JP2010229053A - Bis-tricyclic amine-substituted arylene derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new bis-tricyclic amine-substituted arylene derivative excellent as an element component for an organic EL, especially a positive hole-transport material. <P>SOLUTION: The new bis-tricyclic amine-substituted arylene derivative has two tricyclic amine groups having specific structures on an arylene derivative represented by general formula (1) (wherein, R<SP>1</SP>is hydrogen, 1-4C lower alkyl, 1-4C lower alkoxy or halogen; Ar<SP>1</SP>is alkyl, aralkyl, aryl or heterocycle each of which may have a substituent; Z shows atoms required for forming a 5- to 8-membered saturated hydrocarbon ring or a 5-membered saturated heterocycle with two carbons of the 5-membered ring containing nitrogen; and A is a divalent linking group). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to novel bistricyclic amine-substituted arylene derivatives. More specifically, the present invention relates to a novel bis-tricyclic amine-substituted arylene derivative that can be used as an organic electroluminescence (EL) element component.

  Although the principle possibility of the organic EL element has been conventionally known, the production of a practical element was first reported by Tang et al. Of Kodak in 1987. They separated the light-emitting layer and the hole transport layer and laminated them with a thin film to improve the light-emitting efficiency of the organic EL device and to enable light emission at a low voltage, and showed its potential as a light-emitting device. (For example, refer to Patent Document 1). Since then, many researchers have conducted research for improving luminous efficiency and device lifetime, and many compounds have been proposed as device materials. As a result, a material having sufficient practicality in terms of light emission characteristics has been developed (see, for example, Patent Document 2). However, it is difficult to say that sufficient characteristics have been obtained with respect to the lifetime of the element, and when the element is driven, deterioration such as a decrease in light emission luminance with time or a non-light-emitting portion called a dark spot appears. Has been. Recent research has revealed that one of the causes of deterioration affecting the lifetime of these elements is that the properties of hole transport materials are greatly involved. Specifically, the hole transport material crystallizes by energization and distorts the uniformity of the thin film, causing a short circuit of the device, or the energization causes the hole transport material to decompose and not function, thereby inhibiting light emission. Etc.

  In order to solve such a problem, a hole transport material such as a compound having improved characteristics (common name: α-NPD) is used (for example, see Patent Document 3).

  More recently, it has also been found that a hole transport material having a higher melting point and a higher thermal decomposition point is superior in light emission and storage stability and has a long light emission lifetime (for example, , See Patent Document 4). On the other hand, by providing a hole injection layer containing a hole injection material having an appropriate ionization potential value between the hole transport layer containing the hole transport material and the anode, hole movement occurs more smoothly, As a result, it has also been found that an element having a lower driving voltage, superior stability, and improved deterioration of characteristics due to driving can be obtained as compared with a structure having a single hole transport layer. (For example, see Patent Document 5). However, at present, a hole transport material and a hole injection material having sufficient stability sufficient to make use of the characteristics of the excellent light emitting material developed so far have not yet been obtained.

JP-A 63-295695 JP-A-4-220995 Japanese Patent Laid-Open No. 5-234681 JP 2004-182740 A JP 2007-42973 A

  The present invention is a novel bis-tricyclic compound having excellent characteristics as a hole injection material for organic EL and a hole transport material for organic EL, which has excellent hole injection and transport capability and improved deterioration of characteristics due to driving. An object is to provide an amine-substituted arylene derivative.

  As a result of intensive studies to achieve the above object, the present inventors have found a bistricyclic amine-substituted arylene derivative having a specific structure, which is a novel compound not described in the literature.

  That is, the present invention provides a bistricyclic amine-substituted arylene derivative represented by the general formula (1).

[In General Formula (1), R ¹ represents a hydrogen atom, a C ₁ -C ₄ lower alkyl group, a C ₁ -C ₄ lower alkoxy group, or a halogen atom. Ar ¹ represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group, each of which may have a substituent. Z represents an atom necessary for forming a 5- to 8-membered saturated hydrocarbon ring or a 5-membered saturated heterocyclic ring together with two carbons of a 5-membered ring containing nitrogen. A represents a divalent linking group represented by the general formulas (2) to (6). ]

[In General Formulas (2) to (4), R ^{2 to} R ⁵ represent a hydrogen atom, a C _{1 to} C ₄ lower alkyl group, a C _{1 to} C ₄ lower alkoxy group, or a halogen atom. In the general formula (5), ^{R 6} and ^{R 7} represents a hydrogen _atom, a lower alkyl group or a phenyl group of C 1 -C _4. ]

  By using the bis-tricyclic amine-substituted arylene derivative of the present invention as a hole injection material or a hole transport material, an excellent organic EL device having a sufficiently low driving voltage and a long device life can be obtained.

Specific examples of R ¹ in the general formula (1) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group and other C ₁ -C ₄ lower alkyl groups, and a methoxy group. , an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a lower alkoxy group of C ₁ -C _4, such as a t- butoxy group or a fluorine atom, and a halogen atom such as a chlorine atom.

