JP5011743B2 - Π-conjugated compound having cardo structure, and production method and use thereof - Google Patents

Description

  The present invention relates to a π-conjugated compound having a cardo structure, a production method thereof, and an organic electroluminescence (EL) device. The π-conjugated compound having a cardo structure can be widely used as an organic semiconductor material, and more specifically, can be used as a light emitting material or an electron transport material of an organic EL element used for a flat light source or a display, or an organic transistor material.

  In recent years, an organic electroluminescence element or the like has attracted attention as a flat panel display having features of self-light emission, high-speed response, and high viewing angle. As a constituent material, interest in organic light emitting materials is increasing. The first advantage of organic light-emitting materials is that the optical properties of the materials can be controlled to some extent by the molecular design, and as a result, full-color organic materials that produce all three primary colors of red, blue, and green with each light-emitting material. A light emitting element can be realized.

  Many materials have been developed so far, but many of them are not necessarily suitable compounds as organic EL materials because of their low solubility in organic solvents and their high crystallinity. For example, polyphenylene compounds known as blue light emitting materials or electron transport materials, and representative compounds include sexiphenyl derivatives or similar compounds, but due to their high crystallinity, when a thin film is formed by vacuum deposition, When aggregation occurs and a stable thin film cannot be obtained, and it is applied to an organic thin film device such as an organic EL element, there is a problem that there is a high possibility that a short or dark spot will occur (for example, Patent Document 1). And Non-Patent Document 1).

  Spiro-6φ in which sexiphenyl is bonded with spiro quaternary carbon has a high glass transition temperature (Tg) and does not crystallize for a long time even in an organic EL device produced by spin coating, and emits blue light. Although described as showing, it was not fully satisfactory (see, for example, Patent Document 1).

  Furthermore, although bathophenanthroline useful as an electron transport material and a hole blocking material shows a high value in terms of electron mobility, it has a problem from the viewpoint of device lifetime because of its low long-term thin film stability. Therefore, in order to improve the thin film stability and electron affinity of the phenanthroline derivative, a phenanthroline derivative into which a 9,9-dialkylfluorenylene group is introduced has been reported (for example, see Patent Document 2).

JP-A-7-278537 Japanese Patent Laid-Open No. 2004-277377 Organic EL materials and displays (CMC Publishing) p195

  An object of the present invention is to provide a novel light-emitting material in which a thin film is stably maintained without being crystallized over a long period of time and can be formed by a coating method such as a spin coating method with high solubility in addition to a vacuum deposition method In particular, it is to provide a blue light emitting material, a hole blocking material or an electron transporting material.

  As a result of intensive studies, the present inventors have found that a specific π-conjugated compound having a cardo structure represented by the general formula (1) has a high glass transition temperature, which is an indicator of thermal stability, and many of these compounds Although it is not a crystalline compound, it has an amorphous structure, so it has excellent thin film stability, and even if it shows crystallinity, it has a cardo structure (cardo means a hinge and is cyclic to the main chain. The thin film does not become clouded not only by vacuum deposition but also by a coating method such as spin coating over a long period of time, and particularly in organic electroluminescence devices, It has been found useful as a hole blocking material and an electron transporting material, and the present invention has been completed. That is, the present invention relates to a π-conjugated compound having a cardo structure represented by the general formula (1), and a production method and use thereof.

（式中、Ｒ^１〜Ｒ^２は各々独立して水素原子、置換基を有していてもよい炭素数１〜１８の直鎖，分岐若しくは環状のアルキル基若しくはアルコキシ基、置換基を有していてもよいフェニル基、ナフチル基若しくはフェノキシ基、又はハロゲン原子を表し、Ａｒ^１は各々独立して下記一般式（２）又は（３）で表される基を表す。Ａｒ^２は各々独立して置換基（但し、アミノ基を除く）を有していてもよい炭素数６〜２４のアリール基又は炭素数３〜２４のヘテロアリール基を表す。）

(Wherein R ^{1 and} R ² each independently have a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group having 1 to 18 carbon atoms which may have a substituent, or a substituent. which may be a phenyl group, a naphthyl group or a phenoxy group, or a halogen atom, Ar ¹ is .Ar ² each independently represents a group represented by the following general formula (2) or (3) each independently Represents an aryl group having 6 to 24 carbon atoms or a heteroaryl group having 3 to 24 carbon atoms which may have a substituent (excluding an amino group).

（式中、Ｒ^３〜Ｒ^６は各々独立して水素原子、置換基を有していてもよい炭素数１〜１８の直鎖，分岐若しくは環状のアルキル基若しくはアルコキシ基、置換基（但し、アミノ基を除く）を有していてもよい炭素数６〜２４のアリール基若しくはアリールオキシ基、炭素数３〜２４のヘテロアリール基、又はハロゲン原子を表す。ｌ，ｍは０〜３の整数、ｎは０〜２の整数を表す。）
以下、本発明に関し詳細に説明する。

(In the formula, R ^{3 to} R ⁶ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group having 1 to 18 carbon atoms which may have a substituent, a substituent (provided that Represents an aryl group having 6 to 24 carbon atoms or an aryloxy group, a heteroaryl group having 3 to 24 carbon atoms, or a halogen atom, which may have a non-amino group, and l and m are integers of 0 to 3. , N represents an integer of 0-2.)
Hereinafter, the present invention will be described in detail.

In the π-conjugated compound having a cardo structure represented by the general formula (1), Ar ¹ is each independently a group represented by the following general formula (2) or (3).

（式中、Ｒ^３〜Ｒ^６は各々独立して水素原子、置換基を有していてもよい炭素数１〜１８の直鎖，分岐若しくは環状のアルキル基若しくはアルコキシ基、置換基（但し、アミノ基を除く）を有していてもよい炭素数６〜２４のアリール基若しくはアリールオキシ基、炭素数３〜２４のヘテロアリール基、又はハロゲン原子を表す。ｌ，ｍは０〜３の整数、ｎは０〜２の整数を表す。）
アルキル基としては、置換基を有していてもよい炭素数１〜１８の直鎖，分岐若しくは環状のアルキル基が挙げられ、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ステアリル基、トリクロロメチル基、トリフルオロメチル基、シクロプロピル基、シクロヘキシル基、１，３−シクロヘキサジエニル基又は２−シクロペンテン−１−イル基等を例示することができる。

(In the formula, R ^{3 to} R ⁶ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group having 1 to 18 carbon atoms which may have a substituent, a substituent (provided that Represents an aryl group having 6 to 24 carbon atoms or an aryloxy group, a heteroaryl group having 3 to 24 carbon atoms, or a halogen atom, which may have a non-amino group, and l and m are integers of 0 to 3. , N represents an integer of 0-2.)
Examples of the alkyl group include a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms which may have a substituent. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, stearyl, trichloromethyl, trifluoromethyl, cyclopropyl, cyclohexyl, 1,3-cyclohexadi Examples include an enyl group and a 2-cyclopenten-1-yl group.

  Examples of the alkoxy group include linear, branched or cyclic alkoxy groups having 1 to 18 carbon atoms which may have a substituent, and specifically include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. , N-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, stearyloxy group, trifluoromethoxy group, and the like.

  Specific examples of the aryl group having 6 to 24 carbon atoms which may have a substituent (excluding an amino group) include a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, 2- Methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl Group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 1-biphenylyl group, 1-naphthyl group, 2- A naphthyl group, 9-phenanthryl group, anthryl group, pyrenyl group or 9,9-dimethyl-2-fluorenyl group can be exemplified.

  Specific examples of the heteroaryl group having 3 to 24 carbon atoms that may have a substituent (excluding an amino group) include nitrogen-containing heterocyclic aromatics such as a pyridyl group, a bipyridyl group, or a quinolyl group. Group.

  Among these, a phenyl group and a pyridyl group are more preferable.

