JP2009191050A - Thiophene derivative, fluorescent material and luminescent material for organic electroluminescence each comprising the same, and organic electroluminescence element using the luminescent material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new thiophene derivative and to provide an organic eletroluminescence element using the same. <P>SOLUTION: Provided are a thiophene derivative represented by formula (1) (wherein R<SP>1</SP>and R<SP>2</SP>and R<SP>3</SP>to R<SP>6</SP>are each hydrogen, a 1-6C linear or branched alkyl group, or the like; Qs are groups independently selected from the group consisting of an arylamino group having a 6-16C aryl group which may be substituted, a 10-16C aromatic ring which may be substituted, and a 10-15C heterocyclic ring which may be substituted; and n is an integer of 1-4 provided that when n=1 and Q is the arylamino group, Q is not attached to the para position of the thiophene ring); a fluorescent material and a luminescent material for organic electroluminescence each comprising the same: and an organic electroluminescence element using the luminescent material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel thiophene derivative, a fluorescent material comprising the same, particularly a fluorescent material capable of exhibiting a wide range of fluorescence from blue to red, a light emitting material for organic electroluminescence, and an organic electroluminescent device using the same.

In recent years, display devices have been diversified, and a large number of devices with different light emission methods such as liquid crystal display (LCD), plasma display (PDP), surface conduction electron-emitting device display (SED), and organic electroluminescence display (OLED) have appeared. It was.
Recently, organic electroluminescence displays (OLEDs) have attracted particular attention.

  An organic electroluminescence display (OLED) is a self-luminous display like a plasma display (PDP), and does not require a backlight like a liquid crystal display (LCD). Therefore, the display can be made thin and lightweight, and is suitable as a display means for movement.

で示す４，４′−ビス［２，２−ビス（４−メチルフェニル）エテニル］−１，１′−ビフェニル（ＤＴＶＢｉ）が良く知られている。また緑色蛍光材料では、コダックのＴａｎｇらが最初に有機エレクトロルミネッセンスで使用した下記式

で示されるトリス（８−ヒドロキシキノリノラト）アルミニウム（Ａｌｑ_３）が良く用いられている（非特許文献２）。
また赤色蛍光材料については、レーザー色素としても良く用いられている下記式

で示す４−（ジシアノメチレン）−２−ｔ−ブチル−６−（１，１，７，７−テトラメチルジュロリジル−９−エニル）−４Ｈ−ピラン（ＤＣＪＴＢ）などのピラン化合物が良く用いられている（非特許文献３）。 Recent displays have been developed with full color technology to achieve higher definition. A wide variety of fluorescent materials are also used in organic electroluminescence displays. For example, in a blue fluorescent material, the following formula as shown in Non-Patent Document 1 by Enomoto et al.

4,4′-bis [2,2-bis (4-methylphenyl) ethenyl] -1,1′-biphenyl (DTVBi) is well known. For green fluorescent materials, Kodak's Tang et al. Used the following formula for organic electroluminescence.

Tris (8-hydroxyquinolinolato) aluminum (Alq ₃ ) is often used (Non-patent Document 2).
For red fluorescent materials, the following formula is often used as a laser dye:

A pyran compound such as 4- (dicyanomethylene) -2-t-butyl-6- (1,1,7,7-tetramethyljulolidyl-9-enyl) -4H-pyran (DCJTB) represented by (Non-patent Document 3).

  Such low molecular weight materials are generally formed by vacuum deposition, but the conditions differ depending on the material to be deposited. When vapor-depositing a certain material under a certain vacuum, if the vapor-deposition temperature is too high, the film-forming speed is too high, making it difficult to control the film thickness. In particular, in the case of a light-emitting layer containing a fluorescent dye, it is desirable that the blue, green, and red fluorescent dyes can be deposited under a constant temperature condition as much as possible because the film thickness and the doping concentration may greatly affect the device characteristics. For that purpose, it is important that the structures of the fluorescent dyes are as common as possible.

H. Tokalin, M .; Matsuura, H .; Higashi, C.I. Hosokawa and T.K. Kusumoto, SPIE processings, 1910, 38 (1993) C. W. Tang and S.M. A. VanSlyke, Appl. Phys. Lett. , 51, 913 (1987) C. H. Chen, C.I. W. Tang, J .; Shi and P.M. Klubek, Macromolecular Symposia (1997), 49-58, 125 (1998)

  An object of the present invention is to provide a novel thiophene derivative, a fluorescent material comprising the same, particularly a fluorescent material capable of exhibiting a wide range of fluorescence from blue to red, a light emitting material for organic electroluminescence, and an organic electroluminescent device using the same. In the point.

（Ｒ^１およびＲ^２は、水素または炭素数１〜６の直鎖あるいは分岐のアルキル基よりなる群からそれぞれ独立して選ばれた基であり、
Ｒ^３〜Ｒ^６は、水素、炭素数１〜６の直鎖あるいは分岐のアルキル基、炭素数１〜６の直鎖あるいは分岐のアルコキシ基および炭素数１〜６の直鎖あるいは分岐のアルキルアミノ基よりなる群からそれぞれ独立して選ばれた基であり、
Ｑは、
置換基を有することもある炭素数６〜１６のアリール基を有するアリールアミノ基、
置換基を有することもある炭素数１０〜１６の芳香族環、
置換基を有することもある炭素数１０〜１５の複素環
よりなる群からそれぞれ独立して選ばれた基であり、
ｎは１〜４の整数であるが、ｎ＝１の場合であって、Ｑが前記アリールアミノ基の場合には、Ｑがチオフェン環のｐ−位に付加することはない。）
で示されるチオフェン誘導体に関する。
本発明の第２は、下記一般式（２）

（Ｒ^１およびＲ^２は、水素または炭素数１〜６の直鎖あるいは分岐のアルキル基よりなる群からそれぞれ独立して選ばれた基であり、
Ｒ^３〜Ｒ^６は、水素、炭素数１〜６の直鎖あるいは分岐のアルキル基、炭素数１〜６の直鎖あるいは分岐のアルコキシ基および炭素数１〜６の直鎖あるいは分岐のアルキルアミノ基よりなる群からそれぞれ独立して選ばれた基であり、
Ｑは、
置換基を有することもある炭素数６〜１６のアリール基を有するアリールアミノ基、
置換基を有することもある炭素数１０〜１６の芳香族環、
置換基を有することもある炭素数１０〜１５の複素環
よりなる群からそれぞれ独立して選ばれた基であり、
ｎは１〜４の整数であるが、ｎ＝１の場合であって、Ｑが前記アリールアミノ基の場合には、Ｑがチオフェン環のｐ−位に付加することはない。）
で示されるチオフェン誘導体に関する。
本発明の第３は、Ｑにおける芳香族環がアセナフテン環、アセナフチレン環またはフルオランテン環である請求項２記載のチオフェン誘導体に関する。これらは、青色蛍光染料としてとくに良い性質を示す。
本発明の第４は、請求項１〜３いずれか記載のチオフェン誘導体よりなるチオフェン含有蛍光材料に関する。
本発明の第５は、請求項１〜３いずれか記載のチオフェン誘導体よりなる有機エレクトロルミネッセンス用発光材料に関する。
本発明の第６は、請求項１〜３いずれか記載のチオフェン誘導体を含むことを特徴とする有機エレクトロルミネッセンス素子に関する。 The first of the present invention is the following general formula (1)

(R ¹ and R ² are groups independently selected from the group consisting of hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms,
R ^{3 to} R ⁶ are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkylamino group having 1 to 6 carbon atoms. Each independently selected from the group consisting of groups,
Q is
An arylamino group having an aryl group having 6 to 16 carbon atoms, which may have a substituent,
An aromatic ring having 10 to 16 carbon atoms, which may have a substituent,
Each independently selected from the group consisting of a heterocyclic group having 10 to 15 carbon atoms, which may have a substituent,
n is an integer of 1 to 4, but when n = 1 and Q is the arylamino group, Q is not added to the p-position of the thiophene ring. )
It is related with the thiophene derivative shown by these.
The second of the present invention is the following general formula (2)

(R ¹ and R ² are each independently a group selected from the group consisting of linear or branched alkyl group of hydrogen or 1 to 6 carbon atoms,
R ^{3 to} R ⁶ are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkylamino group having 1 to 6 carbon atoms. Each independently selected from the group consisting of groups,
Q is
An arylamino group having an aryl group having 6 to 16 carbon atoms, which may have a substituent,
An aromatic ring having 10 to 16 carbon atoms, which may have a substituent,
Each independently selected from the group consisting of a heterocyclic group having 10 to 15 carbon atoms, which may have a substituent,
n is an integer of 1 to 4, but when n = 1 and Q is the arylamino group, Q is not added to the p-position of the thiophene ring. )
It is related with the thiophene derivative shown by these.
The third of the present invention relates to the thiophene derivative according to claim 2, wherein the aromatic ring in Q is an acenaphthene ring, an acenaphthylene ring or a fluoranthene ring. These exhibit particularly good properties as blue fluorescent dyes.
4th of this invention is related with the thiophene containing fluorescent material which consists of a thiophene derivative in any one of Claims 1-3.
5th of this invention is related with the luminescent material for organic electroluminescence which consists of a thiophene derivative in any one of Claims 1-3.
6th of this invention is related with the organic electroluminescent element characterized by including the thiophene derivative in any one of Claims 1-3.

Examples of the linear or branched alkyl group having 1 to ⁶ carbon atoms of R ^{1 to} R ⁶ in the present invention include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n -Pentyl, iso-pentyl, n-hexyl and the like can be mentioned.

Examples of the linear or branched alkoxy group having 1 to ⁶ carbon atoms of R ^{3 to} R ⁶ in the present invention include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, n -Pentoxy, iso-pentoxy, n-hexyloxy and the like can be mentioned.

In the present invention, the linear or branched alkylamino group having 1 to ⁶ carbon atoms of R ^{3 to} R ⁶ is one in which part or all of the hydrogen of —NH ₂ is substituted with the alkyl group.

  Examples of the aryl group having 6 to 16 carbon atoms in the “arylamino group having an aryl group” of Q of the present invention include a phenyl group, a naphthyl group, an anthranyl group, a phenanthranyl group, and a pyrenyl group.

  Examples of the “C10-C16 aromatic ring” in the present invention include a naphthalene ring, anthracene ring, phenanthrene ring, acenaphthene ring, acenaphthylene ring, perylene ring, and fluoranthene ring.

  Examples of the heterocyclic ring having 10 to 15 carbon atoms that may have a substituent of Q in the present invention include carbazole ring, indole ring, particularly 1H-indole ring, 1H-benzo [d] imidazole ring and the like. . Examples of the group include a carbazolyl group and an indolinyl group.

