JP4420660B2 - Organic borazine compound and process for producing the same - Google Patents

Description

  The present invention relates to a novel borazine compound and a method for producing the same.

  The borazine compounds themselves have been extensively researched for a long time, but most of them are intended for application to ceramics, polymer materials by a sol-gelation method, and the like. Patent Document 1 describes the manufacture of ceramic products essentially based on boron nitride, Patent Document 2 describes a borazine-containing silicon polymer, and Patent Document 3 describes an invention related to a neutron scavenger having a borazine skeleton. ing.

Regarding the production of borazine compounds, Non-Patent Document 1 describes the synthesis of B-trialkyl or B-triphenylborazine by reacting gaseous boron trichloride (boiling point of about 12 ° C.) with amine or aniline in toluene. Non-Patent Document 2 describes the synthesis of N-tribiphenylborazine from biphenylamine and borane. Non-Patent Document 3 describes the reaction of B-trichloroborazine with aryl Grignard or aryl lithium, but borazine in which a sterically large aromatic ring is introduced into all of the nitrogen and boron atoms of the borazine skeleton. There is no description about the synthesis method of the compound.
JP-A-6-228157 JP 2002-155143 A JP 2002-80480 A J. et al. Am. Chem. Soc. 1958, 80, 1357 Angew. Chem. 1965, 77, 719 J. et al. Org. Chem. 1964, 29, 2094

  The development of organic materials with emission characteristics such as blue, which is one of the three primary colors of light, and the development of organic materials with charge transporting ability such as holes and electrons are possible regardless of whether they are high molecular compounds or low molecular compounds. It has been actively studied so far. However, there are still limited organic materials that have really excellent characteristics in terms of color purity, luminous efficiency, carrier mobility and carrier injection efficiency. Recently, several high-performance organic EL devices have been developed by using phosphorescent light emitting dyes as light emitting materials. The lack of useful host materials for these phosphorescent light emitting dyes is also one major problem at present. It has become a point. Although material development based on fundamentally new molecular design is strongly desired, there is no example where a borazine compound is used as a key structure of an organic electronic material.

  An object of the present invention is to provide a novel borazine compound having excellent characteristics applicable as a light emitting material or a charge transport material as an organic electroluminescence (EL) device and a method for producing the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has firmly introduced the same or two different π-conjugated electron systems by introducing an aromatic functional group rich in specific π electrons into the borazine basic skeleton. It was found that the structure of the aromatic functional group is suppressed due to steric constraints, and that the unique optical properties derived from the through-space interaction are expressed by the steric restriction. In general, it is difficult to synthesize such a sterically crowded compound, but the present inventors have synthesized a borazine skeleton by a reaction between an aromatic amine and boron trihalide, Furthermore, the present inventors have found a method for efficiently synthesizing a borazine compound having the above aromatic substituent by reacting an aromatic metal compound.

That is, the present invention relates to the general formula (3)

[Wherein R ² represents an aryl group. The aryl group may have a substituent, and the substituent is an alkyl group or an alkyl group substituted with a halogen atom. R ³ is an aryl group, heteroaryl group, oligoaryl group, oligoheteroaryl group, alkyl group, silyl group, amino group, alkoxy group, boryl group, stannyl group, mercapto group, sulfide group, hydroxy group, hydrogen atom, halogen Indicates an atom. A borazine compound represented by the formula:

  In addition, the present invention provides a general formula (3)

In the method for producing a borazine compound represented by the formula: R ² and R ³ are the same as above, the general formula (8)

[Wherein R ² is the same as above] and a B, B ′, B ″ -tris (10-bromo-9-anthryl) borazine compound represented by the general formula (9)

[Wherein Y represents a halogen atom, R ³ is the same as the above general formula (3)] and I) the general formula (9) is converted into a Grignard reagent in the presence of a transition metal catalyst. A method of reacting by a cross-coupling reaction,
II) A method in which a compound of the general formula (8) is lithiated with alkyllithium, and then a compound of the general formula (9) is reacted.
III) Lithiation of the compound of general formula (8) with alkyllithium followed by treatment with a metal halide selected from zinc chloride, magnesium chloride or nickel chloride followed by metal exchange followed by the general formula in the presence of a transition metal catalyst A method of cross-coupling reaction of the compound of (9),
It is this manufacturing method characterized by performing by either method of these.

  By introducing an aromatic functional group rich in specific π-electrons into the borazine basic skeleton, the structure becomes a tightly bundled structure of the same or two different π-conjugated electron systems. It was possible to suppress the fluctuation of the structure of the group functional group and to express unique optical characteristics derived from the through-space interaction.

  The present invention is characterized by bundling a plurality of π-conjugated skeletons using a single nuclear structure as a molecular design of a new material having high luminous efficiency and high charge transport ability. In general, the term “bundle” means to bundle, but in the present invention, as shown in Scheme 1 below, a state in which compounds having π electrons are regularly bundled with a borazine skeleton as a nucleus. By bundling in this way, it is possible to introduce a π1 functional group and a π2 functional group into the borazine skeleton.

このような構造では、（１）π共役系骨格が強固に固定されることによる発光特性が期待できる、（２）π共役系骨格間のスルースペース相互作用による電荷輸送能が期待できるといった特徴をもつ。このバンドル化のための核構造として用いたのが、平面６員環構造をもつボラジン骨格である。ホウ素と窒素とからなるボラジンを核構造に用いることにより、それぞれの元素上に異なる２種のπ共役系置換基を合計６個導入することができる。

In such a structure, (1) light emission characteristics due to the rigid fixation of the π-conjugated skeleton can be expected, and (2) charge transport ability due to through-space interaction between the π-conjugated skeletons can be expected. Have. A borazine skeleton having a planar 6-membered ring structure was used as the core structure for bundling. By using borazine composed of boron and nitrogen for the core structure, a total of six different two types of π-conjugated substituents can be introduced on each element.

  This bundling can be realized in principle by using benzene having a similar planar 6-membered ring structure, but its synthesis is based on strict steric hindrance between π-conjugated substituents and an effective synthesis method. It seems to be difficult in practice because of the lack.

  In contrast, the present invention is the first to achieve π-conjugated system bundling by using borazine as a key structure.

The borazine compound of the present invention has the general formula (3)

[ Wherein R ² and R ³ are the same as above. ] Is taken. Examples of the functional group that becomes a π-conjugated skeleton bundled with the borazine nucleus include an aryl group, a heteroaryl group, an oligoaryl group, and an oligoheteroaryl group.

Examples of the aryl group for R ² include a phenyl group, a biphenyl group, a non-condensed carbocyclic aromatic group of a terphenyl group, and a condensed polycyclic hydrocarbon group. Here, examples of the condensed polycyclic hydrocarbon group include a naphthyl group, a fluorenyl group, an acenaphthenyl group, an anthryl group, a naphthacenyl group, a pentacenyl group, a pyrenyl group, a phenanthryl group, a chrycenyl group, and a fluoranthenyl group .

Moreover, these may have a substituent, and as these substituents, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a tert-butyl group, etc. Ru lower alkyl Motodea. Still substituent definitive in the alkyl group, a halogen atom.

R ³ is an aryl group, heteroaryl group, oligoaryl group, oligoheteroaryl group, alkyl group, silyl group, amino group, alkoxy group, boryl group, stannyl group, mercapto group, sulfide group, hydroxy group, hydrogen atom, halogen Indicates an atom. Examples of the aryl group of R ³ include a phenyl group, a biphenyl group, a non-condensed carbocyclic aromatic group of a terphenyl group, and a condensed polycyclic hydrocarbon group. Here, examples of the condensed polycyclic hydrocarbon group include a naphthyl group, a fluorenyl group, an acenaphthenyl group, an anthryl group, a naphthacenyl group, a pentacenyl group, a pyrenyl group, a phenanthryl group, a chrycenyl group, and a fluoranthenyl group.