  Specific examples of the aryloxy group having 6 to 24 carbon atoms which may have a substituent (excluding an amino group) include a phenoxy group, a p-tert-butylphenoxy group, and a 3-fluorophenoxy group. Or 4-fluorophenoxy group etc. can be mentioned.

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

In the π-conjugated compound represented by the general formula (1), each Ar ² is independently an aryl group having 6 to 24 carbon atoms which may have a substituent (excluding an amino group), Specifically, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthryl group, 9-anthryl group, 2-fluorenyl group, phenanthryl group, pyrenyl group, chrysenyl group, perylenyl group, and picenyl group are included. Can be mentioned. The heteroaryl group having 3 to 24 carbon atoms which may have a substituent (excluding an amino group) is an aromatic group containing at least one heteroatom among an oxygen atom, a nitrogen atom and a sulfur atom. Yes, for example, 4-quinolyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 2-dipyridylyl group, 1,10-phenanthrolinyl group, azafluorenyl group, 3-furyl group, 2-furyl Group, 3-thienyl group, 2-thienyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, etc., but are not limited thereto. Is not to be done. The substituent can be exemplified substituents described above R ¹ to R ^6.

  Among them, in addition to naphthyl group, phenanthryl group, fluorenyl group, condensed cyclic aromatic groups such as anthryl group, pyrenyl group, chrysenyl group, picenyl group, perylenyl group or benzo [c] fluorenyl group, 1,10-phenanthroli A heteroaryl group such as a nyl group or an azafluorenyl group, or a substituent represented by the following general formula (6a) or (6b) is preferred.

（式中、Ｒ^１３〜Ｒ^１５は、各々独立して水素原子、置換基を有していてもよい炭素数１〜１０の直鎖，分岐若しくは環状のアルキル基若しくはアルコキシ基、置換基を有していてもよい炭素数６〜２４のアリール基若しくは炭素数３〜２４のヘテロアリール基を表す。ｐ及びｑは１≦ｐ＋ｑ≦３を満たす整数、ｓ，ｘは０〜２の整数を表す。）
中でも、下記一般式（４ａ）、（４ｂ）又は（５）で表される縮合環式芳香族基若しくはヘテロアリール基がより好ましい。

(In the formula, each of R ^{13 to} R ¹⁵ independently has a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group having 1 to 10 carbon atoms which may have a substituent, and a substituent. Represents an aryl group having 6 to 24 carbon atoms or a heteroaryl group having 3 to 24 carbon atoms, p and q are integers satisfying 1 ≦ p + q ≦ 3, and s and x represent integers of 0 to 2. .)
Among these, a condensed cyclic aromatic group or heteroaryl group represented by the following general formula (4a), (4b) or (5) is more preferable.

（式中、Ｒ^７〜Ｒ^９は、各々独立して水素原子、置換基を有していてもよい炭素数１〜１８の直鎖，分岐若しくは環状のアルキル基若しくはアルコキシ基、置換基を有していてもよい炭素数６〜２４のアリール基若しくはアリールオキシ基、炭素数３〜２４のヘテロアリール基、又はハロゲン原子を表す。また、Ｘは炭素原子又は窒素原子を表す。）

(Wherein R ^{7 to} R ⁹ each independently have a hydrogen atom, a C 1-18 linear, branched or cyclic alkyl group or alkoxy group which may have a substituent, or a substituent. And optionally represents an aryl group or aryloxy group having 6 to 24 carbon atoms, a heteroaryl group having 3 to 24 carbon atoms, or a halogen atom, and X represents a carbon atom or a nitrogen atom.)

（式中、Ｒ^１０〜Ｒ^１２は、各々独立して水素原子、置換基を有していてもよい炭素数１〜１８の直鎖，分岐若しくは環状のアルキル基若しくはアルコキシ基、置換基を有していてもよい炭素数６〜２４のアリール基若しくはアリールオキシ基、炭素数３〜２４のヘテロアリール基、又はハロゲン原子を表す。但し、Ｒ^１０とＲ^１１は互いに結合して環を形成していてもよい。また、Ｘは炭素原子又は窒素原子を表す。）
表１〜４に上記一般式（１）で表されるπ共役化合物の具体例を示すが、これら化合物に限定されるものではない。

(Wherein R ^{10 to} R ¹² each independently have a hydrogen atom, a C 1-18 linear, branched or cyclic alkyl or alkoxy group which may have a substituent, or a substituent. Represents an optionally substituted aryl group or aryloxy group having 6 to 24 carbon atoms, a heteroaryl group having 3 to 24 carbon atoms, or a halogen atom, provided that R ¹⁰ and R ¹¹ are bonded to each other to form a ring. X represents a carbon atom or a nitrogen atom.)
Although the specific example of (pi) conjugated compound represented by the said General formula (1) to Tables 1-4 is shown, it is not limited to these compounds.

前記一般式（１）で表されるπ共役化合物は、公知の反応形式（例えば、Ｃｈｅｍ． Ｒｅｖ．１９９５５，９５，ｐ２４５７−２４８３参照）により合成可能である。例えば、下記一般式（７）で表されるフルオレン中間体と下記一般式（８）で表されるボロン酸化合物Ａとを遷移金属触媒存在下に反応させ、酸触媒存在下に脱保護し、更にトリフルオロメタンスルホニル化した後、更に遷移金属触媒存在下にボロン酸化合物Ｂ（９）と反応させることにより合成することができる。

The π-conjugated compound represented by the general formula (1) can be synthesized by a known reaction format (see, for example, Chem. Rev. 1995, 95, p2457-2483). For example, a fluorene intermediate represented by the following general formula (7) and a boronic acid compound A represented by the following general formula (8) are reacted in the presence of a transition metal catalyst, and deprotected in the presence of an acid catalyst, Furthermore, after trifluoromethanesulfonylation, it can be synthesized by further reacting with boronic acid compound B (9) in the presence of a transition metal catalyst.

  Examples of the transition metal catalyst include a nickel catalyst and a palladium catalyst. More specifically, as the nickel catalyst, 1,4-bis (diphenylphosphino) butanenickel (II) chloride, 1,1′-bis (diphenylphosphino) ferrocene nickel (II) chloride, 1,2-bis (Diphenylphosphino) ethane nickel (II) chloride, 1,3-bis (diphenylphosphino) propane nickel (II) chloride and the like. Further, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphino) palladium (II) chloride, 1,1′-bis (diphenylphosphino) ferrocene palladium (II) chloride, 1, 2-bis (diphenylphosphino) ethanepalladium (II) chloride, 1,3-bis (diphenylphosphino) propanepalladium (II) chloride, 1,4-bis (diphenylphosphino) butanepalladium (II) chloride, bis (Tri-tertiary butyl phosphine) palladium (0), polymer fixed palladium catalyst, palladium carbon and the like.

（式中、Ｚはフェノール基の保護基であり、Ｒ^１〜Ｒ^２は各々独立して水素原子、置換基を有していてもよい炭素数１〜１８の直鎖，分岐若しくは環状のアルキル基若しくはアルコキシ基、置換基を有していてもよいフェニル基、ナフチル基若しくはフェノキシ基、又はハロゲン原子を表し、Ｘはヨウ素原子、臭素原子又は塩素原子を表す。）

(In the formula, Z is a protecting group for a phenol group, and R ^{1 and} R ² are each independently a hydrogen atom, a linear, branched or cyclic alkyl having 1 to 18 carbon atoms which may have a substituent. A group or an alkoxy group, an optionally substituted phenyl group, a naphthyl group or a phenoxy group, or a halogen atom, and X represents an iodine atom, a bromine atom or a chlorine atom.)

（式中、Ａｒ^１は各々独立して下記一般式（２）又は（３）で表される基を表す。Ａｒ^２は各々独立して置換基（但し、アミノ基を除く）を有していてもよい炭素数６〜２４のアリール基又は炭素数３〜２４のヘテロアリール基を表す。）

(In the formula, each Ar ¹ independently represents a group represented by the following general formula (2) or (3). Each Ar ² independently has a substituent (excluding an amino group). Represents an aryl group having 6 to 24 carbon atoms or a heteroaryl group having 3 to 24 carbon atoms.

