JP2014114224A - Boron-containing heterocyclic compound - Google Patents

Abstract

（式中Ｙは複素環基を表し、Ａｒ_１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、Ａｒ_２およびＡｒ_３は置換基を有してもよい芳香族炭化水素基を表し、Ａｒ_２とＡｒ_３は共同で環を形成しても良い。またホウ素原子は複素環基と直接結合しても良い。ｎは１、２または３を表す）。
【選択図】図１The present invention provides a novel boron-containing heterocyclic compound that realizes an organic EL device having high durability and high luminous efficiency, as a material for an organic EL device.
A boron-containing heterocyclic compound represented by the following general formula (I):

(In the formula, Y represents a heterocyclic group, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, and Ar ₂ and Ar ₃ represent an aromatic carbon which may have a substituent. Represents a hydrogen group, Ar ₂ and Ar ₃ may form a ring together, and a boron atom may be directly bonded to a heterocyclic group (n represents 1, 2 or 3).
[Selection] Figure 1

Description

  The present invention relates to a boron-containing heterocyclic compound, and this compound has particularly high durability, such as being able to realize an organic EL device having 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 employing various laminated structures, and that 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-phenylene vinylene (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.

  Recently, studies on high efficiency using triplet excitons have also been made vigorously (T. Tsutsui et al. Jpn. J. Appl. Phys. Vol. 38 L 1502 (1999), etc.) and luminous efficiency. It has become clear that is greatly improved. Along with this, there are increasing reports of host materials used in the light emitting layer.

  The present inventors disclosed an external quantum efficiency of 10 several percent as a host material in Japanese Patent Laid-Open No. 2005-154212 (Patent Document 1) and Japanese Patent Laid-Open No. 2005-158691 (Patent Document 2). Clarified what to show. 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.
Boron-containing compounds have been proposed mainly as light-emitting materials, electron-injecting materials, or electron-transporting materials (Patent Documents 1, 2, and 3), but they have sufficient light emission luminance, high light emission efficiency, stability during repeated use, and the like. Still not enough.

  The present invention has been made in view of the current state of the prior art, and provides a novel boron-containing heterocyclic compound that realizes an organic EL element having a particularly high durability and high luminous efficiency as a material for an organic EL element. For the purpose.

As a result of intensive studies, the present inventors have found that by using a boron-containing heterocyclic compound as an organic EL device, it is possible to improve efficiency and improve durability. That is, the present invention comprises the following [1] to [8].
[1] “Boron-containing heterocyclic compound represented by the following general formula (I);

(In the formula, Y represents a heterocyclic group, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, and Ar ₂ and Ar ₃ represent an aromatic carbon which may have a substituent. Represents a hydrogen group, Ar ₂ and Ar ₃ may form a ring together, and a boron atom may be directly bonded to a heterocyclic group. N represents 1, 2 or 3).
[2] “The heterocyclic group is a monovalent group, divalent group or trivalent group of carbazole, a divalent group of 2,1,3-benzothiadiazole, a divalent group or a trivalent group of pyrimidine. The boron-containing heterocyclic compound according to item [1], which is characterized by the above.
[3] “The boron-containing heterocyclic compound according to item [1], wherein the boron-containing heterocyclic compound is represented by the following general formula (II);

(In the formula, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, Ar ₂ and Ar ₃ represent an aromatic hydrocarbon group which may have a substituent, Ar ₂ and Ar ₃ may form a ring together. R represents a substituted or unsubstituted alkyl group or an aromatic hydrocarbon group or heterocyclic group which may have a substituent.
[4] “The boron-containing heterocyclic compound according to item [1], wherein the boron-containing heterocyclic compound is represented by the following general formula (III);

(In the formula, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, Ar ₂ and Ar ₃ represent an aromatic hydrocarbon group which may have a substituent, Ar ₂ and Ar ₃ may form a ring together. R represents a substituted or unsubstituted alkyl group or an aromatic hydrocarbon group or heterocyclic group which may have a substituent.
[5] “The boron-containing heterocyclic compound according to item [1], wherein the boron-containing heterocyclic compound is represented by the following general formula (IV);

(In the formula, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, Ar ₂ and Ar ₃ represent an aromatic hydrocarbon group which may have a substituent, Ar ₂ and Ar ₃ may form a ring together. Ar ₄ represents an aromatic hydrocarbon group or a heterocyclic group which may have a substituent.
[6] “The boron-containing heterocyclic compound according to item [1], wherein the boron-containing heterocyclic compound is represented by the following general formula (V);

(In the formula, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, Ar ₂ and Ar ₃ represent an aromatic hydrocarbon group which may have a substituent, Ar ₂ and Ar ₃ may jointly form a ring.
[7] The boron-containing heterocycle according to item [1], wherein the boron-containing heterocyclic compound represented by the general formula (I) is represented by the following general formula (VI): A ring compound;

(In the formula, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, Ar ₂ and Ar ₃ represent an aromatic hydrocarbon group which may have a substituent, Ar ₂ and Ar ₃ may form a ring together, R ′ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a halogen atom.
[8] “The boron-containing heterocyclic compound according to item [1], wherein the boron-containing heterocyclic compound is represented by the following general formula (VII);

(In the formula, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, Ar ₂ and Ar ₃ represent an aromatic hydrocarbon group which may have a substituent, Ar ₂ and Ar ₃ may form a ring together, and Ar ₅ represents an aromatic hydrocarbon group which may have a substituent.

