 6-methyl-3,3′-biphenylene group, 2, 2'-dimethyl-3,3'-biphenylene group, 4,4'-dimethyl-3,3'-biphenylene group, 2,4'-dimethyl-3,3'-biphenylene group, 2,5'-dimethyl- 3,3′-biphenylene group, 2,6-dimethyl-3,3′-biphenylene group, 2,5-dimethyl-3,3′-biphenylene group, 2,4-dimethyl-3,3′-biphenylene group, 2,4,2 ′, 4′-tetramethyl-3,3′-biphenylene group, 2,5 2 ′, 5′-tetramethyl-3,3′-biphenylene group, 2,6,2 ′, 6′-tetramethyl-3,3′-biphenylene group, 2-methoxy-3,3′-biphenylene group, 4-methoxy-3,3′-biphenylene group, 5-methoxy-3,3′-biphenylene group, 6-methoxy-3,3′-biphenylene group, 2,2′-dimethoxy-3,3′-biphenylene group 4,4′-dimethoxy-3,3′-biphenylene group, 2,4′-dimethoxy-3,3′-biphenylene group, 2,5′-dimethoxy-3,3′-biphenylene group, 2,6- Dimethoxy-3,3′-biphenylene group, 2,5-dimethoxy-3,3′-biphenylene group, 2,4-dimethoxy-3,3′-biphenylene group, 2,4,2 ′, 4′-tetramethoxy -3,3'-biphenylene group, 2,5,2 ', 5'-tetramethoxy- 3,3′-biphenylene group, 2,6,2 ′, 6′-tetramethoxy-3,3′-biphenylene group, 2-cyano-3,3′-biphenylene group, 4-cyano-3,3′- Biphenylene group, 5-cyano-3,3′-biphenylene group, 6-cyano-3,3′-biphenylene group, 2,2′-dicyano-3,3′-biphenylene group, 4,4′-dicyano-3 , 3′-biphenylene group, 2,4′-dicyano-3,3′-biphenylene group, 2,5′-dicyano-3,3′-biphenylene group, 2,6-dicyano-3,3′-biphenylene group 2,5-dicyano-3,3′-biphenylene group, 2,4-dicyano-3,3′-biphenylene group, 2,4,2 ′, 4′-tetracyano-3,3′-biphenylene group, 2 , 5,2 ', 5'-tetracyano-3,3'-biphenylene group, 2,6,2', 6'-tetra Ano-3,3′-biphenylene group, 2-fluoro-3,3′-biphenylene group, 4-fluoro-3,3′-biphenylene group, 5-fluoro-3,3′-biphenylene group, 6-fluoro- 3,3′-biphenylene group, 2,2′-difluoro-3,3′-biphenylene group, 4,4′-difluoro-3,3′-biphenylene group, 2,4′-difluoro-3,3′- Biphenylene group, 2,5′-difluoro-3,3′-biphenylene group, 2,6-difluoro-3,3′-biphenylene group, 2,5-difluoro-3,3′-biphenylene group, 2,4- Difluoro-3,3′-biphenylene group, 2,4,2 ′, 4′-tetrafluoro-3,3′-biphenylene group, 2,5,2 ′, 5′-tetrafluoro-3,3′-biphenylene The group 2,6,2 ′, 6′-tetrafluoro-3,3′-biphe Len group, 2-phenyl-3,3′-biphenylene group, 4-phenyl-3,3′-biphenylene group, 5-phenyl-3,3′-biphenylene group, 6-phenyl-3,3′-biphenylene group 2,2′-diphenyl-3,3′-biphenylene group, 4,4′-diphenyl-3,3′-biphenylene group, 2,4′-diphenyl-3,3′-biphenylene group, 2,5 ′ -Diphenyl-3,3'-biphenylene group, 2,6-diphenyl-3,3'-biphenylene group, 2,5-diphenyl-3,3'-biphenylene group, 2,4-diphenyl-3,3'- Biphenylene group, 2,4,2 ′, 4′-tetraphenyl-3,3′-biphenylene group, 2,5,2 ′, 5′-tetraphenyl-3,3′-biphenylene group, 2,6,2 ', 6'-tetraphenyl-3,3'-biphenylene group, 4,4''-p- Terphenylene group, 3,4 ″ -p-terphenylene group, 2,4 ″ -p-terphenylene group, 3,3 ″ -p-terphenylene group, 2,3 ″ -p-terphenylene group 2,2 ''-p-terphenylene group, 4,4 ''-m-terphenylene group, 3,4 ''-m-terphenylene group, 2,4 ''-p-terphenylene group, 3,3 ″ -m-terphenylene group, 2,3 ″ -m-terphenylene group, 2,2 ″ -m-terphenylene group, 4,4 ″ -o-terphenylene group, 3, 4 ″ -o-terphenylene group, 2,4 ″ -o-terphenylene group, 3,3 ″ -o-terphenylene group, 2,3 ″ -o-terphenylene group, 2,2 ′ '-O-terphenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group, 1-phenylnaphthalene-dii Group, 2-phenylnaphthalene-diyl group, 9,9-dimethylfluorene-2,7-diyl group, 9,9-dioctylfluorene-2,7-diyl group, 9,9-diphenylfluorene-2,7- Diyl group, 9,9′-spirobifluorene-2,7-diyl group, 11,11′-dimethylbenzo [a] fluorene-3,9-diyl group, 11,11′-dimethylbenzo [a] fluorene- 2,9-diyl group, 11,11′-dimethylbenzo [b] fluorene-3,9-diyl group, 11,11′-dimethylbenzo [c] fluorene-2,9-diyl group, fluoranthene-3,8 -Diyl group, pyrene-1,6-diyl group, pyrene-2,3-diyl group, pyrene-2,7-diyl group, pyrene-1,8-diyl group, anthracene-2,6-diyl group, anthracene -1 5-diyl group, anthracene-9,10-diyl group, triphenylene-2,7-diyl group, chrysene-2,8-diyl group, pyrrole-2,5-diyl group, 1-methylpyrrole-2,5- Diyl group, 1-phenylpyrrole-2,5-diyl group, thiophene-2,5-diyl group, 3-hexylthiophene-2,5-diyl group, 3,4-ethylenedioxythiophene-2,5-diyl Group, thiophene-3,4-diyl group, furan-2,5-diyl group, furan-3,4-diyl group, thiazole-diyl group, isothiazole-diyl group, oxazole-diyl group, isoxazole-diyl group Pyridine-2,5-diyl group, pyridine-2,6-diyl group, pyrazine-2,5-diyl group, triazine-2,4-diyl group, benzothiophene-diyl group, Benzofuran-diyl group, benzothiazole-diyl group, benzoisothiazole-diyl group, 2,1,3-benzothiadiazole-diyl group, benzoxazole-diyl group, benzoisoxazole-diyl group, 2,1,3-benzo Oxadiazole-diyl group, thieno [3,2-b] thiophene-2,5-diyl group, thieno [3,2-b] thiophene-3,6-diyl group, dithieno [3,2-b: 2 ', 3'-c] thiophene-2,6-diyl group, benzodithiophene-diyl group, dibenzothiophene-2,8-diyl group, 9-methylcarbazole-2,7-diyl group, 9-phenylcarbazole- 2,7-diyl group, 9-biphenylcarbazole-2,7-diyl group, 9-naphthylcarbazole-2,7-diyl group, 9-methylcarbazo -3,6-diyl group, 9-phenylcarbazole-3,6-diyl group, 9-biphenylcarbazole-3,6-diyl group, 9-naphthylcarbazole-3,6-diyl group, benzothienobenzothiophene- 2,7-diyl group, dibenzofuran-2,8-diyl group, 10-methylphenoxazine-3,7-diyl group, 10-phenylphenoxazine-3,7-diyl group, 10-methylphenothiazine-3,7 -Diyl group, 10-phenylphenothiazine-3,7-diyl group, thianthrene-1,9-diyl group, thianthrene-2,7-diyl group, 2-phenylthiophene-diyl group, 2,5-diphenylthiophene-diyl Group, 2-phenylfuran-diyl group, 2,5-diphenylfuran-diyl group, 2,2′-bithiophene-5,5′-dii Group, 2,2'-bithiophene-3,3'-diyl group, or terthiophene 5,5 '' - can be exemplified diyl group, but is not limited thereto.