  Examples of heteroaryl groups include thienyl, furyl, pyrrole, pyridyl, pyrimidyl, pyridazyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, oxadiazolyl, thiadiazolyl, pyranyl, thiopyranyl, benzo [B] Furyl group, benzo [b] thienyl group, quinolinyl group, isoquinolinyl group, benzo [1,2-b, 4,5-b] bisthiazolyl group, benzo [1,2-b, 4,5-b] A bisoxazolyl group etc. are mentioned. Examples of the oligoaryl group include oligophenylene (n-phenyl: n = 2 to 12), and examples of the heterooligoaryl include oligothiophene (n-thienyl: n = 2 to 12), oligopyridine (n-pyrylyl: n = 2). ~ 12) and the like. Examples of the silyl group include a trialkylsilyl group, a trihalosilyl group, an amino group such as a dialkylamino group, a boronyl group as a dialkoxyboryl group, a stannyl group as a trialkyltin, and a sulfide group as an alkylsulfide group. Can be mentioned. Or as a halogen atom, a fluorine, chlorine, a bromine, an iodine, and a hydrogen atom are mentioned.

  Moreover, these may have a substituent and the following are mentioned as these substituents. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, and a tert-butyl group, and as an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, Examples include lower alkoxy groups such as butoxy group, pentoxy group and hexoxy group, halogen atoms such as fluorine, chlorine, bromine and iodine, aryl group, silyl group, boryl group, amino group, stannyl group, hydroxy group and mercapto group. . Furthermore, examples of the substituent in the alkyl group and alkoxy group include a phenyl group, a halogen atom, an alkoxy group, and an aryloxy group. Examples of the substituent in the phenyl group include lower alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group), lower alkoxy groups (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) and A halogen atom (for example, bromine, chlorine, fluorine, etc.) is mentioned.

In the compound represented by the general formula (3) , particularly preferred substituent R ² includes 4-hexylphenyl, 4-isopropylphenyl, 4-trifluoromethylphenyl and the like, and R ^{3 represents} a hydrogen atom, a halogen atom, and the like. Examples thereof include an atom, a phenyl group, a pentafluorophenyl group, a thienyl group, a diphenylaminophenyl group, and a diisopropylsilyl group. Therefore, if the borazine compound represented by the general formula (3) having those substituents is exemplified, B, B ′, B ″ -tri (9-anthryl) -N, N ′, N ″ -tris (4 -Hexylphenyl) borazine, B, B'B "-tri (9-anthryl) -N, N ', N" -tris (4-isopropylphenyl) borazine, B, B', B "-tri (9-anthryl) ) -N, N ', N "-tris (4-trifluoromethylphenyl) borazine, B, B', B" -tri (10-bromo-9-anthryl) -N, N ', N "-tris ( 4-hexylphenyl) borazine, B, B ′, B ″ -tris (10-phenyl-9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine, B, B ′, B ″ -Tris (10-pentafluorophenyl-9-anthryl)- , N ′, N ″ -tris (4-hexylphenyl) borazine, B, B ′, B ″ -tris (10-thienyl-9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) Borazine, B, B ′, B ″ -tris (10- (4-diphenylaminophenyl) -9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine, B, B ′, B “-Tris (10-diisopropylsilyl-9-anthryl) -N, N ′, N” -tris (4-hexylphenyl) borazine and the like can be mentioned.

The compound represented by the general formula (3) of the present invention can be produced by the following steps.
First step: General formula (4)

[Wherein, R ² is the same as that represented by the general formula (3). ] And general formula (5)

［式中、Ｒ ² およびＸは上記のとおりである］の構造を有するトリハロボラジン化合物を製造する。
第二工程； 上記トリハロボラジン化合物（６）と、一般式（７） [Wherein X represents a halogen atom. A boron halide represented by the general formula (6)

A trihaloborazine compound having the structure [wherein R ² and X are as described above] is produced.
2nd process; The said trihaloborazine compound (6) and General formula (7)

［式中、Ｒ ³ およびＸは上記のとおりである］で表されるハロゲン化アリール化合物をリチオ化あるいはグリニヤール試薬化した芳香族メタル化物を反応させる。

[Wherein R ³ and X are as defined above ] are reacted with an aromatic metal compound obtained by lithiation or Grignard reagent conversion of the halogenated aryl compound.

以下に、第一工程に関して説明する。

Hereinafter, the first step will be described.

  General formula (4) used in the present invention

In the aromatic amine represented by R ² , R ² is the same as in the general formula (3) . Preferably, a phenyl group or a condensed polycyclic hydrocarbon group is used, and aniline, naphthylamine, fluorenylamine, acenaphthenylamine, anthrylamine, aminoacridine, pyrenylamine, phenanthrylamine, chrycenylamine, fluoranthenylamine derivatives Is mentioned. Preferably, aniline, anthrylamine, aminoacridine, and fluorenylamine derivatives are more preferable because aniline derivatives are easily available. As the aniline derivative, aniline, 4-hexylaniline, 4-isopropylaniline or 4-trifluoromethylaniline is more preferable.

These raw materials are commercially available, but dehydrated grades are strongly recommended. When a general reagent is used, it is preferable to perform a drying treatment in advance.

  Boron halides include boron trifluoride, boron trichloride, boron tribromide, boron triiodide, etc., but they are easily available in solution and waste gas generated during the reaction (unreacted trichloride) Boron trichloride is preferred because it can be easily treated outside the system.

  The solvent in the reaction in the first step is not particularly limited as long as it is a solvent that does not react with the raw material, but hydrocarbon solvents such as hexane, toluene, heptane, benzene, xylene, dichloromethane, chloroform, carbon tetrachloride, 2-chloromethanol, etc. A chlorine-containing solvent or the like can be used, and hexane and toluene are preferable. Recommended solvent is dehydrated. The reactor is preferably replaced with a previously dried inert gas.

  Since the reaction is an equimolar reaction, 1 mol of aromatic amine is required for 1 mol of boron halide, but 0.9 to 1.4 mol of boron halide is used for 1 mol of aromatic amine. Adding an excessive amount may cause some boron halides to easily vaporize, and an excessive amount may be necessary so as not to extremely reduce the synthesis yield. Depending on the reactivity of the amine, it may be preferable to carry out the reaction with an excess of amine.

  The mixing of the boron halide and the aromatic amine is performed, for example, by a method in which a toluene solution of the aromatic amine is dropped into a hexane solution of the boron halide. Although the temperature at the time of mixing is implemented at the temperature of -10-30 degreeC, 0 degreeC vicinity is preferable.

  After mixing, if desired, an approximately equal amount of a solvent is added, and the reaction is allowed to proceed by heating to reflux. Although reaction temperature can be implemented at the temperature of 50-150 degreeC, 110 degreeC vicinity is preferable. If the reaction temperature is too low, the reaction does not proceed and the yield does not increase, which is not preferable. If the reaction temperature is too high, a by-product is generated, which is not preferable. By this reaction, the borazine skeleton of the mother nucleus is synthesized.

The aromatic metal compound in the second step is easily synthesized by a reaction of an aryl halide represented by the general formula (7) and alkyl lithium.

Lithiation of the aryl halide represented by the general formula (7) with alkyllithium can be carried out by cooling to 5 ° C. or lower. However, in order to prevent decomposition of the resulting lithiated product, 0 ° C. or lower is preferable, − Since the reaction is slow at a low temperature of 80 ° C. or lower, −80 to 0 ° C. is preferable. Specifically, a method of cooling to -78 ° C with a dry ice-ethanol bath at the time of mixing and gradually raising the temperature to 0 ° C is preferable. Examples of the alkyl lithium include n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium, propyllithium, and the like. n-Butyl lithium and tert-butyl lithium are preferable, and n-butyl lithium is more preferable. The reaction is carried out in a solvent, and ether solvents such as tetrahydrofuran and diethyl ether, hydrocarbon solvents such as pentane, hexane and toluene, and mixed solvents thereof can be used, and tetrahydrofuran is particularly preferable. These solvents are preferably dehydrated in advance.

When an aryl halide is used as a Grignard reagent, a conventional method may be followed. Magnesium dispersed in an ether-based organic solvent such as diethyl ether or tetrahydrofuran is activated with iodine, and then represented by the general formula (7). A method in which the obtained compound is dissolved in the same solvent and dropped is preferred. In order to prevent decomposition of the product, the reaction is preferably 120 ° C. or lower, and preferably 0 ° C. to 120 ° C. If the reaction temperature is too low, the reaction is slow, which is not preferable.