  An arylamino group having an aryl group having 6 to 16 carbon atoms, which may have a substituent of Q in the present invention, an aromatic ring having 10 to 16 carbon atoms which may have a substituent, or a substituent. Examples of the substituent in a certain C10-15 heterocycle include the C1-C6 linear or branched alkyl group, alkoxy group or alkylamino group exemplified above.

なお前記式中、Ｒ^１およびＲ^２は、水素または炭素数１〜６の直鎖あるいは分岐のアルキル基、Ｒ^３〜Ｒ^６は、水素、炭素数１〜６の直鎖あるいは分岐のアルキル基、炭素数１〜６の直鎖あるいは分岐のアルコキシ基、炭素数１〜６の直鎖あるいは分岐のアルキルアミノ基よりなる群からそれぞれ独立して選ばれた基であり、Ｑは、置換基を有することもある炭素数６〜１６のアリール基を有するアリールアミノ基、置換基を有することもあるカルバゾリル基、置換基を有することもある炭素数１０〜１６の芳香族環、置換基を有することもある炭素数１０〜１５の複素環よりなる群からそれぞれ独立して選ばれた基である。ｎは１〜４の整数をしめす。ただしｎ＝１の場合であって、Ｑにアリールアミノ基が付加する場合、チオフェン環のｐ−位に付加することはない。Ｘ、Ｘ^１、Ｘ^２はハロゲンである。 The compound of the present invention can be produced by the following reaction. In addition, in the formulas of the following first reaction and third reaction, the compound surrounded by () in the center is an intermediate and is not a compound that can be isolated.

In the above formula, R ¹ and R ² are hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ^{3 to} R ⁶ are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms. Are groups independently selected from the group consisting of a linear or branched alkoxy group having 1 to 6 carbon atoms and a linear or branched alkylamino group having 1 to 6 carbon atoms, and Q is a substituent. An arylamino group having an aryl group having 6 to 16 carbon atoms that may have, a carbazolyl group that may have a substituent, an aromatic ring having 10 to 16 carbon atoms that may have a substituent, and a substituent Or a group independently selected from the group consisting of certain heterocyclic rings having 10 to 15 carbon atoms. n represents an integer of 1 to 4. However, in the case of n = 1, when an arylamino group is added to Q, it is not added to the p-position of the thiophene ring. X, X ¹ and X ² are halogens.

The production method of the thiophene derivative of the present invention will be specifically described.
The first reaction of this production method is a reaction in which a halogen compound as a raw material is lithiated (lithiated), and then the lithium compound is reacted with an organic boric acid compound to convert it into a desired boric acid ester compound or boric acid compound. is there. In this reaction, an organic halide is dissolved in an ether solvent such as tetrahydrofuran, reacted with butyllithium at a very low temperature, once lithiated, and then reacted with an organic boric acid compound.
As the organic halide used here, chloride, bromide and iodide are used, preferably bromide or iodide, more preferably bromide.
As the solvent used in this reaction, linear saturated ethers such as ethyl ether, isopropyl ether and ethylene glycol dimethyl ether, saturated cyclic ethers such as tetrahydrofuran and 1,4-dioxane, and aromatic ethers such as anisole can be used. Preferably, ethyl ether, tetrahydrofuran or 1,4-dioxane, more preferably tetrahydrofuran is used.
The organolithium reagent used for lithiation is preferably a hydrocarbon solution of n-butyllithium. Further, the n-butyllithium concentration may be in the range of 0.5 mol / liter to 3.0 mol / liter, preferably 1.0 mol / liter to 3.0 mol / liter, more preferably Is 1.5 mol / liter to 2.0 mol / liter. As a solvent used for dilution, a saturated hydrocarbon solvent such as n-pentane, n-hexane and n-heptane, and an aromatic hydrocarbon solvent such as benzene, toluene, xylene and ethylbenzene can be used. N-hexane, n-heptane, toluene and xylene are preferable, and n-hexane is more preferable.
Regarding the reaction temperature of lithiation, it is important to carry out the reaction at a low temperature because the lithiated product to be produced is broken at room temperature. A preferred temperature is −40 ° C. to −200 ° C., more preferably −50 ° C. to −80 ° C. The reaction time is 30 minutes to 12 hours, preferably 1 hour to 4 hours, more preferably 2 hours to 3 hours.
The lithiated product thus reacted can be used for the reaction with the next organic boric acid compound without being taken out.
The organic boric acid compound is not particularly limited, whether it is an alkyl borate ester or an aryl borate ester. Alkyl borate esters include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-n-hexyl borate, tri-n borate -Octyl ester, boric acid tri-n-decyl ester, boric acid tri-n-hexadecyl ester, boric acid tri-n-octadecyl ester, etc. and 2-isopropoxy-4,4,5,5-tetramethyl-1,3 Examples thereof include cyclic borate esters such as 2-dioxaborolane. Examples of the aryl borate ester include boric acid triphenyl ester, boric acid tri (p-chlorophenyl) ester, boric acid tri (o-tolyl) ester, and the like. Preferably, trimethyl borate, triisopropoxy borate or 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, more preferably triisopropoxy borate or Mention may be made of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.
The reaction temperature with the organic boric acid compound is preferably carried out at the temperature usually used under lithiation conditions.
When dropping the organoboric acid compound to the lithiated compound, if it is dripped too early, the temperature of the reaction system rises rapidly and it becomes difficult to maintain the temperature of the reaction system, so the temperature of -65 ° C to -70 ° C is maintained. It is desirable to add it dropwise.
After the completion of the dropping, it is preferable that the temperature at the time of dropping is maintained for a while without raising the temperature immediately because an unreacted organic boric acid compound exists. In this case, the time means 30 minutes to 1 hour, preferably 30 minutes. Thereafter, the cooling bath is removed and the temperature is returned to room temperature to complete the reaction. In this case, room temperature means 15 to 35 ° C, preferably 20 to 30 ° C, more preferably 20 to 25 ° C. The time required for completion is 5 to 24 hours, preferably 10 to 20 hours, more preferably 15 to 20 hours.
The boric acid compound thus obtained can be taken out as a boric acid ester compound or a boric acid compound after hydrolysis. Since the extracted boric acid compound is not pure enough to be used in the next reaction as it is, it is purified by silica gel column chromatography or recrystallization.

The second reaction of this production method is a reaction in which the boric acid ester compound or boric acid compound obtained in the first reaction is reacted with a dihalogenated aryl group to obtain a halogenated aryl compound. The reaction used here is generally called a Suzuki-Miyaura coupling (commonly known as Suzuki coupling) reaction. For details, see Miyaura, N .; : Suzuki, A .; Chem. Rev. 1995, 95, 2457, and the like.
As the halogen of the aryl dihalide used in the reaction, chlorine, bromine or iodine can be used. Preferred is bromine or iodine. These halogens may be the same or different. However, when the same halogen is added, there is a high probability that a dimer is produced as a by-product because there is no selectivity in the reaction. For this reason, those having different halogen atoms bonded thereto are preferred.
Solvents used in this reaction include aromatic hydrocarbons such as toluene, xylene or ethylbenzene and alcohols such as methanol, ethanol, n-propanol, iso-propanol or n-butanol, ethers such as tetrahydrofuran and diglyme, There are water-soluble solvents such as acetone and acetonitrile, and these can be used alone or in combination of two or more kinds of solvents.
The palladium compound used as the catalyst is an organic palladium complex such as tetrakis (triphenylphosphine) palladium or dichlorobis (triphenylphosphine) palladium, but generally Pd (0) [zero-valent palladium]. There is no particular limitation.
In this reaction, a base is added as a reaction aid. Bases used include carbonates, bicarbonates, phosphates and the like. The alkali metals contained in these bases are lithium, sodium, potassium, rubidium, cesium and the like. Preferred examples include sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate and potassium phosphate, and more preferably sodium carbonate and potassium carbonate.
These bases are preferably used as an aqueous solution. About the density | concentration, although it is the range of 0.5-10.0M (mol / liter), Preferably it is 1.0-5.0M, More preferably, it is 1.5-2.5M.
The reaction temperature is generally a temperature at which the solvent boils, and the reaction temperature varies depending on the reaction solvent used. For example, in the case of a mixed solvent of toluene-ethanol, the temperature is 73.0-75.0 ° C, and in the case of a single solvent of tetrahydrofuran, the temperature is 63.0-65.0 ° C.
The time required for completion is 5 to 24 hours, preferably 10 to 20 hours, more preferably 15 to 20 hours.
For the halide thus obtained, the base layer is removed after the reaction, and the organic layer is washed with water, and then the crude product is taken out. Thereafter, the product is purified by silica gel column chromatography to obtain the desired product.

In the third reaction of this production method, the halide obtained in the second reaction is lithiated in the same manner as in the first reaction, reacted with an organic boric acid compound, and converted into a desired boric acid ester compound or boric acid compound. It is a reaction.
The details of the reaction are as described in the first reaction.

The fourth reaction of this production method is a reaction in which the boric acid ester compound or boric acid compound obtained in the third reaction is reacted with a dihalogenated thiophene in the same manner as the second reaction to obtain the target compound.
Details of the reaction are as described in the second reaction.

Specific examples of the compound of the present invention are shown below.
N means an integer of 1 to 4.

  The novel thiophene derivative of the present invention has a high fluorescence quantum yield. Therefore, it can be used as a light emitting material of an organic electroluminescence element. Moreover, since the mobility of holes is high, it can also be used as a hole transport material.

  When the novel thiophene derivative of the present invention is used in a light emitting layer or a hole (hole) transport layer, the compound of the present invention can be used as a light emitting material or a hole transport material. It can also be used in combination with other light emitting materials or hole transport materials.

  Next, the organic electroluminescence element of the present invention will be described. The organic EL device of the present invention is a device in which a plurality of organic compounds functionally separated between an anode and a cathode are stacked, and at least one of the organic compound layers contains the thiophene derivative of the present invention. Examples of the configuration in the case where the organic EL element is a functionally separated multilayer organic EL element include, for example, an anode (ITO) / hole transport layer / light emitting layer / electron transport layer / cathode, ITO / hole transport layer / light emitting layer / Electron transport layer / electron injection layer / cathode, ITO / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode, ITO / hole transport layer / light emitting layer / hole block layer / electron transport layer / electron injection layer / Cathode, ITO / Hole injection layer / Hole transport layer / Light emitting layer / Hole block layer / Electron transport layer / Electron injection layer / Cathode etc. Moreover, you may have a sealing layer on a cathode as needed.

  Each of the hole transport layer (hole transport layer), the electron transport layer, and the light emitting layer may have a single layer structure or a multilayer structure. In addition, the hole transport layer and the electron transport layer can be provided separately with a layer responsible for the injection function (hole injection layer and electron injection layer) and a layer responsible for the transport function (hole transport layer and electron transport layer).

