JP2014105208A - N-arylcarbazole polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel N-arylcarbazole polymer as an organic EL element material, which achieves an organic EL element having particularly high durability and high luminous efficiency.SOLUTION: The N-arylcarbazole polymer is represented by general formula (I) (wherein R1 and R2 each represent a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group; Ar1 represents a divalent or trivalent group of an aromatic hydrocarbon or a divalent or trivalent group of a heterocyclic ring; Ar2 represents a divalent group of an aromatic hydrocarbon; and n represents 2 or 3).

Description

  The present invention relates to a multimer of N-arylcarbazole that realizes an organic EL device having particularly high durability and high luminous efficiency.

  Organic thin-film EL devices have been attracting attention from the viewpoints of being self-luminous and having high viewing angle dependency, high visibility, and being thin-film type completely solid devices that can save space. Practical research is being developed. However, at present, there are many problems to be solved such as further improvement of energy conversion efficiency and light emission quantum efficiency, and improvement of stability of organic thin film over time (improvement of device durability).

So far, organic thin film EL devices have been reported to use low molecules and polymers. In low molecular weight systems, it has been reported that high efficiency is achieved by adopting various laminated structures, and durability is improved by well controlling the doping method.
However, in the case of a low molecular aggregate, it has been reported that the film state changes with time for a long time, and has an essential problem regarding the stability of the film.

On the other hand, with regard to polymer materials, until now, vigorous studies have been made mainly on poly-p-phenylenevinylene (PPV) series, poly-thiophene, and the like.

However, it is difficult to increase the purity of these material systems, and the fluorescence quantum yield is essentially low, so that a high-performance EL device has not been obtained at present. In the case of a polymer material, considering that the glass state is essentially stable, an excellent EL device can be constructed if high fluorescence quantum efficiency can be imparted.

Thus, it is known that there are advantages and disadvantages in the use of low molecules and the use of polymers.
In recent years, studies on high efficiency using triplet excitons have also been made vigorously (T. Tsutsui et al. Jpn. J. Appl. Phys. Vol. 38 L1502 (1999), etc.). It became clear that it was greatly improved. Along with this, there are increasing reports of host materials used in the light emitting layer.

The present inventors have disclosed in Japanese Patent Application Laid-Open No. 2005-154212 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2005-158691 (Patent Document 2) that a 3,6-diphenylcarbazole derivative is used as a host material and has an external quantum of 10 several percent. Clarified to show efficiency. These 3,6-diphenylcarbazole derivatives have also been found to have higher excited triplet energy than 4,4′-bis (carbazolyl-9) biphenyl (CBP), which is known as a representative host material. . However, since these derivatives have low Tg points, it has been estimated that they have problems in durability.

Another important issue for organic thin-film EL devices using triplet excitons is the low external quantum efficiency of blue phosphorescent devices, which requires a host with high excited triplet energy. It has been.

Organic Letters (Non-Patent Document 1) describes 1,3,5-tris (9H-carbazol-9-yl) benzene as a compound having a plurality of carbazole rings, and this was used as a host material. In this case, the external quantum efficiency is 0.1%. This low external quantum efficiency is assumed to be due to the non-planar structure in which the three carbazole rings are significantly twisted from the plane of the central benzene ring (Non-Patent Document 2).

Patent Document 3 and Patent Document 4 show compounds having a plurality of carbazole rings similar to Non-Patent Document 1. Since the compound having a plurality of carbazole rings shown in Patent Document 5 has a paramine structure, the absorption shifts by a long wavelength, so that it is difficult to achieve high triplet energy.

  The present invention has been made in view of the current state of the prior art described above. As a material for an organic EL element, a novel N-arylcarbazole multimer that realizes an organic EL element having particularly high durability and high luminous efficiency is provided. The purpose is to provide.

