JP4810830B2 - Amine compound having fluorene group as mother nucleus and production method and use thereof - Google Patents

Description

  The present invention relates to an amine compound having a fluorene group as a mother nucleus, a production method thereof, and an organic electroluminescence (EL) device. An amine compound having a fluorene group as a core can be used as a photosensitive material or an organic photoconductive material, and more specifically, a hole light transport such as an organic EL element or an electrophotographic photosensitive member used for a planar light source or display, It can be used as a hole injection material and a light emitting material.

  Organic photoconductive materials developed as photosensitive materials and hole transport materials have various advantages such as low cost, various processability, and non-polluting properties, and many compounds have been proposed. For example, oxadiazole derivatives (for example, see Patent Document 1), oxazole derivatives (for example, see Patent Document 2), hydrazone derivatives (for example, see Patent Document 3), triarylpyrazoline derivatives (for example, Patent Documents 4 and 5) Materials) such as arylamine derivatives (see, for example, Patent Documents 6 and 7), stilbene derivatives (see, for example, Patent Documents 8 and 9), and the like.

  Among them, 4,4 ′, 4 ″ -tris [N, N- (1-naphthyl) phenylamino] triphenylamine (1-TNATA), 4,4 ′, 4 ″ -tris [N, N- (m-tolyl) ) Phenylamino] triphenylamine (MTDATA), 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD), 4,4′-bis [N- (m- Arylamine derivatives such as (tolyl) -N-phenylamino] biphenyl (TPD) are often used as hole transporting or hole injecting materials (for example, see Non-Patent Documents 1 and 2).

  Recently, many fluorene derivatives have been developed (see, for example, Patent Documents 10, 11, 12, 13, 14, and 16).

  However, since these materials have difficulties such as poor stability and durability, for example, α-NPD thin films formed by vacuum evaporation are originally crystalline compounds because α-NPD is a crystalline compound. If left for about two weeks, crystallization or aggregation occurs, and the thin film becomes cloudy. Moreover, the 9,9-position which is a typical fluorene derivative is 2,7-bis (dinaphthylamino) -9,9-dimethylfluorene (for example, refer to Patent Document 11) which is a dimethyl group, and 2,9 which is a diphenyl group. Since 7-bis (N, N-diphenylamino) -9,9-diphenylfluorene (see, for example, Patent Document 16) has high crystallinity, it has the same problem as described above. As a result, when applied to an organic thin film device such as an organic EL element, there is a problem that there is a high possibility that a short or dark spot will occur. At present, it is desired to develop a hole transport material having excellent hole transport capability, excellent thin film stability, and high Tg (glass transition temperature). As a method for producing arylamines, a method using a catalyst comprising a trialkylphosphine and a palladium compound in an amination reaction of an aryl halide with an amine compound in the presence of a base is known (for example, Patent Document 15). reference).

US Pat. No. 3,189,447 (claims) US Pat. No. 3,257,203 (claims) JP-A-54-59143 (Claims) JP 51-93224 A (Claims) JP 55-108667 A (Claims) JP-A-55-144250 (Claims) JP-A-56-119132 (Claims) Japanese Patent Laid-Open No. 58-190953 (Claims) JP 59-195658 (Claims) JP-A-11-35532 (Claims) JP-A-12-16773 (Claims) JP-A-12-302756 (Claims) JP-A-12-327638 (Claims) JP-A-13-39933 (Claims) Japanese Patent Laid-Open No. 10-139742 (Claims) JP-A-10-95972 (Claims) “Advanced Materials” (Germany), 1998, Vol. 10, No. 14, p1108-1112 (FIG. 1, Table 1) “Journal of Luminescence” (Netherlands), 1997, 72-74, p985-991 (FIG. 1).

  An object of the present invention is to provide a durable new material having excellent hole transport capability, excellent thin film stability, and having a higher Tg than α-NPD or MTDATA. More specifically, it is to provide a novel amine compound suitable for a hole transport material such as an organic EL device and a light emitting material.

  As a result of intensive studies, the present inventors have found that the amine compound represented by the general formula (1) has a high Tg, and many of these compounds are not crystalline compounds but have an amorphous structure, so that the thin film Even if it has excellent stability and crystallinity, it may be because of the cardo structure (cardo means a hinge, which is a group in which a cyclic group is directly bonded to the main chain) or for a long time. As a result, the present inventors have found that the thin film does not become cloudy and have completed the present invention. That is, this invention relates to the amine compound which uses fluorene represented by General formula (1) as a nucleus, its manufacturing method, and a use.

(Wherein R ^{1 to} R ² each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group, an aryl group, an aryloxy group, or a halogen atom, and Ar ^{1 to} Ar ² each represents Independently represents a substituted or unsubstituted aryl group or heteroaryl group, and may form a nitrogen-containing heterocycle with the nitrogen atom to which Ar ³ is bonded, each Ar ³ independently represents a substituted or unsubstituted phenyl group, A naphthyl group, a biphenylyl group, a terphenylyl group, an anthryl group, a fluorenyl group, or a pyridyl group (excluding an amino substituent). M represents a single bond, an arylene group, or a heteroarylene group.
Hereinafter, the present invention will be described in detail.

In the amine compound represented by the general formula (1), Ar ^{1 to} Ar ² each independently represents a substituted or unsubstituted aryl group or heteroaryl group, and forms a nitrogen-containing heterocycle together with the nitrogen atom to which it is bonded. May be.