（式中、Ｒ^３〜Ｒ^６は各々独立して水素原子、置換基を有していてもよい炭素数１〜１８の直鎖，分岐若しくは環状のアルキル基若しくはアルコキシ基、置換基（但し、アミノ基を除く）を有していてもよい炭素数６〜２４のアリール基若しくはアリールオキシ基、炭素数３〜２４のヘテロアリール基、又はハロゲン原子を表す。ｌ，ｍは０〜３の整数、ｎは０〜２の整数を表す。）
Ｚは、公知のフェノール性水酸基の保護基（例えば、Ｐｒｏｔｅｃｔｉｎｇ Ｇｒｏｕｐ ｉｎ Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｉｓ， Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ）であれば特に制限はないが、脱離の容易さの観点から、エトキシエトキシメチル基、メトキシメチル基等のアルコキシアルキル基が好ましい。

(In the formula, R ^{3 to} R ⁶ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group having 1 to 18 carbon atoms which may have a substituent, a substituent (provided that Represents an aryl group having 6 to 24 carbon atoms or an aryloxy group, a heteroaryl group having 3 to 24 carbon atoms, or a halogen atom, which may have a non-amino group, and l and m are integers of 0 to 3. , N represents an integer of 0-2.)
Z is not particularly limited as long as it is a known protecting group for a phenolic hydroxyl group (for example, Protection Group in Organic Synthesis, John Wiley & Sons), but from the viewpoint of ease of elimination, ethoxyethoxymethyl group, methoxymethyl An alkoxyalkyl group such as a group is preferred.

  The protecting group for the phenolic hydroxyl group can be removed in the presence of an acid catalyst. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, boron trifluoride and the like. Of these acid catalysts, hydrochloric acid is particularly preferred.

  As a more specific synthesis method, a synthesis example in which Z is a methoxymethyl group can be simply illustrated by the following general formula (10).

本発明のカルド構造を有するπ共役化合物は、特に有機エレクトロルミネッセンス素子の青色発光材料、正孔ブロック材料、電子輸送材料に使用できる。正孔ブロック材料は、素子に用いられる発光材料、例えば緑色蛍光材料であるアルミニウムトリスキノリノール錯体（Ａｌｑ_３）、燐光ホスト材料である４，４’−Ｎ，Ｎ’−ジカルバゾール−ビフェニル（ＣＢＰ）のイオン化ポテンシャルより高いほうが好ましい。また、電子輸送材料は、従来のＡｌｑ_３、バソフェナントロリンの電子親和性と同等以上がより好ましい。更に、電子輸送材料は、従来材料のＡｌｑ_３の電子移動度（１０^−６ｃｍ^２／Ｖ・ｓ程度）より大きいことがより好ましい。上記イオン化ポテンシャルは、通常、光電子分光法又はサイクリックボルタンメトリにより測定可能である。更に、電子親和性は、光電子分光法から求められるイオン化ポテンシャル及び吸収スペクトルの吸収末端のエネルギーから求めるか、サイクリックボルタンメトリにより測定可能である。

The π-conjugated compound having a cardo structure of the present invention can be used particularly for a blue light emitting material, a hole blocking material, and an electron transporting material of an organic electroluminescence device. The hole blocking material is a light emitting material used in the device, for example, an aluminum triskinolinol complex (Alq ₃ ) which is a green fluorescent material, or 4,4′-N, N′-dicarbazole-biphenyl (CBP) which is a phosphorescent host material. A higher ionization potential is preferable. The electron transport material is more preferably equal to or higher than the electron affinity of conventional Alq ₃ and bathophenanthroline. Furthermore, the electron transport material is more preferably larger than the electron mobility (about 10 ⁻⁶ cm ² / V · s) of the conventional material Alq ₃ . The ionization potential can usually be measured by photoelectron spectroscopy or cyclic voltammetry. Furthermore, the electron affinity can be determined from the ionization potential obtained from photoelectron spectroscopy and the energy at the absorption end of the absorption spectrum, or can be measured by cyclic voltammetry.

  Further, unlike the conventional materials, the π-conjugated compound having a cardo structure of the present invention has an advantage of excellent thin film stability. Therefore, not only as a light emitting material such as an organic EL element or an electrophotographic photosensitive member, a hole blocking material and an electron transport material, but also in any field of organic semiconductor materials such as organic transistor materials, photoelectric conversion elements, solar cells, and image sensors. Can also be used.

  The π-conjugated compound having a cardo structure of the present invention is a material excellent in thin film stability and durability as compared with conventional materials, and as a light-emitting material and an electron transport material such as an organic EL element or an electrophotographic photosensitive member. In addition, it is useful as a wide range of organic semiconductor materials such as organic transistor materials, photoelectric conversion elements, solar cells, and image sensors.

  Hereinafter, the present invention will be described in more detail based on examples.

  In addition, FDMS (field desorption mass spectrometry) measurement was performed using Hitachi, Ltd. M-80B.

        NMR measurement was performed using GEMINI-200 manufactured by Varian.

        The GCMS measurement was performed using JMS-K9 manufactured by JEOL Ltd.

        Elemental analysis measurement was performed using Perkin Elmer 2400II.

Synthesis Example 1 (Synthesis of 2,7-dibromo-9,9′-bis [4- (methoxymethyloxy) phenyl] -9H-fluorene)
Under a nitrogen stream, 0.82 g (34.2 mmol) of sodium hydride and 25 mL of tetrahydrofuran were added to a 100 mL eggplant-shaped flask, and the reaction solution was cooled to 0 ° C. Thereto, 6.5 g (14.3 mmol) tetrahydrofuran solution of 2,7-dibromo-4,4 ′-(9-fluorenylidene) -diphenol was added dropwise, followed by 3.44 g (42.7 mmol) of chloromethyl methyl ether. After dropping, the mixture was stirred at room temperature for 12 hours, and 10 mL of methanol was added to decompose sodium hydride. Thereafter, 20 mL of toluene was added to separate the organic phase. After washing with water and saturated brine, the organic phase was concentrated. By recrystallizing the concentrated solution from ethanol, 6.7 g (yield = 80%) of 2,7-dibromo-9,9′-bis [4- (methoxymethyloxy) phenyl] -9H-fluorene was isolated. did.

Synthesis Example 2 (Synthesis of 2,7-dibromo-9,9-bis (biphenylyl) fluorene)
While maintaining 0.2 L of a tetrahydrofuran solution separately prepared from 3.3 g (135 mmol) of magnesium and 31.4 g (135 mmol) of 2-bromobiphenyl at 40 ° C., mixing of 35 g (104 mmol) of 2,7-dibromofluorenone and 280 mL of tetrahydrofuran The solution was added dropwise (using a 1 L separable flask as the reaction vessel). After completion of dropping, the mixture was further stirred at the same temperature for 3 hours. After completion of the reaction, 420 g of 10% aqueous ammonium chloride solution was added at room temperature, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate, filtered, concentrated, and finally recrystallized from toluene to obtain 36 g of carbinol. Next, 34 g of carbinol, 107 g of biphenyl, 480 g of acetic acid, and 27 g of sulfuric acid were charged into a 1 L separable flask, and heated and stirred overnight at 80 ° C. After cooling the reaction solution to room temperature, the reaction solution was added to ice water with stirring to complete the reaction. The resulting precipitate was washed with water and further washed with hot ethanol. Finally, recrystallization from toluene gave 27 g of 2,7-dibromo-9,9-bis (biphenylyl) fluorene (melting point = 277-282 ° C., yield = 80%).