Specific examples of Ar ¹ include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, t-butyl groups, hexyl groups, octyl groups and other alkyl groups; benzyl groups, phenethyl groups and other aralkyl groups; phenyl groups 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-butylphenyl group, 4-isopropylphenyl group, 4-t-butylphenyl group; 4-hexylphenyl group, 4-octylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 2 A phenyl group substituted with an alkyl group such as methyl-4-ethylphenyl group or 2-ethyl-5-butyl group; 2-methoxyphenyl group 3-methoxyphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 3-propoxyphenyl group, 3-isopropoxyphenyl group, 4-propoxyphenyl group, 4-butoxyphenyl group, 4-t-butoxyphenyl Group, phenyl group substituted by alkoxy group such as 4-hexyloxy group, 2,4-dimethoxyphenyl group, 2-methoxy-5-ethoxy group; 2-methoxy-4-methylphenyl group, 2,6-dimethyl A phenyl group substituted with both an alkyl group and an alkoxy group such as a 4-methoxyphenyl group, 2-isopropoxy-5-t-butylphenyl group, 3-t-butoxy-4-isopropylphenyl group; 4-styryl Phenyl group, 4- (1-methyl-2-phenylethenyl) phenyl group, 4- (1,2-diphenylethenyl) A phenyl group substituted with an alkenyl group such as an phenyl group, 4- (2,2-diphenylethenyl) phenyl group; 1-naphthyl group, 2-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl- 1-naphthyl group, 1-methyl-2-naphthyl group, 4-ethyl-2-naphthyl group, 4-propyl-1-naphthyl group, naphthyl group substituted with alkyl group such as 4-isopropyl-1-naphthyl group 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 4'-methyl-4-biphenylyl group, 2 ', 4'-dimethyl-4-biphenylyl group, 3', 5'-diethyl-3-biphenylyl A biphenylyl group substituted with an alkyl group such as a group, 3'-methyl-4'-t-butyl-3-biphenylyl group; 4-p-terphenylyl group, 4-m-terphenylyl group, 4- -Terphenylyl group, 4 "-methyl-p-terphenylyl group, 3" -5 "-dimethyl-p-terphenylyl group, 4" -t-butyl-p-terphenylyl group, 4 "-octyl-p A terphenylyl group substituted with an alkyl group such as a terphenylyl group; an aryl group such as a 9-phenanthryl group, a 1-anthryl group, a 9-anthryl group and a 1-pyrenyl group; a hetero group such as a 2-pyridyl group and a 4-pyridyl group A cyclic group can be mentioned.

Specific examples of Z include — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ — and the like which form a saturated chain with two carbons of a 5-membered ring containing nitrogen. And carbon-containing carbon chains such as —CH ₂ —NH—CH ₂ — and —CH ₂ —N (CH ₃ ) —CH ₂ —.

Specific examples of A include divalent linking groups represented by general formulas (2) to (6). Specific examples of R ^{2 to} R ⁵ in the general formulas (2) to (4) include C _{1 to} C ₄ lower alkyl groups such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group, a methoxy group, ethoxy group, a propoxy group, C ₁ -C ₄ lower alkoxy group or a butoxy group or a fluorine atom, and a halogen atom such as a chlorine atom. Specific examples of R ⁶ and R ⁷ in the general formula (5) include a C _{1 to} C ₄ lower alkyl group such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group. .

  Next, the manufacturing method of the bis tricyclic amine substituted arylene derivative shown by the said General formula (1) is demonstrated. The bistricyclic amine-substituted arylene derivative represented by the general formula (1) includes a halogen-substituted tricyclic amine represented by the general formula (7) and a bisboronic acid-substituted arylene derivative represented by the general formula (8) or the general formula It can be synthesized by a coupling reaction with the bisboronic acid ester-substituted arylene derivative represented by (9). Alternatively, a boronic acid-substituted tricyclic amine represented by the general formula (10) or a boronic acid ester-substituted tricyclic amine represented by the general formula (11) and a bishalogen-substituted arylene derivative represented by the general formula (12) Can be synthesized by a coupling reaction.

[In the general formulas (7) to (12), R ¹ , Ar ¹ , Z and A are the same as those in the general formula (1). X represents a halogen atom such as a bromine atom or an iodine atom. ]

  The halogen-substituted tricyclic amine derivative of the general formula (7) is halogenated from the tricyclic amine derivative of the general formula (13) using a single halogen such as bromine or iodine, or N-halogenosuccinimide. Can be obtained.

[In General Formula (13), R ¹ , Ar ¹ and Z are the same as those in General Formula (1). ]

  As described in JP-A No. 2000-169446, a tricyclic amine derivative represented by the general formula (13) is obtained by converting a known precursor N-unsubstituted tricyclic indole derivative to N by aryl halide. -After triarylation, the double ring of the indole ring is reduced by catalytic hydrogenation or the like, or the tricycle obtained by Fisher's indole synthesis method in which 1,1-diphenylhydrazine and cyclopentanone are condensed. Similarly, the double bond of the sex indole derivative can be produced by reduction by a catalytic hydrogenation reaction or the like.

  As the bisboronic acid-substituted arylene derivative of the general formula (8), a commercially available bisboronic acid derivative is used, or the bishalogen-substituted arylene derivative of the general formula (12) is reacted with normal butyl lithium to form a bislithium salt. Thereafter, it can be synthesized by reacting with trimethoxyboron and then hydrolyzing with dilute hydrochloric acid.

  Further, the bisboronic acid ester-substituted arylene derivative of the general formula (9) is obtained by reacting the bishalogen-substituted arylene derivative of the general formula (12) with normal butyl lithium to form a bislithium salt, and then 2-isopropoxy-4,4 , 5,5-tetramethyl-1,3,2-dioxaborolane (DOB).

  In addition, the boronic acid-substituted tricyclic amine represented by the general formula (10) or the boronic acid ester-substituted tricyclic amine represented by the general formula (11) is obtained using a halogen-substituted tricyclic amine derivative represented by the general formula (7) as a raw material. These can be synthesized by the same method as the synthesis method of the bisboronic acid derivative of the general formula (8) and the bisboronic acid ester derivative of the general formula (9).

  Further, as the bishalogen-substituted arylene derivative of the general formula (12), a commercially available chemical is used, or the corresponding arylene derivative of the general formula (14) is replaced with a simple halogen such as bromine or iodine or N-halogenosuccinimide, etc. It can be obtained by halogenation using

[In General Formula (14), A is the same as in General Formula (1). ]

  Specific examples of the halogen-substituted tricyclic amine represented by the general formula (7) include the following formulas (7-01) to (7-22).