The obtained aromatic metallized product is reacted with the trihaloborazine represented by the general formula (6) obtained in the first step to obtain the target borazine compound represented by the general formula (3). be able to. The mixing method is not particularly limited, but a method in which the trihaloborazine represented by the general formula (6) is dropped into a solution of the aromatic metal compound and stirred and mixed is preferable. The reaction can be performed at −80 ° C. to 120 ° C., but preferably 30 ° C. or less and preferably around −80 ° C. to 50 ° C. in order to suppress decomposition of the product and generation of by-products. If the temperature is too low, the reaction is slow, which is not preferable. The reaction is carried out in a solvent, hydrocarbon solvents such as hexane, toluene, heptane, benzene and xylene, ether solvents such as tetrahydrofuran and diethyl ether, chlorine-containing systems such as dichloromethane, chloroform, carbon tetrachloride and 2-chloromethanol. A solvent and a mixed solvent thereof can be used, but tetrahydrofuran and toluene are more preferable. The solvent at this time is preferably dehydrated in advance.

  As a specific aspect, in the first step, boron trichloride is used as the boron trihalide represented by the general formula (5), and 4-hexylaniline is used as the aromatic amine represented by the general formula (4). When 4-isopropylaniline or 4-trifluoromethylaniline is used, the resulting trihaloborazine compound represented by the general formula (6) is B, B ′, B ″ -trichloro-N, N ′, N, respectively. "-Tris (4-hexylphenyl) borazine, B, B ', B" -trichloro-N, N', N "-tris (4-isopropylphenyl) borazine, B, B ', B" -trichloro-N, N ′, N ″ -tris (4-trifluoromethylphenyl) borazine.

  Further, when 9-bromoanthracene is used as the aryl halide represented by the general formula (7) in the second step and lithiated or converted to a Grignard reagent and then reacted with the above compound, B, B ′, B ″ — Tri (9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine, B, B ′, B ″ -tri (9-anthryl) -N, N ′, N ″ -tris (4 -Isopropylphenyl) borazine, B, B ', B "-tri (9-anthryl) -N, N', N" -tris (4-trifluoromethylphenyl) borazine is obtained.

That is, when 9-bromoanthracene is used as the aryl halide represented by the general formula (7) in the second step, R ¹ becomes an anthryl group, so that the general formula (3)

[Wherein R ² and R ³ are the same as above ], which corresponds to the case where R ³ is a hydrogen atom. As described above, a desired trianthryl compound can be produced by selecting an appropriate aromatic amine as the compound containing R ² .

Similarly, in the first step, when 9,10-dibromoanthracene is used as the aryl halide represented by the general formula (7), B, B ′, B represented by the general formula (8) is used. “-Tri (10-bromo-9-anthryl) borazine derivative is obtained . This corresponds to the case where R ³ is a bromine atom in the compound represented by the general formula (3).

In the production of the borazine compound represented by the general formula (3), the above B, B ′, B ″ -tri (10-bromo-9-anthryl) borazine derivative (general formula (8)) is produced and further converted. Various substituents can be introduced by the reaction, that is, when the compound represented by the general formula (8) is reacted with the halide of the compound represented by the general formula (9),
I) A method in which general formula (9) is converted into a Grignard reagent and subjected to a cross-coupling reaction in the presence of a transition metal catalyst,
II) A method in which a compound of the general formula (8) is lithiated with alkyllithium, and then a compound of the general formula (9) is reacted.
III) The compound of the general formula (8) is lithiated with alkyllithium, then treated with an organomagnesium reagent such as an alkyl Grignard reagent, an alkylmagnesium amide, or an alkylzinc reagent to exchange metals, and then a transition metal catalyst. A method of subjecting the compound of the general formula (9) to a cross-coupling reaction in the presence thereof,
It can be done by either method.

  Hereinafter, introduction of a substituent by synthesizing a compound trimethylated by a metal exchange reaction using an organometallic base from the compound of the general formula (8) and using this as a key intermediate is shown. In the following scheme 3, M in the intermediate compound is Li when it is lithiated, and ZnX, MgX or NiX (where X represents a halogen atom) when it is further exchanged with metal, and is in a trimetalated state. Represents that.

このトリメタル化を行うには、ｎ−ブチルリチウム（ｎ−ＢｕＬｉ）、ｓｅｃ−ブチルリチウム（ｓｅｃ−ＢｕＬｉ）、ｔｅｒｔ−ブチルリチウム（ｔｅｒｔ−ＢｕＬｉ）などの有機リチウム試薬、アルキルグリニャール試薬、アルキルマグネシウムアミド、などの有機マグネシウム試薬、あるいはアルキル亜鉛試薬等の有機金属塩基が使用できるが、入手の容易性、操作性の観点から、ｔｅｒｔ−ＢｕＬｉを用いるリチオ化が好ましい。前述のようにリチオ化の後に、金属変換反応を行い、次の反応に供することができる。

For this trimetalation, organic lithium reagents such as n-butyllithium (n-BuLi), sec-butyllithium (sec-BuLi), tert-butyllithium (tert-BuLi), alkyl Grignard reagents, alkylmagnesium amide However, from the viewpoint of easy availability and operability, lithiation using tert-BuLi is preferable. As described above, after lithiation, a metal conversion reaction can be performed for the next reaction.

The metalation of the aryl halide represented by the general formula (8) with the metalation reagent is carried out by cooling to 5 ° C. or lower, but 0 ° C. or lower is preferable in order to prevent decomposition of the resulting metalated product. Since the reaction is slow at a low temperature of 80 ° C. or lower, 0 to −80 ° C. is preferable. Specifically, a method of cooling to -78 ° C with a dry ice-ethanol bath at the time of mixing and gradually raising the temperature to 0 ° C is preferable. The reaction for metalation is carried out in a solvent, and ether solvents such as tetrahydrofuran and diethyl ether, hydrocarbon solvents such as pentane, hexane and toluene, and mixed solvents thereof can be used. Is preferred. These solvents are preferably dehydrated in advance.

  The conversion reaction from the trimetalated compound can be performed by a cross coupling reaction. When the halide to be cross-coupled (general formula (9)) is an electrophile such as chlorosilane, fluoroborane or hexafluorobenzene, it can be directly reacted with a lithiated compound. At this time, no catalyst is required.

  On the other hand, when the halide (general formula (9)) is a compound that is not particularly electrophilic, such as 2-bromothiophene, N, N-diphenyl-N- (4-bromophenyl) amine, A cross-coupling reaction using is performed.

  Examples of the cross-coupling reaction catalyst include transition catalysts such as iron catalysts, cobalt catalysts, nickel catalysts, palladium catalysts, ruthenium catalysts, rhodium catalysts, nickel catalysts and palladium catalysts are preferred, and palladium catalysts are also preferred. preferable.

Examples of the palladium catalyst include palladium bromide, palladium chloride, palladium iodide, palladium cyanide, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate [Pd (acac) ₂ ], diacetate bis (triphenylphosphine) palladium [ Pd (OAc) ₂ (PPh ₃ ) ₂ ], tetrakis (triphenylphosphine) palladium [Pd (PPh ₃ ) ₄ ], dichlorobis (acetonitrile) palladium [Pd (CH ₃ CN) ₂ Cl ₂ ], dichlorobis (benzonitrile) palladium _{[Pd (PhCN) 2 Cl 2} ], dichloro [1,2-bis (diphenylphosphino) ethane] palladium [Pd (dppe) _Cl 2], dichloro [1,1-bis (Jifeniruho ) Ferrocene] palladium [Pd (dppf) _Cl 2], dichlorobis (tricyclohexylphosphine) palladium _{[Pd [P (C 6 H 11} ) 3] 2 Cl 2 ], dichlorobis (triphenylphosphine) palladium [Pd (PPh ₃ ) ₂ Cl ₂ ], tris (dibenzylideneacetone) dipalladium [Pd ₂ (dba) ₃ ], bis (dibenzylideneacetone) palladium [Pd (dba) ₂ ] and the like, but tetrakis (triphenylphosphine) A phosphine-based catalyst such as palladium [Pd (PPh ₃ ) ₄ ], dichloro [1,2-bis (diphenylphosphino) ethane] palladium [Pd (dppe) Cl ₂ ] is preferable.