  The organic electroluminescence element of the present invention is not limited to the above configuration example, and can have various configurations. If necessary, a layer in which a hole transport layer component and a light-emitting layer component or an electron transport layer component and a light-emitting layer component are mixed may be provided.

  Hereinafter, the constituent elements of the organic electroluminescence element of the present invention will be described by taking as an example an element structure composed of an anode / hole transport layer / light emitting layer / electron transport layer / cathode. The organic electroluminescence device of the present invention is preferably supported on a substrate.

  There is no restriction | limiting in particular about the raw material of a board | substrate, What is necessary is just used conventionally for the conventional organic electroluminescent element, For example, what consists of glass, quartz glass, a transparent plastic etc. can be used.

As an anode of the organic electroluminescence device of the present invention, an electrode material may be a single metal having a high work function (4 eV or more), an alloy of metals having a high work function (4 eV or more), a conductive substance, or a mixture thereof. preferable. Specific examples of such electrode materials include metals such as gold, silver, and copper, conductive transparent materials such as ITO (indium-tin oxide), tin oxide (SnO ₂ ), and zinc oxide (ZnO), polypyrrole, and polythiophene. Examples thereof include conductive polymer materials such as For the anode, these electrode materials can be formed by a method such as vapor deposition, sputtering, or coating. The sheet electrical resistance of the anode is preferably several hundred Ω / cm ² or less. The thickness of the anode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm.

As the cathode, a single metal having a low work function (4 eV or less), a single metal having a low work function (4 eV or less), an alloy of metals having a low work function (4 eV or less), a conductive substance, or a mixture thereof is used as the electrode material. It is preferable to do. Specific examples of such electrode materials include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, magnesium, magnesium-silver alloy, magnesium-indium alloy, aluminum, aluminum-lithium alloy, and aluminum-magnesium alloy. Can be mentioned. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet electrical resistance of the cathode is preferably several hundred Ω / cm ² or less. The thickness of the cathode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm. In order to efficiently extract light emitted from the organic EL device of the present invention, at least one of the anode and the cathode is preferably transparent or translucent.

The hole transport layer of the organic electroluminescence device of the present invention is made of a hole transfer compound (hole transfer compound) and has a function of transferring holes (holes) injected from the anode to the light emitting layer. When a hole transfer compound is disposed between two electrodes to which an electric field is applied and holes are injected from the anode, a hole transfer material having a hole mobility of at least 10 ⁻⁶ cm ² / V · sec or more is preferable. The hole transfer material used for the hole transport layer of the organic electroluminescence device of the present invention is not particularly limited as long as it has the above-mentioned preferable performance. Any one of materials conventionally used as charge injection materials for holes in photoconductive materials and known materials used for hole transport layers of organic electroluminescence elements can be selected and used.

ホール輸送材料としては、本発明のチオフェン誘導体のほか下記化学式に示すＴＰＤ、ＤＴＡＳｉ、α−ＮＰＤなどを挙げることができる。

Examples of the hole transfer material include phthalocyanine derivatives such as copper phthalocyanine, N, N, N ′, N′-tetraphenyl-1,4-phenylenediamine, N, N′-di (m-tolyl) -N, Triarylamines such as N′-diphenyl-4,4-diaminophenyl (TPD) and N, N′-di (1-naphthyl) -N, N′-diphenyl-4,4-diaminophenyl (α-NPD) Derivatives, polyphenylenediamine derivatives, polythiophene derivatives, and water-soluble PEDOT-PSS (polyethylenedioxathiophene-polystyrene sulfonic acid). The hole transport layer may be composed of one or more of these other hole transport compounds, or may be a stack of hole transport layers composed of a compound different from the hole transport material.
Examples of the hole injection material include PEDOT-PSS (polymer mixture) and DNTPD represented by the following chemical formula.

Examples of the hole transport material include TPD, DTASi, α-NPD and the like represented by the following chemical formula in addition to the thiophene derivative of the present invention.

  The thiophene derivative of the present invention can be used for the light emitting layer of the organic electroluminescence device of the present invention. Moreover, there is no restriction | limiting in particular also about the conventionally well-known luminescent material, Arbitrary things can be selected and used.

Known light-emitting materials include perylene derivatives, naphthacene derivatives, quinacridone derivatives, coumarin derivatives (eg, coumarin 1, coumarin 540, coumarin 545, etc.), pyran derivatives (eg, DCM-1, DCM-2, DCJTB, etc.), organometallic complexes. For example, fluorescent materials such as tris (8-hydroxyquinolinolato) aluminum complex (Alq ₃ ), tris (4-methyl-8-hydroxyquinolinolato) aluminum complex (Almq ₃ ), and [2- (4,6- Difluorophenyl) pyridyl-N, C2 ′] iridium (III) picolylate (FIrpic), tris {1- [4- (trifluoromethyl) phenyl] -1H-pyrazolate-N, C2 ′} iridium (III) (Irtfmpppz ₃ ), Bis [2- (4 ', 6'-difluorophenyl) Rijinato -N, C2 '] iridium (III) tetrakis (1-pyrazolyl) borate (FIr6), tris (2-phenylpyridinato) iridium (III) (Irppy ₃₎ and the like phosphorescent material such as .

  The light-emitting layer can also be formed of a host material and a guest material (dopant) [Appl. Phys. Lett. , 65 3610 (1989)]. In particular, when a phosphorescent material is used for the light emitting layer, it is necessary to use a host material. As the host material used at this time, 4,4′-di (N-carbazolyl) -1,1′-biphenyl (CBP) ), 1,4-di (N-carbazolyl) benzene-2,2′-di [4 ″-(N-carbazolyl) phenyl] -1,1′-biphenyl (4CzPBP) and the like.

The guest material is preferably 0.01 to 40% by weight, more preferably 0.1 to 20% by weight with respect to the host material. Examples of guest materials include conventionally known FIrpic, Irppy ₃ , FIr 6 and the like shown below.

The electron transport layer of the organic EL device of the present invention is made of an electron transfer compound and has a function of transmitting electrons injected from the cathode to the light emitting layer. When an electron transfer compound is disposed between two electrodes to which an electric field is applied and electrons are injected from the cathode, an electron transfer material having an electron mobility of at least 10 ⁻⁶ cm ² / V · sec or more is preferable. The electron transfer material used for the electron transport layer used in the organic EL device of the present invention is not particularly limited as long as it has the above-mentioned preferable performance. Any one of materials conventionally used as electron charge injection materials in photoconductive materials and known materials used for electron transport layers of organic EL elements can be selected and used.

電子輸送材料としては、下記化学式に示すＡｌｑ_３、ＴＡＺ、ＤＰＢなどを挙げることができる。

本発明の有機エレクトロルミネッセンス素子の電子輸送層の材料は、単独で使用できるが２種類以上の電子輸送材料と併用しても構わない。 Examples of the electron transfer material include quinoline complexes such as tris (8-hydroxyquinolinolato) aluminum complex (Alq ₃ ), 1-N-phenyl-2- (p-biphenylyl) -5- (p- triazine derivatives such as tert-butylphenyl) -1,3,5-triazine (TAZ), phenanthroline derivatives such as 1,4-di (1,10-phenanthroline-2-yl) benzene (DPB), fluoride Examples include alkali metal halides such as lithium. The electron transport layer may be composed of one or more of these other electron transport compounds, or may be a stack of electron transport layers composed of a compound different from the above electron transport material.
Examples of the electron injecting material include lithium fluoride and 8-hydroxyquinolinolatolithium complex (Liq) represented by the following chemical formula, and lithium of a phenanthroline derivative according to Japanese Patent Application No. 2006-292032 of the present applicant. It is also possible to use a complex (LiPB) or a phenoxypyridine lithium complex (LiPP) described in Japanese Patent Application No. 2007-29695.

Examples of the electron transport material include Alq ₃ , TAZ, and DPB represented by the following chemical formula.

The material for the electron transport layer of the organic electroluminescence device of the present invention can be used alone, but may be used in combination with two or more kinds of electron transport materials.

  In the organic electroluminescence device of the present invention, an electron injection layer composed of a conductor may be further provided between the cathode and the electron transport layer for the purpose of further improving the electron injection property. As the conductor used here, it is preferable to use at least one metal compound selected from alkali metal halides, alkaline earth metal halides, and alkali metal organic complexes. Examples of the alkali metal halide include lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, and lithium chloride. Examples of the alkaline earth metal halide include magnesium fluoride, calcium fluoride, barium fluoride, and strontium fluoride. Examples of the alkali metal organic complex include 8-hydroxyquinolinolatolithium and 8-hydroxyquinolinolatocesium.

  The method for forming the hole transport layer and the light emitting layer is not particularly limited. For example, a dry film forming method (for example, a vacuum vapor deposition method, an ionization vapor deposition method) or a wet film forming method [a solvent coating method (for example, a spin coating method, a casting method, an ink jet method, etc.)] can be used. The novel thiophene derivative of the present invention is preferably a dry film forming method (for example, a vacuum deposition method, an ionization deposition method, etc.). The film formation of the electron transport layer is limited to a dry film formation method (for example, a vacuum vapor deposition method, an ionization vapor deposition method, etc.) because the lower layer may be eluted when the wet film formation method is used. For the production of the element, the above film forming method may be used in combination.

When forming each layer such as a hole transport layer, a light emitting layer, and an electron transport layer by a vacuum deposition method, the vacuum deposition conditions are not particularly limited. Usually, under a vacuum of about 10 ⁻⁵ Torr or less, a boat temperature (deposition source temperature) of about 50 to 500 ° C., a substrate temperature of about −50 to 300 ° C., and 0.01 to 50 nm / sec. Vapor deposition is preferred. When each of the hole transport layer, the light emitting layer, and the electron transport layer is formed using a plurality of compounds, it is preferable to co-evaporate the boats containing the compounds while controlling the temperatures of the boats.

  When forming a hole transport layer, a light emitting layer, or the like by a solvent coating method, the constituent components are dissolved or dispersed in a solvent to obtain a coating solution. Solvents include hydrocarbon solvents (eg, heptane, toluene, xylene, cyclohexane, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), halogen solvents (eg, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, etc.) Ester solvents (eg, ethyl acetate, butyl acetate, etc.), alcohol solvents (eg, methanol, ethanol, butanol, methyl cellosolve, ethyl cellosolve, etc.), ether solvents (eg, dibutyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane, etc.), aprotic solvents (eg, N, N′-dimethylacetamide, dimethyl sulfoxide, etc.), water and the like. The solvent may be used alone, or a plurality of solvents may be used in combination.

  The thickness of each layer such as a hole transport layer, a light emitting layer, and an electron transport layer is not particularly limited, but is usually set to 5 to 5,000 nm.

  The organic electroluminescence device of the present invention can be protected by providing a protective layer (sealing layer) for the purpose of blocking contact with oxygen, moisture, etc., or by enclosing the device in an inert material. Examples of the inert substance include paraffin, silicon oil, and fluorocarbon. Examples of the material used for the protective layer include fluororesin, epoxy resin, silicone resin, polyester, polycarbonate, and photocurable resin.