  Specific examples of the bisboronic acid-substituted arylene derivative represented by the general formula (8) include the following formulas (8-01) to (8-39).

  Specific examples of the bisboronic acid ester-substituted arylene derivative represented by the general formula (9) include the following formulas (9-01) to (9-15).

  Specific examples of the boronic acid-substituted tricyclic amine represented by the general formula (10) include the following formulas (10-01) to (10-22).

  Specific examples of the boronic acid ester-substituted tricyclic amine represented by the general formula (11) include the following formulas (11-01) to (11-21).

  Specific examples of the bishalogen-substituted arylene derivative represented by the general formula (12) include the following formulas (12-01) to (12-39).

  Specific examples of the tricyclic amine represented by the general formula (13) include the following formulas (13-01) to (13-22).

  Coupling reaction between the halogen-substituted tricyclic amine of the general formula (7) and the bisboronic acid-substituted arylene derivative of the general formula (8) or the bisboronic acid ester-substituted arylene derivative represented by the general formula (9), or In a coupling reaction between a boronic acid-substituted tricyclic amine of the formula (10) or a boronic acid ester-substituted tricyclic amine represented by the general formula (11) and a bishalogen-substituted arylene derivative represented by the general formula (12) In general, a base is used as a condensing agent. Examples of bases include alkali metal hydroxides, carbonates, hydrides; alkaline earth metal hydroxides, carbonates, hydrides; alkali metal salts of lower alcohols; tertiary amines, Preferably, alkali metal carbonate is used in the form of an aqueous solution.

  In this coupling reaction, a metal catalyst can be used in order to allow the reaction to proceed smoothly. As the metal catalyst, palladium, palladium acetate of its compound, or the like is used. Preferably, a trivalent alkyl phosphorus compound such as tritertiary butylphosphine or tri-o-tolylphosphine is used in combination as the catalyst auxiliary, or directly like tetrakis (triphenylphosphine) palladium. A palladium compound having a trivalent alkyl phosphorus as a ligand may be used.

  As the reaction solvent, any inert organic solvent having a certain degree of solubility can be used. Preferably, a method in which a raw material compound such as toluene or xylene has a high solubility but is not mixed with water and is reacted in a heterogeneous system with an aqueous solution of an alkali metal salt with high stirring efficiency, ethanol, propanol, etc. And a method of using a solvent such as 1,2-dimethoxyethane or 2-methoxyethanol which is relatively high in solubility of the raw material compound and also mixed with water.

  The reaction temperature varies depending on the solubility of the raw material compound in the reaction solvent, the boiling point of the reaction solvent to be used, the ease of reaction, etc., but cannot be generally stated, but is usually 20 to 150 ° C., preferably 70 to 120 ° C. Done in a range.

  Next, although the specific example of the compound of General formula (1) of this invention is given, this invention is not limited to these.

  Representative synthesis examples of the bis-tricyclic amine-substituted arylene derivatives of the present invention are shown below.

Example 1
(1) 4-phenyl-1,2,3,3a, 4,8b-hexahydrocyclopento [b] indole [Exemplary Compound (13-02)] 23.54 g (100 mmol) in a chloroform 500 ml solution at room temperature While being stirred at 17.59 g (110.1 mmol) of bromine is added dropwise over 2 hours. After the dropwise addition, the mixture was further stirred at room temperature for 8.5 hours, the solvent was distilled off under reduced pressure, and 44 g (including solvent) of the resulting crude product was purified by chromatography to give 7-bromo-4-phenyl-1,2, 3,3a, 4,8b-Hexahydrocyclopent [b] indole [Exemplary Compound (7-02)] (27.04 g, yield 86.1%) was obtained.

  (2) 3.14 g (9.99 mmol) of Exemplified Compound (7-02) obtained in (1) above, benzene-1,4-diboronic acid [Exemplary Compound (8-01) / commercially available product] 83 g (5.01 mmol), palladium acetate 90 mg (0.40 mmol), tri-o-tolylphosphine 0.84 g (2.76 mmol), potassium carbonate 2 mol aqueous solution 15.2 ml and 1,2-dimethoxyethane While stirring 24 ml of the mixture under a nitrogen stream, the reaction is completed by heating at 90 ° C. for 6.5 hours. The reaction solution is decanted, and the resulting crystals are isolated, dissolved in 40 ml of chloroform, dried over anhydrous magnesium sulfate, filtered to remove anhydrous magnesium sulfate, and 10 ml of hexane is added to the filtrate and left overnight. The precipitated crystals were collected by filtration and dried to obtain 0.26 g (yield: 9.56%) of the desired bis-tricyclic amine-substituted arylene derivative [Exemplary Compound (1-01)]. The melting point was 218-222 ° C.

The bis-tricyclic amine-substituted arylene derivative [Exemplary Compound (1-01)] is 7.55 to 7.80 (m, 10H), 7.28 to ⁷ H-NMR (δ, ppm, CDCl ₃ ). 7.46 (m, 10H), 4.83 (t, 2H), 3.90 (t, 2H), 1.81 to 2.16 (m, 8H), 1.62 to 1.70 (m, The structure was confirmed from the peak of 2H).

  When the decomposition point of the bistricyclic amine-substituted arylene derivative [Exemplary Compound (1-01)] was measured by thermal analysis, the result was that the thermal decomposition temperature was 350 ° C. or higher.