  As will be understood from the following detailed and specific description, according to the present invention, a novel boron-containing heterocyclic compound is provided, and this novel compound is an organic EL device having high durability and high luminous efficiency. It is extremely useful, such as exhibiting the utility of enabling it.

1 is an infrared absorption spectrum (KBr tablet method) diagram of the boron-containing heterocyclic compound of the present invention obtained in Example 1. FIG. 2 is an infrared absorption spectrum (KBr tablet method) diagram of the boron-containing heterocyclic compound of the present invention obtained in Example 2. FIG. 4 is an infrared absorption spectrum (KBr tablet method) diagram of the boron-containing heterocyclic compound of the present invention obtained in Example 3. FIG. 4 is an infrared absorption spectrum (KBr tablet method) diagram of the boron-containing heterocyclic compound of the present invention obtained in Example 4. FIG. r tablet method). 6 is an infrared absorption spectrum (KBr tablet method) diagram of the boron-containing heterocyclic compound of the present invention obtained in Example 5. FIG. 6 is an infrared absorption spectrum (KBr tablet method) diagram of the boron-containing heterocyclic compound of the present invention obtained in Example 6. FIG. It is an infrared absorption spectrum (KBr tablet method) figure of the boron containing heterocyclic compound of this invention obtained in Example 7. FIG. It is an infrared absorption spectrum (KBr tablet method) figure of the boron containing heterocyclic compound of this invention obtained in Example 8. It is an infrared absorption spectrum (KBr tablet method) figure of the boron containing heterocyclic compound of this invention obtained in Example 9. FIG. 2 is an infrared absorption spectrum (KBr tablet method) diagram of the boron-containing heterocyclic compound of the present invention obtained in Example 10. FIG. 2 is an infrared absorption spectrum (KBr tablet method) diagram of the boron-containing heterocyclic compound of the present invention obtained in Example 11. FIG. 4 is an infrared absorption spectrum (KBr tablet method) diagram of the boron-containing heterocyclic compound of the present invention obtained in Example 12. FIG. It is an infrared absorption spectrum (KBr tablet method) figure of the boron containing heterocyclic compound of this invention obtained in Example 13. It is an infrared absorption spectrum (KBr tablet method) figure of the boron containing heterocyclic compound of this invention obtained in Example 14. FIG. 4 is an infrared absorption spectrum (KBr tablet method) diagram of the boron-containing heterocyclic compound of the present invention obtained in Example 15. It is an infrared absorption spectrum (KBr tablet method) figure of the boron containing heterocyclic compound of this invention obtained in Example 16. It is an infrared absorption spectrum (KBr tablet method) figure of the boron containing heterocyclic compound of this invention obtained in Example 17. FIG.

The present invention is described in further detail below.
The boron-containing heterocyclic compounds represented by the general formula (II), general formula (III), general formula (IV), general formula (V), general formula (VI) and general formula (VII) of the present invention are represented by the following route. Can be manufactured.

(In the above formula, Ar ₁ , Ar ₂ , Ar ₃ and R are as defined above, and X represents a halogen atom.)

(In the above formula, Ar ₁ , Ar ₂ , Ar ₃ , R and X are the same as defined above.)

(In the above formula, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and X have the same definition as described above.)

(In the above formula, Ar ₁ , Ar ₂ , Ar ₄ and X have the same definition as described above.)

(In the above formula, Ar ₁ , Ar ₂ , Ar ₃ , R ′ and X have the same definition as described above.)

(In the above formula, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₅ and X have the same definition as described above.)

The boron-containing heterocyclic compound represented by the general formula (II), general formula (III), general formula (IV) and general formula (VI) of the present invention is an aryl boron compound using a palladium catalyst according to the route of the above formula. It can be obtained by a Suzuki-Miyaura reaction known as a cross-coupling reaction of organic halides.
The boron-containing heterocyclic compound represented by the general formula (V) and the general formula (VII) is obtained by lithiation of the halogen compound represented by the general formula (XI) or the general formula (XVI) as a starting material. It can be obtained by reacting with a diarylboron fluoride represented by (XII).
Instead of the arylboronic acid represented by the general formula (IX), bis (pinacolato) diboron, bis (neopentylglycolato) diboron, or 2-isopropoxyboronic acid that is thermally stable and easily handled in air An aryl boronic acid ester synthesized from pinacol ester and aryl halide may be used.
The halogen atom in the halide represented by general formula (VIII), general formula (X), general formula (XI), general formula (XIII) and general formula (XIV) is an iodide or bromide from the viewpoint of reactivity. preferable. Depending on the reaction conditions, chlorinated products can also be used.
As the palladium catalyst, various catalysts such as Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) _2, and PdCl ₂ can be used, but most commonly used is Pd (PPh ₃ ) _4. Used.