  In addition to the above, a palladium catalyst synthesized by the reaction of a palladium salt and a ligand in the reaction system can be used as the palladium catalyst. Examples of the ligand include triphenylphosphine, trimethylphosphine, triethylphosphine, tris (n-butyl) phosphine, tris (tert-butyl) phosphine, bis (tert-butyl) methylphosphine, tris (i-propyl) phosphine, tris. Cyclohexylphosphine, tris (o-tolyl) phosphine, tris (2-furyl) phosphine, 2-dicyclohexylphosphinobiphenyl, 2-bis (tert-butyl) phosphinobiphenyl, 2-dicyclohexylphosphino-2'-dimethylaminobiphenyl , Diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinobutane, diphenylphosphinoethylene, diphenylphosphinoferrocene, ethylenediamine, N, N ′, N ″, N '' -Tetramethylethylenediamine, 2,2′-bipyridyl, 1,3-diphenyldihydroimidazolylidene, 1,3-dimethyldihydroimidazolylidene, diethyldihydroimidazolylidene, 1,3-bis (2,4,4 6-trimethylphenyl) dihydroimidazolylidene, 1,3-bis (2,6-diisopropylphenyl) dihydroimidazolylidene, and a palladium catalyst coordinated with any of these ligands is a cross-coupling catalyst Can be used as

  The reaction solvent for the coupling reaction is not particularly limited as long as it does not affect the reaction, but aromatic hydrocarbons such as toluene, xylene and benzene, esters such as methyl acetate, ethyl acetate and butyl acetate, diethyl ether, Ethers such as tetrahydrofuran, dioxane, dimethoxyethane, diisopropyl ether, halogenated hydrocarbons such as methyl chloride, chloroform, dichloromethane, dichloroethane, dibromoethane, ketones such as acetone and methyl ethyl ketone, amides such as methylformamide, acetonitrile, etc. Nitriles, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more.

  Moreover, the reaction temperature of this reaction can be normally performed at 0-200 degreeC, Preferably it is 20-150 degreeC. If the reaction temperature is too high, it becomes difficult to control the reaction, and if it is too low, the reaction rate becomes slow, which is not preferable.

  The reaction time varies depending on the reaction temperature, the reaction substrate, the type of metal catalyst for cross-coupling reaction, and the like, but is usually 1 minute to 24 hours, preferably 10 minutes to 3 hours.

By measuring the ultraviolet / visible absorption spectrum and fluorescence spectrum of the borazine compound of the present invention, the optical characteristics can be observed. The quantum yield Φ _F of the fluorescence spectrum analysis of a borazine compound in which a 4-substituted phenyl group is introduced as a nitrogen substituent of the borazine ring and an anthracene derivative is introduced as a boron substituent is generally as high as 0.36 or more. This is a level that can be used as an organic electroluminescent element material. Further, λmax of the fluorescence spectrum also shows a wavelength of slightly less than 400 nm to less than 460 nm, and emits light of purple to blue. Therefore, it can be said that a trianthrylborazine derivative in which three anthryl groups are introduced is particularly useful as a novel compound that can be used as a light-emitting material or a charge transport material.

  When the borazine compound of the present invention is subjected to X-ray structural analysis, a structure in which an aromatic ring is bound around a borazine skeleton as a nucleus is recognized. The aromatic rings are aligned perpendicular to the borazine skeleton, suggesting that the distance between the ipso positions of the aromatic rings is a distance that allows interaction.

Examples 1 to 9 are shown below to describe the present invention in more detail, but the present invention is not limited to these. A synthesis scheme is shown below. In each Example, the target compound having a structure shown on the right side from the reaction step shown in the scheme was produced. ¹ H NMR measurement values of the target compound are shown below each experimental example. In addition, Table 1 shows the ultraviolet / visible absorption spectrum and fluorescence spectrum of the obtained compound.

  Example 1 B, B ′, B ″ -Tri (9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine (1)

還流管をつけた５０ｍＬの二口フラスコを乾燥し、アルゴン置換した。アルゴン雰囲気下、ＢＣｌ_３（１．０Ｍヘキサン溶液）７．２ｍＬ（７．２ｍｍｏｌ）を加え、０℃に冷却した。別途調製した４−ヘキシルアニリン（１．０２ｇ、５．７５ ｍｍｏｌ）のトルエン（４ｍＬ）溶液を０ ℃でゆっくり滴下した。滴下終了後、さらに３．５ｍＬのトルエンを加え、アルゴン雰囲気下、１９時間加熱還流し、Ｂ，Ｂ’，Ｂ”−トリクロロ−Ｎ，Ｎ’，Ｎ”−トリス（４−ヘキシルフェニル）ボラジンを含む混合溶液を調製した。

A 50 mL two-necked flask equipped with a reflux tube was dried and purged with argon. Under an argon atmosphere, 7.2 mL (7.2 mmol) of BCl ₃ (1.0 M hexane solution) was added and cooled to 0 ° C. A separately prepared 4-hexylaniline (1.02 g, 5.75 mmol) solution in toluene (4 mL) was slowly added dropwise at 0 ° C. After completion of the dropwise addition, 3.5 mL of toluene was further added, and the mixture was heated to reflux for 19 hours under an argon atmosphere. B, B ′, B ″ -trichloro-N, N ′, N ″ -tris (4-hexylphenyl) borazine was added. A mixed solution containing was prepared.

A 100 mL two-necked flask was dried and purged with argon. 9-Bromoanthracene (1.45 g, 5.65 mmol) was added and 11.5 mL of THF was added. After cooling to −78 ° C., 7.4 mL (11.3 mmol) of tert-BuLi (1.53 M pentane solution) was added dropwise, and the temperature was raised from −78 ° C. to 0 ° C. over 75 minutes. To this was added the B, B ′, B ″ -trichloro-N, N ′, N ″ -tris (4-hexylphenyl) borazine solution prepared above at 0 ° C. and stirred for 20 hours while slowly warming to room temperature. did. After completion of the reaction, insoluble matters were filtered, and the filtrate was concentrated under reduced pressure and washed with a hexane-diethyl ether mixed solvent to obtain 970 mg (0.89 mmol) of a yellow target compound. Further, the filtrate was concentrated and purified by reverse phase column chromatography (Wakosil 40C18, CH ₃ CN: CH ₂ Cl ₂ = 9: 1) to obtain 461 mg (0.424 mmol) of the desired product. Total yield 1.35 g, 69% yield.

¹ H NMR (400 MHz, CDCl ₃ ): δ 0.45-0.53 (m, 6H), 0.77-1.10 (m, 27H), 1.73 (t, J _HH = 7.2 Hz, 6H), 5.77 (d, J _HH = 8.4 Hz, 6H), 6.57 (d, J _HH = 8.0 Hz, 6H), 7.32 (t, J _HH = 7.2 Hz, 6H) , 7.59 (t, J _HH = 7.2 Hz, 6H), 7.70 (d, J _HH = 8.4 Hz, 6H), 7.96 (s, 3H), 8.44 (d, J _HH = 8.4 Hz, 6H).