(Example 2)
(1) 6.33 g (20.15 mmol) of the exemplified compound (7-02) obtained in (1) of Example 1 was dissolved in 60 ml of tetrahydrofuran, and cooled and stirred at −78 ° C. in a nitrogen stream. Into this is added 13.87 ml (22.19 mmol) of a 15% hexane solution of n-butyllithium (about 1.6 mol / l). After stirring at −78 ° C. for 2 hours, 5.26 ml (46.32 mmol) of trimethyl borate was added, and stirred at −78 ° C. for 1 hour. Return to While stirring the reaction, 60 ml of 1 molar hydrochloric acid is added and stirred for 2 hours, and then the organic layer is separated. The aqueous layer is extracted with 150 ml of ethyl acetate, combined with the organic layer, and washed with saturated brine. After drying over anhydrous magnesium sulfate, the solvent is distilled off under reduced pressure to obtain 4.67 g of crude crystals. This was recrystallized from hexane / chloroform, purified by column chromatography, and 4-phenyl-1,2,3,3a, 4,8b-hexahydrocyclopent [b] indole-7-boronic acid [Exemplary Compound ( 10-02)] was obtained 1.93 g (yield 34.3%).

  (2) 1.93 g (6.91 mmol) of 4-phenyl-1,2,3,3a, 4,8b-hexahydrocyclopent [b] indole-7-boronic acid obtained in (1) above, 4,7'-dibromobiphenyl [Exemplary compound (12-08) / commercially available product] 1.07 g (3.43 mmol), palladium acetate 51 mg (0.227 mmol), tri-o-tolylphosphine 0.49 g ( 1.61 mmol), a mixture of 8.7 ml of a 2 mol aqueous solution of potassium carbonate and 14 ml of 1,2-dimethoxyethane is heated and stirred at 90 ° C. for 8 hours under a nitrogen stream to complete the reaction. After returning to room temperature, the precipitated crystals are collected by filtration to obtain 1.10 g of crude crystals. This was recrystallized from hexane / chloroform to obtain 0.27 g (yield 12.7%) of the desired bis-tricyclic amine-substituted arylene derivative [Exemplary Compound (1-15)]. The melting point was 187-190 ° C.

The bistricyclic amine-substituted arylene derivative [Exemplary Compound (1-15)] is 7.54 to 7.78 (m, 12H), 7.28 to ⁷ H-NMR (δ, ppm, CDCl ₃ ). 7.52 (m, 8H), 7.06 to 7.22 (m, 4H), 4.83 (m, 2H), 3.91 (m, 2H), 1.83 to 2.16 (m, 8H), 1.65 to 1.74 (m, 2H), and 1.50 to 1.63 (m, 2H), indicating the structure.

  When the decomposition point of the bistricyclic amine-substituted arylene derivative [Exemplary Compound (1-15)] was measured by thermal analysis, the result was that the thermal decomposition temperature was 350 ° C. or higher.

Example 3
(1) 2,7-dibromofluorene [Exemplary compound (12-28) / commercially available product] 10.0 g (30.86 mmol), bromoethane 33.6 g (308.34 mmol), tetrabutylammonium chloride 0.46 g ( 1.66 mmol), 90 ml (1721 mmol) of 50% aqueous sodium hydroxide solution and 90 ml of toluene are mixed, heated and stirred at 50 ° C. for 10 hours under a nitrogen stream. After allowing to cool, the organic layer is separated, washed twice with saturated brine and dried over anhydrous magnesium sulfate, and then the solvent is distilled off to obtain 11.29 g of crude crystals. This was recrystallized with hexane / chloroform (3/1), and the obtained crystal was further recrystallized with ethanol to obtain 2,7-dibromo-9,9-diethylfluorene [Exemplary Compound (12-31)]. 6.74 g (yield 57.5%) of purified crystals were obtained. Melting point was 158.9-159.2 ° C.

  (2) 6.08 g (15.99 mmol) of the exemplary compound (12-31) obtained in the above (1) was dissolved in 160 ml of tetrahydrofuran, and cooled and stirred at −78 ° C. under a nitrogen stream. 25.0 ml (40.0 mmol) of a 15% hexane solution of n-butyllithium (about 1.6 mol / l) is added. After stirring for 2 hours at -78 ° C, 7.74 g (41.60 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added, and the temperature was -78 ° C. After stirring for 2 hours, the cooler is turned off, and the temperature is naturally returned to room temperature while stirring under a nitrogen stream. The reaction solution is poured into 350 ml of water, extracted with 400 ml of ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate, and then the solvent is distilled off under reduced pressure to obtain 6.92 g of crude crystals. This was purified by column chromatography using toluene as a solvent to obtain 4.72 g (yield 62.2%) of 9,9-diethylfluorene-2,7-bisboronic acid ester [Exemplary Compound (9-12)]. It was. The melting point was 257-260 ° C.

  (3) 1.491 g (3.14 mmol) of Exemplified Compound (9-12) obtained in (2) above, 1.98 g of Exemplified Compound (7-02) obtained in (1) of Example 1 ( 6.30 mmol), tetrakis (triphenylphosphine) palladium 72.8 mg (0.063 mmol), potassium carbonate 2 mol aqueous solution 18 ml, and toluene 30 ml were stirred and heated at 90 ° C. for 22 hours under nitrogen stream. To complete the reaction. After returning to room temperature, the reaction solution was poured into 150 ml of water, then extracted with 250 ml of toluene, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 2.42 g of crude crystals. obtain. This is purified by column chromatography using toluene as a solvent to obtain 2.10 g of purified crystals. This purified crystal was further recrystallized from hexane / toluene to obtain 0.55 g (yield 25.4%) of the desired bis-tricyclic amine-substituted arylene derivative [Exemplary Compound (1-38)]. The melting point was 195 to 205 ° C.

The bis-tricyclic amine-substituted arylene derivative [Exemplary Compound (1-38)] is 7.60 to 7.80 (m, 6H), 7.52 to ¹ H-NMR (δ, ppm, CDCl ₃ ). 7.58 (m, 6H), 7.30-7.50 (m, 10H), 4.86 (m, 2H), 3.95 (m, 2H), 2.10-2.20 (m, 4H), 1.52 to 2.08 (m, 12H), and 0.43 (t, 6H) peaks, which confirmed the structure.