Identification was performed by FDMS, ¹ H-NMR and ¹³ C-NMR.
FDMS: 628
_{^{· 1 H-NMR (CDCl 3}} , ppm); 7.23-7.64 (m, 24H)
_{^{· 13 C-NMR (CDCl 3}} , ppm); 152.8,143.2,140.4,140.0,138.0,131.0,129.4,128.7,128.3,127. 3, 127.2, 126.9, 121.9, 121.6, 65.2
Synthesis Example 3 (Synthesis of 2-bromo-9,9-bis (biphenylyl) fluorene)
The same operation as in Synthesis Example 2 was performed except that 2,7-dibromofluorenone was changed to 2-bromofluorenone to obtain 2-bromo-9,9-bis (biphenylyl) fluorene.

Identification was performed by FDMS.
・ FDMS: 548
Synthesis Example 4 (Synthesis of 2-bromo-9,9′-spirobifluorene)
2-Bromofluorene (15 g, 40.8 mmol), tetrabutylammonium bromide (329 mg, 2.5 mol%), 48% sodium hydroxide (3.73 g), and toluene (220 mL) were charged into a 500 mL eggplant-shaped flask at 60 ° C. while bubbling air. The mixture was heated and stirred overnight. After concentration, 80 mL of water was added, and the deposited precipitate was filtered and washed until the pH became neutral. Thereafter, recrystallization from an ethanol / tetrahydrofuran mixed solution yielded 10.5 g of yellow needle-like 2-bromofluorenone (melting point = 145-147 ° C.).

Identification was performed by ¹ H-NMR and ¹³ C-NMR.
_{^{· 1 H-NMR (CDCl 3}} , ppm); 7.30-7.76 (m, 7H)
_{^{· 13 C-NMR (CDCl 3}} , ppm); 192.32,143.68,143.00,137.11,135.79,135.04,133.72,129.45,127.59,124. 64, 122.95, 121.74, 120.46
Next, a Grignard solution prepared from 1.0 g (42.2 mmol) of magnesium and 9.85 g (42.2 mmol) of 2-bromobiphenyl was charged into a 300 mL eggplant type flask, and 9.9 g of 2-bromofluorenone / tetrahydrofuran at room temperature. A 130 mL solution was added dropwise and then heated to reflux for 14 hours. After completion of the reaction, the solution was separated, and the organic layer was washed with a 10% ammonium chloride solution. After concentration, 8.8 g of 2-bromo-9- (2-biphenylyl) -9-hydroxyfluorene was obtained by recrystallization from toluene. The obtained 2-bromo-9- (2-biphenylyl) -9-hydroxyfluorene and 65 mL of acetic acid were heated to 100 ° C., several drops of concentrated hydrochloric acid were added, and the mixture was heated and stirred for 1.5 hours. After completion of the reaction, the reaction solution was added to 120 g of ice water, and the resulting precipitate was filtered and washed. The precipitate was recrystallized from chloroform / ethanol to obtain 8.1 g of 2-bromo-9,9′-spirobifluorene (melting point = 181-183 ° C.).

Identification was performed by FDMS and ¹³ C-NMR.
・ FDMS: 394
¹³ C-NMR (CDCl ₃ , ppm); 150.75, 148.48, 147.83, 141.66, 140.71, 140.58, 130.84, 128.20, 127.93, 127. 89, 127.23, 124.05, 124.01, 121.36, 121.26, 120.09, 120.00, 65.85
Synthesis Example 5 (9,9-bis (biphenylyl) fluorene-2,7-bis (synthesis of 4,4,5,5-tetramethyl- [1,3,2] dioxaborolane)
2,7-Dibromo-9,9-bis (biphenylyl) fluorene (1.68 mmol), bis (pinacolato) diborane (3.77 mmol), potassium acetate (10.1 mmol), bis (diphenyl) obtained in Synthesis Example 2 Phosphino) ferrocenedichloropalladium (0.034 mmol) and anhydrous dimethylformamide (15 mL) were added to a 100 mL eggplant-shaped flask, and the mixture was heated and stirred at 80 ° C. for 2 hours. After completion of the reaction, 20 mL of toluene and 20 mL of water were added for extraction. The organic layer was washed with saturated saline and water and then concentrated to obtain a powder. Further, recrystallization with tetrahydrofuran / ethanol gave 0.61 g of the target compound.

Identification was performed by FDMS, ¹ H-NMR and ¹³ C-NMR.
・ FDMS: 721
_{^{· 1 H-NMR (CDCl 3}} , ppm): 1.31 (s, 24H), 7.26~7.58 (m, 18H), 7.84~7.88 (m, 6H)
_{^{· 13 C-NMR (CDCl 3}} , ppm): 25.03,65.10,83.82,119.98,126.96,127.09,128.68,128.85,132.34,134. 39, 139.28, 140.78, 142.84, 144.69, 151.04
Synthesis Example 6 (Synthesis of 4,5-diaza-2-bromo-9,9′-spirobifluorene)
To a Grignard reagent prepared from 0.40 g (16.3 mmol) of magnesium, 3.82 g (16.4 mmol) of 2-bromobiphenyl and 20 mL of tetrahydrofuran, 2.71 g (14.9 mmol) of 4,5-diazafluorenone was heated under reflux. ) / Tetrahydrofuran 65 mL solution was added dropwise and refluxed for 21 hours. Thereafter, the reaction solution was cooled to room temperature, and 50 g of water was added to complete the reaction. The reaction solution was extracted twice with 50 mL of chloroform and further dried over anhydrous magnesium sulfate. Filtration, concentration, and washing with hexane gave 3.75 g of a light brown powder. The obtained powder, 75 mL of acetic acid, was charged into a 200 mL eggplant-shaped flask, heated to 100 ° C., 4.97 g of concentrated sulfuric acid was added, and the mixture was heated and stirred for 22 hours. The reaction solution was added to 50 g of cold water to complete the reaction. The resulting reaction solution was adjusted to pH 11 with a 30% aqueous sodium hydroxide solution. Furthermore, it extracted twice with 100 mL of chloroform, and dried with anhydrous magnesium sulfate. After filtration and concentration, 1.69 g of 4,5-diaza-9,9′-spirobifluorene (yield = 48%, melting point = 208-210 ° C.) was synthesized by recrystallization from hexane / ethanol. did.

The compound was identified by FDMS, ¹ H-NMR and ¹³ C-NMR.
・ FDMS: 318
_{^{· 1 H-NMR (CDCl 3}} , ppm); 8.72-8.76 (m, 2H), 7.87 (d, J = 7.2Hz, 2H), 7.33-7.41 (m, 2H), 7.11-7.18 (m, 6H), 6.73 (d, J = 7.2 Hz, 2H)
¹³ C-NMR (CDCl ₃ , ppm); 158.3, 149.8, 145.6, 143.1, 141.4, 131.4, 128.0, 127.7, 123.5, 123. 3,120.0,61.8
Further, 0.5 g (1.57 mmol) of 4,5-diaza-9,9′-spirobifluorene, 0.25 g (1.56 mmol) of iron chloride and 5 mL of dichloromethane were added to a 50 mL eggplant type flask, After adding 0.25 g (1.56 mmol) of bromine dropwise, the mixture was stirred overnight at room temperature. After the reaction was terminated with a saturated aqueous sodium hydrogen carbonate solution, 15 mL of chloroform was added to extract the target product. After performing extraction twice, it was dried with magnesium sulfate. By concentrating and recrystallizing with toluene, 0.11 g of 4,5-diaza-2-bromo-9,9′-spirobifluorene was obtained (yield = 18%).

¹ H-NMR peaks (δ = 6.86 ppm (br s, 1 H) and 6.73 ppm (d, J = 7.8 Hz, 1 H)) characteristic of monobrominated compounds, and m / e by FDMS = 396 peaks were detected and identified as the target product.