  The organic electroluminescence device of the present invention can be used as a normal DC drive device. When a DC voltage is applied, light emission is usually observed when about 1.5 to 20 V is applied with the positive polarity of the anode and the negative polarity of the cathode. The organic electroluminescence device of the present invention can also be used as an AC drive device. When an AC voltage is applied, light is emitted when the anode is in a positive state and the cathode is in a negative state. The organic electroluminescence element of the present invention is, for example, a flat light emitter such as an electrophotographic photosensitive member or a flat panel display, a copying machine, a printer, a backlight of a liquid crystal display, a light source such as an instrument, various light emitting elements, various display devices, and various signs. It can be used for various sensors and various accessories.

  15 to 28 show preferred examples of the organic electroluminescence element of the present invention.

  FIG. 15 is a cross-sectional view showing an example of the organic electroluminescence element of the present invention. FIG. 15 shows a configuration in which an anode 2, a light emitting layer 3 and a cathode 4 are sequentially provided on a substrate 1. The light-emitting material used here is useful when it has a single hole-transporting property, electron-transporting property, and light-emitting function, or a mixture of compounds having the respective functions. It is.

  FIG. 16 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 16 shows a configuration in which an anode 2, a hole transport layer 5, a light emitting layer 3, and a cathode 4 are sequentially provided on a substrate 1. In this case, the light emitting layer is useful when it has an electron transporting function.

  FIG. 17 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 17 shows a configuration in which an anode 2, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. In this case, the light emitting layer is useful when it has a hole transporting function.

FIG. 18 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 18 shows a configuration in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. This separates the functions of carrier transport (which means both hole transport and electron transport) and light emission, and increases the degree of freedom in material selection, thus increasing the efficiency of light emission and the degree of freedom in light emission color. It will be.

  FIG. 19 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 19 shows a configuration in which an anode 2, a hole injection layer 7, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. In this case, the provision of the hole injection layer 7 improves the adhesion between the anode 2 and the hole transport layer 5, improves the injection of holes from the anode, and is effective in lowering the voltage of the light emitting element.

  FIG. 20 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 20 shows a configuration in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, an electron injection layer 8 and a cathode 4 are sequentially provided on a substrate 1. In this case, injection of electrons from the cathode 4 is improved, which is effective for lowering the voltage of the light emitting element.

  FIG. 21 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 21 shows a structure in which an anode 2, a hole injection layer 7, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, an electron injection layer 8 and a cathode 4 are sequentially provided on a substrate 1. In this case, hole injection from the anode 2 is improved and electron injection from the cathode 4 is improved, which is the most effective for driving at a low voltage.

  22 to 28 are cross-sectional views of the device in which the hole block layer 9 is inserted. The hole blocking layer 9 has an effect of preventing holes injected from the anode or excitons generated by recombination in the light emitting layer 3 from escaping to the cathode 4, and is effective in improving the light emission efficiency of the organic electroluminescence element. There is. The hole blocking layer 9 can be inserted between the light emitting layer 3 and the cathode 4, between the light emitting layer 3 and the electron transport layer 6, or between the light emitting layer 3 and the electron injection layer 8. More preferred is between the light emitting layer 3 and the electron transport layer 6. In addition, although the organic electroluminescent element of the structure which does not have the hole transport layer 5 as shown in FIG. 22 is shown, since the compound of the present invention has a thiophene skeleton, it also has hole transport performance. A hole transport agent and a hole transport layer are not necessarily required.

  26 and 28, each of the hole transport layer 5, the hole injection layer 7, the electron transport layer 6, the electron injection layer 8, the light emitting layer 3, and the hole block layer 9 has a single layer structure or a multilayer structure. There may be.

  15 to 28 are basic device configurations to the last, and the configuration of the organic electroluminescence device using the compound of the present invention is not limited thereto.

  The novel thiophene-containing fluorescent material of the present invention can exhibit a wide range of fluorescence from blue to red depending on the number of substituents and thiophenes added to thiophene. The manufacturing method is also simple because conventional techniques can be applied. The novel thiophene-containing fluorescent material of the present invention is industrially important because it can enrich organic electroluminescent light-emitting materials.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

冷却管、温度計、窒素導入管、メカニカルスターラーのついた４つ口の１リットルコルベンに、ジフェニルアミン（２９．５ｇ，１７７．０ｍｍｏｌ）、３−ヨードブロモベンゼン（５０．０ｇ，１７７．０ｍｍｏｌ）、銅粉末（２０．６ｇ，１７７．０ｍｍｏｌ×１．７当量）、炭酸カリウム（９７．８ｇ，１７７．０ｍｍｏｌ×４．０当量）およびＩｐｓｏｌ−１５０（商品名：出光石油製、溶媒）を加え撹拌する。窒素気流下マントルヒーターでこのコルベンを１９２．０〜１９４．０℃まで加熱し、同温度で１６時間反応する。反応進行は薄層クロマトグラフィー（移動層、ｎ−ヘキサン：トルエン＝２０：１）で確認する。
反応終了後、水浴にて室温まで冷却する。冷却後吸引ろ過にて不溶物をろ別する。
得られたろ液は、水１００ｍｌで水洗を行い、エバポレートで溶媒を回収し、粗製物を５８．６ｇ得た。この粗製物はシリカゲルカラムクロマトグラフ（移動層、ｎ−ヘキサン：トルエン＝２０：１）で精製し、目的のＢＤＦＢを４１．３ｇ（収率 ７２．０％）得た。

２）３−Ｎ，Ｎ−ジフェニルアミノフェニルホウ酸エステル（略称ＤＦＡＢ）の合成

同圧式滴下ロート、温度計、窒素導入管、メカニカルスターラーのついた５００ｍｌの４つ口コルベンに、ＢＤＦＢ（４０．０ｇ，１２３ｍｍｏｌ）、ＴＨＦ（テトラヒドロフラン）（３５０ｍｌ）を加え窒素気流下撹拌する。コルベンはアセトン−ドライアイス浴で−６５．０℃まで冷却する。滴下ロートから１．６Ｍ濃度のｎ−ブチルリチウム（１１５．３ｍｌ，１８４．５ｍｍｏｌ）を１時間かけて滴下する。滴下後−６５．０〜−６３．０℃で２時間撹拌する。
その後２−イソプロポキシ−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン（４６．０ｇ，２４６．０ｍｍｏｌ）を１５分かけて滴下する。滴下終了後、３０分−６５．０〜−６３．０℃で撹拌後アセトン−ドライアイスバスをはずし、室温（２３．０〜２５．０℃）で２０時間撹拌する。
反応終了後、反応液に水１００ｍｌを加え１時間撹拌し、酢酸エチル２５０ｍｌを加え分液する。分液された有機層は、さらに１０％食塩水で洗いエバポレーターで溶媒を回収する。得られた粗製物（５４．１ｇ）はシリカゲルカラムクロマトグラフ（移動層、ｎ−ヘキサン：トルエン＝３：１の混合溶液を、ついで１：１の混合溶液を使用）で精製し、目的のＤＦＡＢを３８．５ｇ（収率 ８４．３％）得た。

３）２，５−ビス（３−Ｎ，Ｎ−ジフェニルアミノフェニル）チオフェン（略称ＳＴ−３１）の合成

冷却管、温度計、窒素導入管、メカニカルスターラーのついた４つ口の５００ｍｌコルベンに、ＤＦＡＢ（１０．０ｇ，２６．９ｍｍｏｌ）、２，５−ジブロモチオフェン（２．６ｇ，１０．８ｍｍｏｌ）、ＴＨＦ（３７５ｍｌ）および２Ｍ−炭酸カリウム水溶液（２モル濃度の水溶液）（６２．５ｍｌ）を加え、室温で撹拌を行う。この溶液に窒素ガスを導入し、窒素バブリングを３０分行う。
その後、窒素気流下、下記式で示すテトラキストリフェニルホスフィンパラジウム〔Ｐｄ（ＰＰｈ_３）_４〕（０．６ｇ，０．５２ｍｍｏｌ）を加え、オイルバスで６３．０〜６５．０℃まで加熱する。さらに同温度で２０時間撹拌する。反応は薄層クロマトグラフ（移動層、ｎ−ヘキサン：トルエン＝７：１）で確認する。反応終了後、水浴で室温まで冷却する。析出した結晶をろ別し、得られたろ液に酢酸エチル３００ｍｌと水５０ｍｌを加え、水洗を行う。得られた有機層はエバポレーターで溶媒留去し、粗製物を１０．５ｇ得た。得られた粗製物はシリカゲルカラムクロマトグラフ（移動層、ｎ−ヘキサン：トルエン＝７：１の混合溶液を、ついで５：１の混合溶液を使用）で精製し、目的のＳＴ−３１を１．７ｇ（収率 ２７．６％）得た。目的物の確認はＬＣ−Ｍａｓｓ（液体クロマロトグラフ質量分析装置）で行った。このＬＣ−Ｍａｓｓの結果を図１に示す。またＴＨＦ溶液（１．０×１０^−７モル／リットル）でのフォトルミネッセンスの結果を図２に示す。

Example 1
Synthesis of 2,5-bis (3-N, N-diphenylaminophenyl) thiophene (abbreviation ST-31) 1) Synthesis of 3-bromo-N, N-diphenylaminobenzene (abbreviation BDFB)

To a 4 liter 1 liter Kolben equipped with a condenser, thermometer, nitrogen inlet tube, mechanical stirrer, diphenylamine (29.5 g, 177.0 mmol), 3-iodobromobenzene (50.0 g, 177.0 mmol), Copper powder (20.6 g, 177.0 mmol × 1.7 eq), potassium carbonate (97.8 g, 177.0 mmol × 4.0 eq) and Isol-150 (trade name: Idemitsu Petroleum, solvent) were added and stirred. To do. The Kolben is heated to 192.0-194.0 ° C. with a mantle heater under a nitrogen stream and reacted at the same temperature for 16 hours. The progress of the reaction is confirmed by thin layer chromatography (moving bed, n-hexane: toluene = 20: 1).
After completion of the reaction, it is cooled to room temperature in a water bath. After cooling, the insoluble material is filtered off by suction filtration.
The obtained filtrate was washed with 100 ml of water and the solvent was recovered by evaporation to obtain 58.6 g of a crude product. This crude product was purified by silica gel column chromatography (mobile bed, n-hexane: toluene = 20: 1) to obtain 41.3 g (yield 72.0%) of the desired BDFB.