This reaction always requires a base, but relatively weak bases such as Na ₂ CO ₃ and NaHCO ₃ give good results. When affected by steric hindrance or the like, a strong base such as Ba (OH) ₂ or K ₃ PO ₄ is 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.

The general formula (I), the general formula (II), the general formula (III), the general formula (IV), the general formula (V), the general formula (VI), and the general formula of the present invention thus obtained. Specific examples of the boron-containing heterocyclic compound represented by (VII) are shown below.
In the general formula (I), general formula (II), general formula (III), general formula (IV)), general formula (V), general formula (VI) and general formula (VII) of the present invention, Ar ₁ Examples of aromatic hydrocarbons include divalent groups of benzene, naphthalene, biphenyl, terphenyl, and pyrene. Examples of aromatic hydrocarbon groups in Ar ₂ and Ar ₃ include monovalent groups of benzene, naphthalene, biphenyl, terphenyl, and pyrene. Group, and these may have a substituted or unsubstituted alkyl group or alkoxy group as a substituent. In particular, Ar ₂ and Ar ₃ preferably have a substituted or unsubstituted alkyl group at the ortho position of the boron atom bonding position in order to stabilize the boron atom. Ar ₂ and Ar ₃ may jointly form a ring.

Examples of the substituted or unsubstituted alkyl group include the following.
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.
Specific examples of the substituted or unsubstituted alkoxy group include those in which an oxygen atom is inserted into the bonding position of the substituted or unsubstituted alkyl group to form an alkoxy group.

In the general formula (II), when R is a substituted or unsubstituted alkyl group, specific examples similar to the above-described substituted or unsubstituted alkyl group can be given.
In the general formula (II), examples of the aromatic hydrocarbon group in R include benzene, naphthalene, biphenyl, terphenyl, pyrene, fluorene, and monovalent groups of 9,9-dimethyl-2-fluorene. Or you may have an unsubstituted alkyl group and an alkoxy group as a substituent. Examples of the heterocyclic group in R include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a quinolyl group, and a thienyl group, which may have a substituted or unsubstituted alkyl group or an alkoxy group as a substituent.

In the general formula (IV), when Ar ₄ is an aromatic hydrocarbon group or a heterocyclic group, it represents a divalent group of a specific example represented by the aromatic hydrocarbon group or the heterocyclic group in the above R.
In the general formula (VI), when R ′ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group, examples similar to the specific examples described above can be given.

  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]
13.37 g of p-dibromobenzene was dissolved in 45 ml of THF, and 34.8 ml of a hexane solution of 1.63 M of n-butyllithium was added dropwise thereto at −78 to −72 ° C. under a nitrogen stream. After dropping, the mixture was stirred at −75 ° C. for 30 minutes, and a solution prepared by dissolving 15.21 g of dimesityl boron fluoride in 30 ml of THF was added dropwise at −75 to −70 ° C. After stirring at −70 ° C. for 30 minutes, the mixture was stirred overnight at room temperature. After adding ammonium chloride solution, THF was distilled off. After extraction with toluene, washing with water, and drying, the solvent was distilled off, and recrystallization from hexane gave 16.4 g of colorless prism crystal p-dimesitylboryl bromobenzene.
Melting point: 184.0 to 187.0 ° C
Infrared absorption spectrum (KBr tablet method)
νB-C 1240, 1225, 1214 cm ⁻¹
p-Dimesitylboryl bromobenzene 12.3 g, bis (neopentylglycolato) diboron 8.20 g, potassium acetate 8.95 g, [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane 750 mg of the adduct and 150 ml of dioxane were heated to reflux for 40 minutes under a nitrogen stream. After standing to cool, the insoluble material was removed by filtration using Celite. Dioxane was distilled off under reduced pressure, extracted with ethyl acetate, washed with water, dried, and purified by silica gel column chromatography (eluent 5% ethyl acetate in toluene), toluene / ethanol Recrystallized from a mixed solvent of 4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) dimesitylborylbenzene in the form of colorless plate crystals of the following structural formula (1) 9.02 g Got.