Synthesis Example 7 (Synthesis of 2-bromo-9,9-dimethyl-4,5-diazafluorene)
18 g (99.9 mmol) of phenanthroline, 18 g (320.8 mmol) of potassium hydroxide and 900 g of water were added to a 2 L separable flask and heated to 80 ° C. While stirring at the same temperature, a mixed solution of 45 g of potassium permanganate and 720 g of water was added dropwise. After completion of the dropwise addition, the reaction was terminated by further stirring for 30 minutes. After removing the produced manganese dioxide by filtration while hot, the reaction solution was cooled to room temperature. The reaction solution was extracted with chloroform, treated in a conventional manner, and concentrated to obtain a yellow powder. Further, recrystallization with acetone gave 7.54 g of yellow needle crystals (yield = 41%).

The compound was identified by ¹ H-NMR and ¹³ C-NMR.
_{^{· 1 H-NMR (CDCl 3}} , ppm); 8.80 (d, J = 5.2,2H), 8.05 (dd, J = 7.6,1.6,2H), 7.36 ( dd, J = 7.6, 5.2, 2H)
_{^{· 13 C-NMR (CDCl 3}} , ppm); 189.42,163.31,155.10,131.45,129.30,124.69
4,5-diazafluorenone 7.5 g (41.4 mmol), sodium hydroxide 7.5 g (187.5 mmol), 98% hydrazine 5.3 g (165.4 mmol) and diethylene glycol 130 mL were added to a 300 mL eggplant type flask, The mixture was heated and stirred at 160 ° C. for 18 hours. After completion of the reaction, 250 mL of water was added and extracted with chloroform. The chloroform layer was dried over magnesium sulfate, filtered and concentrated. Furthermore, 6.43 g of greenish gray crystals were isolated by purification with an alumina column.

It was confirmed to be the desired 4,5-diazafluorene by GCMS and ¹ H-NMR.
GCMS: 168
¹ H-NMR (CDCl ₃ , ppm); 8.74 (d, J = 4.8, 2H), 7.89 (d, J = 7.8, 2H), 7.36 (dd, 2H) , 3.88 (s, 2H)
Next, 6.4 g of the obtained 4,5-diazafluorene and 150 mL of dimethylformamide were charged into a 300 mL eggplant type flask, and the reaction solution was cooled to 5 ° C. or lower in an ice bath. At the same temperature, 4.82 g of sodium methoxide was added little by little, followed by dropwise addition of 21.5 g of methyl iodide. After completion of the addition, the mixture was stirred at room temperature for 17 hours. After completion of the reaction, 250 mL of water was added and extracted with chloroform. The chloroform layer was dried over magnesium sulfate, filtered and concentrated. Further, 2.84 g of a greenish purple crystal was isolated by purification with an alumina column (yield = 38%).
GCMS: 196
¹ H-NMR (CDCl ₃ , ppm); 8.83 (d, 2H), 8.02 (d, 2H), 7.59 (dd, 2H), 1.61 (s, 6H)
9,9-dimethyl-4,5-diazafluorene (2 g, 10.2 mmol) and nitrobenzene (30 mL) were placed in a three-necked flask and heated to 130 ° C. Thereto, a mixed solution of 1.6 g of bromine and 5 mL of nitrobenzene was added dropwise over 1 hour. After reacting for 5 hours, the reaction solution was cooled to room temperature, and saturated aqueous sodium hydrogen carbonate solution was added to complete the reaction. After extraction with chloroform, it was dried over anhydrous magnesium sulfate, and 0.59 g (yield = 21%) of the target product was isolated by alumina chromatography.

Identification was performed by FDMS.
・ FDMS: 274
Example 1 (Synthesis of Compound 1)
In a 100 mL eggplant-shaped flask equipped with a reflux condenser, 2,7-dibromo-9,9′-bis [4- (methoxymethyloxy) phenyl] -9H-fluorene obtained in Synthesis Example 1 2.6 g (4 0.4 mmol), 1.82 g (9.2 mmol) of biphenylboronic acid, 14.6 g of 20 wt% sodium carbonate, 10 mg of tetrakis (triphenylphosphine) palladium, and 20 mL of tetrahydrofuran were added, and the mixture was heated to reflux for 5 hours. After stirring for a predetermined time, the reaction solution was cooled and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and concentrated to give 2,7-bis (4-phenylphenyl) -9,9′-bis [4- (methoxymethyloxy) phenyl] -9H-fluorene. 2.44 g (Yield = 75%) was isolated.

  Next, to the reaction solution obtained by dissolving 2,7-bis (4-phenylphenyl) -9,9′-bis [4- (methoxymethyloxy) phenyl] -9H-fluorene obtained in 20 mL of dichloromethane, -5 mL (30 mmol) of hydrochloric acid aqueous solution was added and reacted at room temperature for 5 hours, and then water was added to separate the organic phase. To the obtained organic phase, 1.03 g (13.0 mmol) of pyridine and 3.1 g (9.9 mmol) of trifluoromethanesulfonic anhydride were added and stirred at room temperature. By adding water and separating and concentrating the organic phase, the desired 2,7-bis (4-phenylphenyl) -9,9'-bis [4- (trifluoromethanesulfonyloxy) phenyl] -9H- 2.7 g of fluorene was isolated (Yield = 90%).

The target product was confirmed by FDMS.
FDMS: 918
Next, 2,7-bis (4-phenylphenyl) -9,9′-bis [4- (trifluoromethanesulfonyloxy) phenyl] -9H-fluorene obtained 2.7 g, biphenylboronic acid 1.2 g, 14.6 g of 20 wt% sodium carbonate, 10 mg of tetrakis (triphenylphosphine) palladium and 20 mL of tetrahydrofuran were added to a 100 mL eggplant-shaped flask equipped with a reflux condenser and heated to reflux for 4 hours. After stirring for a predetermined time, the reaction solution was cooled and the organic layer was separated. The organic layer is dried over anhydrous magnesium sulfate and concentrated to give the desired 2,7-bis (4-phenylphenyl) -9,9'-bis (terphenyl-1-yl) -9H- 1.9 g of fluorene (compound 1, yield = 66%) was isolated as a pale yellow powder.

Identification was performed by FDMS.
FDMS: 926

実施例２（化合物２の合成）
実施例１において、２回目の合成に供したビフェニルボロン酸をターフェニルボロン酸に変更した以外は、実施例１と同様の操作を行い、２，７−ビス（４−フェニルフェニル）−９，９’−ビス（クオーターフェニル−１−イル）−９Ｈ−フルオレン ２．０ｇ（化合物２）を単離した。
・ＦＤＭＳ：１０７８

Example 2 (Synthesis of Compound 2)
In Example 1, except that the biphenylboronic acid subjected to the second synthesis was changed to terphenylboronic acid, the same operation as in Example 1 was performed, and 2,7-bis (4-phenylphenyl) -9, 2.0 g (compound 2) of 9′-bis (quarterphenyl-1-yl) -9H-fluorene was isolated.
FDMS: 1078

実施例３（化合物２４の合成）
実施例１において、２回目の合成に供したビフェニルボロン酸を２−ピリジンボロン酸ピナコールエステルに変更した以外は、実施例１と同様の操作を行い、２，７−ビス（４−フェニルフェニル）−９，９’−ビス（２−ピリジルフェニル）−９Ｈ−フルオレン ２．０ｇ（化合物２４）を単離した。
・ＦＤＭＳ：７７６

Example 3 (Synthesis of Compound 24)
In Example 1, the same operation as in Example 1 was performed except that biphenylboronic acid subjected to the second synthesis was changed to 2-pyridineboronic acid pinacol ester, and 2,7-bis (4-phenylphenyl) 2.0 g (Compound 24) of -9,9'-bis (2-pyridylphenyl) -9H-fluorene was isolated.
FDMS: 776