2) Synthesis of 3-N, N-diphenylaminophenyl borate (abbreviation DFAB)

BDFB (40.0 g, 123 mmol) and THF (tetrahydrofuran) (350 ml) are added to a 500 ml four-necked colben equipped with a same pressure dropping funnel, a thermometer, a nitrogen inlet tube, and a mechanical stirrer, and stirred under a nitrogen stream. Kolben is cooled to −65.0 ° C. in an acetone-dry ice bath. From the dropping funnel, 1.6M n-butyllithium (115.3 ml, 184.5 mmol) is added dropwise over 1 hour. After dropping, the mixture is stirred at -65.0 to -63.0 ° C for 2 hours.
Then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (46.0 g, 246.0 mmol) is added dropwise over 15 minutes. After completion of dropping, the mixture is stirred for 30 minutes at −65.0 to −63.0 ° C., then the acetone-dry ice bath is removed, and the mixture is stirred at room temperature (23.0 to 25.0 ° C.) for 20 hours.
After completion of the reaction, 100 ml of water is added to the reaction solution and stirred for 1 hour, and 250 ml of ethyl acetate is added to separate the layers. The separated organic layer is further washed with 10% saline and the solvent is recovered with an evaporator. The obtained crude product (54.1 g) was purified by silica gel column chromatography (moving layer, n-hexane: toluene = 3: 1 mixed solution, then 1: 1 mixed solution), and the target DFAB was purified. 38.5 g (yield 84.3%) was obtained.

3) Synthesis of 2,5-bis (3-N, N-diphenylaminophenyl) thiophene (abbreviation ST-31)

A four-necked 500 ml Kolben equipped with a condenser, thermometer, nitrogen inlet tube, mechanical stirrer, DFAB (10.0 g, 26.9 mmol), 2,5-dibromothiophene (2.6 g, 10.8 mmol), Add THF (375 ml) and 2M aqueous potassium carbonate (2 molar aqueous solution) (62.5 ml) and stir at room temperature. Nitrogen gas is introduced into this solution and nitrogen bubbling is performed for 30 minutes.
Thereafter, tetrakistriphenylphosphine palladium [Pd (PPh ₃ ) ₄ ] (0.6 g, 0.52 mmol) represented by the following formula is added under a nitrogen stream and heated to 63.0 to 65.0 ° C. in an oil bath. The mixture is further stirred at the same temperature for 20 hours. The reaction is confirmed by thin layer chromatography (moving bed, n-hexane: toluene = 7: 1). After completion of the reaction, it is cooled to room temperature in a water bath. The precipitated crystals are separated by filtration, and 300 ml of ethyl acetate and 50 ml of water are added to the obtained filtrate, followed by washing with water. The obtained organic layer was evaporated using an evaporator to obtain 10.5 g of a crude product. The obtained crude product was purified by silica gel column chromatography (moving layer, n-hexane: toluene = 7: 1 mixed solution, then 5: 1 mixed solution). 7 g (yield 27.6%) was obtained. Confirmation of the target product was performed with LC-Mass (liquid chromatograph mass spectrometer). The LC-Mass results are shown in FIG. The results of photoluminescence in a THF solution (1.0 × 10 ⁻⁷ mol / liter) are shown in FIG.

同圧式滴下ロート、温度計、窒素導入管、メカニカルスターラーのついた５００ｍｌの４つ口コルベンに、４−ブロモトリフェニルアミン（２５．０ｇ，７７．１ｍｍｏｌ）、ＴＨＦ（２２０ｍｌ）を加え、窒素気流下で撹拌する。コルベンはアセトン−ドライアイス浴で−６５．０℃まで冷却する。滴下ロートから１．６Ｍ濃度のｎ−ブチルリチウム溶液（７４．８ｍｌ，１１８．７ｍｍｏｌ）を１時間かけて滴下する。滴下後−６５．０〜−６３．０℃で２時間撹拌する。
その後、２−イソプロポキシ−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン（２８．７ｇ，１５４．２ｍｍｏｌ）を１５分かけて滴下する。滴下終了後、３０分−６５．０〜−６３．０℃で撹拌後、アセトン−ドライアイスバスをはずし、室温（２３．０〜２５．０℃）で２０時間撹拌する。
反応終了後、反応液に水１００ｍｌを加え、１時間撹拌し、酢酸エチル３００ｍｌを加え、分液する。分液された有機層は、さらに１０％食塩水で洗い、エバポレーターで溶媒を回収する。得られた粗製物（３３．８ｇ）はシリカゲルカラムクロマトグラフ（移動層、ｎ−ヘキサン：トルエン＝１：１）で精製し、目的のＤＦＡＰを１８．６ｇ（収率 ６４．８％）得た。

２）５，５′−ビス（４−Ｎ，Ｎ−ジフェニルアミノフェニル）２，２′−ビチオフェン（略称ＳＴ−０５）の合成

冷却管、温度計、窒素導入管、メカニカルスターラーのついた４つ口の１リットルコルベンに、ＤＦＡＰ（１４．３ｇ，３８．６ｍｍｏｌ）、５，５′−ジブロモ−２，２′ビチオフェン（５．０ｇ，１５．４ｍｍｏｌ）、ＴＨＦ（６００ｍｌ）および２Ｍ−炭酸カリウム水溶液（１００ｍｌ）を加え、室温で撹拌を行う。この溶液に窒素ガスを導入し、窒素バブリングを３０分行う。
その後、窒素気流下テトラキストリフェニルホスフィンパラジウム〔Ｐｄ（ＰＰｈ_３）_４〕（１．０ｇ，０．８６ｍｍｏｌ）を加え、オイルバスで６３．０〜６５．０℃まで加熱する。さらに同温度で２０時間撹拌する。反応終了後、水浴で室温まで冷却する。析出した結晶をろ過し、得られた結晶は水５０ｍｌで水洗を行う。得られた粗製物（８．３ｇ）はトルエン（２７０ｍｌ）で精製し、目的のＳＴ−０５を６．８ｇ（収率 ６６．４％）得た。目的物の確認は^１Ｈ−ＮＭＲおよびＬＣ−Ｍａｓｓで行った。^１Ｈ−ＮＭＲおよびＬＣ−Ｍａｓｓの結果をそれぞれ図３と図４に示す。またＴＨＦ溶液（１．０×１０^−８モル／リットル）でのフォトルミネッセンスの結果を図５に示す。 Example 2
Synthesis of 5,5'-bis (4-N, N-diphenylaminophenyl) 2,2'-bithiophene (abbreviation ST-05) 1) Synthesis of 4-N, N-diphenylaminophenyl borate (DFAP)

4-Bromotriphenylamine (25.0 g, 77.1 mmol) and THF (220 ml) were added to a 500 ml four-necked colben equipped with a same pressure dropping funnel, thermometer, nitrogen inlet tube, and mechanical stirrer, and a nitrogen stream Stir under. Kolben is cooled to −65.0 ° C. in an acetone-dry ice bath. A 1.6M n-butyllithium solution (74.8 ml, 118.7 mmol) is dropped from the dropping funnel over 1 hour. After dropping, the mixture is stirred at -65.0 to -63.0 ° C for 2 hours.
Thereafter, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (28.7 g, 154.2 mmol) is added dropwise over 15 minutes. After completion of dropping, the mixture is stirred for 30 minutes at -65.0 to -63.0 ° C, then the acetone-dry ice bath is removed, and the mixture is stirred at room temperature (23.0 to 25.0 ° C) for 20 hours.
After completion of the reaction, 100 ml of water is added to the reaction solution, and the mixture is stirred for 1 hour. The separated organic layer is further washed with 10% saline, and the solvent is recovered with an evaporator. The obtained crude product (33.8 g) was purified by silica gel column chromatography (mobile bed, n-hexane: toluene = 1: 1) to obtain 18.6 g (yield 64.8%) of the desired DFAP. .

2) Synthesis of 5,5′-bis (4-N, N-diphenylaminophenyl) 2,2′-bithiophene (abbreviation ST-05)

A four-necked 1 liter Kolben equipped with a cooling pipe, a thermometer, a nitrogen introduction pipe, and a mechanical stirrer was mixed with DFAP (14.3 g, 38.6 mmol), 5,5′-dibromo-2,2′bithiophene (5. 0 g, 15.4 mmol), THF (600 ml) and 2M aqueous potassium carbonate solution (100 ml) are added and stirred at room temperature. Nitrogen gas is introduced into this solution and nitrogen bubbling is performed for 30 minutes.
Thereafter, tetrakistriphenylphosphine palladium [Pd (PPh ₃ ) ₄ ] (1.0 g, 0.86 mmol) is added under a nitrogen stream and heated to 63.0 to 65.0 ° C. in an oil bath. The mixture is further stirred at the same temperature for 20 hours. After completion of the reaction, it is cooled to room temperature in a water bath. The precipitated crystals are filtered, and the obtained crystals are washed with 50 ml of water. The obtained crude product (8.3 g) was purified with toluene (270 ml) to obtain 6.8 g (yield 66.4%) of the target ST-05. Confirmation of the desired product was performed in ¹ H-NMR and LC-Mass. The results of ¹ H-NMR and LC-Mass are shown in FIGS. 3 and 4, respectively. Further, the results of photoluminescence in a THF solution (1.0 × 10 ⁻⁸ mol / liter) are shown in FIG.

冷却管、温度計、窒素導入管、メカニカルスターラーのついた４つ口の５００ｍｌコルベンに、ＤＦＡＰ（８．０ｇ，２１．５ｍｍｏｌ）、５，５″−ジブロモ−２，２′：５′，２″−ターチオフェン（３．４ｇ，１５．４ｍｍｏｌ）、ＴＨＦ（３００ｍｌ）および２Ｍ−炭酸カリウム水溶液（５０ｍｌ）を加え、室温で撹拌を行う。この溶液に窒素ガスを導入し、窒素バブリングを３０分行う。
その後、窒素気流下、テトラキストリフェニルホスフィンパラジウム〔Ｐｄ（ＰＰｈ_３）_４〕（０．６ｇ，０．９ｍｍｏｌ）を加え、オイルバスで６３．０〜６５．０℃まで加熱する。さらに同温度で２０時間撹拌する。反応終了後、水浴で室温まで冷却する。析出した結晶をろ過し、得られた結晶は水５０ｍｌで水洗を行う。得られた粗製物（５．９ｇ）はトルエン（１２０ｍｌ）で精製し、目的のＳＴ−０６を５．２ｇ（収率 ８５．２％）得た。目的物の確認は^１Ｈ−ＮＭＲおよびＬＣ−Ｍａｓｓで行った。^１Ｈ−ＮＭＲおよびＬＣ−Ｍａｓｓの結果をそれぞれ図６と図７に示す。またＴＨＦ溶液（１．０×１０^−７モル／リットル）でのフォトルミネッセンスの結果を図８に示す。 Example 3
Synthesis of 5,5 ″ -bis (4-N, N-diphenylaminophenyl) -2,2 ′: 5 ′, 2 ″ -terthiophene (abbreviation ST-06)

DFAP (8.0 g, 21.5 mmol), 5,5 ″ -dibromo-2,2 ′: 5 ′, 2 was added to a four-necked 500 ml Kolben equipped with a cooling pipe, thermometer, nitrogen introduction pipe, and mechanical stirrer. “-Terthiophene (3.4 g, 15.4 mmol), THF (300 ml) and 2M aqueous potassium carbonate solution (50 ml) are added, and the mixture is stirred at room temperature. Nitrogen gas is introduced into this solution and nitrogen bubbling is performed for 30 minutes.
Thereafter, tetrakistriphenylphosphine palladium [Pd (PPh ₃ ) ₄ ] (0.6 g, 0.9 mmol) is added under a nitrogen stream and heated to 63.0 to 65.0 ° C. in an oil bath. The mixture is further stirred at the same temperature for 20 hours. After completion of the reaction, it is cooled to room temperature in a water bath. The precipitated crystals are filtered, and the obtained crystals are washed with 50 ml of water. The obtained crude product (5.9 g) was purified with toluene (120 ml) to obtain 5.2 g (yield: 85.2%) of the target ST-06. The target product was confirmed by ¹ H-NMR and LC-Mass. The results of ¹ H-NMR and LC-Mass are shown in FIGS. 6 and 7, respectively. Further, the results of photoluminescence in a THF solution (1.0 × 10 ⁻⁷ mol / liter) are shown in FIG.