融点 １８４．０〜１８７．０℃
赤外吸収スペクトル（ＫＢｒ錠剤法）
νボロン酸エステル １４７６、１３４１、１３１７、１１３２ｃｍ^−１
νＢ−Ｃ １２４０ｃｍ^−１
ＮＭＲ(CDCl3)
δppm 7.75(d,aromatic,2H)7.49(d,aromatic,2H)7.32(t,aromatic,1H)6.80(s,aromatic,4H)3.77(s,CH2,4H)2.30(s,CH3,6H)1.98(s,CH3,12H)1.03(s,CH3,6H)

Melting point: 184.0 to 187.0 ° C
Infrared absorption spectrum (KBr tablet method)
ν boronic acid ester 1476, 1341, 1317, 1132 cm ⁻¹
νB-C 1240 cm ⁻¹
NMR (CDCl3)
δppm 7.75 (d, aromatic, 2H) 7.49 (d, aromatic, 2H) 7.32 (t, aromatic, 1H) 6.80 (s, aromatic, 4H) 3.77 (s, CH2,4H) 2.30 (s, CH3,6H) 1.98 (s, CH3,12H) 1.03 (s, CH3,6H)

[Production Example 2 of Intermediate]
The procedure of Intermediate Preparation Example 1 was repeated except that m-dibromobenzene was used instead of p-dibromobenzene used in Preparation Example 1 of the intermediate, and 3- (5,5-dimethyl- 1,3,2-Dioxaborin-2-yl) dimesitylborylbenzene was obtained.
Melting point 219.0 ° C
Infrared absorption spectrum (KBr tablet method)
ν boronic acid ester 1476, 1341, 1321, 1135 cm ⁻¹
νB-C 1240 cm ⁻¹
NMR (CDCl3)
δppm 7.98 (s, aromatic, 1H) 7.91 (m, aromatic, 1H) 7.53 (m, aromatic, 1H) 7.32 (t, aromatic, 1H) 6.80 (s, aromatic, 4H) 3.72 (s, CH2,4H) 2.30 (s, CH3,6H) 1.97 (s, CH3,12H) 1.00 (s, CH3,6H)

[Production Example 3 of Intermediate]
3.25 g of 3,6-dibromocarbazole, 5.66 g of p-bromoiodobenzene, 2.76 g of potassium carbonate and 0.2 g of copper powder were heated and stirred at 190 ° C. for 6 hours in a nitrogen stream. After cooling to room temperature, the insoluble material was removed by filtration and washed with toluene. After distilling off the solvent, the residue was purified by silica gel column chromatography (eluent: toluene / hexane = 1/4), and colorless needle-shaped N- (4-bromophenyl) -3,6- of the following structural formula (2) 2.82 g of dibromocarbazole was obtained.
Melting point 203.0-204.5 ° C

[Production Example 4 of Intermediate]
The same procedure as in Intermediate Production Example 3 was followed, except that m-bromoiodobenzene was used instead of p-bromoiodobenzene used in Intermediate Production Example 3, and N- (3-bromophenyl) -3, 6-Dibromocarbazole was obtained.
Melting point: 182.0-183.5 ° C

[Production Example 5 of Intermediate]
N- (4-Bromophenyl)-was prepared in the same manner as in Intermediate Production Example 3 except that 2,7-dibromocarbazole was used instead of 3,6-dibromocarbazole used in Intermediate Production Example 3. 2,7-dibromocarbazole was obtained.
Melting point: 183.0-184.5 ° C

[Production Example 6 of Intermediate]
2-Bromo-7-dimesitylboryl-9,9-dioctylfluorene 3.94 g, bis (neopentylglycolato) diboron 1.50 g, potassium acetate 1.64 g, [1,1′-bis (diphenylphosphino) ferrocene] Palladium (II) dichloride dichloromethane adduct 140 mg and dioxane 30 ml were heated to reflux for 3 hours under a nitrogen stream. After standing to cool, the insoluble material was removed by filtration using Celite, and dioxane was distilled off under reduced pressure, extracted with ethyl acetate, washed with water, dried, and purified by silica gel column chromatography (eluent: toluene), and colorless with the following structural formula (3) 1.92 g of acicular boronate ester was obtained.

融点 １２２．０〜１２３．５℃
赤外吸収スペクトル（ＫＢｒ錠剤法）
１４２２、１３７６、１３３７、１３０６、１２４４、１１２３ｃｍ^−１
ＮＭＲ(CDCl3)
δppm 7.77(m,aromatic,4H)7.49(d,aromatic,2H)6.83(s,aromatic,4H)3.80(s,CH2,4H)2.32(s,CH3,6H)2.01(s,CH3,12H)1.85-0.96(m,CH2)1.06(s,CH3,6H)0.82(t,CH3,6H)

Melting point 122.0-123.5 ° C
Infrared absorption spectrum (KBr tablet method)
1422, 1376, 1337, 1306, 1244, 1123 cm ^-1
NMR (CDCl3)
δppm 7.77 (m, aromatic, 4H) 7.49 (d, aromatic, 2H) 6.83 (s, aromatic, 4H) 3.80 (s, CH2,4H) 2.32 (s, CH3,6H) 2.01 (s, CH3,12H) 1.85 -0.96 (m, CH2) 1.06 (s, CH3,6H) 0.82 (t, CH3,6H)