As a result of intensive studies, the present inventors have found that the use of a N-arylcarbazole multimer as an organic EL device can improve the efficiency and durability.
That is, the said subject is solved by following (1)-(3) of this invention.
(1) a multimer of N-arylcarbazole represented by the following general formula (I);

（式中Ｒ１およびＲ２は水素原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基あるいは置換基を有してもよいアリール基を表し、Ａｒ１は置換基を有してもよい芳香族炭化水素の２価基または３価基、置換基を有してもよい複素環の２価基または３価基を表し、Ａｒ２は置換基を有してもよい芳香族炭化水素の２価基を表し、ｎは２または３を表す）
（２）前記第（１）項における一般式（Ｉ）で表されるＮ−アリールカルバゾールの多量体が下記一般式（II）で表されることを特徴とするＮ−アリールカルバゾールの多量体；

(Wherein R1 and R2 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or an aryl group which may have a substituent, and Ar1 represents an aromatic which may have a substituent) Represents a divalent or trivalent group of an aromatic hydrocarbon, or a divalent or trivalent group of a heterocyclic ring which may have a substituent, and Ar2 represents a divalent aromatic hydrocarbon which may have a substituent And n represents 2 or 3)
(2) The N-arylcarbazole multimer represented by the general formula (I) in the above (1) is represented by the following general formula (II);

（式中Ｒ１、Ｒ２およびＲ３は水素原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基あるいは置換基を有してもよいアリール基を表し、Ａｒ１は置換基を有してもよい芳香族炭化水素の２価基または３価基、置換基を有してもよい複素環の２価基または３価基を表し、ｎは２または３を表す）
（３）前記第（１）項における一般式（I）で表されるＮ−アリールカルバゾールの多量体が下記一般式（III）で表されることを特徴とするＮ−アリールカルバゾールの多量体。

(Wherein R1, R2 and R3 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or an aryl group which may have a substituent, and Ar1 may have a substituent. A divalent or trivalent group of a good aromatic hydrocarbon, a divalent or trivalent group of a heterocyclic ring which may have a substituent, and n represents 2 or 3)
(3) An N-arylcarbazole multimer represented by the following general formula (III):

（式中Ｒ３、Ｒ４およびＲ５は水素原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基あるいは置換基を有してもよいアリール基を表し、Ａｒ１は置換基を有してもよい芳香族炭化水素の２価基または３価基、置換基を有してもよい複素環の２価基または３価基を表し、ｎは２または３を表す）

(Wherein R3, R4 and R5 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or an aryl group which may have a substituent, and Ar1 may have a substituent. A divalent or trivalent group of a good aromatic hydrocarbon, a divalent or trivalent group of a heterocyclic ring which may have a substituent, and n represents 2 or 3)

As will be understood from the following detailed and specific description, according to the present invention, an N-arylcarbazole multimer capable of improving the efficiency and durability of an organic EL device is provided.

FIG. 1 shows the red color of 3,6-diphenyl-N- [3- (5,5-dimethyl-1,3,2-dioxaborin-2-yl) phenyl)] carbazole obtained in Intermediate Production Example 1. It is an external absorption spectrum (KBr tablet method) figure. FIG. 2 shows the red color of 3,6-diphenyl-N- [4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) phenyl)] carbazole obtained in Intermediate Production Example 2. It is an external absorption spectrum (KBr tablet method) figure. FIG. 3 is an infrared absorption spectrum (KBr tablet method) diagram of the N-arylcarbazole multimer of the present invention obtained in Example 1. FIG. 4 is an infrared absorption spectrum (KBr tablet method) diagram of the N-arylcarbazole multimer of the present invention obtained in Example 2. FIG. 5 is an infrared absorption spectrum (KBr tablet method) diagram of the N-arylcarbazole multimer of the present invention obtained in Example 3. FIG. 6 is an infrared absorption spectrum (KBr tablet method) diagram of the N-arylcarbazole multimer of the present invention obtained in Example 4. FIG. 7 is an infrared absorption spectrum (KBr tablet method) diagram of the N-arylcarbazole multimer of the present invention obtained in Example 5. FIG. 8 is an infrared absorption spectrum (KBr tablet method) diagram of the N-arylcarbazole multimer of the present invention obtained in Example 6. FIG. 9 shows the red color of 2,7-diphenyl-N- [4- (5,5-dimethyl-1,3,2-dioxaborin-2-yl) phenyl)] carbazole obtained in Intermediate Production Example 5. It is an external absorption spectrum (KBr tablet method) figure. FIG. 10 is an infrared absorption spectrum (KBr tablet method) diagram of the N-arylcarbazole multimer of the present invention obtained in Example 7. FIG. 11 is an infrared absorption spectrum (KBr tablet method) diagram of the N-arylcarbazole multimer of the present invention obtained in Example 8. FIG. 12 is an infrared absorption spectrum (KBr tablet method) diagram of the N-arylcarbazole multimer of the present invention obtained in Example 9.