同圧式滴下ロート、温度計、窒素導入管、メカニカルスターラーのついた１リットルの４つ口コルベンに、５−ブロモアセナフテン（２５．０ｇ，１０７．０ｍｍｏｌ）、ＴＨＦ（２９０ｍｌ）を加え、窒素気流下で撹拌する。コルベンはアセトン−ドライアイス浴で−６５．０℃まで冷却する。滴下ロートから１．６Ｍ濃度のｎ−ブチルリチウム溶液（１００．５ｍｌ，１６１．３ｍｍｏｌ）を１時間かけて滴下する。滴下後−６５．０〜−６３．０℃で２時間撹拌する。
その後、２−イソプロポキシ−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン（３９．５ｇ，２１４．０ｍｍｏｌ）を１５分かけて滴下する。滴下終了後、３０分−６５．０〜−６３．０℃で撹拌後アセトン−ドライアイスバスをはずし室温（２３．０〜２５．０℃）で２０時間撹拌する。
反応終了後、反応液に水１００ｍｌを加え、１時間撹拌し、酢酸エチル３５０ｍｌを加え、分液する。分液された有機層は、さらに１０％食塩水で洗い、エバポレーターで溶媒を回収する。得られた粗製物（３０．５ｇ）はシリカゲルカラムクロマトグラフ（移動層、ｎ−ヘキサン：トルエン＝１：１）で精製し、目的の５−ＡＮＢＥを２０．５ｇ（収率 ６８．８％）得た。

２）４−（アセナフテン−５−イル）ブロモベンゼン（略称４−ＡＮＰＢ）の合成

冷却管、温度計、窒素導入管、メカニカルスターラーのついた４つ口の５００ｍリットルコルベンに、５−ＡＮＢＥ（２０．０ｇ，７１．９ｍｍｏｌ）、４−ブロモヨードベンゼン（２２．３ｇ，７９．１ｍｍｏｌ）、トルエン（７００ｍｌ）、エタノール（２２５ｍｌ）および２Ｍ−炭酸カリウム水溶液（２３５ｍｌ）を加え、室温で撹拌を行う。この溶液に窒素ガスを導入し、窒素バブリングを３０分行う。
その後、窒素気流下でテトラキストリフェニルホスフィンパラジウム〔Ｐｄ（ＰＰｈ_３）_４〕（０．６ｇ，０．９ｍｍｏｌ）を加え、オイルバスで７３．０〜７５．０℃まで加熱する。さらに同温度で２０時間撹拌する。反応終了後、水浴で室温まで冷却する。その後、静置し水層を分液し、さらに有機層は水洗（１５０ｍｌ）する。有機層はエバポレートし、粗製物（２９．３ｇ）を得た。得られた粗製物はシリカゲルカラムクロマトグラフ（移動層、ｎ−ヘキサン：トルエン＝１２：１および１０：１）で精製し、目的の４−ＡＮＰＢを２０．２ｇ（収率 ９０．９％）得た。

３）４−（アセナフテン−５−イル）フェニルホウ酸エステル（略称４−ＡＮＰＥ）の合成

同圧式滴下ロート、温度計、窒素導入管、メカニカルスターラーのついた５００ｍｌの４つ口コルベンに、４−ＡＮＰＢ（２０．０ｇ，７１．６ｍｍｏｌ）、ＴＨＦ（３２０ｍｌ）を加え窒素気流下撹拌する。コルベンはアセトン−ドライアイス浴で−６５．０℃まで冷却する。滴下ロートから１．６Ｍ濃度のｎ−ブチルリチウム（６７．１ｍｌ，１０７．４ｍｍｏｌ）を１時間かけて滴下する。滴下後−６５．０〜−６３．０℃で２時間撹拌する。
その後、２−イソプロポキシ−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン（２６．４ｇ，１４３．２ｍｍｏｌ）を１５分かけて滴下する。滴下終了後、３０分−６５．０〜−６３．０℃で撹拌後、アセトン−ドライアイスバスをはずし、室温（２３．０〜２５．０℃）で２０時間撹拌する。
反応終了後、反応液に水５０ｍｌを加え、１時間撹拌し、酢酸エチル２００ｍｌを加え、分液する。分液された有機層は、さらに１０％食塩水で洗いエバポレーターで溶媒を回収する。得られた粗製物（２６．７ｇ）はシリカゲルカラムクロマトグラフ（移動層、ｎ−ヘキサン：トルエン＝３：１）で精製し、目的の４−ＡＮＰＥを２１．５ｇ（収率 ８４．８％）得た。

４）２，５−ビス〔４−（アセナフテン−５−イル）フェニル〕チオフェン（略称ＳＡ−０３）の合成

冷却管、温度計、窒素導入管、メカニカルスターラーのついた４つ口の５００ｍリットルコルベンに、４−ＡＮＰＥ（１０．０ｇ，２８．３ｍｍｏｌ）、２，５−ジブロモチオフェン（２．７ｇ，１１．３ｍｍｏｌ）、ＴＨＦ（４００ｍｌ）および２Ｍ−炭酸カリウム水溶液（７０ｍｌ）を加え、室温で撹拌を行う。この溶液に窒素ガスを導入し、窒素バブリングを３０分行う。
その後、窒素気流下、テトラキストリフェニルホスフィンパラジウム〔Ｐｄ（ＰＰｈ_３）_４〕（０．７ｇ，０．５７ｍｍｏｌ）を加え、オイルバスで６３．０〜６５．０℃まで加熱する。さらに同温度で２０時間撹拌する。反応終了後、水浴で室温まで冷却する。析出した結晶をろ過し、得られた結晶は水２００ｍｌで水洗を行う。得られた粗製物（３．８ｇ）はトルエン（６０ｍｌ）で精製し、目的のＳＡ−０３を２．４ｇ（収率 ３９．６％）得た。目的物の確認はＬＣ−Ｍａｓｓで行った。ＬＣ−Ｍａｓｓの結果を図９に示す。またＴＨＦ溶液（１．０×１０^−８モル／リットル）でのフォトルミネッセンスの結果を図１０に示す。 Example 4
Synthesis of 2,5-bis [4- (acenaphthen-5-yl) phenyl] thiophene (abbreviation SA-03) 1) Synthesis of 5-acenaphthene borate ester (abbreviation 5-ANBE)

Add 5-bromoacenaphthene (25.0 g, 107.0 mmol) and THF (290 ml) to a 1 liter four-necked Kolben equipped with a same pressure dropping funnel, thermometer, nitrogen inlet tube, and mechanical stirrer. Stir under. Kolben is cooled to −65.0 ° C. in an acetone-dry ice bath. A 1.6M n-butyllithium solution (100.5 ml, 161.3 mmol) is dropped from the dropping funnel over 1 hour. After dropping, the mixture is stirred at -65.0 to -63.0 ° C for 2 hours.
Thereafter, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (39.5 g, 214.0 mmol) is added dropwise over 15 minutes. After completion of dropping, the mixture is stirred for 30 minutes at −65.0 to −63.0 ° C., then the acetone-dry ice bath is removed, and the mixture is stirred at room temperature (23.0 to 25.0 ° C.) for 20 hours.
After completion of the reaction, 100 ml of water is added to the reaction solution and stirred for 1 hour. The separated organic layer is further washed with 10% saline, and the solvent is recovered with an evaporator. The obtained crude product (30.5 g) was purified by silica gel column chromatography (moving bed, n-hexane: toluene = 1: 1), and 20.5 g (yield 68.8%) of the desired 5-ANBE. Obtained.

2) Synthesis of 4- (acenaphthen-5-yl) bromobenzene (abbreviation 4-ANPB)

A four-necked 500 ml Kolben equipped with a condenser, thermometer, nitrogen inlet tube and mechanical stirrer was added to 5-ANBE (20.0 g, 71.9 mmol), 4-bromoiodobenzene (22.3 g, 79.1 mmol). ), Toluene (700 ml), ethanol (225 ml) and 2M aqueous potassium carbonate solution (235 ml) are added and stirred at room temperature. Nitrogen gas is introduced into this solution and nitrogen bubbling is performed for 30 minutes.
Thereafter, tetrakistriphenylphosphine palladium [Pd (PPh ₃ ) ₄ ] (0.6 g, 0.9 mmol) is added under a nitrogen stream and heated to 73.0-75.0 ° C. in an oil bath. The mixture is further stirred at the same temperature for 20 hours. After completion of the reaction, it is cooled to room temperature in a water bath. Thereafter, the mixture is allowed to stand to separate the aqueous layer, and the organic layer is washed with water (150 ml). The organic layer was evaporated to give a crude product (29.3 g). The resulting crude product was purified by silica gel column chromatography (mobile bed, n-hexane: toluene = 12: 1 and 10: 1) to obtain 20.2 g (yield 90.9%) of the desired 4-ANPB. It was.