  [Example 2] B, B ', B "-tri (9-anthryl) -N, N', N" -tris (4-isopropylphenyl) borazine (2)

還流管をつけた５０ｍＬのシュレンクチューブを乾燥し，アルゴン置換した。アルゴン雰囲気下、ＢＣｌ_３（１．０Ｍヘキサン溶液）８ｍＬ（８．０ｍｍｏｌ）を加え、０℃に冷却した。別途調製した４−イソプロピルアニリン（８３０ｍｇ、６．１４ｍｍｏｌ）のトルエン（４ｍＬ）溶液を０ ℃でゆっくり滴下した。滴下終了後、さらに４ ｍＬのトルエンを加え、アルゴン雰囲気下、１８時間加熱還流し、Ｂ， Ｂ’，Ｂ”−トリクロロ−Ｎ，Ｎ’，Ｎ”−トリス（４−イソプロピルフェニル）ボラジンを含む混合溶液を調製した。

A 50 mL Schlenk tube fitted with a reflux tube was dried and purged with argon. Under an argon atmosphere, 8 mL (8.0 mmol) of BCl ₃ (1.0 M hexane solution) was added and cooled to 0 ° C. A separately prepared 4-isopropylaniline (830 mg, 6.14 mmol) solution in toluene (4 mL) was slowly added dropwise at 0 ° C. After completion of the dropwise addition, 4 mL of toluene is further added, and the mixture is heated under reflux for 18 hours under an argon atmosphere, and contains B, B ′, B ″ -trichloro-N, N ′, N ″ -tris (4-isopropylphenyl) borazine. A mixed solution was prepared.

A 100 mL two-necked flask was dried and purged with argon. 9-Bromoanthracene (1.58 g, 6.14 mmol) was added and 12.5 mL of THF was added. After cooling to −78 ° C., 8.6 mL (1.23 mmol) of tert-BuLi (1.43 M pentane solution) was added dropwise, and the temperature was raised from −78 ° C. to 0 ° C. over 75 minutes. To this was added the B, B ′, B ″ -trichloro-N, N ′, N ″ -tris (4-isopropylphenyl) borazine solution prepared above at 0 ° C., and the mixture was stirred for 19 hours while slowly warming to room temperature. did. After completion of the reaction, water was added and extracted with chloroform. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The obtained crude product was washed with chloroform to obtain 998 mg (1.04 mmol) of a yellow target compound. Further, the filtrate was concentrated and purified by column chromatography (silica gel 60N, Hexane: Toluene = 1: 1) to obtain 101 mg (0.105 mmol) of the desired product. Total yield 1.10 g, 56% yield.
¹ H NMR (400 MHz, CDCl ₃ ): δ 0.47 (d, J _HH = 6.8 Hz, 18 H), 2.00 (hep, J _HH = 6.8 Hz, 3 H), 5.77 (d, J _HH = 8.8 Hz, 6H), 6.51 (d, J _HH = 8.8 Hz, 6H), 7.30 (t, J _HH = 7.2 Hz, 6H), 7.55 (t, J _HH = 7.2 Hz, 6H), 7.68 (d, J _HH = 8.4 Hz, 6H), 7.94 (s, 3H), 8.38 (d, J _HH = 8.8 Hz, 6H).

  Example 3 B, B ′, B ″ -Tri (9-anthryl) -N, N ′, N ″ -tris (4-trifluoromethylphenyl) borazine (3)

還流管をつけた５０ｍＬのシュレンクチューブを乾燥し、アルゴン置換した。アルゴン雰囲気下、ＢＣｌ_３（１．０Ｍヘキサン溶液）８．２ｍＬ（８．２ｍｍｏｌ）を加え、０℃に冷却した。別途調製した４−トリフルオロメチルアニリン（１．０１ｇ、６．２７ｍｍｏｌ）のトルエン（４ｍＬ）溶液を０ ℃でゆっくり滴下した。滴下終了後、さらに４ ｍＬのトルエンを加え、アルゴン雰囲気下、１５時間加熱還流し、Ｂ，Ｂ’，Ｂ”−トリクロロ−Ｎ，Ｎ’，Ｎ”−トリス（４−トリフルオロメチルフェニル）ボラジンを含む混合溶液を調製した。

A 50 mL Schlenk tube fitted with a reflux tube was dried and purged with argon. Under an argon atmosphere, 8.2 mL (8.2 mmol) of BCl ₃ (1.0 M hexane solution) was added and cooled to 0 ° C. A separately prepared solution of 4-trifluoromethylaniline (1.01 g, 6.27 mmol) in toluene (4 mL) was slowly added dropwise at 0 ° C. After completion of the dropwise addition, 4 mL of toluene was further added, and the mixture was heated to reflux for 15 hours under an argon atmosphere. B, B ′, B ″ -trichloro-N, N ′, N ″ -tris (4-trifluoromethylphenyl) borazine A mixed solution containing was prepared.

  A 100 mL two-necked flask was dried and purged with argon. 9-Bromoanthracene (1.61 g, 6.28 mmol) was added and 12.8 mL of THF was added. After cooling to −78 ° C., 9.4 mL (12.5 mmol) of tert-BuLi (1.33 M pentane solution) was added dropwise, and the temperature was raised from −78 ° C. to 0 ° C. over 1 hour. To this was added the B, B ′, B ″ -trichloro-N, N ′, N ″ -tris (4-trifluoromethylphenyl) borazine solution prepared above at 0 ° C., and the temperature was slowly raised to room temperature. Stir for 5 hours. After completion of the reaction, insoluble matters were filtered off, and the filtrate was concentrated under reduced pressure. Reprecipitation was performed using a chloroform-hexane mixed solution, and the precipitate and the filtrate were separated. The precipitate was purified by column chromatography (silica gel 60N, Hexane: Toluene = 1: 1) to obtain 258 mg (0.248 mmol) of a pale yellow target compound. Further, the filtrate was concentrated and purified again by column chromatography (silica gel 60N, Hexane: Toluene = 2: 1) to obtain 157 mg (0.151 mmol) of a pale yellow target compound. Total yield 415 mg (0.398 mmol), yield 19%.

¹ H NMR (400 MHz, CDCl ₃ ): δ 6.28 (d, J _HH = 8.4 Hz, 6H), 6.78 (d, J _HH = 8.4 Hz, 6H), 7.36 (t, J _HH = 7.6 Hz, 6H), 7.63 (t, J _HH = 7.6 Hz, 6H), 7.75 (d, J _HH = 8.4 Hz, 6H), 8.05 (s, 3H), 8.30 (d, J _HH = 8.8 Hz, 6H).

  Example 4 B, B ′, B ″ -tri (10-bromo-9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine (4)

還流管をつけた１００ ｍＬの二口フラスコを乾燥し、アルゴン置換した。アルゴン雰囲気下、ＢＣｌ_３（１．０Ｍヘキサン溶液）２２ ｍＬ（２２．０ｍｍｏｌ）を加え、０℃に冷却した。別途調製した４−ヘキシルアニリン（２．９６ｇ、１６．７ｍｍｏｌ）のトルエン（１８ｍＬ）溶液を０℃でゆっくり滴下した。滴下終了後、さらに５ｍＬのトルエンを加え、アルゴン雰囲気下、１５時間加熱還流し、Ｂ， Ｂ’，Ｂ”−トリクロロ−Ｎ，Ｎ’，Ｎ”−トリス（４−ヘキシルフェニル）ボラジンを含む混合溶液を調製した。

A 100 mL two-necked flask equipped with a reflux tube was dried and purged with argon. Under an argon atmosphere, 22 mL (22.0 mmol) of BCl ₃ (1.0 M hexane solution) was added and cooled to 0 ° C. A separately prepared solution of 4-hexylaniline (2.96 g, 16.7 mmol) in toluene (18 mL) was slowly added dropwise at 0 ° C. After completion of the dropwise addition, 5 mL of toluene is further added, and the mixture is heated to reflux for 15 hours under an argon atmosphere, and mixed with B, B ′, B ″ -trichloro-N, N ′, N ″ -tris (4-hexylphenyl) borazine. A solution was prepared.

  The 200 mL two-necked flask was dried and purged with argon. 9,10-Dibromoanthracene (5.63 g, 16.8 mmol) was added and 65 mL of THF was added. After cooling to −78 ° C., 10.5 mL of n-BuLi (1.56 M hexane solution) was added dropwise, and the mixture was stirred at −78 ° C. for 1.5 hours. To this was added the B, B ′, B ″ -trichloro-N, N ′, N ″ -tris (4-hexylphenyl) borazine solution prepared above, and the temperature was raised slowly to room temperature at −78 ° C. for 5 hours. The mixture was stirred for 13 hours. After completion of the reaction, it was quenched with water and extracted with chloroform. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained crude product was washed with hexane to obtain 4.31 g (3.25 mmol) of a pale yellow target compound. Further, the filtrate was concentrated and purified by column chromatography (silica gel 60N, Hexane: Toluene = 5: 1) to obtain 843 mg (0.635 mmol) of the desired product. Total yield 5.15 g, yield 70%.