  In the benzothienofluorene compound represented by the general formula (1), M is a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, or a fluorene-diyl group (these groups) because of excellent hole transport properties. Each independently represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic group having 3 to 18 carbon atoms. Alkoxy group, halogenated alkyl group having 1 to 3 carbon atoms, halogenated alkoxy group having 1 to 3 carbon atoms, aryl group having 6 to 12 carbon atoms, aryloxy group having 6 to 18 carbon atoms, 3 to 20 carbon atoms Selected from the group consisting of heteroaryl groups, trialkylsilyl groups having 3 to 18 carbon atoms, triarylsilyl groups having 18 to 40 carbon atoms, cyano groups, halogen atoms, and deuterium atoms It is preferable that a that the substituents may be 1 or more).

  Among these, 1,4-phenylene group, 1,3-phenylene group, 4,4′-biphenylene group, 3,3′-biphenylene group, 3,4′-biphenylene group, 4,4 ″ -p- A terphenylene group, a 4,4 ″ -m-terphenylene group, a 2,6-naphthylene group, or a fluorene-2,7-diyl group (these groups are each independently methyl, ethyl, carbon, A linear, branched, or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, C1-C3 halogenated alkoxy group, C6-C12 aryl group, C6-C18 aryloxy group, C3-C20 heteroaryl group, C3-C18 trialkylsilyl group , Tria with 18 to 40 carbon atoms Rushiriru group, a cyano group, and more preferably a halogen atom, and a substituent selected from the group consisting of heavy hydrogen atoms may have one or more).

  Of these, a 1,4-phenylene group, a 1,3-phenylene group, or a 4,4′-biphenylene group (these groups are each independently a methyl group, a methoxy group, a cyano group, and fluorine More preferably one or more substituents selected from the group consisting of:

In the benzothienofluorene compound represented by the general formula (1), R ^{1 to} R ¹⁰ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms. (These groups are each independently a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear or branched chain having 3 to 18 carbon atoms. Or a cyclic alkoxy group, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a carbon number 1 to a substituent selected from the group consisting of a heteroaryl group having 3 to 20 carbon atoms, a trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a halogen atom, and a deuterium atom. More than species A methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms. Group, alkyl group having 1 to 3 carbon atoms, aryloxy group having 6 to 18 carbon atoms, trialkylsilyl group having 3 to 18 carbon atoms, triarylsilyl group having 18 to 40 carbon atoms, cyano group, halogen atom Represents a deuterium atom or a hydrogen atom.

The aromatic hydrocarbon group having 6 to 20 carbon atoms in R ¹ to R ^10, is not particularly limited, and an aromatic hydrocarbon group having 6 to 20 carbon atoms shown in ^Ar 1 to Ar ³ of the The same substituents can be mentioned.

The hetero aromatic group having 3 to 20 carbon atoms in R ¹ to R ^10, is not particularly limited, the same substituents as the hetero-aromatic groups of 3 to 20 carbon atoms shown in ^Ar 1 to Ar ³ of the Groups.

Linear 3 to 18 carbon atoms in R ¹ to R ^10, branched, or cyclic alkyl group, a linear 3 to 18 carbon atoms, branched, or cyclic alkoxy group, a halogenated alkyl group having 1 to 3 carbon atoms A halogenated alkoxy group having 1 to 3 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, and a trialkylsilyl having 3 to 18 carbon atoms Examples of the group, the triarylsilyl group having 18 to 40 carbon atoms, and the halogen atom include the same substituents as those described above for Ar ^{1 to} Ar ³ and M.

R ^{1 to} R ¹⁰ are each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, or a fluorenyl group (these groups are each independently a methyl group in terms of excellent hole transport properties). Group, ethyl group, linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, methoxy group, ethoxy group, linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and 1 to 3 carbon atoms A halogenated alkyl group of 1 to 3, a halogenated alkoxy group of 1 to 3 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aryloxy group of 6 to 18 carbon atoms, a heteroaryl group of 3 to 20 carbon atoms, 3 to 3 carbon atoms May have one or more substituents selected from the group consisting of 18 trialkylsilyl groups, 18 to 40 carbon triarylsilyl groups, cyano groups, halogen atoms, and deuterium atoms), methyl Group, ethyl group, C3-C18 linear, branched, or cyclic alkyl group, methoxy group, ethoxy group, C3-C18 linear, branched, or cyclic alkoxy group, C6-C18 Are preferably an aryloxy group, a cyano group, a deuterium atom, or a hydrogen atom.

  Among these, a phenyl group, a naphthyl group, or a biphenyl group (these groups are each independently a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, An ethoxy group, a C3-C18 linear, branched, or cyclic alkoxy group, a cyano group, fluorine, and a substituent selected from the group consisting of a deuterium atom), methyl Group, ethyl group, C3-C18 linear, branched, or cyclic alkyl group, methoxy group, ethoxy group, C3-C18 linear, branched, or cyclic alkoxy group, phenoxy group, cyano group And more preferably a deuterium atom or a hydrogen atom.

  Of these, a phenyl group, a methyl group, a methoxy group, a cyano group, a deuterium atom, or a hydrogen atom is more preferable.