  The substituted or unsubstituted aryl group is an aromatic group having 6 to 24 carbon atoms which may have a substituent, and specifically includes, for example, a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. 2-anthryl group, 9-anthryl group, 2-fluorenyl group, phenanthryl group, pyrenyl group, chrysenyl group, perylenyl group, picenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4 -Ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group 4-sec-butylphenyl group, 2-sec-butylphenyl group, 4-tert-butylphenyl group, 3-tert-butylphenyl Group, 2-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 2-neopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4 -(2'-ethylbutyl) phenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4- (2'-ethylhexyl) phenyl group, 4-tert-octylphenyl group, 4-n-decyl Phenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4- (4'-methylcyclohexyl) phenyl group, 4- (4'- tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4- Til-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,4-diethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,6- Diethylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisobutylphenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 4,6-di- tert-butyl-2-methylphenyl group, 5-tert-butyl-2-methylphenyl group, 4-tert-butyl-2,6-dimethylphenyl group, 9-methyl-2-fluoro Renyl, 9-ethyl-2-fluorenyl, 9-n-hexyl-2-fluorenyl, 9,9-dimethyl-2-fluorenyl, 9,9-diethyl-2-fluorenyl, 9,9-di -N-propyl-2-fluorenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n- Propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 2-isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4 -N-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopene Tyloxyphenyl group, 2-neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2′-ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n-decyloxyphenyl Group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-methoxy-1-naphthyl group, 4-methoxy-1- Naphthyl group, 4-n-butoxy-1-naphthyl group, 5-ethoxy-1-naphthyl group, 6-methoxy-2-naphthyl group, 6-ethoxy-2-naphthyl group, 6-n-butoxy-2-naphthyl group Group, 6-n-hexyloxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 7-n-butoxy-2-naphthyl group 2-methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 3-ethyl-5-methoxyphenyl group, 2-methoxy-4-methylphenyl group, 3-methoxy-4-methylphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl Group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy-6-ethoxyphenyl group 3,4,5-trimethoxyphenyl group, 4-biphenylyl group, 3-biphenylyl group, 2-biphenylyl group, 4- (4′-methylphenyl) ) Phenyl group, 4- (3′-methylphenyl) phenyl group, 4- (4′-methoxyphenyl) phenyl group, 4- (4′-n-butoxyphenyl) phenyl group, 2- (2′-methoxyphenyl) ) Phenyl group, 4- (4′-chlorophenyl) phenyl group, 3-methyl-4-phenylphenyl group, 3-methoxy-4-phenylphenyl group, terphenyl group, 3,5-diphenylphenyl group, 10-phenyl Anthryl group, 10- (3,5-diphenylphenyl) -9-anthryl group, 9-phenyl-2-fluorenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl Group, 3-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 2-bromophenyl group, 4-chloro-1-naphthyl Group, 4-chloro-2-naphthyl group, 6-bromo-2-naphthyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl Group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5- Dichlorophenyl group, 2,5-dibromophenyl group, 2,4,6-trichlorophenyl group, 2,4-dichloro-1-naphthyl group, 1,6-dichloro-2-naphthyl group, 2-fluoro-4-methyl Phenyl group, 2-fluoro-5-methylphenyl group, 3-fluoro-2-methylphenyl group, 3-fluoro-4-methylphenyl group, 2-methyl 4-fluorophenyl group, 2-methyl-5-fluorophenyl group, 3-methyl-4-fluorophenyl group, 2-chloro-4-methylphenyl group, 2-chloro-5-methylphenyl group, 2-chloro- 6-methylphenyl group, 2-methyl-3-chlorophenyl group, 2-methyl-4-chlorophenyl group, 3-chloro-4-methylphenyl group, 3-methyl-4-chlorophenyl group, 2-chloro-4,6 -Dimethylphenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group, 2-fluoro-4-ethoxyphenyl group, 2-fluoro-6-methoxyphenyl group, 3-fluoro-4 -Ethoxyphenyl group, 3-chloro-4-methoxyphenyl group, 2-methoxy-5-chlorophenyl group, 3-methoxy-6-chloropheny Group, 5-chloro-2,4-dimethoxyphenyl group and the like, but are not limited thereto.

  The substituted or unsubstituted heteroaryl group is an aromatic group containing at least one heteroatom among an oxygen atom, a nitrogen atom and a sulfur atom. For example, a 4-quinolyl group, a 4-pyridyl group, a 3-pyridyl group Group, 2-pyridyl group, 3-furyl group, 2-furyl group, 3-thienyl group, 2-thienyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, Examples thereof include, but are not limited to, 2-benzimidazolyl group.

In order to achieve a high Tg, at least one of Ar ¹ and Ar ² is a substituted or unsubstituted condensed cyclic aromatic group such as a naphthyl group, a phenanthryl group, a fluorenyl group, an anthryl group, a pyrenyl group. Group, chrycenyl group, picenyl group, perylenyl group and the like are preferable. More preferable examples include 1-naphthyl group, 9-phenanthryl group, pyrenyl group, and 2-fluorenyl group. In the case of the amine compound represented by the general formula (1) in which at least one of Ar ¹ and Ar ² has a substituted or unsubstituted fused aromatic group having more than 16 carbon atoms, the yield at the time of synthesis may be increased. Ar ¹ and Ar ² are any one of a phenyl group, a 4-methylphenyl group, a 4-biphenylyl group, and a 1-naphthyl group because the rate tends to decrease or the amount of isomer tends to remain about several thousand ppm. It may be preferable to be.