¹ H NMR (400 MHz, CDCl ₃ ): δ 0.48-0.55 (m, 6H), 0.73-1.07 (m, 27H), 1.74 (t, J _HH = 7.2 Hz, 6H), 5.76 (d, J _HH = 8.4 Hz, 6H), 6.47 (d, J _HH = 8.4 Hz, 6H), 7.45 (t, J _HH = 7.2 Hz, 6H) , 7.63 (t, J _HH = 7.2 Hz, 6H), 8.26 (d, J _HH = 8.8 Hz, 6H), 8.39 (d, J _HH = 8.8 Hz, 6H).

  Example 5 B, B ′, B ″ -Tris (10-phenyl-9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine (5)

２０ｍＬのシュレンクチューブを乾燥し、アルゴン置換した。Ｂ，Ｂ’，Ｂ”−トリス（１０−ブロモ−９−アントリル）−Ｎ，Ｎ’，Ｎ”−トリス（４−ヘキシルフェニル）ボラジン（３９６ｍｇ、０．２９８ｍｍｏｌ）、ＮｉＣｌ_２（ｄｐｐｂ）（６．８ ｍｇ、８．９５mｍｏｌ）をそれぞれ加え、ＴＨＦを加えた。０℃に冷却し、フェニルマグネシウムブロマイド（０．８７Ｍ ＴＨＦ溶液）１．１５ｍＬ（１．００ｍｍｏｌ）を滴下後、室温に戻して３１．５時間攪拌した。反応終了後、１Ｎ ＨＣｌ水溶液を加え、クロロホルムで抽出した。有機層を飽和食塩水で洗い、硫酸マグネシウムで乾燥し、ろ過後、ろ液を減圧濃縮した。得られた粗生成物をカラムクロマトグラフィー（シリカゲル６０Ｎ、Ｈｅｘａｎｅ：Ｔｏｌｕｅｎｅ＝３：１）、続いてＧＰＣ（ＣＨＣｌ_３）で精製することにより、１８４ ｍｇ（０．１４０ｍｍｏｌ）の淡黄色の目的化合物を得た。収率４７％。

A 20 mL Schlenk tube was dried and purged with argon. B, B ′, B ″ -Tris (10-bromo-9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine (396 mg, 0.298 mmol), NiCl ₂ (dppb) (6 .8 mg, 8.95 mmol) were added respectively, and THF was added. After cooling to 0 ° C., 1.15 mL (1.00 mmol) of phenylmagnesium bromide (0.87 M THF solution) was added dropwise, and the mixture was returned to room temperature and stirred for 31.5 hours. 1N HCl aqueous solution was added after completion | finish of reaction, and chloroform extracted. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained crude product was purified by column chromatography (silica gel 60N, Hexane: Toluene = 3: 1), followed by GPC (CHCl ₃ ) to obtain 184 mg (0.140 mmol) of a pale yellow target compound. Obtained. Yield 47%.

¹ H NMR (400 MHz, CDCl ₃ ): δ 0.63-0.68 (m, 6H), 0.73 (t, J _HH = 7.6 Hz, 9H), 0.84-1.07 (m, 18H), 1.82 (t, J _HH = 7.6 Hz, 6H), 5.85 (d, J _HH = 8.4 Hz, 6H), 6.61 (d, J _HH = 8.4 Hz, 6H) , 7.12-7.13 (m, 6H), 7.19 (t, J _HH = 7.6 Hz, 6H), 7.36 (d, J _HH = 8.8 Hz, 6H), 7.42- 7.43 (m, 9H), 7.57 (t, J _HH = 7.4 Hz, 6H), 8.49 (d, J _HH = 8.8 Hz, 6H).

  Example 6 B, B ′, B ″ -Tris (10-pentafluorophenyl-9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine (6)

２０ｍＬのシュレンクチューブを乾燥し、アルゴン置換した。Ｂ，Ｂ’，Ｂ”−トリス（１０−ブロモ−９−アントリル）−Ｎ，Ｎ’，Ｎ”−トリス（４−ヘキシルフェニル）ボラジン（４０４ｍｇ、０．３０４ ｍｍｏｌ）を加え、ＴＨＦを加えた。−７８℃に冷却しｔｅｒｔ−ＢｕＬｉ（１．４４Ｍペンタン溶液）１．３ ｍＬ（１．８７ｍｍｏｌ）を滴下し、−７８℃で１時間攪拌した。これに大過剰のヘキサフルオロベンゼン（３ｍＬ）を加え、室温までゆっくり昇温しながら１５時間攪拌した。反応終了後、水を加え、クロロホルムで抽出した。有機層を飽和食塩水で洗い、硫酸マグネシウムで乾燥し、ろ過後、ろ液を減圧濃縮した。得られた粗生成物をカラムクロマトグラフィー（シリカゲル６０Ｎ、Ｈｅｘａｎｅ：Ｔｏｌｕｅｎｅ＝５：２）、続いてＧＰＣ（ＣＨＣｌ_３）で精製することにより、１８６ ｍｇ（０．１１７ｍｍｏｌ）の淡黄色の目的化合物を得た。収率３８％。

A 20 mL Schlenk tube was dried and purged with argon. B, B ′, B ″ -Tris (10-bromo-9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine (404 mg, 0.304 mmol) was added and THF was added. . After cooling to −78 ° C., 1.3 mL (1.87 mmol) of tert-BuLi (1.44 M pentane solution) was added dropwise, and the mixture was stirred at −78 ° C. for 1 hour. A large excess of hexafluorobenzene (3 mL) was added thereto, and the mixture was stirred for 15 hours while slowly warming to room temperature. After completion of the reaction, water was added and extracted with chloroform. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained crude product was purified by column chromatography (silica gel 60N, Hexane: Toluene = 5: 2), followed by GPC (CHCl ₃ ) to obtain 186 mg (0.117 mmol) of a pale yellow target compound. Obtained. Yield 38%.

¹ H NMR (400 MHz, CDCl ₃ ): δ 0.58-0.65 (m, 6H), 0.71 (t, J _HH = 7.0 Hz, 9H), 0.78-1.03 (m, 18H), 1.77 (t, J _HH = 7.4 Hz, 6H), 5.83 (d, J _HH = 8.0 Hz, 6H), 6.52 (d, J _HH = 7.2 Hz, 6H) , 7.23 (d, J _HH = 8.8 Hz, 6H), 7.33 (t, J _HH = 7.6 Hz, 6H), 7.62 (t, J _HH = 7.6 Hz, 6H), 8 .51 (d, J _HH = 8.4 Hz, 6H).