[Example 1]
4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) dimesitylborylbenzene obtained in Intermediate Production Example 1 (3.07 g) and 3,6-dibromocarbazole (1.08 g) 20 ml of degassed toluene and 4 ml of ethanol were added, 115 mg of tetrakistriphenylphosphine palladium and 6.70 g of degassed 2M sodium carbonate aqueous solution were added thereto, and the mixture was heated to reflux for 2 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 1.87 g of 3,6-bis (4-dimesitylborylphenyl) carbazole as a white powder.
Melting point> 220 ° C
Infrared absorption spectrum (KBr tablet method)
νNH 3456cm ^-1
νB-C 1240,1221 cm ⁻¹
3,6-bis (4-dimesitylborylphenyl) carbazole (0.30 g), iodobenzene (6 ml), potassium carbonate (0.11 g), copper powder (0.1 g) and nitrobenzene (5 ml) were heated and stirred at 190 ° C. for 12 hours in a nitrogen stream. After cooling to room temperature, the insoluble material was removed by filtration and washed with toluene. After the solvent was distilled off, silica gel column chromatography treatment (eluent: toluene / hexane = 1/3) was performed, and the boron-containing carbazole compound 3,6-bis of the present invention represented by the following structural formula (4) as a colorless powder 0.24 g of (4-dimesitylborylphenyl) -N-phenylcarbazole was obtained.

融点 ＞２００℃
赤外吸収スペクトル（ＫＢｒ錠剤法）を図１に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８８．５８/８８．８８、Ｈ ７．２２/７．１２、Ｎ １．４９/１．５７

Melting point> 200 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 88.58 / 88.88, H 7.22 / 7.12, N 1.49 / 1.57

[Example 2]
3- (5,5-Dimethyl-1,3,2-dioxaborin-2-yl) dimesitylborylbenzene 0.92 g, 3,6-dibromo-N-phenylcarbazole obtained in Preparation Example 2 of Intermediate 10 ml of toluene degassed to 0.40 g and 4 ml of ethanol were added, 36 mg of tetrakistriphenylphosphine palladium and 2.50 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 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), and the boron-containing carbazole compound 3,6-bis (3-dimesityl) of the present invention represented by the following structural formula (5) as a colorless powder. Borylphenyl) -N-phenylcarbazole (0.63 g) was obtained.

融点 ＞２２０℃
赤外吸収スペクトル（ＫＢｒ錠剤法）を図２に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８８．７５/８８．８８、Ｈ ７．０４/７．１２、Ｎ １．３９/１．５７

Melting point> 220 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 88.75 / 88.88, H 7.04 / 7.12, N 1.39 / 1.57

[Example 3]
Toluene degassed to 0.29 g of N- (3-bromophenyl) -3,6-dibromocarbazole obtained in Intermediate Production Example 4 and 0.79 g of boronic acid ester obtained in Intermediate Production Example 2 8 ml and 2 ml of ethanol were added. To this, 70 mg of tetrakistriphenylphosphine palladium and 1.57 g of 2M sodium carbonate aqueous solution degassed were added and heated under reflux for 6 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 = 1/2) to obtain 0.59 g of a boron-containing carbazole compound of the present invention represented by the following structural formula (6) as a colorless powder.

融点 １６７．０〜１６９．０℃
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 ８８．５９/８８．８９、Ｈ ７．２２/７．２９、Ｎ ０．９３/１．１５

Melting point: 167.0 to 169.0 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 88.59 / 88.89, H 7.22 / 7.29, N 0.93 / 1.15

[Example 4]
The N- (4-bromophenyl) -3,6-dibromocarbazole obtained in Production Example 3 was used in place of the N- (3-bromophenyl) -3,6-dibromocarbazole used in Example 3. The same operation as in Example 3 was performed to obtain a boron-containing carbazole compound of the present invention represented by the following structural formula (7) as a colorless powder.

融点 １９０．０℃（glassy）
赤外吸収スペクトル（ＫＢｒ錠剤法）を図４に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８８．５０/８８．８９、Ｈ ７．３１/７．２９、Ｎ １．００/１．１５

Melting point 190.0 ° C (glassy)
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 88.50 / 88.89, H 7.31 / 7.29, N 1.00 / 1.15

[Example 5]
The present invention represented by the following structural formula (8) of colorless powder was operated in the same manner as in Example 4 except that the boronic acid ester obtained in Production Example 1 was used instead of the boronic acid ester used in Example 4. An inventive boron-containing carbazole compound was obtained.

融点 ＞２００℃
赤外吸収スペクトル（ＫＢｒ錠剤法）を図５に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８８．４０/８８．８９、Ｈ ７．２７/７．２９、Ｎ ０．９５/１．１５

Melting point> 200 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 88.40 / 88.89, H 7.27 / 7.29, N 0.95 / 1.15

[Example 6]
The present invention represented by the following structural formula (9) of colorless powder was operated in the same manner as in Example 3 except that the boronic acid ester obtained in Production Example 1 was used instead of the boronic acid ester used in Example 3. An inventive boron-containing carbazole compound was obtained.