In the amine compound represented by the general formula (1), Ar ¹ and Ar ² may form a nitrogen-containing heterocyclic ring together with the nitrogen atom bonded thereto, and a substituted or unsubstituted —N-carbazolyl group, —N A -phenoxazinyl group or a -N-phenothiazinyl group may be formed. In the nitrogen-containing heterocycle, examples of the substituent include a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group, and an aryl group having 6 to 10 carbon atoms, and may be mono- or poly-substituted. Of these, an unsubstituted halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, or an —N-carbazolyl group monosubstituted or polysubstituted with an aryl group having 6 to 10 carbon atoms, -N-phenoxazinyl group or -N-phenothiazinyl group, more preferably unsubstituted -N-carbazolyl group, -N-phenoxazinyl group, or -N-phenothazinyl group. It is. Specific examples of the substituted -N-carbazolyl group, -N-phenoxazinyl group, or -N-phenothiazinyl group include, for example, 2-methyl-N-carbazolyl group, 3-methyl-N-carbazolyl group 4-methyl-N-carbazolyl group, 3-n-butyl-N-carbazolyl group, 3-n-hexyl-N-carbazolyl group, 3-n-octyl-N-carbazolyl group, 3-n-decyl-N -Carbazolyl group, 3,6-dimethyl-N-carbazolyl group, 2-methoxy-N-carbazolyl group, 3-methoxy-N-carbazolyl group, 3-ethoxy-N-carbazolyl group, 3-isopropoxy-N-carbazolyl group Group, 3-n-butoxy-N-carbazolyl group, 3-n-octyloxy-N-carbazolyl group, 3-n-decyloxy group -N-carbazolyl group, 3-phenyl-N-carbazolyl group, 3- (4'-methylphenyl) -N-carbazolyl group, 3- (4'-tert-butylphenyl) -N-carbazolyl group, 3-chloro -N-carbazolyl group, 2-methyl-N-phenothiazinyl group, etc. can be mentioned.

Ar ³ each independently represents a substituted or unsubstituted phenyl group, naphthyl group, biphenylyl group, terphenylyl group, anthryl group, fluorenyl group, or pyridyl group (excluding an amino-substituted product). Examples of the substituent for Ar ³ include an alkyl group such as a methyl group, an ethyl group, and a propyl group, an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group, an aryl group such as a phenyl group, an aryloxy group such as a phenoxy group, and a pyridyl group. And heteroaryl groups such as groups. Among them, preferred substituents for Ar ³ include phenyl group, 3,5-diphenylphenyl group, 1-naphthyl group, 4-biphenylyl group, 4-terphenylyl group, 9-anthryl group, 10-phenyl-9-anthryl group, Or 10- (3,5-diphenylphenyl) -9-anthryl group.

In the amine compound represented by the general formula (1), R ^{1 and} R ² are each independently a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group, an aryl group, an aryloxy group, or a halogen atom. is there.

  Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 18 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert. -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group, 1,3-cyclohexadienyl group, 2-cyclopentene-1- Il group can be exemplified.

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

As an aryl group, it is a C6-C24 aromatic group which may have a substituent, and specifically, a phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl. Group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4-dimethylphenyl group, 1-biphenyl group, 1-naphthyl group, 2-naphthyl group , 9-phenanthryl group, 9,9-dialkyl-fluoren-2-yl group, 9,9-di-trifluoromethyl-fluoren-2-yl group, etc. mention may be made of r ¹ and Ar ² identical substituents.

  Moreover, as an aryloxy group, it is a C6-C24 aromatic group which may have a substituent, Specifically, a phenoxy group, p-tert- butylphenoxy group, 3-fluoro phenoxy group , 4-fluorophenoxy group and the like.

  Examples of halogen atoms include fluorine, chlorine, bromine, or iodine atoms.

  In the amine compound represented by the general formula (1), M represents a single bond, an arylene group, or a heteroarylene group. As an arylene group, a phenylene group, 1,4-naphthalenediyl group, 4,4′-biphenyldiyl group, 4,4′-terphenyldiyl group, 2,6-naphthalenediyl group, 9,10-anthracenediyl group 2,7-9,9′-dialkyl fluorenediyl group and the like. The heteroarylene group includes a 2,5-thiophenediyl group, a 5,5′-2,2′-bithiophenediyl group, a 4,7-benzothiadiazolediyl group, a 2,5-oxadiazolediyl group, Examples include 3,5-4-phenyl-triazole group, 2,6-pyridinediyl group, 6,6′-2,2′-bipyridinediyl group and the like.

  Furthermore, the substituent represented by the following general formula (2a)-(2f) which the aryl group connected can be illustrated.

(In the formula, R ³ represents a hydrogen atom, an alkyl or alkoxy group having 1 to 18 carbon atoms, or an aryl group having 6 to 12 carbon atoms. L, m, and n are positive integers satisfying 1 ≦ l + m + n ≦ 4. Represents.)
Specific examples of R ³ include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups and other alkyl groups, methoxy groups, Group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group, hexyloxy group, phenyl group, 4-methylphenyl group, 3- Methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 1- Examples thereof include aryl groups such as a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

Of the compounds represented by the general formula (1), an amine compound in which R ¹ and R ² are hydrogen atoms, preferably an amine compound represented by the following general formula (3) in which M is a single bond It is.