  When the decomposition point of the bistricyclic amine-substituted arylene derivative [Exemplary Compound (1-38)] was measured by thermal analysis, the result was that the thermal decomposition temperature was 350 ° C. or higher.

Example 4
Example Compound (7-02) obtained in Example 1 (1) and Example Compound (8-02) obtained from Example Compound (12-02) in the same manner as Example 2 (1) Were reacted in the same manner as (2) of Example 1 to obtain the exemplary compound (1-02) in a yield of 11.5%. The structure was confirmed by ¹ H-NMR.

(Example 5)
Exemplified compound (8-03) obtained from Exemplified compound (12-03) in the same manner as Exemplified compound (12-03) obtained in Example 1 (1) and Example 2 (1) Were reacted in the same manner as (2) of Example 1 to obtain Exemplified Compound (1-07) in a yield of 6.52%. The structure was confirmed by ¹ H-NMR.

(Example 6)
Example compound (7-02) obtained in Example 1 (1) and Example compound (8-04) obtained from Example compound (12-04) in the same manner as Example 2 (1) Were reacted in the same manner as (2) of Example 1 to obtain the exemplified compound (1-06) in a yield of 10.1%. The structure was confirmed by ¹ H-NMR.

(Example 7)
Exemplified compound (8-09) obtained from Exemplified compound (12-09) in the same manner as Exemplified compound (7-02) obtained in Example 1 (1) and Example 2 (1) Were reacted in the same manner as (2) of Example 1 to obtain the exemplary compound (1-16) in a yield of 20.2%. The structure was confirmed by ¹ H-NMR.

(Example 8)
Exemplified compound (8-10) obtained from Exemplified compound (12-10) in the same manner as Exemplified compound (7-02) obtained in Example 1 (1) and Example 2 (1) Were reacted in the same manner as in Example 1 (2) to give Exemplified Compound (1-17) in a yield of 8.59%. The structure was confirmed by ¹ H-NMR.

Example 9
(1) 4- (p-biphenyl) -1,2,3,3a, 4,8b-hexahydrocyclopent [b] indole [Exemplary Compound (13-06)] 6.23 g (20.0 mmol) To a 160 ml solution of chloroform, 3.15 g (21.94 mmol) of bromine is added dropwise over 1 hour while stirring at room temperature. After the dropwise addition, the mixture was further stirred at room temperature for 5 hours, the solvent was distilled off under reduced pressure, and 8.66 g of the resulting crude product was purified by chromatography to give 7-bromo-4- (p-biphenyl) -1,2, 3.65 g (yield: 98.0%) of 3,3a, 4,8b-hexahydrocyclopent [b] indole [Exemplary Compound (7-06)] was obtained.

(2) Exemplified compound (7-06) obtained in (1) of Example 9 and benzene-1,4-diboronic acid [Exemplary compound (8-01) / commercially available product] of Example 1 The reaction was conducted in the same manner as in (2) to obtain Exemplified Compound (1-04) in a yield of 13.2%. The structure was confirmed by ¹ H-NMR.

(Example 10)
Exemplified compound (7-04) obtained by brominating Exemplified compound (13-04) in the same manner as in Example 9 (1) and benzene-1,4-diboronic acid [Exemplified compound (8-01) ) · Commercial product] was reacted in the same manner as (2) of Example 1 to obtain Exemplified Compound (1-03) in a yield of 10.4%. The structure was confirmed by ¹ H-NMR.

(Example 11)
(1) 4- [4- (2,2-diphenylethenyl) phenyl)]-1,2,3,3a, 4,8b-hexahydrocyclopent [b] indole [Exemplary Compound (13-01)] To a solution of 4.13 g (9.99 mmol) in chloroform (80 ml), 1.92 g (12.04 mmol) of bromine is added dropwise over 40 minutes while stirring at room temperature. After the dropwise addition, the mixture was further stirred at room temperature for 2.5 hours, the solvent was distilled off under reduced pressure, and 6.17 g (including solvent) of the resulting crude product was purified by chromatography to give 7-bromo-4- [4- ( 2,2-diphenylethenyl) phenyl)]-1,2,3,3a, 4,8b-hexahydrocyclopent [b] indole [Exemplary Compound (7-01)] 4.44 g (yield 90.2) %).

(2) Example compound (7-01) obtained in (1) of Example 11 and benzene-1,4-diboronic acid [Exemplary compound (8-01), commercially available product] The reaction was conducted in the same manner as in (2) to obtain Exemplified Compound (1-05) in a yield of 14.1%. The structure was confirmed by ¹ H-NMR.

Example 12
(1) The exemplified compound (13-21) was brominated by the same method as (1) of Example 11 to obtain the exemplified compound (7-21) in a yield of 89.7%.

(2) Exemplified compound (7-21) obtained in (1) of Example 12 and benzene-1,4-diboronic acid [Exemplary compound (8-01) / commercial product] of Example 1 The reaction was conducted in the same manner as in (2) to obtain Exemplified Compound (1-09) in a yield of 19.8%. The structure was confirmed by ¹ H-NMR.

(Example 13)
(1) The exemplified compound (13-05) was brominated in the same manner as in (1) of Example 11 to obtain the exemplified compound (7-05) in a yield of 87.1%.

(2) Example compound (7-05) obtained in (1) of Example 13 and benzene-1,4-diboronic acid [Exemplary compound (8-01), commercially available product] The reaction was conducted in the same manner as in (2) to obtain Exemplified Compound (1-08) in a yield of 22.6%. The structure was confirmed by ¹ H-NMR.