3) Synthesis of 4- (acenaphthen-5-yl) phenyl borate (abbreviation 4-ANPE)

4-ANPB (20.0 g, 71.6 mmol) and THF (320 ml) are added to a 500 ml four-necked colben equipped with a same pressure dropping funnel, a thermometer, a nitrogen inlet tube, and a mechanical stirrer, and stirred under a nitrogen stream. Kolben is cooled to −65.0 ° C. in an acetone-dry ice bath. From the dropping funnel, 1.6M n-butyllithium (67.1 ml, 107.4 mmol) is added dropwise over 1 hour. After dropping, the mixture is stirred at -65.0 to -63.0 ° C for 2 hours.
Thereafter, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (26.4 g, 143.2 mmol) is added dropwise over 15 minutes. After completion of dropping, the mixture is stirred for 30 minutes at -65.0 to -63.0 ° C, then the acetone-dry ice bath is removed, and the mixture is stirred at room temperature (23.0 to 25.0 ° C) for 20 hours.
After completion of the reaction, 50 ml of water is added to the reaction solution, stirred for 1 hour, 200 ml of ethyl acetate is added, and the mixture is separated. The separated organic layer is further washed with 10% saline and the solvent is recovered with an evaporator. The obtained crude product (26.7 g) was purified by silica gel column chromatography (mobile bed, n-hexane: toluene = 3: 1), and 21.5 g of the desired 4-ANPE (yield 84.8%). Obtained.

4) Synthesis of 2,5-bis [4- (acenaphthen-5-yl) phenyl] thiophene (abbreviation SA-03)

A four-necked 500 ml Kolben equipped with a condenser, thermometer, nitrogen inlet tube and mechanical stirrer was added to 4-ANPE (10.0 g, 28.3 mmol), 2,5-dibromothiophene (2.7 g, 11. 3 mmol), THF (400 ml) and 2M aqueous potassium carbonate solution (70 ml) are added and stirred at room temperature. Nitrogen gas is introduced into this solution and nitrogen bubbling is performed for 30 minutes.
Thereafter, tetrakistriphenylphosphine palladium [Pd (PPh ₃ ) ₄ ] (0.7 g, 0.57 mmol) is added under a nitrogen stream and heated to 63.0 to 65.0 ° C. in an oil bath. The mixture is further stirred at the same temperature for 20 hours. After completion of the reaction, it is cooled to room temperature in a water bath. The precipitated crystals are filtered, and the obtained crystals are washed with 200 ml of water. The obtained crude product (3.8 g) was purified with toluene (60 ml) to obtain 2.4 g (yield 39.6%) of the desired SA-03. The target product was confirmed by LC-Mass. The result of LC-Mass is shown in FIG. Further, the results of photoluminescence in a THF solution (1.0 × 10 ⁻⁸ mol / liter) are shown in FIG.

冷却管、温度計、窒素導入管、メカニカルスターラーのついた４つ口の１リットルコルベンに、４−ＡＮＰＥ（１３．６ｇ，３８．６ｍｍｏｌ）、５，５′−ジブロモ−２，２′−ビチオフェン（５．０ｇ，１５．４ｍｍｏｌ）、ＴＨＦ（５４０ｍｌ）および２Ｍ−炭酸カリウム水溶液（９２．３ｍｌ）を加え、室温で撹拌を行う。この溶液に窒素ガスを導入し、窒素バブリングを３０分行う。
その後、窒素気流下、テトラキストリフェニルホスフィンパラジウム〔Ｐｄ（ＰＰｈ_３）_４〕（１．０ｇ，０．８６ｍｍｏｌ）を加え、オイルバスで６３．０〜６５．０℃まで加熱する。さらに同温度で２０時間撹拌する。反応終了後、水浴で室温まで冷却する。析出した結晶をろ過し、得られた結晶は水１００ｍｌで水洗を行う。このようにしてＳＡ−０４を７．４ｇ（収率 ７７．１％）得た。目的物の確認はＤＩ−Ｍａｓｓ（直接導入質量分析といい、微量資料を測定室の中に直接挿入して分子量を測定する方法）で行った。ＤＩ−Ｍａｓｓの結果を図１１に示す。またＴＨＦ溶液（１．０×１０^−８モル／リットル）でのフォトルミネッセンスの結果を図１２に示す。 Example 5
Synthesis of 5,5′-bis [4- (acenaphthen-5-yl) phenyl] 2,2′-bithiophene (abbreviation SA-04)

4-ANPE (13.6 g, 38.6 mmol), 5,5′-dibromo-2,2′-bithiophene in a four-necked 1 liter Kolben equipped with a condenser, thermometer, nitrogen inlet tube and mechanical stirrer (5.0 g, 15.4 mmol), THF (540 ml) and 2M aqueous potassium carbonate solution (92.3 ml) are added and stirred at room temperature. Nitrogen gas is introduced into this solution and nitrogen bubbling is performed for 30 minutes.
Thereafter, tetrakistriphenylphosphine palladium [Pd (PPh ₃ ) ₄ ] (1.0 g, 0.86 mmol) is added under a nitrogen stream and heated to 63.0 to 65.0 ° C. in an oil bath. The mixture is further stirred at the same temperature for 20 hours. After completion of the reaction, it is cooled to room temperature in a water bath. The precipitated crystals are filtered, and the obtained crystals are washed with 100 ml of water. In this way, 7.4 g (yield 77.1%) of SA-04 was obtained. The object was confirmed by DI-Mass (direct introduction mass spectrometry, a method of measuring a molecular weight by directly inserting a small amount of data into a measurement chamber). The result of DI-Mass is shown in FIG. Moreover, the result of the photoluminescence in a THF solution (1.0 * 10 < ^-8 > mol / liter) is shown in FIG.

冷却管、温度計、メカニカルスターラーのついた４つ口の２リットルコルベンに、フルオランテン（５０．０ｇ，２４７．０ｍｍｏｌ）、Ｎ−ブロモコハク酸イミド（４４．０ｇ，２４７．０ｍｍｏｌ）および２０％硫酸７００ｍｌを加え撹拌する。このコルベンをオイルバスで６０．０〜６４．０℃に加熱する。さらに同温度で５時間撹拌する。反応終了後、水浴で室温まで冷却し、トルエン（１リットル）を加えスラリーを溶解させる。得られた溶液は静置し、水層を分液する。有機層は、５％の炭酸水素ナトリウム水（５００ｍｌ）で中和し、水洗い（５００ｍｌ）を行い、エバポレートする。
得られた粗製物（６９．７ｇ）はエタノール（１リットル）で再結晶を行い、目的の３−ＢＦを３６．４ｇ（収率 ４３．９％）得た。

２）３−フルオランテンホウ酸エステル（略称３−ＦＢＥ）の合成

同圧式滴下ロート、温度計、窒素導入管、メカニカルスターラーのついた５００ｍｌの４つ口コルベンに、３−ＢＦ（３３．０ｇ，１１７．０ｍｍｏｌ）、ＴＨＦ（６９０ｍｌ）を加え、窒素気流下撹拌する。コルベンはアセトン−ドライアイス浴で−６５．０℃まで冷却する。滴下ロートから１．６Ｍ濃度のｎ−ブチルリチウム（１１０．１ｍｌ，１７５．５ｍｍｏｌ）を１時間かけて滴下する。滴下後−６５．０〜−６３．０℃で２時間撹拌する。
その後、２−イソプロポキシ−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン（４３．８ｇ，２３４．０ｍｍｏｌ）を１５分かけて滴下する。滴下終了後、３０分−６５．０〜−６３．０℃で撹拌後アセトン−ドライアイスバスをはずし、室温（２３．０〜２５．０℃）で２０時間撹拌する。
反応終了後、反応液に水６０ｍｌを加え、１時間撹拌し、酢酸エチル２００ｍｌを加え、分液する。分液された有機層は、さらに１０％食塩水で洗い、エバポレーターで溶媒を回収する。得られた粗製物（４４．８ｇ）はシリカゲルカラムクロマトグラフ（移動層、ｎ−ヘキサン：トルエン＝３：１）で精製し、目的の３−ＦＢＥを２３．４ｇ（収率 ６０．９％）得た。

３）４−（フルオランテン−３−イル）ブロモベンゼン（略称４−ＢＦＢ）の合成

冷却管、温度計、窒素導入管、メカニカルスターラーのついた４つ口の１リットルコルベンに、３−ＦＢＥ（２３．０ｇ，７１．９ｍｍｏｌ）、４−ブロモヨードベンゼン（２０．６ｇ，７３．３ｍｍｏｌ）、トルエン（７００ｍｌ）、エタノール（２２５ｍｌ）および２Ｍ−炭酸カリウム水溶液（２３５ｍｌ）を加え、室温で撹拌を行う。この溶液に窒素ガスを導入し、窒素バブリングを３０分行う。
その後、窒素気流下、テトラキストリフェニルホスフィンパラジウム〔Ｐｄ（ＰＰｈ_３）_４〕（１．８ｇ，１．６２ｍｍｏｌ）を加え、オイルバスで７３．０〜７５．０℃まで加熱する。さらに同温度で２０時間撹拌する。反応終了後、水浴で室温まで冷却する。その後、静置し、水層を分液し、さらに有機層は水洗（１５０ｍｌ）する。有機層はエバポレートし粗製物（４６．４ｇ）を得た。得られた粗製物はシリカゲルカラムクロマトグラフ（移動層、ｎ−ヘキサン：トルエン＝１５：１）で精製し、目的の４−ＢＦＢを１９．６ｇ（収率 ７６．３％）得た。

４）４−（フルオランテン−３−イル）フェニルボロン酸エステル（略称４−ＦＰＢＥ）の合成

同圧式滴下ロート、温度計、窒素導入管、メカニカルスターラーのついた５００ｍｌの４つ口コルベンに、４−ＢＦＢ（１６．２ｇ，４５．３ｍｍｏｌ）、ＴＨＦ（３８０ｍｌ）を加え、窒素気流下で撹拌する。コルベンはアセトン−ドライアイス浴で−６５．０℃まで冷却する。滴下ロートから１．６Ｍ濃度のｎ−ブチルリチウム（４２．５ｍｌ，６８．０ｍｍｏｌ）を１時間かけて滴下する。滴下後−６５．０〜−６３．０℃で２時間撹拌する。
その後、２−イソプロポキシ−４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン（１７．０ｇ，９０．８ｍｍｏｌ）を１５分かけて滴下する。滴下終了後、３０分−６５．０〜−６３．０℃で撹拌後、アセトン−ドライアイスバスをはずし、室温（２３．０〜２５．０℃）で２０時間撹拌する。
反応終了後、反応液に水４５ｍｌを加え、１時間撹拌し、酢酸エチル２００ｍｌを加え、分液する。分液された有機層は、さらに１０％食塩水で洗い、エバポレーターで溶媒を回収する。得られた粗製物（１８．７ｇ）はシリカゲルカラムクロマトグラフ（移動層、ｎ−ヘキサン：トルエン＝３：１）で精製し、目的の４−ＦＰＢＥを１１．４ｇ（収率 ６２．２％）得た。