(In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group or heteroaryl group, and Ar ¹ and Ar ² may form a nitrogen-containing heterocycle together with the nitrogen atom to which Ar ¹ and Ar ² are bonded. Ar is a phenyl group, 4-methylphenyl group, 3,5-diphenylphenyl group, 1-naphthyl group, 4-biphenylyl group, 4-terphenylyl group, 9-anthryl group, 10-phenyl-9-anthryl group, Or represents a 10- (3,5-diphenylphenyl) -9-anthryl group.)
Among these, an amine compound in which Ar ¹ and Ar ² are a phenyl group, a 4-methylphenyl group, a 4-biphenylyl group, or a 1-naphthyl group is preferable.

  Although the specific example of the amine compound represented by the said General formula (1) to the following Tables 1-11 is shown, it is not limited to these compounds.

  The amine compound represented by the general formula (1) is represented by the general formula (4).

(Wherein R ^{1 and} R ² each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group, an aryl group, an aryloxy group, or a halogen atom, and Ar ¹ and Ar ² each represent Independently represents a substituted or unsubstituted aryl group or heteroaryl group, and Ar ¹ and Ar ² may form a nitrogen-containing heterocycle together with the nitrogen atom to which M is bonded, M is a single bond, an arylene group, or Represents a heteroarylene group, and Tf represents a trifluoromethanesulfonyl group.) And a fluorene derivative represented by the general formula (5)

(In the formula, Ar ³ represents a substituted or unsubstituted phenyl group, naphthyl group, biphenylyl group, terphenylyl group, anthryl group, fluorenyl group, or pyridyl group (excluding an amino-substituted product).
It can synthesize | combine by making the boronic acid compound represented by these react with a palladium catalyst.

  The fluorene derivative represented by the general formula (4) includes, for example, a Suzuki coupling reaction (see, for example, Chem. Rev. 1995, 95, p2457-2483) or an amination reaction using a palladium catalyst (the above-mentioned patent document). 15)).

(Wherein R ^{1 and} R ² are each independently a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group, an aryl group, an aryloxy group, or a halogen atom. Z represents protection of a phenolic hydroxyl group. The group is not particularly limited as long as it is used as a group, but is preferably a methoxyethoxymethyl group or a methoxymethyl group, and Ar ⁴ is a substituent represented by the following general formula (6).

(In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group or heteroaryl group, and Ar ¹ and Ar ² may form a nitrogen-containing heterocycle together with the nitrogen atom to which Ar ¹ and Ar ² are bonded. M represents a single bond, an arylene group, or a heteroarylene group.)
The palladium catalyst used in the amine compound synthesis reaction is not particularly limited. For example, palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium acetylacetonate (II), dichlorobis (Benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II) Divalent palladium compounds such as palladium trifluoroacetate (II), tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium chloroform complex (0), tetrakis (tri 0-valent palladium compounds such as E sulfonyl phosphine) palladium (0) and the like. Moreover, fixed palladium catalysts, such as a polymer fixed palladium catalyst and palladium carbon, can also be illustrated. These include monodentate aryl phosphines such as triphenylphosphine and tri (o-tolyl) phosphine, monodentate alkylphosphines such as tri (cyclohexyl) phosphine, tri (isopropyl) phosphine and tri (tert-butyl) phosphine, and 1,2-bis. Bidentate phosphines such as (diphenylphosphino) ethane, 1,2-bis (diphenylphosphino) propane, 1,2-bis (diphenylphosphino) butane and 1,2-bis (diphenylphosphino) ferrocene May be reacted.

  Although the usage-amount of a palladium catalyst is not specifically limited, Usually, it is the range of 0.000001-20 mol% with respect to 1 mol of fluorene derivatives represented by General formula (4). If the catalyst is within the above range, the amine compound can be synthesized with high selectivity, but from the viewpoint of reducing the amount of expensive catalyst used, a more preferable amount of catalyst used is 0 in terms of palladium with respect to 1 mole of fluorene derivative. The range is 0.0001 to 5 mol%.

  The base used in the amine compound synthesis reaction of the present invention may be selected from inorganic bases and / or organic bases, and is not particularly limited, but more preferably sodium hydroxide, potassium hydroxide, sodium carbonate. Alkaline metals such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide, etc. Alkoxide, triethylamine, tributylamine, and pyridine, and more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium phosphate, and sodium phosphate.

  The amount of the base used is preferably 0.5 moles or more based on the fluorene derivative represented by the general formula (4). If the amount of the base is less than 0.5 times mol, the yield of the amine compound may be low. Moreover, even if a base is added in large excess, the yield of the amine compound does not change, and the post-treatment operation after the completion of the reaction becomes complicated. Therefore, the more preferable amount of the base is in the range of 1 to 5 times mol. .

  The reaction in the present invention is usually carried out in the presence of an inert solvent. The solvent used is not particularly limited as long as it does not significantly inhibit this reaction, and is not limited to aromatic solvents such as benzene, toluene, xylene, diethyl ether, tetrahydrofuran (THF). And ether organic solvents such as dioxane, acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide, hexamethylphosphortriamide and the like. Of these, aromatic organic solvents such as benzene, toluene and xylene are more preferable.

  The reaction in the present invention can be carried out under normal pressure, under an inert gas atmosphere such as nitrogen or argon, or under pressure.

  The reaction in the present invention is carried out at a reaction temperature in the range of 20 to 300 ° C, more preferably in the range of 30 to 150 ° C.

  In the present invention, the reaction time is determined by the amount of fluorene derivative, arylboronic acid, base, palladium catalyst and reaction temperature, but may be selected from the range of several minutes to 72 hours.

  After completion of the reaction, the desired compound can be obtained by treatment according to a conventional method.