(Example 14)
The exemplified compound (7-02) obtained in (1) of Example 1 and the exemplified compound (8-05) are reacted in the same manner as in (2) of Example 1 to give the exemplified compound (1 -11) was obtained in a yield of 12.8%. The structure was confirmed by ¹ H-NMR.

(Example 15)
The exemplified compound (7-02) obtained in (1) of Example 1 and the exemplified compound (8-06) are reacted in the same manner as in (2) of Example 1 to give the exemplified compound (1 -12) was obtained in a yield of 14.0%. The structure was confirmed by ¹ H-NMR.

(Example 16)
The exemplified compound (7-02) obtained in (1) of Example 1 and the exemplified compound (8-07) are reacted in the same manner as in (2) of Example 1 to give the exemplified compound (1 -13) was obtained in a yield of 8.15%. The structure was confirmed by ¹ H-NMR.

(Example 17)
(1) Exemplified compound (7-03) was converted to boronic acid by the same method as (2) of Example 2 to obtain Exemplified compound (10-03) in a yield of 35.1%.

(2) Exemplified compound (10-03) obtained in (1) of Example 17 and 1,4-dibromobenzene [Exemplary compound (12-01), commercially available product] ) To give Exemplified Compound (1-10) in a yield of 22.2%. The structure was confirmed by ¹ H-NMR.

(Example 18)
(1) In the same manner as in (2) of Example 2, the exemplified compound (7-01) obtained in (1) of Example 11 was converted to boronic acid, and the exemplified compound (10-01) was recovered. Obtained at a rate of 41.9%.

(2) Exemplified compound (10-01) obtained in Example 18 (1) and 1,2-dibromobenzene [Exemplary compound (12-07) / commercially available product] ) To give exemplary compound (1-14) in a yield of 20.8%. The structure was confirmed by ¹ H-NMR.

(Example 19)
The exemplified compound (7-06) obtained in Example 9 (1) and the exemplified compound (8-08) are reacted in the same manner as in Example 1 (2) to give the exemplified compound (1 -18) was obtained in a yield of 19.9%. The structure was confirmed by ¹ H-NMR.

(Example 20)
Exemplified compound (10-01) obtained in (1) of Example 18 and 4,4′-dibromobiphenyl [Exemplary compound (12-08), commercially available product] were combined with (2) of Example 2 By reacting in the same manner, Exemplified compound (1-19) was obtained in a yield of 13.8%. The structure was confirmed by ¹ H-NMR.

(Example 21)
The exemplified compound (7-06) obtained in Example 9 (1) and the exemplified compound (8-11) are reacted in the same manner as in Example 1 (2) to give the exemplified compound (1 -20) was obtained in a yield of 9.82%. The structure was confirmed by ¹ H-NMR.

(Example 22)
The exemplified compound (7-02) obtained in (1) of Example 1 and the exemplified compound (8-12) are reacted in the same manner as in (2) of Example 1 to give the exemplified compound (1 -21) was obtained in a yield of 5.31%. The structure was confirmed by ¹ H-NMR.

(Example 23)
The exemplified compound (7-02) obtained in (1) of Example 1 and the exemplified compound (8-13) are reacted in the same manner as in (2) of Example 1 to give exemplified compound (1 -22) was obtained in a yield of 10.5%. The structure was confirmed by ¹ H-NMR.

(Example 24)
The exemplified compound (7-02) obtained in (1) of Example 1 and the exemplified compound (8-15) are reacted in the same manner as in (2) of Example 1 to give the exemplified compound (1 -24) was obtained in a yield of 18.8%. The structure was confirmed by ¹ H-NMR.

(Example 25)
The exemplified compound (7-02) obtained in (1) of Example 1 and the exemplified compound (8-17) are reacted in the same manner as in (2) of Example 1 to give the exemplified compound (1 -26) was obtained in a yield of 25.5%. The structure was confirmed by ¹ H-NMR.

(Example 26)
The exemplified compound (7-02) obtained in (1) of Example 1 and the exemplified compound (8-19) are reacted in the same manner as in (2) of Example 1 to give the exemplified compound (1 -28) was obtained in a yield of 11.1%. The structure was confirmed by ¹ H-NMR.

(Example 27)
The exemplified compound (1-01) obtained in Example 11 (1) and the exemplified compound (8-21) are reacted in the same manner as in Example 1 (2) to give the exemplified compound (1). -30) was obtained in a yield of 14.2%. The structure was confirmed by ¹ H-NMR.

(Example 28)
The exemplified compound (7-02) obtained in (1) of Example 1 and the exemplified compound (8-23) are reacted in the same manner as in (2) of Example 1 to give the exemplified compound (1 -32) was obtained in a yield of 12.7%. The structure was confirmed by ¹ H-NMR.

(Example 29)
The exemplified compound (7-02) obtained in (1) of Example 1 and the exemplified compound (8-26) are reacted in the same manner as in (2) of Example 1 to give the exemplified compound (1 -34) was obtained in a yield of 23.4%. The structure was confirmed by ¹ H-NMR.

(Example 30)
(1) In the same manner as in Example 1, (1), 2,7-dibromofluorenone [Exemplary Compound (12-28) / commercial product] was converted to bisboronic acid, and Exemplified Compound (8-28) was recovered. Obtained at a rate of 21.9%.

(2) The exemplary compound (8-28) obtained in (1) of Example 30 and the exemplary compound (7-02) obtained in (1) of Example 1 were combined with (2) of Example 1. ) To give Exemplified compound (1-36) in a yield of 12.7%. The structure was confirmed by ¹ H-NMR.

(Example 31)
(1) Bismethylation of 2,7-dibromofluorenone [Exemplary compound (12-28) / commercially available product] using methyl iodide instead of bromoethane in the same manner as in Example 3 (1), 2,7-Dibromo-9,9-dimethylfluorenone [Exemplary Compound (12-29)] was obtained in a yield of 41.8%.