In the benzothienofluorene compound represented by the general formula (1), Ar ¹ and Ar ² are connected directly or via —O—, —NH—, —CH ₂ —, or —S—, and contain 5-membered nitrogen. A ring or a 6-membered ring may be formed. Examples of the substituent composed of Ar ¹ , Ar ² , and a single bond or a linking group are not particularly limited, and examples thereof include a carbazole group, a carboline group, a phenoxazine group, a phenothiazine group, or a phenazine group. It is done.

When Ar ¹ and Ar ² are linked, they are preferably linked directly or via —O— or —S—, more preferably directly, from the viewpoint of excellent hole transport properties.

  Although the preferable compound is illustrated below about the benzothienofluorene compound of this invention, it is not limited to these compounds.

前記一般式（１）で表されるベンゾチエノフルオレン化合物は、例えば、ハロゲン原子を有する化合物（８）を公知の方法（Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ，１９９８年，第３９巻，２３６７頁）でアミノ化することにより合成することができる。具体的には、下記のスキーム１に従って合成することができる。

The benzothienofluorene compound represented by the general formula (1) is obtained by, for example, aminating a compound (8) having a halogen atom by a known method (Tetrahedron Letters, 1998, Vol. 39, page 2367). Can be synthesized. Specifically, it can be synthesized according to the following scheme 1.

  A compound having at least one halogen atom by coupling the compound (3) having at least two halogen atoms and the boronic acid compound represented by the general formula (4) using a transition metal catalyst in the presence of a base (5) is obtained. Subsequently, the compound (5) is Grignarded or lithiated, reacted with the carbonyl compound represented by the general formula (6), and quenched with an acid to obtain the alcohol form (7). Next, the alcohol form (7) is cyclized in the presence of an acid catalyst to derive the compound (8). Furthermore, the compound (8) and the secondary amine compound (9) are reacted using a copper catalyst or a palladium catalyst in the presence of a base.

（式中、Ａｒ^１〜Ａｒ^３、Ｍ及びＲ^１〜Ｒ^１０は前記と同義であり、Ｘ^１〜Ｘ^３は各々独立してハロゲン原子［ヨウ素、臭素、塩素、又はフッ素］を表す。Ａｒ^１とＡｒ^２は直接又は−Ｏ−、−ＮＨ−、−ＣＨ_２−、若しくは−Ｓ−を介して連結し、含窒素５員環又は６員環を形成してもよい。）
本発明の前記一般式（１）で表されるベンゾチエノフルオレン化合物は、有機ＥＬ素子の発光層、正孔輸送層又は正孔注入層として使用することができる。

(In the formula, Ar ^{1 to} Ar ³ , M and R ^{1 to} R ¹⁰ are as defined above, and X ^{1 to} X ³ each independently represent a halogen atom [iodine, bromine, chlorine, or fluorine]. ¹ and Ar ² may be linked directly or via —O—, —NH—, —CH ₂ —, or —S— to form a nitrogen-containing 5-membered ring or 6-membered ring.
The benzothienofluorene compound represented by the general formula (1) of the present invention can be used as a light emitting layer, a hole transport layer or a hole injection layer of an organic EL device.

  In particular, since the benzothienofluorene compound represented by the general formula (1) is excellent in hole transport ability, when used as a hole transport layer and / or a hole injection layer, low driving of an organic EL device is achieved. Voltage, high luminous efficiency, and improved durability can be realized. In addition, since the benzothienofluorene compound represented by the general formula (1) has a higher triplet level than a conventional material, in an element using not only a fluorescent light emitting material but also a phosphorescent light emitting material for a light emitting layer. In addition, high luminous efficiency can be obtained.

  In the light-emitting layer when the benzothienofluorene compound represented by the general formula (1) is used as a hole injection layer and / or a hole transport layer of an organic EL device, known fluorescent or conventionally used Phosphorescent materials can be used. The light emitting layer may be formed of only one kind of light emitting material, or one or more kinds of light emitting materials may be doped in the host material.

  When forming the hole injection layer and / or hole transport layer composed of the benzothienofluorene compound represented by the general formula (1), two or more kinds of materials may be contained or laminated as necessary. Well, for example, oxides such as molybdenum oxide, 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, A known electron-accepting material such as hexacyanohexaazatriphenylene may be contained or laminated.

  Moreover, the benzothienofluorene compound represented by the general formula (1) of the present invention can also be used as a light emitting layer of an organic EL device. When the benzothienofluorene compound represented by the general formula (1) is used as the light emitting layer of the organic EL device, the benzothienofluorene compound is used alone, used by doping a known light emitting host material, or known The light emitting dopant can be used by doping.

  Examples of a method for forming a hole injection layer, a hole transport layer, or a light emitting layer containing the benzothienofluorene compound represented by the general formula (1) include a vacuum deposition method, a spin coating method, and a casting method. A known method can be applied.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited by these Examples.

¹ H-NMR and ¹³ C-NMR measurements were performed using Gemini 200 manufactured by Varian.

  FDMS measurement was performed using M-80B manufactured by Hitachi, Ltd.

  The light emission characteristics of the organic EL element were evaluated by applying a direct current to the produced element and using a luminance meter of LUMINANCEMETER (BM-9) manufactured by TOPCON.

合成例１ （［式（１０）］の合成）
窒素気流下、５００ｍＬの三口フラスコに、１，２−ジブロモベンゼン ２３．５ｇ（１００．８ｍｍｏｌ）、ジベンゾチオフェン−４−ボロン酸 ２３．０ｇ（１００．８ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム ３．４ｇ（３．０ｍｍｏｌ）、テトラヒドロフラン １２０ｍＬ、４０ｗｔ％のりん酸三カリウム水溶液 １３３ｇ（りん酸三カリウムとして２５２．１ｍｍｏｌ）を加え、１５時間加熱還流した。室温まで冷却した後、水層と有機層を分液し、有機層を飽和塩化アンモニウム水溶液と飽和塩化ナトリウム水溶液で洗浄した。無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。残渣をシリカゲルカラムクロマトグラフィー（ヘキサン）で精製し、更にヘキサンで再結晶することにより、［式（１０）］の白色結晶を１７．０ｇ（５０．２ｍｍｏｌ）単離した（収率５０％）。

Synthesis Example 1 (Synthesis of [Formula (10)])
2. In a 500 mL three-necked flask under a nitrogen stream, 1,2-dibromobenzene 23.5 g (100.8 mmol), dibenzothiophene-4-boronic acid 23.0 g (100.8 mmol), tetrakis (triphenylphosphine) palladium. 4 g (3.0 mmol), 120 mL of tetrahydrofuran, and 133 g of a 40 wt% tripotassium phosphate aqueous solution (252.1 mmol as tripotassium phosphate) were added and heated to reflux for 15 hours. After cooling to room temperature, the aqueous layer and the organic layer were separated, and the organic layer was washed with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane), and further recrystallized from hexane to isolate 17.0 g (50.2 mmol) of white crystals of [Formula (10)] (yield 50%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.16 (d, 2H), 7.75 (t, 2H), 7.21-7.57 (m, 7H)
¹³ C-NMR (CDCl ₃ ); 140.45, 139.21, 139.15, 135.60, 135.27, 132.72, 130.45, 129.24, 127.10, 127.05, 126 31, 123.97, 123.91, 122.71, 122.25, 121.31, 120.45.