  Unlike conventional materials, many amine compounds of the present invention having a fluorene group as a nucleus have an amorphous structure at the time of synthesis, and thus have an advantage of excellent film stability. Therefore, it can be used not only as a hole transport material such as an organic EL element or an electrophotographic photosensitive member but also in any field of organic photoconductive materials such as a photoelectric conversion element, a solar cell, and an image sensor.

  The amine compound having the fluorene group represented by the above general formula (1) as a parent nucleus according to the present invention has a high Tg and many amorphous structures, so that it is compared with conventionally reported materials. The material is excellent in stability and durability, and can be used as a hole transport material such as an organic EL element or an electrophotographic photosensitive member, or a light emitting material.

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

  In addition, the measurement of the glass transition temperature shown by the following Example was performed on temperature rising conditions of 10 degree-C / min using Seiko Denshi Kogyo's SSC-5000.

¹ H-NMR and ¹³ C-NMR measurements were performed using Gemini 200 manufactured by Varian.

  The FDMS measurement was performed using M-80B manufactured by Hitachi, Ltd.

Synthesis example 1
Under a nitrogen stream, 0.82 g (34.2 mmol) of sodium hydride and 25 ml of THF were added to a 100 ml eggplant type flask, and the reaction solution was cooled to 0 ° C. 2,7-dibromo-4,4 ′-(9-fluorenylidene) -diphenol 6.5 g (14.3 mmol) in THF was added dropwise thereto, followed by 5.3 g (42.7 mmol) of 2-methoxyethoxymethyl chloride. ) Was added dropwise, and the mixture was stirred at room temperature for 12 hours, and 10 ml of methanol was added to decompose sodium hydride. Thereafter, 20 ml of toluene was added to separate the organic phase. After washing with water and saturated brine, the organic phase was concentrated. By recrystallizing the concentrated solution from ethanol, 7.7 g (yield) of 2,7-dibromo-9,9′-bis [4- (2-methoxyethoxymethoxy) phenyl] -9H-fluorene (intermediate A) was obtained. (Rate = 80%). Identification was performed by ¹ H-NMR and ¹³ C-NMR.

Melting point: 94-96 ° C
¹ H-NMR (CDCl ₃ ): δ = 7.42-7.57 (m, 6H), 7.06 (d, 4H, J = 8.8 Hz), 6.92 (d, 4H, J = 8) .8 Hz), 5.23 (s, 4H), 3.77-3.82 (m, 4H), 3.51-3.56 (m, 4H), 3.35 (s, 6H)
¹³ C-NMR (CDCl ₃ ): δ = 156.2, 153.4, 137.8, 137.6, 130.8, 129.2, 129.0, 121.7, 121.5, 116.1 93.4, 71.6, 67.7, 64.4, 59.0
Next, in a 100 ml eggplant-shaped flask equipped with a reflux condenser, 3 g (4.4 mmol) of 2,7-dibromo-9,9′-bis [4- (2-methoxyethoxymethoxy) phenyl] -9H-fluorene, 1.5 g (9.2 mmol) of diphenylamine, 1.01 g (10.6 mmol) of sodium-tert-butoxide and 20 ml of xylene were added under a nitrogen atmosphere. Thereafter, 4 mg of palladium acetate and 10 mg of tri-tert-butylphosphine were added, the temperature was raised to 120 ° C., the mixture was stirred at the same temperature for 3 hours, and then cooled to room temperature. 30 ml of water was added and the organic phase was separated and concentrated. As a result, 2.8 g (yield = 75%) of 2,7-bis (diphenylamino) -9,9′-bis [4- (2-methoxyethoxymethoxy) phenyl] -9H-fluorene (intermediate B) Was isolated. Identification was performed by ¹ H-NMR and ¹³ C-NMR.

¹ H-NMR (CDCl ₃ ): δ = 6.81-7.45 (m, 34H), 5.22 (s, 4H), 3.78-3.83 (m, 4H), 3.52- 3.57 (m, 4H), 3.36 (s, 6H)
¹³ C-NMR (CDCl ₃ ): δ = 155.8, 152.5, 147.6, 146.6, 139.0, 129.2, 129.0, 123.9, 123.3, 122.5 , 121.8, 120.0, 115.6, 93.5, 71.6, 67.6, 64.0, 59.0
To a reaction solution in which the obtained compound was dissolved in 20 ml of dichloromethane, 5 ml (30 mmol) of 6N-hydrochloric acid aqueous solution was added and reacted at room temperature for 5 hours, and then water was added to separate the organic phase. To the obtained organic phase, 1.03 g (13.0 mmol) of pyridine and 3.1 g (9.9 mmol) of trifluoromethanesulfonic anhydride were added and stirred at room temperature. By adding water and separating and concentrating the organic phase, the desired 2,7-bis (diphenylamino) -9,9′-bis [4- (trifluoromethanesulfonyloxy) phenyl] -9H-fluorene ( Intermediate C) was isolated. The target product was confirmed by FDMS.

FDMS; 948
Synthesis example 2
To a 100 ml eggplant-shaped flask equipped with a reflux condenser, 2,7-dibromo-9,9′-bis [4- (2-methoxyethoxymethoxy) phenyl] -9H-fluorene obtained in Synthesis Example 1 2.0 g (2.9 mmol), 1.70 g (5.9 mmol) of triphenylamine boronic acid, 9.4 g of 20% sodium carbonate, 10 mg of tetrakistriphenylphosphine and 15 ml of THF were added, and the mixture was heated to reflux for 5 hours. After stirring for a predetermined time, the reaction solution was cooled and the organic layer was separated. The organic layer is dried over anhydrous magnesium sulfate and then concentrated to give 2,7-bis (4-diphenylaminophenyl) -9,9′-bis [4- (2-methoxyethoxymethoxy) phenyl]- 9H-fluorene (Intermediate D) was isolated as 2.37 g pale yellow powder. Identification was performed by ¹ H-NMR and ¹³ C-NMR.