  (2) The exemplified compound (12-29) obtained in (1) of Example 31 was converted to bisboronic acid in the same manner as in (1) of Example 2, and the exemplified compound (8-29) was recovered. Obtained at a rate of 21.9%.

(3) The exemplified compound (8-29) obtained in (2) of Example 31 and the exemplified compound (7-02) obtained in (1) of Example 1 were combined with (2) of Example 1. ) To give exemplary compound (1-37) in a yield of 14.3%. The structure was confirmed by ¹ H-NMR.

(Example 32)
The exemplified compound (7-02) obtained in (1) of Example 1 and the exemplified compound (8-32) are reacted in the same manner as in (2) of Example 1 to give the exemplified compound (1 -40) was obtained in a yield of 8.34%. The structure was confirmed by ¹ H-NMR.

(Example 33)
(1) In the same manner as in Example 3, (2), 2,7-dibromonaphthalene [Exemplary Compound (12-33) / commercially available product] is converted to a bisboronic acid ester to give Exemplified Compound (9-13) Was obtained in a yield of 58.8%.

(2) The exemplified compound (9-13) obtained in (1) of Example 33 and the exemplified compound (7-02) obtained in (1) of Example 1 were combined with (3) of Example 3 ) To give exemplary compound (1-41) in a yield of 19.6%. The structure was confirmed by ¹ H-NMR.

(Example 34)
(1) In the same manner as in (2) of Example 3, 1,4-dibromonaphthalene [Exemplary Compound (12-37) / commercial product] is converted to a bisboronic acid ester to give Exemplified Compound (9-14) Was obtained in a yield of 60.6%.

(2) The exemplified compound (9-14) obtained in (1) of Example 34 and the exemplified compound (7-02) obtained in (1) of Example 1 were combined with (3) of Example 3 ) To give Exemplified compound (1-44) in a yield of 29.1%. The structure was confirmed by ¹ H-NMR.

(Example 35)
1,4-dibromobenzene [Exemplary compound (12-01) / commercially available product] and Exemplified compound (11-07) are reacted in the same manner as in Example 3 (3) to give Exemplified compound (1 -46) was obtained in a yield of 4.96%. The structure was confirmed by ¹ H-NMR.

(Example 36)
1,4-dibromobenzene [Exemplary Compound (12-01) / commercially available product] and Exemplified Compound (11-08) are reacted in the same manner as in Example 3 (3) to give Exemplified Compound (1 -47) was obtained in a yield of 10.5%. The structure was confirmed by ¹ H-NMR.

(Example 37)
(1) The exemplified compound (13-12) was brominated in the same manner as in (1) of Example 11 to obtain the exemplified compound (7-12) in a yield of 79.1%.

(2) Exemplified compound (7-12) obtained in (1) of Example 37 and benzene-1,4-diboronic acid [Exemplary compound (8-01), commercially available product] Reaction was carried out in the same manner as in (2) to give Exemplified Compound (1-49) in a yield of 12.0%. The structure was confirmed by ¹ H-NMR.

(Example 38)
(1) The exemplified compound (13-20) was brominated by the same method as (1) in Example 11 to obtain the exemplified compound (7-20) in a yield of 95.7%.

(2) Example compound (7-20) obtained in (1) of Example 38 and benzene-1,4-diboronic acid [Exemplary compound (8-01), commercially available product] Reaction was carried out in the same manner as in (2) to obtain Exemplified Compound (1-50) in a yield of 18.4%. The structure was confirmed by ¹ H-NMR.

(Example 39)
(1) Exemplified compound (11-19) was obtained in a yield of 33.6% by converting Exemplified compound (7-19) to bisboronic acid ester in the same manner as (2) of Example 3. .

(2) Exemplified compound (11-19) obtained in Example 39 (1) and 1,4-dibromobenzene [Exemplary compound (12-01) / commercially available product] were combined with (3) of Example 3. In the same manner as in Example 1, the exemplary compound (1-52) was obtained in a yield of 11.3%. The structure was confirmed by ¹ H-NMR.

(Example 40)
(1) The exemplified compound (13-22) was brominated in the same manner as in (1) of Example 11 to obtain the exemplified compound (7-22) in a yield of 50.9%.

(2) Exemplified compound (7-22) obtained in Example 40 (1) and benzene-1,4-diboronic acid [Exemplary compound (8-01) / commercially available product] of Example 1 Reaction was carried out in the same manner as in (2) to obtain Exemplified Compound (1-53) in a yield of 11.5%. The structure was confirmed by ¹ H-NMR.

(Example 41)
(1) The exemplified compound (13-18) was brominated by the same method as in (1) of Example 11 to obtain the exemplified compound (7-18) in a yield of 84.9%.

(2) Example compound (7-18) obtained in (1) of Example 41 and benzene-1,4-diboronic acid [Exemplary compound (8-01) / commercial product] The reaction was conducted in the same manner as in (2) to obtain Exemplified compound (1-55) in a yield of 6.53%. The structure was confirmed by ¹ H-NMR.

(Example 42)
(1) The exemplified compound (13-17) was brominated in the same manner as in (1) of Example 11 to obtain the exemplified compound (7-17) in a yield of 83.5%.

(2) The exemplified compound (7-17) obtained in (1) of Example 42 and the exemplified compound (8-07) were reacted in the same manner as in (2) of Example 1, and exemplified. Compound (1-57) was obtained with a yield of 10.0%. The structure was confirmed by ¹ H-NMR.

(Example 43)
(1) The exemplified compound (13-13) was brominated by the same method as (1) of Example 11 to obtain the exemplified compound (7-13) in a yield of 23.1%.