融点 ＞２００℃
赤外吸収スペクトル（ＫＢｒ錠剤法）を図６に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８８．３７/８８．８９、Ｈ ７．１９/７．２９、Ｎ ０．９４/１．１５
MALDI-TOF/MS：1215.439［M⁺］(1215.72)

Melting point> 200 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 88.37 / 88.89, H 7.19 / 7.29, N 0.94 / 1.15
MALDI-TOF / MS: 1215.439 [M ⁺ ] (1215.72)

[Example 7]
Instead of N- (4-bromophenyl) -3,6-dibromocarbazole used in Example 5, N- (4-bromophenyl) -2,7-dibromocarbazole boronate obtained in Preparation Example 5 was used. A boron-containing carbazole compound of the present invention represented by the following structural formula (10) as a colorless powder was obtained in the same manner as in Example 5 except that it was used.

融点 ＞２００℃
赤外吸収スペクトル（ＫＢｒ錠剤法）を図７に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８８．６０/８８．８９、Ｈ ７．１５/７．２９、Ｎ １．０１/１．１５
MALDI-TOF/MS：1215.782［M⁺］(1215.72)

Melting point> 200 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 88.60 / 88.89, H 7.15 / 7.29, N 1.01 / 1.15
MALDI-TOF / MS: 1215.782 [M ⁺ ] (1215.72)

[Example 8]
Intermediate (Production Example 1) 4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) dimesitylborylbenzene 0.55 g, 3-bromo-6-dimesitylboryl-N- To 10 g of phenylcarbazole, 10 ml of degassed toluene and 4 ml of ethanol were added. To this, 20 mg of tetrakistriphenylphosphine palladium and then 1.60 g of 2M sodium carbonate aqueous solution degassed were added and heated under reflux for 3 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 = 1/4) to obtain 0.77 g of a boron-containing heterocyclic compound of the present invention represented by the following structural formula (11) as a white powder.

融点 ガラス質
赤外吸収スペクトル（ＫＢｒ錠剤法）を図８に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８８．２８/８８．３４ Ｈ ７．１７/７．２９ Ｎ １．４４/１．７２

Melting point Glassy Infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 88.28 / 88.34 H 7.17 / 7.29 N 1.44 / 1.72

[Example 9]
The boron of the present invention represented by the following structural formula (12) was prepared in the same manner as in Example 8 except that the boronic acid ester obtained in Production Example 6 was used instead of the boronic acid ester used in Example 8. A containing heterocyclic compound was obtained.

融点 １５１．０〜１５２．０℃
赤外吸収スペクトル（ＫＢｒ錠剤法）を図９に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８８．２３/８８．３６ Ｈ ８．３５ /８．４９ Ｎ １．０４/１．２４

Melting point 151.0-152.0 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 88.23 / 88.36 H 8.35 /8.49 N 1.04 / 1.24

[Example 10]
Intermediate Preparation 0.46 g of boronic acid ester obtained in Example 6, 0.16 g of 3,6-dibromo-N-phenylcarbazole was added 10 ml of degassed toluene and 4 ml of ethanol, and 11 mg of tetrakistriphenylphosphine palladium was added thereto. Subsequently, 0.75 g of 2M sodium carbonate aqueous solution deaerated was added, and the mixture was heated to reflux for 6 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 = 1/4) to obtain a boron-containing heterocyclic compound of the present invention represented by the following structural formula (13) as colorless plate crystals.

融点 ガラス質
赤外吸収スペクトル（ＫＢｒ錠剤法）を図１０に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８８．４４/８８．６８ Ｈ ８．８０/８．９７ Ｎ ０．７３/０．９２

Melting point Glassy Infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 88.44 / 88.68 H 8.80 / 8.97 N 0.73 / 0.92

[Example 11]
A colorless powder represented by the following structural formula was prepared in the same manner as in Example 10 except that 2,7-dibromo-N-phenylcarbazole was used instead of 3,6-dibromo-N-phenylcarbazole used in Example 10. The boron-containing heterocyclic compound of the present invention represented by (14) was obtained.

融点 ガラス質
赤外吸収スペクトル（ＫＢｒ錠剤法）を図１１に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８７．８９/８８．６８ Ｈ ９．１５/８．９７ Ｎ ０．７７/０．９２

Melting point Glassy Infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 87.89 / 88.68 H 9.15 / 8.97 N 0.77 / 0.92

[Example 12]
1.85 g of 4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) dimesitylborylbenzene obtained in Preparation Example 1 of the intermediate, 2,7-dibromo-N-phenylcarbazole 20 ml of degassed toluene and 8 ml of ethanol were added to 0.80 g, and 72 mg of tetrakistriphenylphosphine palladium and 5.00 g of 2M sodium carbonate aqueous solution degassed were added thereto, and the mixture was heated to reflux for 3 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 = 1/2) to obtain 1.42 g of a boron-containing heterocyclic compound of the present invention represented by the following structural formula (15) as a pale yellow powder.