¹ H-NMR (CDCl ₃ ): δ = 7.77 (d, 2H), 7.54-7.58 (m, 4H), 7.44 (d, 4H, J = 8.8 Hz), 6. 97-7.29 (m, 28H), 6.90 (d, 4H, J = 8.8 Hz), 5.20 (s, 4H), 3.76-3.80 (m, 4H), 3. 49-3.54 (m, 4H), 3.33 (s, 6H)
¹³ C-NMR (CDCl ₃ ): δ = 155.9, 152.5, 147.5, 147.0, 139.9, 139.2, 138.4, 135.1, 129.2, 127.7 , 126.0, 124.3, 124.2, 123.8, 122.8, 120.3, 115.9, 93.4, 71.6, 67.6, 64.4, 59.0
As in Synthesis Example 1, 2,7-bis (4-diphenylaminophenyl) -9,9′-bis [4- (trifluoromethanesulfonyl) was treated with 6N-hydrochloric acid aqueous solution and trifluoromethanesulfonic anhydride. Oxy) phenyl] -9H-fluorene was isolated (intermediate E). The target product was confirmed by FDMS.

FDMS; 1100
Synthesis example 3
2,7-bis (diphenylamino) -9,9′-bis [4- (trifluoromethanesulfonyloxy) phenyl] according to Synthesis Example 1 except that 2-methoxyethoxymethyl chloride was changed to chloromethyl methyl ether -9H-fluorene (intermediate C) was isolated. The intermediate obtained in each reaction was identified by ¹ H-NMR and ¹³ C-NMR.
(1) 2,7-dibromo-9,9′-bis (4-methoxymethyloxyphenyl) -9H-fluorene
¹ H-NMR (CDCl ₃ ): δ = 7.44-7.59 (m, 6H), 7.06 (d, 4H, H = 8.8 Hz), 6.91 (d, 4H, J = 8) .8 Hz), 5.14 (s, 4H), 3.46 (s, 6H)
¹³ C-NMR (CDCl ₃ ): δ = 156.2, 153.4, 137.8, 137.6, 130.8, 129.3, 129.0, 121.8, 121.5, 116.1 , 94.3, 64.5, 56.1
(2) 2,7-bis (diphenylamino) -9,9'-bis (4-methoxymethyloxyphenyl) -9H-fluorene
¹ H-NMR (THF-d ₈ ): δ = 7.57 (d, 2H, J = 8.2 Hz), 6.78-7.22 (m, 32H), 5.09 (s, 4H), 3.38 (s, 6H)
¹³ C-NMR (THF-d ₈ ): δ = 156.9, 153.6, 148.5, 147.5, 139.5, 135.4, 129.7, 124.6, 123.8, 123 .3,122.4,120.8,116.2,95.0,64.9,55.8
(3) 2,7-bis (diphenylamino) -9,9′-bis (4-hydroxyphenyl) -9H-fluorene
¹ H-NMR (THF-d ₈ ): δ = 8.07 (br s, 2H), 7.55 (d, 2H, J = 8.2 Hz), 6.84-7.18 (m, 24H) 6.52 (d, 4H, J = 8.8 Hz).

¹³ C-NMR (THF-d ₈ ): δ = 157.1, 154.4, 148.7, 127.5, 137.2, 135.7, 129.9, 129.8, 124.7, 123 .9, 123.3, 122.9, 120.8, 115.4, 64.9
Synthesis Example 4 (2,7-di (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9'-bis (4-methoxymethyloxyphenyl) -9H -Synthesis of fluorene)
1,7-dibromo-9,9′-bis (4-methoxymethyloxyphenyl) -9H-fluorene 1 g (1.68 mmol), bis (pinacolato) diboron 0.94 g (3.70 mmol), dichlorobis (diphenylphosphino) ) 36.9 mmg of ferrocene palladium, 0.991 g of sodium acetate and 20 ml of DMF were added to a 100 ml eggplant-shaped flask under a nitrogen stream, and the mixture was heated and stirred at 80 ° C. overnight. After cooling, extraction with toluene was performed, and the obtained organic phase was washed twice with 20 ml of water. The organic phase was dried over anhydrous magnesium sulfate and after concentration, 1.1 g of 2,7-di (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9 '-Bis (4-methoxymethyloxyphenyl) -9H-fluorene (intermediate F) was synthesized. The identification was performed by FDMS, ¹ H-NMR and ¹³ C-NMR, and the target product was confirmed.