合成例２ （［式（１１）］の合成）
窒素気流下、１００ｍＬの三口フラスコに、マグネシウム ３９３ｍｇ（１６．２ｍｍｏｌ）と脱水テトラヒドロフラン １０ｍｌを仕込み、脱水テトラヒドロフラン ２０ｍｌに溶解させた式（１０） ５．０ｇ（１４．７ｍｍｏｌ）を滴下した。滴下終了後、反応液を４０℃に加熱し、３０分間攪拌して式（１０）のグリニヤール溶液を調整した。別途準備した２００ｍＬの三口フラスコに、４−ベンゾイル−４’−ブロモビフェニル ４．７ｇ（１４．０ｍｍｏｌ）と脱水テトラヒドロフラン ５０ｍｌを加え、そこに、調整したグリニヤール溶液を滴下して、５０℃で一晩攪拌した。室温まで冷却後、飽和塩化アンモニウム水溶液 ５０ｇを加えて分液し、有機層を飽和塩化ナトリウム水溶液で洗浄し、無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。次に、濃縮後に得られたオイル状の生成物に酢酸 ３０ｍｌ及び濃硫酸 １．３ｇ（１４．０ｍｍｏｌ）を添加し、１００℃で３０分間反応させた。室温まで冷却後、析出した粉末をろ取し、純水とメタノールで洗浄することにより、式（１１）の白色粉末を３．６ｇ（６．３ｍｍｏｌ）単離した（収率４５％）。

Synthesis Example 2 (Synthesis of [Formula (11)])
Under a nitrogen stream, 393 mg (16.2 mmol) of magnesium and 10 ml of dehydrated tetrahydrofuran were charged into a 100 mL three-necked flask, and 5.0 g (14.7 mmol) of the formula (10) dissolved in 20 ml of dehydrated tetrahydrofuran was added dropwise. After completion of dropping, the reaction solution was heated to 40 ° C. and stirred for 30 minutes to prepare a Grignard solution of the formula (10). To a separately prepared 200 mL three-necked flask, 4.7 g (14.0 mmol) of 4-benzoyl-4′-bromobiphenyl and 50 ml of dehydrated tetrahydrofuran are added, and the prepared Grignard solution is added dropwise thereto at 50 ° C. overnight. Stir. After cooling to room temperature, 50 g of a saturated aqueous ammonium chloride solution was added for liquid separation, and the organic layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Next, 30 ml of acetic acid and 1.3 g (14.0 mmol) of concentrated sulfuric acid were added to the oily product obtained after concentration, and reacted at 100 ° C. for 30 minutes. After cooling to room temperature, the precipitated powder was collected by filtration and washed with pure water and methanol to isolate 3.6 g (6.3 mmol) of a white powder of formula (11) (yield 45%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.02-8.17 (m, 3H) 7.95 (t, 1H), 7.20-7.56 (m, 19H)
¹³ C-NMR (CDCl ₃ ); 151.20, 149.55, 144.79, 144.63, 139.11, 139.02, 138.88, 137.83, 135.41, 134.44, 133 78, 131.29, 128.22, 128.00, 127.85, 127.69, 127.36, 127.21, 126.40, 126.26, 125.51, 124.23, 122.49 121.94, 121.91, 121.11, 120.95, 120.36, 65.40.

合成例３（［式（１３）］の合成）
窒素気流下、５０ｍＬの三口フラスコに、マグネシウム ５１１ｍｇ（２１．１ｍｍｏｌ）と脱水テトラヒドロフラン ５ｍＬを仕込み、脱水テトラヒドロフラン ２０ｍＬに溶解させた式（１０） ６．５ｇ（１９．２ｍｍｏｌ）を滴下した。滴下終了後、反応液を４０℃に加熱し、３０分間攪拌して式（１０）のグリニヤール溶液を調整した。別途準備した２００ｍＬの三口フラスコに、４−ブロモベンゾフェノン ４．７ｇ（１８．２ｍｍｏｌ）と脱水テトラヒドロフラン ５０ｍＬを加え、そこに、調整したグリニヤール溶液を滴下して、６０℃で一晩攪拌した。室温まで冷却後、飽和塩化アンモニウム水溶液 ５０ｇを加えて分液し、有機層を飽和塩化ナトリウム水溶液で洗浄し、無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。次に、濃縮後に得られたオイル状の生成物に酢酸 ６０ｍＬ及び濃硫酸 １．７ｇ（１８．０ｍｍｏｌ）を添加し、１００℃で３０分間反応させた。室温まで冷却後、析出した粉末をろ取し、純水とメタノールで洗浄することにより、式（１３）の白色粉末を８．１ｇ（１６．１ｍｍｏｌ）単離した（収率８８％）。

Synthesis Example 3 (Synthesis of [Formula (13)])
Under a nitrogen stream, 511 mg (21.1 mmol) of magnesium and 5 mL of dehydrated tetrahydrofuran were charged into a 50 mL three-necked flask, and 6.5 g (19.2 mmol) of the formula (10) dissolved in 20 mL of dehydrated tetrahydrofuran was added dropwise. After completion of dropping, the reaction solution was heated to 40 ° C. and stirred for 30 minutes to prepare a Grignard solution of the formula (10). To a separately prepared 200 mL three-necked flask, 4.7 g (18.2 mmol) of 4-bromobenzophenone and 50 mL of dehydrated tetrahydrofuran were added, and the adjusted Grignard solution was added dropwise thereto and stirred at 60 ° C. overnight. After cooling to room temperature, 50 g of a saturated aqueous ammonium chloride solution was added for liquid separation, and the organic layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Next, 60 mL of acetic acid and 1.7 g (18.0 mmol) of concentrated sulfuric acid were added to the oily product obtained after concentration, and reacted at 100 ° C. for 30 minutes. After cooling to room temperature, the precipitated powder was collected by filtration and washed with pure water and methanol to isolate 8.1 g (16.1 mmol) of the white powder of formula (13) (yield 88%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.13 (t, 1H), 8.05 (d, 1H), 8.01-8.08 (m, 1H), 7.93 (t, 1H), 7 .43-7.52 (m, 5H) 7.31-7.35 (m, 3H), 7.21 (s, 5H), 7.10 (d, 2H)
¹³ C-NMR (CDCl ₃ ); 151.70, 149.99, 145.27, 145.09, 139.95, 139.65, 136.33, 135.21, 134.56, 132.69, 131 68, 130.27, 128.72, 128.39, 128.28, 128.08, 127.31, 127.11, 126.20, 125.06, 123.30, 122.79, 122.55 121.94, 121.22, 121.19, 65.91.
Example 1 (Synthesis of Compound (A48))
In a 50 mL three-necked flask under a nitrogen stream, 3.5 g (6.0 mmol) of the formula (11) obtained in Synthesis Example 2, 1.9 g (6.0 mmol) of N, N-bisbiphenylamine, sodium-tert- 0.81 g (8.4 mmol) of butoxide and 10 mL of o-xylene were added, and 27 mg (0.12 mmol) of palladium acetate and 85 mg (0.42 mmol) of tri (tert-butyl) phosphine were added to the slurry reaction solution. Stir at 0 ° C. for 3 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 1)), and 3.2 g (3.9 mmol) of a pale yellow glassy solid of the compound (A48) was isolated (yield). Rate 65%).