The present invention is described in further detail below.
The N-arylcarbazole multimer represented by the general formula (I) of the present invention can be produced by the following route.

（式中Ｒ１およびＲ２は水素原子、置換または無置換のアルキル基、置換または無置換のアルコキシ基あるいは置換基を有してもよいアリール基を表し、Ａｒ１は置換基を有してもよい芳香族炭化水素の２価基または３価基、置換基を有してもよい複素環の２価基または３価基を表し、Ａｒ２は置換基を有してもよい芳香族炭化水素の２価基を表し、Ｘはハロゲン原子を表し、ｎは２または３を表す）

(Wherein R1 and R2 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or an aryl group which may have a substituent, and Ar1 represents an aromatic which may have a substituent) Represents a divalent or trivalent group of an aromatic hydrocarbon, or a divalent or trivalent group of a heterocyclic ring which may have a substituent, and Ar2 represents a divalent aromatic hydrocarbon which may have a substituent Represents a group, X represents a halogen atom, and n represents 2 or 3.

  The N-arylcarbazole multimers represented by the general formula (I) and the general formula (II) of the present invention are prepared as a cross-coupling reaction between an aryl boron compound and an organic halide using a palladium catalyst according to the route of the above formula. Obtained by the known Suzuki-Miyaura reaction.

Instead of the arylboronic acid represented by the general formula (IV), bis (pinacolato) diboron, bis (neopentylglycolato) diboron or 2-isopropoxyboronate pinacol which is thermally stable and can be easily handled in the air An aryl boronic acid ester synthesized from an ester and an aryl halide may be used.

The halogen atom in the polyvalent halide represented by the general formula (V) is preferably an iodide or bromide from the viewpoint of reactivity. Depending on the reaction conditions, chlorinated products can also be used.

Various catalysts such as Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) _2, and PdCl ₂ can be used as the palladium catalyst, but most commonly used is Pd (PPh ₃ ) _4. Can be used.

This reaction requires a base, and relatively weak bases such as Na ₂ CO ₃ and NaHCO ₃ give good results. When affected by steric hindrance or the like, strong bases such as Ba (OH) ₂ and K ₃ PO ₄ are effective. Other caustic soda, caustic potash, metal alkoxide, etc., for example, potassium t-butoxide, sodium t-butoxide, lithium t-butoxide, potassium 2-methyl-2-butoxide, sodium 2-methyl-2-butoxide, sodium methoxide, sodium ethoxide Potassium ethoxide, potassium methoxide, etc. can also be used. An organic base such as triethylamine can also be used.

Examples of the reaction solvent include alcohols such as methanol, ethanol, isopropanol, butanol, 2-methoxyethanol, 1,2-dimethoxyethane, and bis (2-methoxyethyl) ether, and ether ethers, and cyclic ethers such as dioxane and tetrahydrofuran. Examples thereof include benzene, toluene, xylene, dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like.

Specific examples of the N-arylcarbazole multimer represented by the general formula (I) of the present invention thus obtained are shown below.
In the general formula (I), general formula (II), and general formula (III), when R1, R2, R3, R4, and R5 are substituted or unsubstituted alkyl groups, the following may be mentioned.

A linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, and these alkyl groups are further substituted with a fluorine atom, a cyano group, a phenyl group, a halogen atom or a linear or branched alkyl group It may contain a phenyl group.
Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, pentyl group, hexyl group, heptyl group, Octyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, 2-ethylhexyl group, trifluoromethyl group, 2-cyanoethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, cyclopentyl group, A cyclohexyl group etc. are mentioned.

  When R1, R2, R3, R4, and R5 in the general formula (I), general formula (II), and general formula (III) are substituted or unsubstituted alkoxy groups, bonding of the substituted or unsubstituted alkyl group Specific examples include an alkoxy group formed by inserting an oxygen atom at the position.