(2) Exemplified compound (7-13) obtained in (1) of Example 43 and benzene-1,4-diboronic acid [Exemplary compound (8-01) / commercially available product] of Example 1 Reaction was carried out in the same manner as in (2) to obtain Exemplified Compound (1-65) in a yield of 11.7%. The structure was confirmed by ¹ H-NMR.

(Example 44)
(1) The exemplified compound (13-15) was brominated by the same method as (1) of Example 11 to obtain the exemplified compound (7-15) in a yield of 93.5%.

(2) Exemplified compound (7-15) obtained in (1) of Example 44 and benzene-1,4-diboronic acid [Exemplary compound (8-01), commercially available product] Reaction was carried out in the same manner as in (2) to give Exemplified Compound (1-66) in a yield of 13.4%. The structure was confirmed by ¹ H-NMR.

  The target compounds other than Examples 1 to 44 were also synthesized in accordance with the above-described method for the bis-tricyclic amine-substituted arylene derivative exemplified compounds.

  Among representative compounds and α-NPD as a comparative compound, purified tetrahydrofuran was used as a solvent, and cyclic voltammetry (CV) measurement, which is a kind of electrochemical measurement method, was performed to oxidize them. The half wave potential was determined. Tetrabutylammonium perchlorate (TBAP) was used as the supporting electrolyte, and the concentration was 0.1 mol / l. The measurement was performed using a platinum disk electrode as the working electrode, a platinum wire as the counter electrode, and a saturated calomel electrode (SCE) as the reference electrode. The measurement conditions were sample concentration: about 0.1 to 1.0 mmol / l, and recording was performed at an XY recorder sweep rate (applied voltage) of 200 mV / sec. The results were as shown in Table 1 below.

  From the results of the above CV measurement, it can be seen that the novel bis-tricyclic amine-substituted arylene derivative of the present invention has an oxidation half-wave potential lower by about 250 mV than the α-NPD of the comparative substance. From conventional knowledge, it is known that the oxidation half-wave potential obtained by the electrochemical measurement method is correlated with the ionization potential corresponding to the highest occupied molecular orbital (HOMO) in terms of energy level. From this point of view, these compounds are used as a hole transport material used in the hole transport layer, and in addition to hole injection that facilitates the movement of holes between the anode and the hole transport layer. It is suggested that it is also useful as a layer.

(Application 1)
Exemplified compounds (1-01), (1-15), (1-38), (1-02), (1-07), (1-06), (1-06) obtained in Examples 1-44 above 1-16), (1-17), (1-04), (1-03), (1-05), (1-09), (1-08), (1-11), (1- 12), (1-13), (1-10), (1-14), (1-18), (1-19), (1-20), (1-21), (1-22) , (1-24), (1-26), (1-28), (1-30), (1-32), (1-34), (1-36), (1-37), ( 1-40), (1-41), (1-44), (1-46), (1-47), (1-49), (1-50), (1-52), (1- 53), (1-55), (1-57), (1-65), (1-66) To produce an EL device was confirmed functions as a hole transporting material. In the organic EL element, a thin film of the compound of the present invention is formed as a hole transport material on a transparent electrode on which an ITO electrode is previously formed on a glass substrate, and aluminum quinoline 3 is formed thereon as a light emitting layer and an electron transport layer. A thin film of a polymer was formed, and an Mg / Al electrode thin film was further formed thereon.

When an electric current of 100 mA / cm ² was applied to the organic EL element produced as described above using a constant current device, it was confirmed that the organic EL element emitted light continuously with sufficient light emission luminance. When any of the exemplified compounds was used, the light emission lifetime until the initial sensitivity was halved was 100 hours or longer.

(Comparative Application Example 1)
On the other hand, when α-NPD was used as a comparative compound, a similar organic EL element was produced, and a current of 100 mA / cm ² was applied using a similar constant current device. However, the emission lifetime was shorter than that of the exemplified compound, which was about 50 hours.

(Application example 2)
Next, the example compound of the present invention used in Application Example 1 was used as the hole injection layer instead of the hole transport layer, and the sample was prepared in Application Example 1 instead of the hole transport layer prepared in Application Example 1. A hole injection layer having a thickness about half that of the hole transport layer is formed, and a comparative example of α-NPD is used on the hole injection layer, and the thickness is about half that of the hole transport layer manufactured in Application Example 1. By forming a hole transport layer, an element having a two-layer structure of a hole injection layer / a hole transport layer having substantially the same film thickness was prepared instead of the hole transport layer having a normal structure. As a result of comparison with a device having a normal configuration using α-NPD as the hole transport material of Comparative Application Example 1, in the device having a two-layer configuration, the driving voltage required to give the same current density is 10 to 10. It was confirmed that it was reduced by 20%.

  As an application example of the present invention, an organic EL device having a particularly low driving voltage and an excellent light emission lifetime can be realized.

Claims (1)

A bis-tricyclic amine-substituted arylene derivative represented by the general formula (1).

[In General Formula (1), R ¹ represents a hydrogen atom, a C ₁ -C ₄ lower alkyl group, a C ₁ -C ₄ lower alkoxy group, or a halogen atom. Ar ¹ represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group, each of which may have a substituent. Z represents an atom necessary for forming a 5- to 8-membered saturated hydrocarbon ring or a 5-membered saturated heterocyclic ring together with two carbons of a 5-membered ring containing nitrogen. A represents a divalent linking group represented by the general formulas (2) to (6). ]

[In General Formulas (2) to (4), R ^{2 to} R ⁵ represent a hydrogen atom, a C _{1 to} C ₄ lower alkyl group, a C _{1 to} C ₄ lower alkoxy group, or a halogen atom. In the general formula (5), ^{R 6} and ^{R 7} represents a hydrogen _atom, a lower alkyl group or a phenyl group of C 1 -C _4. ]