実施例４（化合物３の合成）
実施例１において、２回目の合成に供したビフェニルボロン酸をフェニルボロン酸に変更した以外は、実施例１と同様の操作を行い、２，７−ビス（４−フェニルフェニル）−９，９’−ビス（４−フェニルフェニル）−９Ｈ−フルオレン ２．０ｇ（化合物３）を単離した。融点、ガラス転移温度は、それぞれ２８９℃、１５９℃であった。尚、薄膜での最大蛍光測定において、４１７ｎｍの青色蛍光を観測した。また、オプテル社製の移動度測定装置を用い、タイムオブフライト法により正孔移動度及び電子移動度を測定（電界強度＝約４００（Ｖ／ｃｍ）^１／２）すると、各々１．５×１０^−４ｃｍ^２／Ｖ・ｓｅｃ、４．０×１０^−５ｃｍ^２／Ｖ・ｓｅｃであった。バイポーラー性を示すことから、発光材料として利用可能であることがわかった。
・ＦＤＭＳ：７７４
・^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３）；１５２．１０，１４４．７７，１４０．６０，１４０．６４，１４０．３３，１４０．１３，１４０．０５，１３９．６１，１３９．１４，１２８．７９，１２８．６８，１２７．４９，１２７．３３，１２７．１２，１２７．００，１２６．７６，１２４．８４，１２０．６８，６５．３２

Example 4 (Synthesis of Compound 3)
In Example 1, 2,7-bis (4-phenylphenyl) -9,9 was performed in the same manner as in Example 1 except that biphenylboronic acid used for the second synthesis was changed to phenylboronic acid. 2.0 g (compound 3) of '-bis (4-phenylphenyl) -9H-fluorene was isolated. The melting point and glass transition temperature were 289 ° C. and 159 ° C., respectively. In the maximum fluorescence measurement with a thin film, blue fluorescence of 417 nm was observed. In addition, when using a mobility measuring apparatus manufactured by Optel, hole mobility and electron mobility were measured by a time-of-flight method (electric field strength = about 400 (V / cm) ^1/2 ), respectively. It was 10 ⁻⁴ cm ² / V · sec, 4.0 × 10 ⁻⁵ cm ² / V · sec. It was found that it can be used as a light emitting material because of its bipolar property.
・ FDMS: 774
¹³ C-NMR (CDCl ₃ ); 152.10, 144.77, 140.60, 140.64, 140.33, 140.13, 140.05, 139.61, 139.14, 128.79, 128.68, 127.49, 127.33, 127.12, 127.00, 126.76, 124.84, 120.68, 65.32

比較例１
実施例１で得られた２，７−ビス（４−フェニルフェニル）−９，９’−ビス［４−（メトキシメチルオキシ）フェニル］−９Ｈ−フルオレンをジクロロメタン２０ｍＬに溶解させた反応液に、６Ｎ−塩酸水溶液 ５ｍＬ（３０ｍｍｏｌ）を加え、室温で５時間反応させてから、水を添加して有機相を分離した。得られた有機相は、ジメチル硫酸にてメチル化することにより、２，７−ビス（４−フェニルフェニル）−９，９’−ビス（４−メトキシフェニル）−９Ｈ−フルオレンを単離した。

Comparative Example 1
To the reaction solution obtained by dissolving 2,7-bis (4-phenylphenyl) -9,9′-bis [4- (methoxymethyloxy) phenyl] -9H-fluorene obtained in Example 1 in 20 mL of dichloromethane, After adding 5 mL (30 mmol) of 6N-hydrochloric acid aqueous solution and reacting at room temperature for 5 hours, water was added and the organic phase was separated. The resulting organic phase was methylated with dimethyl sulfate to isolate 2,7-bis (4-phenylphenyl) -9,9′-bis (4-methoxyphenyl) -9H-fluorene.

Identification was performed by FDMS.
FDMS: 682
Example 5
The compounds 1 to 3 obtained in Examples 1, 2, and 4, the compound obtained in Comparative Example 1 and 20 mg of Spiro-6Φ were each dissolved in 2 mL of toluene to prepare a 1% solution. A thin film was prepared on a quartz substrate by a spin coating method (rotating condition = 1000 rpm (1 minute), vacuum heating condition = 60 ° C. (1 hour) vacuum heating), and left at room temperature (1 month) to leave the thin film cloudy ( (Or aggregation) was observed. As a result, no turbidity was observed in the compounds 1 to 3.

実施例６（化合物７の合成）
合成例２で得られた２，７−ジブロモ−９，９−ビス（ビフェニリル）フルオレンと２−ブロモ−９，９−ビス（ビフェニリル）フルオレンとを公知のニッケル触媒を用いて、ｙａｍａｍｏｔｏ ｃｏｕｐｌｉｎｇ反応を行うことにより、化合物７を合成した。
・ＦＤＭＳ：１４０６
実施例７（化合物６の合成）
１００ｍＬナス型フラスコに、合成例４で得られた２−ブロモ−９，９’−スピロビフルオレン １．１ｇ（２．８ｍｍｏｌ）、合成例５で得られた９，９−ビス（ビフェニリル）フルオレン−２，７−ビス（４，４，５，５−テトラメチル−［１，３，２］ジオキサボロラン） １．０ｇ（１．３９ｍｍｏｌ）、２０％炭酸ナトリウム水溶液５．５ｇ（１１．４ｍｍｏｌ）、テトラヒドロフラン２０ｍＬを加え、触媒としてビス（ジフェニルホスフィノフェロセン）ジクロロパラジウム４１ｍｇを窒素雰囲気下添加し、一晩還流した。冷却後、反応液を分液ロートに移し、有機層を分離した。有機層は、飽和塩化アンモニウム水溶液、飽和食塩水で洗浄した後、濃縮することにより結晶を得た。シリカゲルカラムクロマトグラフィー（トルエン／ヘキサン）を用い精製することにより、目的とする化合物６を収率＝６６％で得た。

Example 6 (Synthesis of Compound 7)
A 2,7-dibromo-9,9-bis (biphenylyl) fluorene obtained in Synthesis Example 2 and 2-bromo-9,9-bis (biphenylyl) fluorene were subjected to a yamamoto coupling reaction using a known nickel catalyst. By doing so, Compound 7 was synthesized.
FDMS: 1406
Example 7 (Synthesis of Compound 6)
In a 100 mL eggplant-shaped flask, 1.1 g (2.8 mmol) of 2-bromo-9,9′-spirobifluorene obtained in Synthesis Example 4 and 9,9-bis (biphenylyl) fluorene obtained in Synthesis Example 5 -2,7-bis (4,4,5,5-tetramethyl- [1,3,2] dioxaborolane) 1.0 g (1.39 mmol), 20% aqueous sodium carbonate solution 5.5 g (11.4 mmol), Tetrahydrofuran (20 mL) was added, and 41 mg of bis (diphenylphosphinoferrocene) dichloropalladium as a catalyst was added under a nitrogen atmosphere and refluxed overnight. After cooling, the reaction solution was transferred to a separatory funnel and the organic layer was separated. The organic layer was washed with a saturated aqueous ammonium chloride solution and saturated brine, and then concentrated to obtain crystals. Purification by silica gel column chromatography (toluene / hexane) gave the target compound 6 in a yield = 66%.

The glass transition temperature was 232 ° C. In the maximum fluorescence measurement with a thin film, blue fluorescence of 421 nm was observed.
FDMS: 1098
_{^{· 13 H-NMR (CDCl 3}} , ppm); 6.67-6.76 (m, 6H), 6.89 (s, 2H), 7.04-7.11 (t, 6H), 7.24 -7.64 (m, 34H), 7.78-7.85 (m, 6H)
Elemental analysis: Measured value C: 95.2%, H: 4.8%
Calculated value C: 95.05%, H: 4.95%
Example 8 (Synthesis of Compound 5)
By using 1-bromopyrene (2.8 mmol) instead of 2-bromo-9,9′-spirobifluorene and carrying out the same operation as in Example 7, 0.91 g (yield) of the target compound 5 was obtained. = 75%).