When R1, R2, R3, R4 and R5 in the general formula (I), general formula (II) and general formula (III) represent an aryl group which may have a substituent, the following may be mentioned: it can.
Phenyl, naphthyl, biphenylyl, terphenylyl, pyrenyl, fluorenyl, 9,9-dimethyl-2-fluorenyl, azulenyl, anthryl, triphenylenyl, chrysenyl, fluorenylidenephenyl, 5H-dibenzo [A, d] cycloheptenylidenephenyl group, furyl group, benzofuranyl group, carbazolyl group, pyridyl group, pyrrolidyl group, oxazolyl group, etc., which are substituted with the above-mentioned substituted or unsubstituted alkyl group or alkoxy group You may have as a group.

Examples of the aromatic hydrocarbon divalent group in Ar2 of the general formula (I) include divalent groups of benzene, naphthalene, biphenyl, terphenyl, pyrene, fluorene, and 9,9-dimethyl-2-fluorene. May have a substituent defined by R1 to R5.

The aromatic hydrocarbon in Ar1 of the general formula (I), general formula (II) and general formula (III) includes benzene, naphthalene, biphenyl, terphenyl, pyrene, fluorene, 9,9-dimethyl-2-fluorene. And a divalent group or a trivalent group, and these may have a substituent defined by R1 to R5.
In addition, examples of the heterocyclic ring include divalent or trivalent groups of N-phenylcarbazole, pyridine, pyrazine, pyrimidine, quinoline, thiophene, 2,1,3-benzothiadiazole, and 2,1,3-benzoselenadiazole. These may have a substituent defined by R1 to R5.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example.

[Example 1]
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples unless it exceeds the gist.

[Production Example 1 of Intermediate]
10 ml of nitrobenzene was added to 3.19 g of 3,6-diphenylcarbazole, 8.49 g of 3-bromoiodobenzene, 2.76 g of potassium carbonate and 0.1 g of copper powder, and the mixture was heated and stirred at 190 ° C. for 11 hours in a nitrogen stream. After standing to cool, the insoluble part was removed by filtration using Celite, and nitrobenzene was distilled off under reduced pressure. The obtained crude product was subjected to silica gel column chromatography (eluent toluene / hexane = 1/2) to obtain 3.28 g of colorless powdery 3,6-diphenyl-N- (3-bromophenyl) carbazole. Melting point: 163.0 to 164.0 ° C

3,6-diphenyl-N- (3-bromophenyl) carbazole 3.28 g, bis (neopentylglycolato) diboron 1.90 g, potassium acetate 2.06 g, [1,1′-bis (diphenylphosphino) ferrocene ] 173 mg of palladium (II) dichloride dichloromethane adduct and 35 ml of dioxane were heated to reflux for 4 hours under a nitrogen stream.
After standing to cool, the insoluble part was removed by filtration using Celite, and dioxane was distilled off under reduced pressure. The obtained crude product was subjected to silica gel column chromatography (eluent: 10% ethyl acetate in toluene solution), and colorless powdery 3,6-diphenyl-N- [3- (5,5) represented by the following structural formula (1) -Dimethyl-1,3,2-dioxaborin-2-yl)] phenylcarbazole 3.01 g was obtained. Melting point 163 ° C

赤外吸収スペクトル（ＫＢｒ錠剤法）を図１に示した。
νＢ−Ｏ １３１７ｃｍ−１ νＢ−Ｃ １１３５ｃｍ−１

The infrared absorption spectrum (KBr tablet method) is shown in FIG.
νB-O 1317 cm-1 νB-C 1135 cm-1

[Production Example 2 of Intermediate]
3,6-Diphenyl-N- (4-bromophenyl) carbazole was obtained in the same manner by the Ullmann reaction using 4-bromoiodobenzene instead of 3-bromoiodobenzene used in [Intermediate Production Example 1]. .
Using this, in the same manner as in Production Example 1, 3,6-diphenyl-N- [4- (5,5-dimethyl-1,3,2-dioxaborin-2-yl] represented by the following structural formula (3) was used. ]] Phenylcarbazole was obtained.