融点 ＞２００℃
赤外吸収スペクトル（ＫＢｒ錠剤法）を図１２に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８８．７２/８８．８８ Ｈ ６．９４/７．１２ Ｎ １．３３/１．５７

Melting point> 200 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 88.72 / 88.88 H 6.94 / 7.12 N 1.33 / 1.57

[Example 13]
1.85 g of 4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) dimesitylborylbenzene obtained in Preparation Example 1 of the intermediate, 4,7-dibromo-2,1, 20 ml of degassed toluene and 8 ml of ethanol were added to 0.58 g of 3-benzothiadiazole, 72 mg of tetrakistriphenylphosphine palladium and 5.00 g of degassed 2M sodium carbonate aqueous solution were added thereto, and the mixture was heated to reflux for 4 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), recrystallized from a mixed solvent of toluene / hexane, and the boron-containing heterocyclic compound of the present invention represented by the following structural formula (16) of yellow prism crystals. 23 g was obtained.

融点 ＞２２０℃
赤外吸収スペクトル（ＫＢｒ錠剤法）を図１３に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８２．７０/８２．６５ Ｈ ６．８４/６．９４ Ｎ ３．２９/３．５７

Melting point> 220 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 82.70 / 82.65 H 6.84 / 6.94 N 3.29 / 3.57

[Example 14]
1.60 g of 2,7-dibromo-N-phenylcarbazole was dissolved in 15 ml of THF, and 7.3 ml of a hexane solution of 1.65 M of n-butyllithium was added dropwise thereto at −78 to −72 ° C. under a nitrogen stream. After dropping, the mixture was stirred at -70 ° C for 1 hour, and then a solution prepared by dissolving 3.22 g of dimesityl boron fluoride in 10 ml of THF was added dropwise at -75 to -70 ° C. After stirring at −70 ° C. for 30 minutes, the mixture was stirred overnight at room temperature. After adding ammonium chloride solution, THF was distilled off. After extraction with toluene, washing with water and drying, the solvent was distilled off. This was purified by silica gel column chromatography (eluent toluene / hexane = 1/4) to obtain 1.02 g of a boron-containing heterocyclic compound of the present invention represented by the following structural formula (17) as a pale yellow powder.

融点 ＞２００℃
赤外吸収スペクトル（ＫＢｒ錠剤法）を図１４に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８７．６９/８７．６９ Ｈ ７．３２/７．５０ Ｎ １．７１/１．８９

Melting point> 200 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 87.69 / 87.69 H 7.32 / 7.50 N 1.71 / 1.89

[Example 15]
0.70 g of 3,6-dibromo-N- (4-bromophenyl) carbazole was dissolved in 15 ml of THF, and 5.4 ml of a hexane solution of 1.65 M of n-butyllithium was added to this at −78 to −72 ° C. under a nitrogen stream. It was dripped at. After the dropwise addition, the mixture was stirred at -70 ° C for 1 hour, and then a solution obtained by dissolving 2.34 g of dimesityl boron fluoride in 10 ml of THF was added dropwise at -75 to -70 ° C. After stirring at −70 ° C. for 30 minutes, the mixture was stirred overnight at room temperature. After adding ammonium chloride solution, THF was distilled off. After extraction with toluene, washing with water and drying, the solvent was distilled off. This was purified by silica gel column chromatography (eluent toluene / hexane = 1/4) to obtain 0.42 g of a boron-containing heterocyclic compound of the present invention represented by the following structural formula (18) as a colorless powder.

融点 １８７℃
赤外吸収スペクトル（ＫＢｒ錠剤法）を図１５に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８７．２７/８７．５４ Ｈ ７．４７/７．７５ Ｎ １．４２/１．４２

Melting point 187 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 87.27 / 87.54 H 7.47 / 7.75 N 1.42 / 1.42

[Example 16]
1.38 g of 4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) dimesitylborylbenzene obtained in Preparation Example 1 of the intermediate, 2-phenyl-4,6-bis ( 4-bromophenyl) pyrimidine (manufactured according to Japanese Patent No. 4963357) (0.70 g) was added 15 ml of degassed toluene and 6 ml of ethanol, to which 54 mg of tetrakistriphenylphosphine palladium and 2M sodium carbonate aqueous solution degassed were added. 80 g was added and heated under reflux for 4 hours under a nitrogen stream. After allowing to cool to room temperature, the precipitate was filtered, washed with water, and washed with methanol to obtain a colorless powder. This was dissolved in heated toluene, treated with Pd scavenger; QuadraSil MP (manufactured by Wako) and activated carbon, and then toluene was distilled off and washed with methanol to obtain a colorless powder of the following structural formula (19). 1.06 g of a boron-containing heterocyclic compound was obtained.