The compound was identified by ¹ H-NMR measurement, ¹³ C-NMR, and FDMS measurement.
¹ H-NMR (CDCl ₃ ); 8.18 (t, 1H), 8.12 (d, 1H), 8.05 (d, 1H), 7.97 (t, 1H), 7.17-7 .58 (m, 37H)
¹³ C-NMR (CDCl ₃ ); 152.19, 150.55, 147.06, 145.79, 144.47, 140.85, 139.94, 139.68, 139.32, 136.17, 135 .90, 135.34, 135.29, 134.59, 132.61, 129.02, 128.91, 128.59, 128.50, 128.15, 128.07, 127.99, 127.13 , 127.15, 127.00, 126.96, 126.81, 126.34, 125.00, 124.70, 124.56, 123.28, 122.75, 122.69, 121.88, 121 .11, 66.13
FDMS: 819
Example 2 (Synthesis of Compound (A7))
In a 50 mL three-necked flask under a nitrogen stream, 3.6 g (7.1 mmol) of the formula (13) obtained in Synthesis Example 3 and 1.5 g (7.1 mmol) of N-phenyl-N- (1-naphthyl) amine were obtained. , Sodium-tert-butoxide 0.96 g (10.0 mmol) and o-xylene 15 mL were added, and palladium acetate 32 mg (0.14 mmol) and tri (tert-butyl) phosphine 101 mg (0.50 mmol) And stirred at 130 ° C. for 3 hours. After cooling to room temperature, 20 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)), and 3.8 g (6.0 mmol) of a pale yellow glassy solid of compound (A7) was isolated (recovery). 84%).

The compound was identified by FDMS measurement.
FDMS: 641
Example 3 (Synthesis of Compound (A14))
In a 50 mL three-necked flask under a nitrogen stream, 1.1 g (2.2 mmol) of the formula (13) obtained in Synthesis Example 3 and 0.72 g (2.2 mmol) of N-phenyl-N- (p-terphenyl) amine were obtained. ), 0.30 g (3.1 mmol) of sodium-tert-butoxide and 5 mL of o-xylene, and 10 mg (0.45 mmol) of palladium acetate and 31 mg (0.15 mmol) of tri (tert-butyl) phosphine were added to the slurry reaction solution. ) Was added and stirred at 130 ° C. for 2 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)), and 1.3 g (1.7 mmol) of a pale yellow glassy solid of compound (A14) was isolated (yield). 79%).

The compound was identified by FDMS measurement.
FDMS: 743
Example 4 (Synthesis of Compound (A19))
In a 50 mL three-necked flask under a nitrogen stream, 4.2 g (8.4 mmol) of the formula (13) obtained in Synthesis Example 3 and N-phenyl-N- (9,9-dimethylfluoren-2-yl) amine 2 .4 g (8.4 mmol), sodium-tert-butoxide 1.1 g (11.8 mmol) and o-xylene 15 mL were added, and palladium acetate 37 mg (0.16 mmol), tri (tert-butyl) was added to the slurry reaction solution. 118 mg (0.58 mmol) of phosphine was added and stirred at 130 ° C. for 5 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 2)), and 4.8 g (6.8 mmol) of a colorless glassy solid of compound (A19) was isolated (yield) 82%).

The compound was identified by FDMS measurement.
FDMS: 707
Example 5 (Synthesis of Compound (A25))
In a 50 mL three-necked flask under a nitrogen stream, 2.5 g (5.0 mmol) of the formula (13) obtained in Synthesis Example 3 and N-phenyl-N- (4- (4-dibenzothienyl) phenyl) amine 7 g (5.0 mmol), 0.67 g (7.0 mmol) of sodium-tert-butoxide, and 10 mL of o-xylene were added, and 22 mg (0.10 mmol) of palladium acetate and tri (tert-butyl) phosphine were added to the slurry reaction solution. 71 mg (0.35 mmol) was added and stirred at 130 ° C. for 10 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)), and 2.9 g (3.7 mmol) of a pale yellow glassy solid of compound (A25) was isolated (yield). Rate 75%).

The compound was identified by FDMS measurement.
FDMS: 773
Example 6 (Synthesis of Compound (A27))
In a 50 mL three-necked flask under a nitrogen stream, 3.1 g (6.2 mmol) of the formula (13) obtained in Synthesis Example 3 and N-phenyl-N- (4- (4-dibenzofuranyl) phenyl) amine 2 0.1 g (6.2 mmol), 0.84 g (8.7 mmol) of sodium-tert-butoxide, and 15 mL of o-xylene were added, and 28 mg (0.12 mmol) of palladium acetate and tri (tert-butyl) were added to the slurry reaction solution. 88 mg (0.43 mmol) of phosphine was added and stirred at 130 ° C. for 6 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)), and 3.1 g (4.1 mmol) of a pale yellow glassy solid of compound (A27) was isolated (recovery). 66%).

The compound was identified by FDMS measurement.
FDMS: 757
Example 7 (Synthesis of Compound (A47))
In a 50 mL three-necked flask under nitrogen flow, 0.68 g (1.1 mmol) of the formula (11) obtained in Synthesis Example 2 and 0.30 g of N- (p-tolyl) -N- (4-biphenyl) amine ( 1.1 mmol), 0.15 g (1.6 mmol) of sodium-tert-butoxide, and 8 mL of o-xylene, and 5 mg (0.02 mmol) of palladium acetate and 16 mg of tri (tert-butyl) phosphine were added to the slurry reaction solution. 0.08 mmol) was added and the mixture was stirred at 130 ° C. for 2 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 2)), and 0.68 g (0.91 mmol) of a colorless glassy solid of compound (A47) was isolated (yield) 83%).