赤外吸収スペクトル（ＫＢｒ錠剤法）を図２に示した。

The infrared absorption spectrum (KBr tablet method) is shown in FIG.

[Production Example 3 of Intermediate]
3,6-Dibromo-N- (3-bromophenyl) carbazole is obtained by carrying out Ullmann reaction in the same manner as [Intermediate Production Example 1] using 3,6-dibromocarbazole and 3-bromoiodobenzene. It was. Melting point: 182.0-183.5 ° C

[Production Example 4 of Intermediate]
By operating in the same manner as in Intermediate Production Example 3 except that 4-bromoiodobenzene was used instead of 3-bromoiodobenzene used in [Intermediate Production Example 3], 3,6-dibromo- N- (4-bromophenyl) carbazole was obtained. Melting point 203.0-204.5 ° C

[Example 1]
Degassed to 0.65 g of 3,5-dibromoanisole and 2.60 g of 3,6-diphenyl-N- [3- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl)] phenylcarbazole Toluene (25 ml) and ethanol (10 ml) were added, tetrakistriphenylphosphine palladium (88 mg), degassed 21.5% aqueous sodium carbonate solution (4.80 g) was added thereto, and the mixture was heated to reflux for 7 hours under a nitrogen stream.
After allowing to cool to room temperature, the organic layer was separated, washed with water and dried, and the solvent was distilled off under reduced pressure.
This was purified by silica gel column chromatography (eluent toluene / hexane = 2/1) to obtain 2.13 g of a white powder multimer of N-arylcarbazole of the present invention represented by the following structural formula (3).

・上記メトキシ体２．１３ｇを塩化メチレン２０ｍＬに溶解した後、１Ｍ三臭化ホウ素の塩化メチレン溶液２．９ｍＬを−１０℃で滴下し、その後室温で攪拌した。次に、水洗した後、乾燥し、溶媒を留去して、ヒドロキシ体２．０６ｇを得た。
得られたヒドロキシ体を実施例２と同様にして、１２−ブロモドデカノールとの反応によりエーテル化し、ついでトシル化、チオアセチル化、加水分解して下記構造式（４）で表される本発明の本発明のＮ−アリールカルバゾールの多量体を得た。融点 １２０℃

-After dissolving 2.13 g of the methoxy compound in 20 mL of methylene chloride, 2.9 mL of a 1M boron tribromide methylene chloride solution was added dropwise at -10 ° C, followed by stirring at room temperature. Next, after washing with water, it was dried and the solvent was distilled off to obtain 2.06 g of a hydroxy compound.
The obtained hydroxy compound was etherified by reaction with 12-bromododecanol in the same manner as in Example 2, and then tosylated, thioacetylated, and hydrolyzed, and represented by the following structural formula (4). A multimer of N-arylcarbazole of the present invention was obtained. Melting point 120 ° C

赤外吸収スペクトル（ＫＢｒ錠剤法）を図３に示した。
元素分析値（％）実測値（計算値）：Ｃ ８６．４９/８６．６３、Ｈ ６．３０/６．３４、Ｎ ２．５２/２．５９、Ｓ ２．９３ /２．９６

The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Measured value (calculated value): C 86.49 / 86.63, H 6.30 / 6.34, N 2.52 / 2.59, S 2.93 / 2.96

[Example 2]
3,6-dibromo-N-phenylcarbazole 0.20 g, 3,6-diphenyl-N- [3- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl)] phenylcarbazole (intermediate) Preparation Example 1) 0.53 g, 5 ml of degassed toluene and 2 ml of ethanol were added, 18 mg of tetrakistriphenylphosphine palladium and 1.0 g of degassed 21.5% sodium carbonate aqueous solution were added thereto, Heated to reflux for 5 hours.
After allowing to cool to room temperature, the organic layer was separated, washed with water and dried, and the solvent was distilled off under reduced pressure.
This was purified by silica gel column chromatography (eluent toluene / hexane = 2/1) to obtain 0.41 g of the N-arylcarbazole multimer of the present invention represented by the following structural formula (5) as a colorless powder.