  Example 7 B, B ′, B ″ -Tris (10-thienyl-9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine (7)

２０ｍＬのシュレンクチューブを乾燥し、アルゴン置換した。Ｂ，Ｂ’，Ｂ”−トリス（１０−ブロモ−９−アントリル）−Ｎ，Ｎ’，Ｎ”−トリス（４−ヘキシルフェニル）ボラジン（４００ｍｇ、０．３０１ｍｍｏｌ）を加え、ＴＨＦを加えた。−７８ ℃に冷却しｔｅｒｔ−ＢｕＬｉ（１．４７Ｍペンタン溶液）１．２５ ｍＬ（１．８４ｍｍｏｌ）を滴下し、−７８℃で３０分攪拌した。０ ℃まで昇温した後、ＺｎＣｌ_２（ｔｍｅｄａ）（２２９ｍｇ、０．９０６ｍｍｏｌ）を加え、さらに０℃で７５分間攪拌した。これに２−ブロモチオフェン（１８０ ｍｇ、１．１０ｍｍｏｌ）、Ｐｄ（ＰＰｈ_３）_４（３４．９ｍｇ、３０．２mｍｏｌ）を加え、１７．５時間加熱還流した。反応終了後、１Ｎ ＨＣｌ水溶液を加え、クロロホルムで抽出した。有機層を飽和食塩水で洗い、硫酸マグネシウムで乾燥し、ろ過後、ろ液を減圧濃縮した。得られた粗生成物をカラムクロマトグラフィー（シリカゲル６０Ｎ、Ｈｅｘａｎｅ：Ｔｏｌｕｅｎｅ＝５：２）、さらにＧＰＣ（ＣＨＣｌ_３）で精製することにより、２１６ｍｇ（０．１６２ ｍｍｏｌ）の橙色の目的化合物を得た。収率５４％。

A 20 mL Schlenk tube was dried and purged with argon. B, B ′, B ″ -Tris (10-bromo-9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine (400 mg, 0.301 mmol) was added and THF was added. After cooling to −78 ° C., 1.25 mL (1.84 mmol) of tert-BuLi (1.47 M pentane solution) was added dropwise, and the mixture was stirred at −78 ° C. for 30 minutes. After raising the temperature to 0 ° C., ZnCl ₂ (tmeda) (229 mg, 0.906 mmol) was added, and the mixture was further stirred at 0 ° C. for 75 minutes. 2-Bromothiophene (180 mg, 1.10 mmol) and Pd (PPh ₃ ) ₄ (34.9 mg, 30.2 mmol) were added thereto, and the mixture was heated to reflux for 17.5 hours. 1N HCl aqueous solution was added after completion | finish of reaction, and chloroform extracted. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained crude product was purified by column chromatography (silica gel 60N, Hexane: Toluene = 5: 2) and further purified by GPC (CHCl ₃ ) to obtain 216 mg (0.162 mmol) of an orange target compound. . Yield 54%.

¹ H NMR (500 MHz, CDCl ₃ ): δ 0.65-0.71 (m, 6H), 0.74 (t, J _HH = 7.3 Hz, 9H), 0.85-1.09 (m, 18H), 1.81 (t, J _HH = 7.5 Hz, 6H), 5.84 (d, J _HH = 8.3 Hz, 6H), 6.58 (d, J _HH = 8.3 Hz, 6H) 6.89 (dd, J _HH = 3.5, 1.1 Hz, 3H), 7.16 (dd, J _HH = 5.1, 3.4 Hz, 3H), 7.26 (t, J _HH = 8.0 Hz, 6H), 7.47 (dd, J _HH = 5.2, 0.9 Hz, 3H), 7.56 (d, J _HH = 8.3 Hz, 6H), 7.58 (t, J _HH = 6.9 Hz, 6H), 8.47 (d, J _HH = 8.6 Hz, 6H).

  Example 8 B, B ′, B ″ -Tris (10- (4-diphenylaminophenyl) -9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine (8)

２０ｍＬのシュレンクチューブを乾燥し、アルゴン置換した。Ｂ，Ｂ’，Ｂ”−トリス（１０−ブロモ−９−アントリル）−Ｎ，Ｎ’，Ｎ”−トリス（４−ヘキシルフェニル）ボラジン（４０３ｍｇ，０．３０４ｍｍｏｌ）を加え，ＴＨＦを加えた。−７８ ℃に冷却しｔｅｒｔ−ＢｕＬｉ（１．４７Ｍペンタン溶液）１．２５ ｍＬ（１．８４ｍｍｏｌ）を滴下し、−７８ ℃で１時間攪拌した。０ ℃まで昇温した後、ＺｎＣｌ_２（ｔｍｅｄａ）（２３０．４ｍｇ、０．９１３ｍｍｏｌ）を加え、さらに０℃で７５分間攪拌した。これにＮ，Ｎ−ジフェニル−Ｎ−（４−ブロモフェニル）アミン（３２６ｍｇ、１．０１ｍｍｏｌ）、Ｐｄ（ＰＰｈ_３）_４（３５．５ｍｇ、３０．７mｍｏｌ）を加え、２４時間加熱還流した。反応終了後、水を加え、クロロホルムで抽出した。有機層を飽和食塩水で洗い、硫酸ナトリウムで乾燥し、ろ過後、ろ液を減圧濃縮した。得られた粗生成物をカラムクロマトグラフィー（シリカゲル６０Ｎ、Ｈｅｘａｎｅ：Ｔｏｌｕｅｎｅ＝３：２）で精製することにより、１３３ｍｇ（０．０７３１ｍｍｏｌ）の黄色の目的化合物を得た。収率２４％。

A 20 mL Schlenk tube was dried and purged with argon. B, B ′, B ″ -Tris (10-bromo-9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine (403 mg, 0.304 mmol) was added and THF was added. After cooling to −78 ° C., 1.25 mL (1.84 mmol) of tert-BuLi (1.47 M pentane solution) was added dropwise, and the mixture was stirred at −78 ° C. for 1 hour. After heating up to 0 ° C., ZnCl ₂ (tmeda) (230.4 mg, 0.913 mmol) was added, and the mixture was further stirred at 0 ° C. for 75 minutes. N, N-diphenyl-N- (4-bromophenyl) amine (326 mg, 1.01 mmol) and Pd (PPh ₃ ) ₄ (35.5 mg, 30.7 mmol) were added thereto, and the mixture was heated to reflux for 24 hours. After completion of the reaction, water was added and extracted with chloroform. The organic layer was washed with saturated brine, dried over sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained crude product was purified by column chromatography (silica gel 60N, Hexane: Toluene = 3: 2) to obtain 133 mg (0.0731 mmol) of a yellow target compound. Yield 24%.

¹ H NMR (500 MHz, CDCl ₃ ): δ 0.56-0.62 (m, 6H), 0.66 (t, J _HH = 7.5 Hz, 9H), 0.79-0.99 (m, 18H), 1.76 (t, J _HH = 7.5 Hz, 6H), 5.81 (d, J _HH = 8.0 Hz, 6H), 6.59 (d, J _HH = 8.0 Hz, 6H) , 6.99 (d, J _HH = 8.0 Hz, 6H), 7.01 (t, J _HH = 7.0 Hz, 6H), 7.13 (d, J _HH = 8.5 Hz, 6H), 7 .23-7.28 (m, 30H), 7.51 (d, J _HH = 8.5 Hz, 6H), 7.58 (t, J _HH = 7.8 Hz, 6H), 8.48 (d, _JHH = 8.5 Hz, 6H).

  Example 9 B, B ′, B ″ -Tris (10-diisopropylsilyl-9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine (9)

２０ｍＬのシュレンクチューブを乾燥し、アルゴン置換した。Ｂ，Ｂ’，Ｂ”−トリス（１０−ブロモ−９−アントリル）−Ｎ，Ｎ’，Ｎ”−トリス（４−ヘキシルフェニル）ボラジン（４０１ｍｇ、０．３０３ｍｍｏｌ）を加え、ＴＨＦを加えた。−７８ ℃に冷却しｔｅｒｔ−ＢｕＬｉ（１．４７ Ｍペンタン溶液）１．２５ｍＬ（１．８４ｍｍｏｌ）を滴下し、−７８℃で１時間攪拌した。−３０℃までゆっくり昇温した後、ジイソプロピルクロロシラン（１５０ｍｇ、１．００ｍｍｏｌ）を−３０℃で加え、室温まで昇温し、１７．５時間攪拌した。反応終了後、炭酸水素ナトリウム水溶液を加え、ジクロロメタンで抽出した。有機層を飽和食塩水で洗い、硫酸マグネシウムで乾燥し、ろ過後、ろ液を減圧濃縮した。得られた粗生成物をカラムクロマトグラフィー（シリカゲル６０Ｎ、Ｈｅｘａｎｅ：Ｔｏｌｕｅｎｅ＝５：１）で精製することにより、１９９ｍｇ（０．１３９ｍｍｏｌ）の橙色の目的化合物を得た。収率４６％。

A 20 mL Schlenk tube was dried and purged with argon. B, B ′, B ″ -Tris (10-bromo-9-anthryl) -N, N ′, N ″ -tris (4-hexylphenyl) borazine (401 mg, 0.303 mmol) was added and THF was added. After cooling to −78 ° C., 1.25 mL (1.84 mmol) of tert-BuLi (1.47 M pentane solution) was added dropwise, and the mixture was stirred at −78 ° C. for 1 hour. After slowly raising the temperature to −30 ° C., diisopropylchlorosilane (150 mg, 1.00 mmol) was added at −30 ° C., the temperature was raised to room temperature, and the mixture was stirred for 17.5 hours. After completion of the reaction, an aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with dichloromethane. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained crude product was purified by column chromatography (silica gel 60N, Hexane: Toluene = 5: 1) to obtain 199 mg (0.139 mmol) of an orange target compound. Yield 46%.