The compound was identified by FDMS measurement.
FDMS: 757
Example 8 (Synthesis of Compound (A50))
In a 50 mL three-necked flask under a nitrogen stream, 0.83 g (1.4 mmol) of the formula (11) obtained in Synthesis Example 2 and 0.38 g (1.4 mmol) of N-phenyl-N- (2-dibenzothienyl) amine were obtained. ), 0.19 g (2.0 mmol) of sodium-tert-butoxide and 5 mL of o-xylene, and 6 mg (0.03 mmol) of palladium acetate and 20 mg (0.10 mmol) of tri (tert-butyl) phosphine in the slurry reaction solution. ) Was added and stirred at 130 ° C. for 5 hours. After cooling to room temperature, 5 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)), and 0.75 g (0.98 mmol) of a pale yellow glassy solid of compound (A50) was isolated (recovery). 70%).

The compound was identified by FDMS measurement.
FDMS: 773
Example 9 (Synthesis of Compound (A51))
In a 50 mL three-necked flask under a nitrogen stream, 0.83 g (1.4 mmol) of the formula (11) obtained in Synthesis Example 2 and 0.36 g of N-phenyl-N- (2-dibenzofuranyl) amine (1. 4 mmol), 0.19 g (2.0 mmol) of sodium-tert-butoxide, 5 mL of o-xylene, and 6 mg (0.03 mmol) of palladium acetate and 20 mg (0. 0 of tri (tert-butyl) phosphine) in the slurry-like reaction solution. 10 mmol) was added and stirred at 130 ° C. for 5 hours. After cooling to room temperature, 5 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 1)), and 0.85 g (1.1 mmol) of a pale yellow glassy solid of the compound (A51) was isolated (recovery). Rate 81%).

The compound was identified by FDMS measurement.
FDMS: 757
Example 10 (Synthesis of Compound (A86))
In a 50 mL three-necked flask under a nitrogen stream, 2.7 g (5.3 mmol) of the formula (13) obtained in Synthesis Example 3 and 1.5 g of N-phenyl-N- (4- (1-naphthyl) phenyl) amine were obtained. (5.3 mmol), 0.72 g (7.5 mmol) of sodium-tert-butoxide and 10 mL of o-xylene were added, and 12 mg (0.05 mmol) of palladium acetate and 37 mg of tri (tert-butyl) phosphine were added to the slurry reaction solution. (0.18 mmol) was added and stirred at 130 ° C. for 7 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)), and 3.3 g (4.6 mmol) of a pale yellow glassy solid of compound (A86) was isolated (recovery). Rate 87%).

The compound was identified by FDMS measurement.
FDMS: 717
Example 11 (Synthesis of Compound (A89))
In a 50 mL three-necked flask under a nitrogen stream, 2.1 g (4.1 mmol) of the formula (13) obtained in Synthesis Example 3 and 1.1 g (4.1 mmol) of N-phenyl-N- (9-phenanthryl) amine were obtained. , Sodium-tert-butoxide 0.56 g (5.8 mmol) and o-xylene 10 mL were added, and 9 mg (0.04 mmol) of palladium acetate and 29 mg (0.14 mmol) of tri (tert-butyl) phosphine were added to the slurry reaction solution. And stirred at 130 ° C. for 8 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (a mixed solvent of toluene and hexane (volume ratio = 1: 1)), and 2.0 g (2.9 mmol) of a pale yellow glassy solid of compound (A89) was isolated (yield). 71%).

The compound was identified by FDMS measurement.
FDMS: 691
Example 12 (Synthesis of Compound (A93))
In a 50 mL three-neck flask under a nitrogen stream, 1.7 g (3.5 mmol) of the formula (13) obtained in Synthesis Example 3 and 1.1 g of N-phenyl-N- (4- (9-carbazolyl) phenyl) amine were obtained. (3.5 mmol), 0.47 g (4.9 mmol) of sodium-tert-butoxide and 10 mL of o-xylene were added, and 8 mg (0.03 mmol) of palladium acetate and 24 mg of tri (tert-butyl) phosphine were added to the slurry reaction solution. (0.12 mmol) was added and stirred at 130 ° C. for 3 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)), and 2.0 g (2.7 mmol) of a colorless glassy solid of compound (A93) was isolated (yield) 77%).

The compound was identified by FDMS measurement.
FDMS: 756
Example 13 (Synthesis of Compound (A95))
In a 50 mL three-necked flask under nitrogen stream, 1.5 g (3.0 mmol) of the formula (13) obtained in Synthesis Example 3 and 1.0 g of N-phenyl-N- (9-phenylcarbazol-3-yl) amine were obtained. (3.0 mmol), 0.40 g (4.2 mmol) of sodium-tert-butoxide and 10 mL of o-xylene were added, and 13 mg (0.06 mmol) of palladium acetate and 42 mg of tri (tert-butyl) phosphine were added to the slurry reaction solution. (0.21 mmol) was added and stirred at 130 ° C. for 2 hours. After cooling to room temperature, 10 mL of pure water was added and stirred. Next, the aqueous layer and the organic layer were separated, and the organic layer was further washed with pure water and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane (volume ratio = 1: 1)), and 1.8 g (2.4 mmol) of a colorless glassy solid of compound (A95) was isolated (yield) 80%).

The compound was identified by FDMS measurement.
FDMS: 756
Example 14 (Element evaluation of compound (A48))
The glass substrate on which the ITO transparent electrode (anode) having a thickness of 200 nm was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Furthermore, ultraviolet ozone cleaning was performed, and after evacuation with a vacuum pump until it was 1 × 10 ⁻⁴ Pa after installation in a vacuum deposition apparatus. First, copper phthalocyanine was deposited on the ITO transparent electrode at a deposition rate of 0.1 nm / second to form a 25 nm hole injection layer. Subsequently, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD) was deposited at a deposition rate of 0.3 nm / second to 20 nm, and then compound (A48) was deposited at a deposition rate of 0. A 25-nm vapor deposition was performed at 3 nm / second to form two hole transport layers. Subsequently, 4,4′-bis (2- (4- (N, N-diphenylamino) phenyl) vinyl) biphenyl (DPAVBi) as a light emitting dopant material and 2-tert-butyl-9,10 as a host material. -Di (2-naphthyl) anthracene (TBADN) was co-deposited at a deposition rate of 0.25 nm / second so that the weight ratio was 3:97, to obtain a 40 nm light-emitting layer. Next, tris (8-quinolinolato) aluminum (Alq ₃ ) was vapor-deposited at 0.3 nm / second to form a 20 nm electron transport layer. Subsequently, lithium fluoride was deposited as an electron injection layer by 1 nm at a deposition rate of 0.01 nm / second, and aluminum was deposited by 100 nm at a deposition rate of 0.25 nm / second to form a cathode. In a nitrogen atmosphere, a sealing glass plate was bonded with a UV curable resin to obtain an organic EL element for evaluation. A current of 20 mA / cm ² was applied to the device thus fabricated, and driving voltage, current efficiency, and luminance half time were measured. The results are shown in Table 1.