融点 ＞２５０℃
元素分析（％）実測値/計算値
Ｃ ９０．７９ /９０．９３ Ｈ ５．０３/４．９９ Ｎ ３．９４/４．０８
赤外吸収スペクトル（ＫＢｒ錠剤法）を図４に示した。

Melting point> 250 ° C
Elemental analysis (%) Measured value / Calculated value C 90.79 / 90.93 H 5.03 / 4.99 N N 3.94 / 4.08
The infrared absorption spectrum (KBr tablet method) is shown in FIG.

[Example 3]
0.157 g of 1,3,5-tribromobenzene, 3,6-diphenyl-N- [3- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl)] phenylcarbazole Production Example 1) 0.785 g of degassed toluene 10 ml and ethanol 4 ml were added, tetrakistriphenylphosphine palladium 54 mg, degassed 21.5% sodium carbonate aqueous solution 3.0 g was added, and heated under a nitrogen stream for 4 hours. Refluxed.
After allowing to cool to room temperature, the organic layer was separated, washed with water and dried, and the solvent was distilled off under reduced pressure.
This was purified by silica gel column chromatography (eluent toluene / hexane = 3/2) to obtain 0.48 g of the N-arylcarbazole multimer of the present invention represented by the following structural formula (6) as a colorless powder.

融点 ＞２２０℃
元素分析値（％）実測値／計算値
Ｃ ９１．４７／９１．６２ Ｈ ５．１６／５．０５ Ｎ ３．１５／３．３４
赤外吸収スペクトル（ＫＢｒ錠剤法）を第５図に示した。

Melting point> 220 ° C
Elemental analysis value (%) Measured value / Calculated value C 91.47 / 91.62 H 5.16 / 5.05 N 3.15 / 3.34
The infrared absorption spectrum (KBr tablet method) is shown in FIG.

[Example 4]
0.26 g of 3,6-dibromo-N- (3-bromophenyl) carbazole (Production Example 3 of Intermediate), 3,6-diphenyl-N- [3- (5,5-dimethyl-1,3,2) -Dioxaborinan-2-yl)] phenylcarbazole (Intermediate Production Example 1) 0.70 g of degassed toluene 10 ml and ethanol 4 ml were added, and tetrakistriphenylphosphine palladium 54 mg, followed by degassed 21.5% carbonic acid. 1.20 g of an aqueous sodium solution was added, and the mixture was heated to reflux for 7 hours under a nitrogen stream.
After allowing to cool to room temperature, the organic layer was separated, washed with water and dried, and the solvent was distilled off under reduced pressure.
This was purified by silica gel column chromatography (eluent: toluene / hexane = 2/1) to obtain 0.24 g of the N-arylcarbazole multimer of the present invention represented by the following structural formula (7) as a colorless powder.

融点 ＞２２０℃
MALDI-TOF/MS：１４２２．７５４［M+］(１４２２．５６)
元素分析値（％）実測値／計算値
Ｃ ９０．９４／９１．１１ Ｈ ５．０７／４．９６ Ｎ ３．７５／３．９４
赤外吸収スペクトル（ＫＢｒ錠剤法）を第６図に示した。

Melting point> 220 ° C
MALDI-TOF / MS: 1422.754 [M +] (1422.56)
Elemental analysis value (%) Measured value / Calculated value C 90.94 / 91.11 H 5.07 / 4.96 N 3.75 / 3.94
The infrared absorption spectrum (KBr tablet method) is shown in FIG.

[Example 5]
Other than using 3,6-dibromo-N- (4-bromophenyl) carbazole (Intermediate Production Example 4) instead of 3,6-dibromo-N- (3-bromophenyl) carbazole used in Example 4 Were operated in the same manner as in Example 4 to obtain 0.31 g of the N-arylcarbazole multimer of the present invention in the form of colorless needles represented by the following structural formula (8).

融点＞２２０℃
元素分析値（％）実測値／計算値
Ｃ ９１．００／９１．１１ Ｈ ５．０５／４．９６ Ｎ ３．８５／３．９４
赤外吸収スペクトル（ＫＢｒ錠剤法）を第７図に示した。

Melting point> 220 ° C
Elemental analysis value (%) Measured value / Calculated value C 91.00 / 91.11 H 5.05 / 4.96 N 3.85 / 3.94
The infrared absorption spectrum (KBr tablet method) is shown in FIG.