The compound was identified by FDMS and elemental analysis.
・ FDMS: 870
Elemental analysis: Measured value C: 95.2%, H: 4.8%
Calculated value C: 95.14%, H: 4.86%
Example 9 (Synthesis of Compound 12)
The same operation as in Example 7 is carried out using 4,5-diaza-2′-bromo-9,9′-spirofluorene (2.8 mmol) instead of 2-bromo-9,9′-spirobifluorene. As a result, 0.49 g (yield = 32%) of the target compound 12 was obtained.

The compound was identified by FDMS and elemental analysis.
FDMS: 1102
Elemental analysis: Measured value C: 90.3%, H: 4.6%, N: 5.1%
Calculated value C: 90.35%, H: 4.57%, N: 5.08%
Example 10 (Synthesis of Compound 13)
The same procedure as in Example 7 is performed using 2-bromo-9,9-dimethyl-4,5-diazafluorene (2.8 mmol) instead of 2-bromo-9,9′-spirobifluorene. As a result, 0.49 g (yield = 38%) of the target compound 13 was obtained.

The compound was identified by FDMS and elemental analysis.
・ FDMS: 858
Elemental analysis: Measured value C: 88.1%, H: 5.4%, N: 6.5%
Calculated value C: 88.08%, H: 5.4%, N: 6.52%
Example 11 (Synthesis of Compound 10)
The target compound 10 was prepared by carrying out the same operation as in Example 7 using 5-bromo-2,3′-bipyridine (2.8 mmol) instead of 2-bromo-9,9′-spirobifluorene. 0.43 g (yield = 40%) was obtained. The melting point and glass transition temperature were 346 ° C. and 164 ° C., respectively.
・ FDMS: 778
_{^{· 13 C-NMR (CDCl 3}} , ppm); 153.38,152.54,149.85,148.48,148.07,144.23,140.40,139.94,139.69,137. 23, 135.57, 135.20, 134.39, 134.16, 128.74, 128.50, 128.17, 127.23, 126.92, 124.82, 123.61, 121.25, 120.29, 65.41
Example 12 (Synthesis of Compound 11)
By using 2- (4-bromophenyl) pyridine (2.8 mmol) instead of 2-bromo-9,9′-spirobifluorene and carrying out the same operation as in Example 7, the target compound 11 was obtained. 0.49 g (yield = 45%) was obtained. The glass transition temperature was 174 ° C.
FDMS: 776
_{^{· 1 H-NMR (CDCl 3}} , ppm); 7.19-7.57 (m, 22H), 7.69-7.92 (m, 12H), 8.03-8.07 (d, 4H) , 8.68-8.70 (d, 2H)
_{^{· 13 C-NMR (CDCl 3}} , ppm); 156.86,152.16,149.67,144.74,141.61,140.62,140.27,139.67,139.28,138. 26, 136.70, 128.70, 127.45, 127.27, 127.16, 126.98, 126.90, 124.74, 122.11, 120.75, 120.42, 65.38
Example 13 (Synthesis of Compound 17)
By subjecting 4-bromo-2,4′-bipyridine (2.8 mmol) in place of 2-bromo-9,9′-spirobifluorene to the operation similar to that of Example 7, the target compound 17 0.87 g (yield = 80%) was obtained. The glass transition temperature was 176 ° C.

The compound was identified by FDMS, ¹ H-NMR and elemental analysis.
FDMS: 776
_{^{· 1 H-NMR (CDCl 3}} , ppm); 8.99 (s, 2H), 8.73 (d, 4H, J = 6.2), 7.26-8.03 (m, 32H)
Elemental analysis: Measured value C: 88.2%, H: 4.7%, N: 7.1%
Calculated value C: 87.9%, H: 4.9%, N: 7.2%
Example 14 (Synthesis of Compound 18)
60 mL of a tetrahydrofuran solution of 2.0 g (7.3 mmol) of 3-bromo-9,9-dimethyl-4,5-diazafluorene was added to a 300 mL eggplant-shaped flask and cooled to -78 ° C. While maintaining the same temperature, a hexane solution of n-butyllithium (1.6 M) (5 mL, 8 mmol) was added dropwise and stirred for 30 minutes. Thereafter, 2.0 g of dichloro (N, N, N ′, N′-tetramethylethylenediamine) zinc was added as a solid, and the reaction mixture was stirred at room temperature for 1 hour. Further, 2.2 g (3.5 mmol) of 2,6-dibromo-9,9-di (biphenylyl) fluorene and 51 mg of dichlorobis (triphenylphosphine) palladium were added and heated under reflux overnight, and then the reaction solution was cooled to room temperature. did. After adding 30 mL of water and extracting with toluene twice, the organic layer was washed with water, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane / chloroform mixed solution) to obtain 1.02 g of yellow crystals (yield = 34%).

The obtained crystal was identified by FDMS.
・ FDMS: 858
Example 15 (Synthesis of Compound 19)
Compound 19 was synthesized according to the method of Example 14, except that 6-bromo-2,2′-bipyridine was used instead of 3-bromo-9,9-dimethyl-4,5-diazafluorene.

The compound was identified by FDMS.
・ FDMS: 778
Example 16 (Evaluation of electron affinity and electron mobility in cyclic voltammetry)
Measurement was performed using a cell manufactured by BAS Co., Ltd., using a platinum electrode as a counter electrode, a glassy carbon electrode as a working electrode, Ag / Ag ⁺ as a reference electrode, and tetrabutylammonium perchloride as an electrolyte, and a scan speed = The test was performed under the condition of 100 mV / sec. As a solvent, dichloromethane and tetrahydrofuran were used in combination.

As a result, the compounds 12 and 13 showed −2.40 eV, −2.38 eV on the basis of ferrocene (Fc / Fc ⁺ ), and values equal to or higher than the values −2.41 eV of Alq ₃ and bathophenanthroline. Moreover, when the electron mobility was measured by the time-of-flight method using a mobility measuring device manufactured by Optel Co., Ltd., it showed a value of about 10 ⁻⁴ cm ² / V · sec, which was higher than the conventional material Alq ₃ . Confirmed that it was fast.

Example 17 (Evaluation of electrochemical stability by cyclic voltammetry)
Under the same conditions as in Example 16, the reversibility of the peak was evaluated by cyclic voltammetry.

  As a representative example, FIG. 1 shows the results of compound 10 and bathophenanthroline which has been conventionally reported. As a result, while bathophenanthroline showed irreversibility, the compounds shown in Examples 1 to 15 all showed peaks showing reversibility. Therefore, since the electrochemical stability of the material is excellent, the durability of the organic EL element is expected to be improved.

Example 18 (Ionization potential measurement by photoelectron spectroscopy)
As a representative example, the ionization potential of Compound 17 was measured using AC-3 manufactured by Riken Keiki Co., Ltd. and found to be 6.24 eV. Since this is larger than the values of Alq ₃ (= 5.7 eV) and CBP (= 5.97 eV), it was confirmed that it can be used as a hole blocking material.

Example 19 (device evaluation of compound 17)
A glass substrate having an ITO transparent electrode having a thickness of 130 nm was ultrasonically washed successively with acetone and isopropyl alcohol, then boiled and washed with isopropyl alcohol, and then dried. Furthermore, what was UV / ozone treated was used as a transparent conductive support substrate. On the ITO transparent electrode, copper phthalocyanine was formed into a film with a thickness of 20 nm by vacuum deposition. Next, α-NPD was formed into a film with a thickness of 40 nm by a vacuum vapor deposition method to form a hole transport layer. Next, an aluminum triskinolinol complex was formed into a film with a thickness of 40 nm by vacuum deposition. Further, Compound 17 was deposited to a thickness of 20 nm to form an electron transport layer. The organic compound was deposited under the same conditions of a vacuum degree of 1.0 × 10 ⁻⁴ Pa and a deposition rate of 0.3 nm / sec.

  Next, LiF was deposited to 0.5 nm and Al was deposited to 150 nm as a cathode to form a metal electrode.