FDMS: 690
¹ H-NMR (THF-d ₈ ): δ = 7.76-7.84 (m, 6H), 7.07 (d, 4H, J = 8.8 Hz), 6.85 (d, 4H, J = 8.8 Hz), 5.08 (s, 4H), 3.37 (s, 6H), 1.29 (s, 24H)
¹³ C-NMR (THF-d ₈ ): δ = 157.20, 152.57, 143.50, 139.73, 134.84, 132.85, 129.88, 120.45, 116.46, 95 12, 84.36, 65.18, 55.92, 25.28.
Example 1 (Synthesis of Compound 1)
In a 50 ml eggplant type flask, 1.0 g (1.1 mmol) of the intermediate C obtained in Synthesis Example 1, 0.13 g (1.1 mmol) of phenylboronic acid, 5 g of 20% sodium carbonate, 20 mg of tetrakistriphenylphosphine palladium, 20 ml of THF And reacted under reflux for 2 hours. After cooling the reaction solution to room temperature, the upper organic layer was separated and concentrated, and the resulting concentrate was subjected to silica gel chromatography to isolate the desired product. FDMS and ¹³ C-NMR confirmed the target product. The obtained compound was an amorphous compound having no melting point and a glass transition temperature of 135 ° C.

FDMS: 804
¹³ C-NMR (CDCl ₃ ): 153.1, 148.7, 147.8, 145.7, 141.6, 140.3, 135.7, 129.9, 129.4, 127.8, 127 5, 127.4, 124.9, 124.1, 123.5, 122.7, 121.1, 65.7

Example 2 (Synthesis of Compound 23)
In a 50 ml eggplant-shaped flask, 1.2 g (1.1 mmol) of the intermediate E obtained in Synthesis Example 1, 0.13 g (1.1 mmol) of phenylboronic acid, 5 g of 20% sodium carbonate, 20 mg of tetrakistriphenylphosphine palladium, 20 ml of THF And reacted under reflux for 2 hours. After cooling the reaction solution to room temperature, the upper organic layer was separated and concentrated, and the resulting concentrate was subjected to silica gel chromatography to isolate the desired product. The target product was confirmed by FDMS. The glass transition temperature was 207 ° C. and an amorphous compound.

  FDMS: 956

Example 3 (Synthesis of Compound 3)
Compound 3 was isolated in the same manner as in Example 1 except that phenylboronic acid was changed to biphenylboronic acid. The compound was identified by FDMS.

  FDMS: 956

Example 4 (Synthesis of Compound 4)
Compound 4 was isolated in the same manner as in Example 1 except that phenylboronic acid was changed to terphenylboronic acid. The compound was identified by FDMS.

  FDMS: 1108

Example 5 (Synthesis of Compound 5)
Compound 5 was isolated in the same manner as in Example 1 except that phenylboronic acid was changed to 9-anthrylboronic acid. The compound was identified by FDMS.

  FDMS: 1004

Examples 6 to 12 (Synthesis of compounds 9, 10, 12, 15, 21, 22, and 78)
According to Synthesis Example 1 and Example 1, compounds 9, 10, 12, 15, 21, 22, and 78 were respectively synthesized. Table 12 summarizes the glass transition temperature of each compound.

Example 13 (Synthesis of Compound 23)
Into a 50 ml eggplant-shaped flask, 2,7-di (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9′-bis (obtained in Synthesis Example 4) 4-methoxymethyloxyphenyl) -9H-fluorene 1 g (1.45 mmol) (intermediate F) and bromotriphenylamine 0.94 g (2.90 mmol), 20% sodium carbonate 4 g, tetrakistriphenylphosphine palladium 20 mg, THF 20 ml And allowed to react for 8 hours under reflux. After cooling the reaction solution to room temperature, the upper organic layer was separated and concentrated, and the resulting concentrate was subjected to silica gel chromatography to isolate the desired product. It was confirmed by FDMS that it was 2,7-bis (4-diphenylaminophenyl) -9,9′-bis (4-methoxymethyloxyphenyl) -9H-fluorene (intermediate G).

FDMS: 924
According to Synthesis Example 1 and Example 1, hydrochloric acid treatment, trifluoromethanesulfonylation, and coupling treatment were performed to synthesize Compound 23. Identification was performed by FDMS.

FDMS: 956
Example 14 (Synthesis of Compound 40)
Except that bromotriphenylamine was changed to 4′-di (p-tolyl) amino-4-bromobiphenyl, the same operation as in Example 13 was performed, and 2,7-bis [4′-di (p-tolylamino) was obtained. Biphenyl-4-yl) -9,9'-bis (4-methoxymethyloxyphenyl) -9H-fluorene was obtained. The same treatment as in Example 13 was performed to give compound 40. Identification was performed by FDMS.

FDMS: 1164
Example 15 (Synthesis of Compound 51)
Except that bromotriphenylamine was changed to 7-di (p-tolyl) amino-9,9′-dimethyl-2-bromofluorene, the same operation as in Example 13 was carried out, and 2,7-bis [7-di (P-Tolyl) amino-9,9′-dimethylfluoren-2-yl) -9,9′-bis (4-methoxymethyloxyphenyl) -9H-fluorene was obtained. The same treatment as in Example 13 was performed to give compound 51. Identification was performed by FDMS.

FDMS: 1244
Example 16 (Synthesis of Compound 62)
The same procedure as in Example 13 was performed, except that bromotriphenylamine was changed to 7-[(4-di-p-tolylamino) phenyl] -4-bromo-2,1,3-benzothiadiazole, and 2,7 -Bis (7- (4-di-p-tolylamino) phenyl-2,1,3-benzothiadiazol-4-yl) -9,9'-bis (4-methoxymethyloxyphenyl) -9H-fluorene is obtained It was. The same treatment as in Example 13 was performed to give compound 62. Identification was performed by FDMS.