¹ H NMR (400 MHz, CDCl ₃ ): δ 0.54 (d, J _HH = 7.6 Hz, 18 H), 0.60-0.74 (m, 21 H), 0.84-0.92 (m, 6H), 0.85-1.05 (m, 12H), 1.11 (d, J _HH = 7.6 Hz, 18H), 1.39-1.47 (m, 6H), 1.65 (t , J _HH = 7.6 Hz, 6H), 5.70 (d, J _HH = 7.6 Hz, 6H), 6.48 (d, J _HH = 7.2 Hz, 6H), 7.26-7. 32 (m, 6H), 7.53 (t, J _HH = 7.4 Hz, 6H), 8.21 (d, J _HH = 8.8 Hz, 6H), 8.42 (d, J _HH = 8. 4Hz, 6H).

With respect to the compounds obtained in Examples 1 to 3 and Examples 5 to 9, ultraviolet / visible absorption spectra and fluorescence spectra were measured. Further, with respect to the fluorescence spectrum, the fluorescence quantum yield (Φ _f ) was measured. The results are shown in Table 1. In addition, since the compound of Example 4 was an intermediate raw material of the compound of Examples 5-9, it did not measure.
The measurement conditions for each spectrum are as follows.

UV, fluorescence measurement conditions Solvent: THF for fluorescence analysis (manufactured by Nacalai Tesque) distilled with sodium-benzophenone ketyl was subjected to freeze degassing three times at liquid nitrogen temperature UV measurement conditions: maximum absorbance (Abs.) Measured at a concentration at which ≦ 1 Fluorescence measurement conditions: Measured at a concentration at which the maximum UV absorbance was 0.05 or less. In the measurement, the UV measurement sample was diluted to satisfy the conditions.

    All of these sample preparations were performed in an inert gas atmosphere.

The quantum yields Φ _F of these fluorescence spectrum analyzes were approximately 0.36 or higher, indicating a high quantum yield. In particular, the fluorescent quantum yield of compound 9 is 0.80, which is extremely high. The maximum emission wavelength of Compound 8 was 459 nm, and blue emission was exhibited.

Here, the quantum yield of these samples is relative to anthracene (Φ _F = 0.27) or 9,10-diphenylanthracene (Φ _F = 0.90) whose quantum yield is already known. The quantum yield was determined. The calculation was performed as follows.

φ _F = [(A _s F _u n ² )] / (A _u F _s n ₀ ² )] * φ _s

Where F _s : fluorescence spectrum area of the standard substance, A _s : UV absorbance of the standard substance

φ _s : Quantum yield of standard substance, n ₀ : Refractive index of measurement solvent of standard substance

F _s : fluorescence spectrum area of the measurement substance, A _s : UV absorbance of the standard substance

n: refractive index of measurement solvent,

Claims (8)

General formula (3)

[Wherein R ² represents an aryl group. The aryl group may have a substituent, and the substituent is an alkyl group or an alkyl group substituted with a halogen atom. R ³ is an aryl group, heteroaryl group, oligoaryl group, oligoheteroaryl group, alkyl group, silyl group, amino group, alkoxy group, boryl group, stannyl group, mercapto group, sulfide group, hydroxy group, hydrogen atom, halogen A borazine compound represented by the formula: General formula (3)

In the method for producing a borazine compound represented by the formula: R ² and R ³ are the same as above, the general formula (8)

[Wherein R ² is the same as above] and a B, B ′, B ″ -tris (10-bromo-9-anthryl) borazine compound represented by the general formula (9)

[Wherein Y represents a halogen atom, R ³ is the same as the above general formula (3)] and I) the general formula (9) is converted into a Grignard reagent and cross-linked in the presence of a transition metal catalyst. A method of reacting by a coupling reaction,
II) A method in which a compound of the general formula (8) is lithiated with alkyllithium, and then a compound of the general formula (9) is reacted.
III) Lithiation of the compound of general formula (8) with alkyllithium followed by treatment with a metal halide selected from zinc chloride, magnesium chloride or nickel chloride followed by metal exchange followed by the general formula in the presence of a transition metal catalyst A method of cross-coupling reaction of the compound of (9),
The production method, which is performed by any one of the methods. General formula (10)

Wherein, R ² is as defined above] B represented by, B ', B "- In the production method of tris (10-phenyl-9-anthryl) borazine compound represented by the general formula (8)

[Wherein R ² is the same as above] B, B ′, B ″ -tris (10-bromo-9-anthryl) borazine compound and phenylmagnesium bromide are subjected to a cross-coupling reaction in the presence of a transition metal catalyst. The manufacturing method of Claim 2 characterized by the above-mentioned. Formula (11)

In the method for producing a B, B ′, B ″ -tris (10-pentafluorophenyl-9-anthryl) borazine compound represented by the formula: wherein R ² is the same as above, general formula (8)

[Wherein R ² is the same as above] A reaction of B, B ′, B ″ -tris (10-bromo-9-anthryl) borazine compound with hexafluorobenzene is represented by the compound of the general formula (8) The method according to claim 2 , wherein the method is carried out after lithiation by treating with alkyllithium. Formula (12)

Wherein, R ² is as defined above] B represented by, B ', B "- In the production method of tris (10-thienyl-9-anthryl) borazine compound represented by the general formula (8)

[Wherein R ² is the same as above] The reaction of B, B ′, B ″ -tris (10-bromo-9-anthryl) borazine compound with 2-bromothiophene represented by the general formula (8) The method according to claim 2 , wherein the compound is treated with alkyllithium to lithiate, then treated with zinc chloride to exchange metals, and then cross-coupled in the presence of a palladium catalyst. Formula (13)

Wherein, R ² is as defined above] B represented by, B ', B "- In the production method of tris (10- (4-diphenylamino-phenyl) -9-anthryl) borazine compound represented by the general formula (8)

[Wherein R ² is the same as above] B, B ′, B ″ -tris (10-bromo-9-anthryl) borazine compound and N, N-diphenyl-N- (4-bromophenyl) The reaction with amine is carried out by treating the compound of general formula (8) with alkyllithium to lithiate, then treating with zinc chloride to exchange metals, and then performing cross-coupling in the presence of a palladium catalyst. The manufacturing method according to claim 2 . General formula (14)

In the method for producing a B, B ′, B ″ -tris (10-diisopropylsilyl-9-anthryl) borazine compound represented by the formula: wherein R ² is the same as above, general formula (8)

[Wherein R ² is the same as above] The reaction of B, B ′, B ″ -tris (10-bromo-9-anthryl) borazine compound with diisopropylchlorosilane is represented by the following formula (8): The method according to claim 2 , which is carried out after lithiation by treatment with alkyllithium. The production method according to any one of claims 2 to 7 , wherein the compound represented by the general formula (8) is produced by the steps shown below .
[First step]
Formula (4),

[Wherein R ² represents an aryl group. The aryl group may have a substituent, and the substituent is an alkyl group or a haloalkyl group] and the general formula (5),

[Wherein X represents a halogen atom] is reacted with a boron halide represented by the general formula (6),

A step of obtaining a trihaloborazine compound represented by the formula: wherein R ² and X are the same as above.
[Second step]
The following formula,

[In the formula, X is the same as above] The aromatic metalated product obtained by lithiation or Grignard reagent conversion of the compound represented by the above and the trihaloborazine compound represented by the general formula (6) obtained in the first step are reacted. And obtaining general formula (8).