[Example 6]
0.48 g of 3,6-dibromo-N- (3-bromophenyl) carbazole (Production Example 3 of intermediate), 3,6-diphenyl-N- [4- (5,5-dimethyl-1,3,2) -Dioxaborinan-2-yl)] phenylcarbazole (Intermediate Production Example 2) 20 ml of degassed toluene and 8 ml of ethanol were added to 1.67 g, and then 108 mg of tetrakistriphenylphosphine palladium and 21.5% carbonic acid degassed. 6.0 g of sodium aqueous solution was added, and it heated and refluxed under nitrogen stream for 7 hours.
After cooling to room temperature, the solvent was distilled off under reduced pressure.
The contents were washed with water, washed with methanol and dried. After treating with toluene and Pd scavenger; QuadraSil MP (manufactured by Wako), purification by silica gel column chromatography (eluent: toluene / hexane = 3/2 charge; toluene) gave a pale yellow powder. This was recrystallized three times from toluene to obtain 0.28 g of the N-arylcarbazole multimer of the present invention as colorless needle crystals represented by the following structural formula (9).

融点＞２２０℃
MALDI-TOF/MS：１４２２．６７８［M+］(１４２２．５６)
元素分析値（％）実測値／計算値
Ｃ ９０．７０／９１．１１ Ｈ ５．０１／４．９６ Ｎ ３．９５／３．９４赤外吸収スペクトル（ＫＢｒ錠剤法）を第８図に示した。

Melting point> 220 ° C
MALDI-TOF / MS: 1422.2678 [M +] (1422.56)
Elemental analysis value (%) Measured value / calculated value C 90.70 / 91.11 H 5.01 / 4.96 N 3.95 / 3.94 Infrared absorption spectrum (KBr tablet method) is shown in FIG. It was.

[Production Example 5 of Intermediate]
Using 2,7-diphenylcarbazole in place of 3,6-diphenylcarbazole and 4-bromoiodobenzene in place of 3-bromoiodobenzene used in [Intermediate Production Example 1], a similar reaction was conducted by the Ullmann reaction. , 7-Diphenyl-N- (4-bromophenyl) carbazole was obtained. In the same manner as [Intermediate Production Example 1], 2,7-diphenyl-N- [4- (5,5-dimethyl-1,3,2-) represented by the following structural formula (10) was used. Dioxaborin-2-yl)] phenylcarbazole was obtained.

赤外吸収スペクトル（ＫＢｒ錠剤法）を図９に示した。
νＢ−Ｏ １３１６ｃｍ−１ νＢ−Ｃ １１３４ｃｍ−１

The infrared absorption spectrum (KBr tablet method) is shown in FIG.
νB-O 1316 cm-1 νB-C 1134 cm-1

[Example 7]
Instead of the boronic acid ester used in Example 3, 2,7-diphenyl-N- [4- (5,5-dimethyl-1,3,2-dioxaborinane) obtained in [Preparation Example 5 of Intermediate] 2-yl)] N-arylcarbazole multimer of the present invention represented by the following structural formula (11) of colorless needle-like crystals was operated in the same manner as in Example 3 except that phenylcarbazole was used. (70.0%) was obtained.

融点 ＞２２０℃
元素分析値（％）実測値／計算値
Ｃ ９１．３０／９１．６２ Ｈ ５．０１／５．０５ Ｎ ３．１２／３．３４
赤外吸収スペクトル（ＫＢｒ錠剤法）を第１０図に示した。

Melting point> 220 ° C
Elemental analysis value (%) Measured value / Calculated value C 91.30 / 91.62 H 5.01 / 5.05 N 3.12 / 3.34
The infrared absorption spectrum (KBr tablet method) is shown in FIG.