Examples 15 to 26 (Element evaluation)
Compound (A48) is converted into Compound (A7), (A14), (A19), (A25), (A27), (A47), (A50), (A51), (A86), (A89), (A93), Or the organic EL element similar to Example 14 was produced except having changed into (A95). Table 1 shows the drive voltage and current efficiency when a current of 20 mA / cm ² was applied.

Comparative Example 1
An organic EL device was produced in the same manner as in Example 14 except that the compound (A48) was changed to NPD. Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied.
Comparative Example 2
An organic EL device was produced in the same manner as in Example 14 except that the compound (A48) was changed to the comparative compound (1). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied. Comparative compound (1) was synthesized according to the examples described in EP2450975.
Comparative Example 3
An organic EL device was produced in the same manner as in Example 14 except that the compound (A48) was changed to the comparative compound (2). Table 1 shows the driving voltage and current efficiency when a current of 20 mA / cm ² was applied. Comparative compound (2) was synthesized according to the following scheme.

式（１４）の合成
窒素気流下、２００ｍＬの三口フラスコに、マグネシウム ７８７ｍｇ（３２．５ｍｍｏｌ）と脱水テトラヒドロフラン ２０ｍＬを仕込み、脱水テトラヒドロフラン ４０ｍＬに溶解させた式（１０） １０．０ｇ（２９．５ｍｍｏｌ）を滴下した。滴下終了後、反応液を４０℃に加熱し、３０分間攪拌して式（１０）のグリニヤール溶液を調整した。別途準備した３００ｍＬの三口フラスコに、２−ブロモフルオレノン ７．２ｇ（２８．１ｍｍｏｌ）と脱水テトラヒドロフラン ５０ｍＬを加え、そこに、調整したグリニヤール溶液を滴下して、５０℃で一晩攪拌した。室温まで冷却後、飽和塩化アンモニウム水溶液 １００ｇを加えて分液し、有機層を飽和塩化ナトリウム水溶液で洗浄し、無水硫酸マグネシウムで乾燥後、減圧下に濃縮した。次に、濃縮後に得られた薄黄色粉末の生成物に酢酸 ９０ｍＬ及び濃硫酸 ２．７ｇ（２８．１ｍｍｏｌ）を添加し、１００℃で３０分間反応させた。室温まで冷却後、析出した粉末をろ取し、純水とメタノールで洗浄することにより、式（１４）の白色粉末を１２．４ｇ（２４．７ｍｍｏｌ）単離した（収率８８％）。

Synthesis of Formula (14) Under a nitrogen stream, 10.0 g (29.5 mmol) of Formula (10) dissolved in 40 mL of dehydrated tetrahydrofuran was charged with 787 mg (32.5 mmol) of magnesium and 20 mL of dehydrated tetrahydrofuran in a 200 mL three-necked flask. It was dripped. After completion of dropping, the reaction solution was heated to 40 ° C. and stirred for 30 minutes to prepare a Grignard solution of the formula (10). To a separately prepared 300 mL three-necked flask, 7.2 g (28.1 mmol) of 2-bromofluorenone and 50 mL of dehydrated tetrahydrofuran were added, and the adjusted Grignard solution was added dropwise thereto, followed by stirring at 50 ° C. overnight. After cooling to room temperature, 100 g of a saturated aqueous ammonium chloride solution was added for liquid separation, and the organic layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Next, 90 mL of acetic acid and 2.7 g (28.1 mmol) of concentrated sulfuric acid were added to the product of the light yellow powder obtained after concentration, and reacted at 100 ° C. for 30 minutes. After cooling to room temperature, the precipitated powder was collected by filtration and washed with pure water and methanol to isolate 12.4 g (24.7 mmol) of the white powder of formula (14) (yield 88%).

The compound was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.08-8.17 (m, 2H), 7.92-8.01 (m, 2H), 7.83 (d, 1H), 7.72 (d, 1H), 7.46-7.57 (m, 4H), 7.37 (t, 1H), 7.08-7.24 (m, 2H), 6.79-6.86 (m, 3H) , 6.72 (d, 1H)
¹³ C-NMR (CDCl ₃ ); 149.84, 147.85, 147.58, 146.35, 140.38, 140.30, 140.19, 139.02, 135.85, 134.48, 131 64, 130.54, 127.83, 127.74, 127.56, 127.36, 126.81, 126.30, 124.23, 123.64, 123.42, 122.52, 121.68 , 121.15, 121.00, 120.89, 120.51, 119.74, 119.63, 65.87
Synthesis of Comparative Compound (2) In a 100 mL three-necked flask under a nitrogen stream, 6.0 g (12.0 mmol) of formula (14), 3.8 g (12.0 mmol) of N, N-bisbiphenylamine, sodium-tert- 1.6 g (16.8 mmol) of butoxide and 30 mL of o-xylene were added, and 26 mg (0.12 mmol) of palladium acetate and 84 mg (0.42 mmol) of tri (tert-butyl) phosphine were added to the slurry reaction solution. Stir for 2 hours at ° C. After cooling to room temperature, 20 mL of pure water was added and stirred. The precipitated product was collected by filtration, washed with pure water and methanol, and dried. The obtained brown powder was recrystallized from o-xylene, and 6.2 g (8.3 mmol) of a white powder of comparative compound (2) was isolated (yield 70%).

  The compound was identified by FDMS measurement.

  FDMS: 741

  The benzothienofluorene compound of the present invention can be used as a light emitting material, a hole injection material, or a hole transport material of an organic EL device. In particular, the benzothienofluorene compound of the present invention is useful as a hole injection material or a hole transport material because of its excellent hole transport ability. Furthermore, the benzothienofluorene compound of the present invention is not only used as a hole injection material or a hole transport material of an organic EL device or an electrophotographic photoreceptor, but also to an organic device such as an organic thin film solar cell, an organic transistor, or an image sensor. Application is also possible.