５）２，５−ビス〔４−（フルオランテン−４−イル）フェニル〕チオフェン（略称ＳＦ−０３）の合成

冷却管、温度計、窒素導入管、メカニカルスターラーのついた４つ口の１リットルコルベンに、４−ＦＰＢＥ（６．０ｇ，１４．８ｍｍｏｌ）、２，５−ジブロモチオフェン（１．５ｇ，５．９ｍｍｏｌ）、ＴＨＦ（３００ｍｌ）および２Ｍ−炭酸カリウム水溶液（５０．０ｍｌ）を加え、室温で撹拌を行う。この溶液に窒素ガスを導入し、窒素バブリングを３０分行う。
その後、窒素気流下でテトラキストリフェニルホスフィンパラジウム〔Ｐｄ（ＰＰｈ_３）_４〕（０．５ｇ，０．４３ｍｍｏｌ）を加え、オイルバスで６３．０〜６５．０℃まで加熱する。さらに同温度で２０時間撹拌する。反応終了後、水浴で室温まで冷却する。析出した結晶をろ過し、得られた粗製物は水２００ｍｌで水洗を行う。さらにこの粗製物（４．０ｇ）は、ｍ−ジクロロベンゼン（２００ｍｌ）と活性白土（１．０ｇ）で再結晶を行い、ＳＦ−０３を２．１ｇ（収率５５．５％）得た。目的物の確認はＬＣ−Ｍａｓｓで行った。ＬＣ−Ｍａｓｓの結果を図１３に示す。またＴＨＦ溶液（１．０×１０^−８モル／リットル）でのフォトルミネッセンスの結果を図１４に示す。 Example 6
Synthesis of 2,5-bis [4- (fluoranthen-4-yl) phenyl] thiophene (abbreviation SF-03) 1) Synthesis of 3-bromofluoranthene (3-BF)

To a 4 liter 2 liter Kolben equipped with a condenser, thermometer and mechanical stirrer, fluoranthene (50.0 g, 247.0 mmol), N-bromosuccinimide (44.0 g, 247.0 mmol) and 20% sulfuric acid 700 ml Add and stir. The Kolben is heated to 60.0-64.0 ° C. in an oil bath. The mixture is further stirred at the same temperature for 5 hours. After completion of the reaction, the reaction mixture is cooled to room temperature in a water bath, and toluene (1 liter) is added to dissolve the slurry. The resulting solution is allowed to stand and the aqueous layer is separated. The organic layer is neutralized with 5% aqueous sodium hydrogen carbonate (500 ml), washed with water (500 ml) and evaporated.
The obtained crude product (69.7 g) was recrystallized from ethanol (1 liter) to obtain 36.4 g (yield 43.9%) of the desired 3-BF.

2) Synthesis of 3-fluoranthene borate ester (abbreviation 3-FBE)

3-BF (33.0 g, 117.0 mmol) and THF (690 ml) are added to a 500 ml four-necked Kolben equipped with a same pressure dropping funnel, thermometer, nitrogen inlet tube, and mechanical stirrer, and stirred under a nitrogen stream. . Kolben is cooled to −65.0 ° C. in an acetone-dry ice bath. From the dropping funnel, 1.6M n-butyllithium (110.1 ml, 175.5 mmol) is added dropwise over 1 hour. After dropping, the mixture is stirred at -65.0 to -63.0 ° C for 2 hours.
Thereafter, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (43.8 g, 234.0 mmol) is added dropwise over 15 minutes. After completion of dropping, the mixture is stirred for 30 minutes at −65.0 to −63.0 ° C., then the acetone-dry ice bath is removed, and the mixture is stirred at room temperature (23.0 to 25.0 ° C.) for 20 hours.
After completion of the reaction, 60 ml of water is added to the reaction solution and stirred for 1 hour, and 200 ml of ethyl acetate is added to separate the layers. The separated organic layer is further washed with 10% saline, and the solvent is recovered with an evaporator. The obtained crude product (44.8 g) was purified by silica gel column chromatography (mobile bed, n-hexane: toluene = 3: 1), and 23.4 g (yield 60.9%) of the desired 3-FBE. Obtained.

3) Synthesis of 4- (fluoranthen-3-yl) bromobenzene (abbreviation 4-BFB)

Four-necked 1 liter Kolben with a condenser, thermometer, nitrogen inlet tube, and mechanical stirrer were added to 3-FBE (23.0 g, 71.9 mmol), 4-bromoiodobenzene (20.6 g, 73.3 mmol). ), Toluene (700 ml), ethanol (225 ml) and 2M aqueous potassium carbonate solution (235 ml) are added and stirred at room temperature. Nitrogen gas is introduced into this solution and nitrogen bubbling is performed for 30 minutes.
Thereafter, tetrakistriphenylphosphine palladium [Pd (PPh ₃ ) ₄ ] (1.8 g, 1.62 mmol) is added under a nitrogen stream and heated to 73.0-75.0 ° C. in an oil bath. The mixture is further stirred at the same temperature for 20 hours. After completion of the reaction, it is cooled to room temperature in a water bath. Thereafter, the mixture is allowed to stand to separate the aqueous layer, and the organic layer is washed with water (150 ml). The organic layer was evaporated to obtain a crude product (46.4 g). The obtained crude product was purified by silica gel column chromatography (mobile bed, n-hexane: toluene = 15: 1) to obtain 19.6 g (yield 76.3%) of the desired 4-BFB.

4) Synthesis of 4- (fluoranthen-3-yl) phenylboronic acid ester (abbreviation 4-FPBE)

4-BFB (16.2 g, 45.3 mmol) and THF (380 ml) are added to a 500 ml four-necked Kolben equipped with a same pressure dropping funnel, thermometer, nitrogen inlet tube and mechanical stirrer, and stirred under a nitrogen stream. To do. Kolben is cooled to −65.0 ° C. in an acetone-dry ice bath. From the dropping funnel, 1.6 M n-butyllithium (42.5 ml, 68.0 mmol) is added dropwise over 1 hour. After dropping, the mixture is stirred at -65.0 to -63.0 ° C for 2 hours.
Thereafter, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (17.0 g, 90.8 mmol) is added dropwise over 15 minutes. After completion of dropping, the mixture is stirred for 30 minutes at -65.0 to -63.0 ° C, then the acetone-dry ice bath is removed, and the mixture is stirred at room temperature (23.0 to 25.0 ° C) for 20 hours.
After completion of the reaction, 45 ml of water is added to the reaction solution and stirred for 1 hour. The separated organic layer is further washed with 10% saline, and the solvent is recovered with an evaporator. The obtained crude product (18.7 g) was purified by silica gel column chromatography (mobile bed, n-hexane: toluene = 3: 1), and 11.4 g of the desired 4-FPBE (yield 62.2%). Obtained.

5) Synthesis of 2,5-bis [4- (fluoranthen-4-yl) phenyl] thiophene (abbreviation SF-03)

To 4-liter 1 liter Kolben equipped with a condenser, thermometer, nitrogen inlet tube and mechanical stirrer, 4-FPBE (6.0 g, 14.8 mmol), 2,5-dibromothiophene (1.5 g, 5. 9 mmol), THF (300 ml) and 2M aqueous potassium carbonate (50.0 ml) are added and stirred at room temperature. Nitrogen gas is introduced into this solution and nitrogen bubbling is performed for 30 minutes.
Thereafter, tetrakistriphenylphosphine palladium [Pd (PPh ₃ ) ₄ ] (0.5 g, 0.43 mmol) is added under a nitrogen stream and heated to 63.0-65.0 ° C. in an oil bath. The mixture is further stirred at the same temperature for 20 hours. After completion of the reaction, it is cooled to room temperature in a water bath. The precipitated crystals are filtered, and the resulting crude product is washed with 200 ml of water. Furthermore, this crude product (4.0 g) was recrystallized with m-dichlorobenzene (200 ml) and activated clay (1.0 g) to obtain 2.1 g (yield 55.5%) of SF-03. The target product was confirmed by LC-Mass. The results of LC-Mass are shown in FIG. Moreover, the result of the photoluminescence in a THF solution (1.0 * 10 < ^-8 > mol / liter) is shown in FIG.

The LC-Mass of ST-31 of Example 1 is shown. The photoluminescence curve in the THF solution of ST-31 of Example 1 is shown. ¹ H-NMR of ST-05 of Example 2 is shown. The LC-Mass of ST-05 of Example 2 is shown. The photoluminescence curve in the THF solution of ST-05 of Example 2 is shown. ¹ H shows ¹ H-NMR of ST-06 in Example 3. The LC-Mass of ST-06 of Example 3 is shown. The photoluminescence curve in the THF solution of ST-06 of Example 3 is shown. 3 shows LC-Mass of SA-03 of Example 4. The photoluminescence curve in the THF solution of SA-03 of Example 4 is shown. The DI-Mass of SA-04 of Example 5 is shown. The photoluminescence curve in the THF solution of SA-04 of Example 5 is shown. The LC-Mass of SF-03 of Example 6 is shown. The photoluminescence curve in the THF solution of SF-03 of Example 5 is shown. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention.

Explanation of symbols

1 Substrate 2 Anode (ITO)
3 Light emitting layer 4 Cathode 5 Hole transport layer (hole transport layer)
6 Electron transport layer 7 Hole injection layer (hole injection layer)
8 Electron injection layer 9 Hole blocking layer (hole blocking layer)

Claims (6)

The following general formula (1)

(R ¹ and R ² are groups independently selected from the group consisting of hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms,
R ^{3 to} R ⁶ are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkylamino group having 1 to 6 carbon atoms. Each independently selected from the group consisting of groups,
Q is
An arylamino group having an aryl group having 6 to 16 carbon atoms, which may have a substituent,
An aromatic ring having 10 to 16 carbon atoms, which may have a substituent,
Each independently selected from the group consisting of a heterocyclic group having 10 to 15 carbon atoms, which may have a substituent,
n is an integer of 1 to 4, but when n = 1 and Q is the arylamino group, Q is not added to the p-position of the thiophene ring. )
A thiophene derivative represented by: The following general formula (2)

(R ¹ and R ² are groups independently selected from the group consisting of hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms,
R ^{3 to} R ⁶ are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkylamino group having 1 to 6 carbon atoms. Each independently selected from the group consisting of groups,
Q is
An arylamino group having an aryl group having 6 to 16 carbon atoms, which may have a substituent,
An aromatic ring having 10 to 16 carbon atoms, which may have a substituent,
Each independently selected from the group consisting of a heterocyclic group having 10 to 15 carbon atoms, which may have a substituent,
n is an integer of 1 to 4, but when n = 1 and Q is the arylamino group, Q is not added to the p-position of the thiophene ring. )
A thiophene derivative represented by:   The thiophene derivative according to claim 2, wherein the aromatic ring in Q is an acenaphthene ring, an acenaphthylene ring or a fluoranthene ring.   A thiophene-containing fluorescent material comprising the thiophene derivative according to claim 1.   A light emitting material for organic electroluminescence comprising the thiophene derivative according to any one of claims 1 to 3.   An organic electroluminescence device comprising the thiophene derivative according to claim 1.

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