融点 ＞２００℃
赤外吸収スペクトル（ＫＢｒ錠剤法）を図１６に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８７．６２/８７．８６ Ｈ ６．８０/６．９５ Ｎ ２．７２/２．９３

Melting point> 200 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 87.62 / 87.86 H 6.80 / 6.95 N 2.72 / 2.93

[Example 17]
1.40 g of 2-phenyl-4,6-bis (4-bromophenyl) pyrimidine was dissolved in 25 ml of THF, and 5.5 ml of a hexane solution of 1.65M of n-butyllithium was added to this solution under a nitrogen stream at -78 to -72. It was dripped at ° C. After dropping, the mixture was stirred at -70 ° C for 1 hour, and then a solution prepared by dissolving 2.42 g of dimesityl boron fluoride in 10 ml of THF was added dropwise at -75 to -70 ° C. After stirring at −70 ° C. for 30 minutes, the mixture was stirred overnight at room temperature. After adding ammonium chloride solution, THF was distilled off. After extraction with toluene, washing with water and drying, the solvent was distilled off. This was purified by silica gel column chromatography (eluent toluene / hexane = 1/2) to obtain 1.01 g of a boron-containing heterocyclic compound of the present invention represented by the following structural formula (20) as a colorless powder.

融点 ＞２００℃
赤外吸収スペクトル（ＫＢｒ錠剤法）を図１７に示した。
元素分析値（％）実測値（計算値）：
Ｃ ８６．４０/８６．５７ Ｈ ７．１３/７．２６ Ｎ ３．４２/３．４８

Melting point> 200 ° C
The infrared absorption spectrum (KBr tablet method) is shown in FIG.
Elemental analysis value (%) Actual measurement value (calculated value):
C 86.40 / 86.57 H 7.13 / 7.26 N 3.42 / 3.48

JP 2000-290645 A JP 2011-155282 A Japanese Unexamined Patent Publication No. 2007-027587

Claims (8)

A boron-containing heterocyclic compound represented by the following general formula (I).

(In the formula, Y represents a heterocyclic group, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, and Ar ₂ and Ar ₃ represent an aromatic carbon which may have a substituent. Represents a hydrogen group, Ar ₂ and Ar ₃ may form a ring together, and a boron atom may be directly bonded to a heterocyclic group (n represents 1, 2 or 3).   The heterocyclic group is a monovalent group, divalent group or trivalent group of carbazole, a divalent group of 2,1,3-benzothiadiazole, or a divalent group or trivalent group of pyrimidine. Item 6. A boron-containing heterocyclic compound according to Item 1. The boron-containing heterocyclic compound according to claim 1, wherein the boron-containing heterocyclic compound is represented by the following general formula (II).

(In the formula, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, Ar ₂ and Ar ₃ represent an aromatic hydrocarbon group which may have a substituent, Ar ₂ and Ar ₃ may form a ring together, and R represents a substituted or unsubstituted alkyl group or an aromatic hydrocarbon group or heterocyclic group which may have a substituent.) The boron-containing heterocyclic compound according to claim 1, wherein the boron-containing heterocyclic compound is represented by the following general formula (III).

The boron-containing heterocyclic compound according to claim 1, wherein the boron-containing heterocyclic compound is represented by the following general formula (IV).

(In the formula, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, Ar ₂ and Ar ₃ represent an aromatic hydrocarbon group which may have a substituent, Ar ₂ and Ar ₃ may form a ring together, and Ar ₄ represents an aromatic hydrocarbon group or a heterocyclic group which may have a substituent. The boron-containing heterocyclic compound according to claim 1, wherein the boron-containing heterocyclic compound is represented by the following general formula (V).

(In the formula, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, Ar ₂ and Ar ₃ represent an aromatic hydrocarbon group which may have a substituent, Ar ₂ and Ar ₃ may jointly form a ring. The boron-containing heterocyclic compound according to claim 1, wherein the boron-containing heterocyclic compound represented by the general formula (I) is represented by the following general formula (VI).

(In the formula, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, Ar ₂ and Ar ₃ represent an aromatic hydrocarbon group which may have a substituent, Ar ₂ and Ar ₃ may form a ring together, and R ′ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a halogen atom.) The boron-containing heterocyclic compound according to claim 1, wherein the boron-containing heterocyclic compound is represented by the following general formula (VII).

(In the formula, Ar ₁ represents a divalent group of an aromatic hydrocarbon which may have a substituent, Ar ₂ and Ar ₃ represent an aromatic hydrocarbon group which may have a substituent, Ar ₂ and Ar ₃ may form a ring together, and Ar ₅ represents an aromatic hydrocarbon group which may have a substituent.)

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