Claims (6)

General formula (1)

(Where
Ar ^{1 to} Ar ³ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, ethyl group, Group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and a halogenated group having 1 to 3 carbon atoms An alkyl group, a C 1-3 halogenated alkoxy group, a C 6-20 aryl group, a C 6-18 aryloxy group, a C 3-20 heteroaryl group, a C 3-18 tri It may have one or more substituents selected from the group consisting of an alkylsilyl group, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a halogen atom, and a deuterium atom].
M is a bivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, ethyl group, carbon A linear, branched, or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, C1-C3 halogenated alkoxy group, C6-C12 aryl group, C6-C18 aryloxy group, C3-C20 heteroaryl group, C3-C18 trialkylsilyl group And may have one or more substituents selected from the group consisting of a C18-C40 triarylsilyl group, cyano group, halogen atom, and deuterium atom].
R ^{1 to} R ¹⁰ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, ethyl group, Group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and a halogenated group having 1 to 3 carbon atoms An alkyl group, a C 1-3 halogenated alkoxy group, a C 6-20 aryl group, a C 6-18 aryloxy group, a C 3-20 heteroaryl group, a C 3-18 tri An alkylsilyl group, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a halogen atom, and one or more substituents selected from the group consisting of deuterium atoms may be present], a methyl group, an ethyl group , A straight chain having 3 to 18 carbon atoms, Bi- or cyclic alkyl group, methoxy group, ethoxy group, linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, aryloxy having 6 to 18 carbon atoms Group, a trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a halogen atom, a deuterium atom, or a hydrogen atom.
Ar ¹ and Ar ² may be linked directly or via —O—, —NH—, —CH ₂ —, or —S— to form a nitrogen-containing 5-membered ring or 6-membered ring. )
A benzothienofluorene compound represented by: M is a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, or a fluorene-diyl group (these groups are each independently a methyl group, an ethyl group, a straight chain having 3 to 18 carbon atoms, branched, or A cyclic alkyl group, a methoxy group, an ethoxy group, a linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, An aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a trialkylsilyl group having 3 to 18 carbon atoms, and a triarylsilyl group having 18 to 40 carbon atoms , A cyano group, a halogen atom and a substituent selected from the group consisting of deuterium atoms (which may have one or more substituents selected from the group consisting of deuterium atoms), Benzothienopyridine fluorene compound according to 1. Ar ¹ and Ar ² are each independently a phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group, fluorenyl group, benzofluorenyl group, dibenzothienyl group, dibenzofuranyl group, or carbazolyl group ( These groups are each independently a methyl group, an ethyl group, a C3-C18 linear, branched, or cyclic alkyl group, a methoxy group, an ethoxy group, a C3-C18 linear, branched, Or a cyclic alkoxy group, a C1-C3 halogenated alkyl group, a C6-C20 aryl group, a C6-C18 aryloxy group, a C3-C20 heteroaryl group, a C3-C3 One or more substituents selected from the group consisting of 18 trialkylsilyl groups, 18 to 40 carbon triarylsilyl groups, cyano groups, halogen atoms, and deuterium atoms And characterized in that it is also may) have, according to claim 1 or benzothienopyridine fluorene compound according to claim 2. R ^{1 to} R ¹⁰ are each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, or a fluorenyl group (these groups are each independently a methyl group, an ethyl group, a carbon number of 3 to 18). A linear, branched or cyclic alkyl group, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a carbon number of 1 to 3 halogenated alkoxy groups, aryl groups having 6 to 20 carbon atoms, aryloxy groups having 6 to 18 carbon atoms, heteroaryl groups having 3 to 20 carbon atoms, trialkylsilyl groups having 3 to 18 carbon atoms, 18 carbon atoms May have one or more substituents selected from the group consisting of ˜40 triarylsilyl groups, cyano groups, halogen atoms, and deuterium atoms), methyl groups, ethyl groups, and those having 3 to 18 carbon atoms. straight A branched or cyclic alkyl group, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a cyano group, a deuterium atom, or The benzothienofluorene compound according to any one of claims 1 to 3, wherein the benzothienofluorene compound is a hydrogen atom. Ar ³ is a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, a benzofluorenyl group, a dibenzothienyl group, a dibenzofuranyl group, or a carbazolyl group (these groups are each independently A methyl group, an ethyl group, a C3-C18 linear, branched or cyclic alkyl group, a methoxy group, an ethoxy group, a C3-C18 linear, branched or cyclic alkoxy group, a carbon number 1 to 3 halogenated alkyl groups, aryl groups having 6 to 20 carbon atoms, aryloxy groups having 6 to 18 carbon atoms, heteroaryl groups having 3 to 20 carbon atoms, trialkylsilyl groups having 3 to 18 carbon atoms, carbon (It may have one or more substituents selected from the group consisting of a triarylsilyl group, a cyano group, a halogen atom, and a deuterium atom of formula 18 to 40). The benzothienofluorene compound according to any one of claims 1 to 4, characterized in that: A hole transport material, a hole injection material, or a light-emitting material containing the benzothienofluorene compound represented by the general formula (1).

(Where
Ar ^{1 to} Ar ³ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, ethyl group, Group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and a halogenated group having 1 to 3 carbon atoms An alkyl group, a C 1-3 halogenated alkoxy group, a C 6-20 aryl group, a C 6-18 aryloxy group, a C 3-20 heteroaryl group, a C 3-18 tri It may have one or more substituents selected from the group consisting of an alkylsilyl group, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a halogen atom, and a deuterium atom].
M is a bivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, ethyl group, carbon A linear, branched, or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched, or cyclic alkoxy group having 3 to 18 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, C1-C3 halogenated alkoxy group, C6-C12 aryl group, C6-C18 aryloxy group, C3-C20 heteroaryl group, C3-C18 trialkylsilyl group And may have one or more substituents selected from the group consisting of a C18-C40 triarylsilyl group, cyano group, halogen atom, and deuterium atom].
R ^{1 to} R ¹⁰ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms [these groups are each independently a methyl group, ethyl group, Group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and a halogenated group having 1 to 3 carbon atoms An alkyl group, a C 1-3 halogenated alkoxy group, a C 6-20 aryl group, a C 6-18 aryloxy group, a C 3-20 heteroaryl group, a C 3-18 tri An alkylsilyl group, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a halogen atom, and one or more substituents selected from the group consisting of deuterium atoms may be present], a methyl group, an ethyl group , A straight chain having 3 to 18 carbon atoms, Bi- or cyclic alkyl group, methoxy group, ethoxy group, linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, aryloxy having 6 to 18 carbon atoms Group, a trialkylsilyl group having 3 to 18 carbon atoms, a triarylsilyl group having 18 to 40 carbon atoms, a cyano group, a halogen atom, a deuterium atom, or a hydrogen atom.
Ar ¹ and Ar ² may be linked directly or via —O—, —NH—, —CH ₂ —, or —S— to form a nitrogen-containing 5-membered ring or 6-membered ring. )