Further, a protective glass substrate was stacked in a nitrogen atmosphere and sealed with a UV curable resin. When a DC voltage of 6 V is applied to the device thus obtained with a positive electrode of ITO and a negative electrode of LiF-Al, a current density of 86 mA / cm ² is obtained, and a green color with a luminance of 3400 cd / m ² is obtained. Was observed. The electron transport layer as compared to the device which was changed to aluminum tris quinolinol complex (Alq _3), 2.7 times the current density was obtained. FIG. 2 shows a voltage-current density, and FIG. 3 shows a voltage-luminance curve. Incidentally, the luminance half life, indicated a value substantially equal to that of Alq _3.

Example 20
The device was evaluated according to the method of Example 19 except that Compound 19 was used instead of Compound 17. As a result, a current density of 95 mA / cm ² was obtained with an applied voltage of 6 V, and a luminance of 3950 cd / m ² was obtained. A green light emission was observed.

Comparative Example 2
A similar device was prepared using 4,7-diphenyl-1,10-phenanthroline (BCP) instead of compound 17. As a result, when a DC voltage of 6 V was applied, only a current density of 15 mA / cm ² was obtained, and green light emission was observed with a luminance of 510 cd / m ² .

The reversibility evaluation of the peak by cyclic voltammetry is shown. Voltage-current density is shown. A voltage-luminance curve is shown.

Claims (3)

A π-conjugated compound having a cardo structure represented by the general formula (1).

(In the formula, R ^{1 and} R ² are each independently a hydrogen atom, 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, or 3 to 3 carbon atoms. 18 represents a straight-chain, branched or cyclic alkoxy group, and Ar ¹ each independently represents a group represented by the following general formula (2) or (3): Ar ² each independently represents a 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-n-butylphenyl group 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3 4-dimethylphenyl group, pyridyl group, bipyridyl group, quinolyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, fluorenyl group, benzo [c] fluorenyl group, azafluorenyl group, 1,10-phenanthrolinyl group, Or a substituent represented by the following general formula (4a), (4b), (5), (6a), or (6b) .

(In the formula, R ³ and R ⁴ are each independently a hydrogen atom, 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, or 3 to 3 carbon atoms. Represents a straight-chain, branched or cyclic alkoxy group of 18. R ⁵ and R ⁶ each independently represents a hydrogen atom, a methyl group, an ethyl group, a 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 , 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-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentyl Phenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 1-biphenylyl group, 1-naphthyl group, 2-naphthyl group, 9- Phenanthryl group, anthryl group, pyrenyl group, 9,9-dimethyl-2-fluorenyl group, phenoxy group, p-tert-butylphenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group , pyridyl group, bipyridyl group, or Represents a quinolyl group, l represents 0 or 1. m represents an integer of 0 to 3, and n represents an integer of 0 to 2.)

(Wherein R ^{7 to} R ⁹ each independently represents a hydrogen atom, 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, or a carbon number of 3 to 18). Linear, branched or cyclic alkoxy group, 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-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 1-biphenylyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthryl group Anthryl group, pyrenyl group, 9,9-dimethyl-2-fluorenyl group, phenoxy group, p-tert-butylphenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, pyridyl group, bipyridyl group, or quinolyl group X represents a carbon atom or a nitrogen atom.)

(In the formula, R ^{10 to} R ¹² are each independently a hydrogen atom, 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, and a 3 to 18 carbon atoms. Linear, branched or cyclic alkoxy group, 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-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 1-biphenylyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthri Group, anthryl group, pyrenyl group, 9,9-dimethyl-2-fluorenyl group, phenoxy group, p-tert-butylphenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, pyridyl group, bipyridyl group, or quinolyl group Represents a group, provided that R ¹⁰ and R ¹¹ may be bonded to each other to form a ring, and X represents a carbon atom or a nitrogen atom.)

(In the formula, each of R ^{13 to} R ¹⁵ is independently a hydrogen atom, 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, or a C 3-18 group. Linear, branched or cyclic alkoxy group, 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-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 1-biphenylyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthri A group, anthryl group, pyrenyl group, 9,9-dimethyl-2-fluorenyl group, pyridyl group, bipyridyl group, or quinolyl group, p and q are integers satisfying 1 ≦ p + q ≦ 3, and s and x are 0 to 0 Represents an integer of 2.) A fluorene intermediate represented by the following general formula (7) and a boronic acid compound A represented by the following general formula (8) are reacted in the presence of a transition metal catalyst, deprotected in the presence of an acid catalyst, and further trifluorinated. 2. The method for producing a π-conjugated compound according to claim 1, further comprising reacting with boronic acid compound B represented by the following general formula (9) in the presence of a transition metal catalyst after romethanesulfonylation.

(In the formula, Z is a protecting group for a phenol group, and R ^{1 and} R ² are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 18 carbon atoms , methoxy A group, an ethoxy group, or a linear, branched or cyclic alkoxy group having 3 to 18 carbon atoms, and X represents an iodine atom, a bromine atom or a chlorine atom.)

(In the formula, each Ar ¹ independently represents a group represented by the following general formula (2) or (3). Ar ² each independently represents a phenyl group, a 4-methylphenyl group, or a 3-methylphenyl group. 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-tert -Butylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, pyridyl group, bipyridyl group, quinolyl group, Naphthyl, anthryl, phenanthryl, pyrenyl, fluorenyl, benzo [c] fluorenyl, azafluorenyl, 1,10-phenyl Nantororiniru group, or the following general formula (4a), (4b), (5), (6a), or a substituent represented by (6b).)

(In the formula, R ³ and R ⁴ are each independently a hydrogen atom, 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, or 3 to 3 carbon atoms. Represents a straight-chain, branched or cyclic alkoxy group of 18. R ⁵ and R ⁶ each independently represents a hydrogen atom, a methyl group, an ethyl group, a 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, 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-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentyl Phenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 1-biphenylyl group, 1-naphthyl group, 2-naphthyl group, 9- Phenanthryl group, anthryl group, pyrenyl group, 9,9-dimethyl-2-fluorenyl group, phenoxy group, p-tert-butylphenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group , pyridyl group, bipyridyl group, or Represents a quinolyl group, l represents 0 or 1. m represents an integer of 0 to 3, and n represents an integer of 0 to 2.)

(Wherein R ^{7 to} R ⁹ each independently represents a hydrogen atom, 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, or a carbon number of 3 to 18). Linear, branched or cyclic alkoxy group, 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-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 1-biphenylyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthryl group Anthryl group, pyrenyl group, 9,9-dimethyl-2-fluorenyl group, phenoxy group, p-tert-butylphenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, pyridyl group, bipyridyl group, or quinolyl group X represents a carbon atom or a nitrogen atom.)

(In the formula, R ^{10 to} R ¹² are each independently a hydrogen atom, 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, and a 3 to 18 carbon atoms. Linear, branched or cyclic alkoxy group, 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-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 1-biphenylyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthri Group, anthryl group, pyrenyl group, 9,9-dimethyl-2-fluorenyl group, phenoxy group, p-tert-butylphenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, pyridyl group, bipyridyl group, or quinolyl group Represents a group, provided that R ¹⁰ and R ¹¹ may be bonded to each other to form a ring, and X represents a carbon atom or a nitrogen atom.)

(In the formula, each of R ^{13 to} R ¹⁵ is independently a hydrogen atom, 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, or a C 3-18 group. Linear, branched or cyclic alkoxy group, 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-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 1-biphenylyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthri A group, anthryl group, pyrenyl group, 9,9-dimethyl-2-fluorenyl group, pyridyl group, bipyridyl group, or quinolyl group, p and q are integers satisfying 1 ≦ p + q ≦ 3, and s and x are 0 to 0 Represents an integer of 2.) An organic electroluminescence device, wherein the π-conjugated compound according to claim 1 is used in any one of a light emitting layer, a hole blocking layer, and an electron transporting layer.

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