[Example 8]
0.47 g of 4,7-dibromo-2,1,3-benzothiadiazole, 3,6-diphenyl-N- [3- (5,5-dimethyl-1,3,2-dioxaborin-2-yl)] phenyl 20 ml of degassed toluene and 8 ml of ethanol were added to 1.60 g of carbazole, 54 mg of tetrakistriphenylphosphine palladium and 3.75 g of 2M sodium carbonate aqueous solution degassed were added thereto, and the mixture was heated to reflux for 4 hours under a nitrogen stream.
After cooling to room temperature, the contents were diluted with hexane and the precipitate was filtered.
This was recrystallized from toluene together with a Pd scavenger; QuadraSil MP (Wako), and the multimer 1 of the N-arylcarbazole of the present invention represented by the formula represented by the following structural formula (12) of orange-yellow needle crystals 0.0 g was obtained.

融点 ＞２００℃
元素分析値（％）実測値／計算値
Ｃ ８５．８３／８５．８７ Ｈ ４．６１／４．５９ Ｎ ５．８８／６．０７
赤外吸収スペクトル（ＫＢｒ錠剤法）を第１１図に示した。

Melting point> 200 ° C
Elemental analysis value (%) Measured value / calculated value C 85.83 / 85.87 H 4.61 / 4.59 N 5.88 / 6.07
The infrared absorption spectrum (KBr tablet method) is shown in FIG.

[Example 9]
After dissolving 34.5 mg of bis (dibenzylideneacetone) palladium and 26.2 mg of 1,3-di-tert-butyl-1,3,2-diazaphosphoridine-2-oxide in 10 ml of THF, 1.52 g of the boronic acid ester obtained in Production Example 1], 0.18 g of 2,4,6-trichloropyrimidine and 1.0 g of potassium tert-butoxide were added, and the mixture was heated to reflux for 8 hours under a nitrogen stream.
After cooling, it is diluted with water, extracted with toluene, washed with water, dried, and purified by silica gel column chromatography (eluent: toluene / hexane = 3/2). 0.93 g of an aryl carbazole multimer was obtained.
In this reaction, 2,4,6-tris-substituted pyrimidine was targeted. However, as a result of analysis, 3-substituent was not obtained, and it was found to be a multimer of N-arylcarbazole represented by the following structural formula (13). It was.

融点 １３６．０〜１３７．０℃
元素分析値（％）実測値／計算値
Ｃ ９０．８３／９１．３４ Ｈ ５．４１／５．１１ Ｎ ３．４６／３．５５
MALDI-TOF/MS：７８８．３９３［M+］(７８８．３２)
赤外吸収スペクトル（ＫＢｒ錠剤法）を第１２図に示した。

Melting point 136.0-137.0 ° C.
Elemental analysis value (%) Measured value / calculated value C 90.83 / 91.34 H 5.41 / 5.11 N 3.46 / 3.55
MALDI-TOF / MS: 788.393 [M +] (788.32)
The infrared absorption spectrum (KBr tablet method) is shown in FIG.

JP 2005-154212 A JP 2005-158691 A JP 2003-335754 A JP 2011-256143 A JP 2004-178896 A

Non-Patent Document 1 Organic Letters Vol.13 (12) 3146 (2011) Non-Patent Document 2 Polymer Papers Vol.53 (12) 829 (1996)

Claims (3)

A multimer of N-arylcarbazole represented by the following general formula (I).

(Wherein R1 and R2 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or an aryl group which may have a substituent, and Ar1 represents an aromatic which may have a substituent) Represents a divalent or trivalent group of an aromatic hydrocarbon, or a divalent or trivalent group of a heterocyclic ring which may have a substituent, and Ar2 represents a divalent aromatic hydrocarbon which may have a substituent And n represents 2 or 3)
The N-arylcarbazole multimer represented by the general formula (I) in claim 1 is represented by the following general formula (II).

(Wherein R1, R2 and R3 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or an aryl group which may have a substituent, and Ar1 may have a substituent. A divalent or trivalent group of a good aromatic hydrocarbon, a divalent or trivalent group of a heterocyclic ring which may have a substituent, and n represents 2 or 3)
The N-arylcarbazole multimer represented by the general formula (I) in claim 1 is represented by the following general formula (III).

(Wherein R3, R4 and R5 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or an aryl group which may have a substituent, and Ar1 may have a substituent. A divalent or trivalent group of a good aromatic hydrocarbon, a divalent or trivalent group of a heterocyclic ring which may have a substituent, and n represents 2 or 3)

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