FDMS: 1280
Example 17 (Synthesis of Compound 34)
Into a 50 ml eggplant-shaped flask, 2,7-di (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9′-bis (obtained in Synthesis Example 4) 4-methoxymethyloxyphenyl) -9H-fluorene (intermediate F) 5.18 g (7.50 mmol) and 4-bromo-4 ′-(diphenylamino) biphenyl 5.70 g (14.3 mmol), 20% sodium carbonate 30 g, dichlorobis (diphenylaminophenylferrocene) palladium 233 mg, and THF 60 ml were added, and the mixture was reacted overnight under reflux. After cooling the reaction solution to room temperature, the upper organic layer was separated and concentrated, and the resulting concentrate was subjected to silica gel chromatography to isolate the desired product. It was confirmed by ¹³ C-NMR and FDMS that it was 2,7-bis (4-diphenylaminobiphenyl) -9,9′-bis (4-methoxymethyloxyphenyl) -9H-fluorene (intermediate H).

¹³ C-NMR (THF-d ₈ ): 157.14, 153.66, 148.47, 148.07, 140.84, 140.16, 140.09, 139.83, 139.72, 135.29 , 129.87, 129.81, 128.09, 127.89, 127.32, 126.90, 124.98, 124.56, 123.59, 121.26, 116.47, 94.99, 65 .36, 55.82
FDMS: 1076
Next, 6N-hydrochloric acid aqueous solution was added dropwise at room temperature to 60 ml of the obtained intermediate H in THF solution, and then stirred at 40 ° C. overnight. After completion of the reaction, 50 ml of toluene was added for extraction, and further washed with 30 ml of water three times. The organic layer was dried over magnesium sulfate and concentrated. Further, the obtained concentrated liquid, 2.99 g (10.6 mmol) of trifluoromethanesulfonic anhydride, 3.82 g (48.3 mmol) of pyridine and 50 ml of toluene were charged and stirred overnight at room temperature, followed by ordinary treatment. And the corresponding sulfonic acid ester was obtained. Finally, the compound 34 was synthesized by reacting with phenylboronic acid in the presence of a tetrakistriphenylphosphine palladium catalyst. Identification was performed by FDMS, ¹ H-NMR and ¹³ C-NMR. The glass transition temperature was 183 ° C.

Moreover, when the element of the compound 34 which has a film thickness of 1.2 micrometers on an ITO electrode by vacuum evaporation was produced and the mobility was measured by Time of Flight method (TOF-301 by Optel), hole mobility = ^{Bipolarity of} 1 × 10 ⁻³ cm ² / V · s and electron mobility = 4 × 10 ⁻⁴ cm ² / V · s was exhibited. From this, it confirmed that it could be used as a luminescent material.

FDMS: 1108
¹ H-NMR (THF-d ₈ ): 7.9 (d, 2H, J = 8 Hz), 6.97-7.87 (m, 48H)
¹³ C-NMR (THF-d ₈ ): 153.0, 148.47, 148.07, 145.78, 141.39, 141.02, 140.31, 140.18, 140.09, 139.92 , 135.27, 129.81, 129.38, 129.23, 128.08, 127.89, 127.67, 127.51, 127.34, 127.12, 125.16, 124.98, 124. 56, 123.52, 121.34, 66.13
Example 18 (Synthesis of Compound 37)
Compound 37 was synthesized in the same manner as in Example 17 except that phenylboronic acid was changed to 9-anthraceneboronic acid. Identification was performed by FDMS.

FDMS: 1308
Example 19 (Synthesis of Compound 38)
Compound 38 was synthesized in the same manner as in Example 17, except that phenylboronic acid was changed to 10-phenyl-9-anthraceneboronic acid. Identification was performed by FDMS.

FDMS: 1406
Example 20 (Synthesis of Compound 39)
Compound 39 was synthesized in the same manner as in Example 17, except that phenylboronic acid was changed to 2-9,9′-dimethylfluoreneboronic acid. Identification was performed by FDMS.

FDMS: 1340
Comparative Examples 1-3
In the compound 1 shown in Example 1, a compound having a p-methoxyphenyl group, a benzyl group and an n-octyl group at the 9,9′-position of the fluorene group was synthesized according to the following reaction route, and its melting point and glass transition temperature. Was measured by differential thermal analysis. Table 13 shows the melting point and glass transition temperature of Compound 1 described in Example 1 together. The compounds of Comparative Examples 1 to 3 were crystalline compounds having a clear melting point, and the glass transition temperature was 110 ° C. or lower. On the other hand, Compound 1 was an amorphous substance having a glass transition temperature of 135 ° C. that did not show a clear melting point. FIG. 1 shows a suggested thermal analysis chart of each compound.

Example 21
The compound 1 obtained in Example 1 and 20 mg of the compounds of Comparative Examples 1 to 3 were each dissolved in 2 ml of toluene to prepare a 1% solution. A thin film was prepared on a quartz substrate by spin coating method (rotating condition = 1000 rpm (1 minute), vacuum heating condition = 60 ° C. (1 hour) vacuum heating), and left at room temperature (1 month) to leave the thin film cloudy (Or aggregation) was observed. As a result, no cloudiness was observed for the thin film of Compound 1. On the other hand, some of the compounds of Comparative Examples 1 to 3 were found cloudy.

Example 22
Using a glass substrate on which an ITO electrode (anode) subjected to acetone, ion-exchanged water, isopropyl alcohol boiling liquid, and UV-ozone cleaning in sequence was formed, compound 1 was deposited on the ITO anode at a deposition rate of 4 angstroms / second and a film thickness of 40 nm. Until the hole transport layer was formed. Next, tris (8-quinolinolato) aluminum was deposited on the compound 1 at a deposition rate of 4 angstroms / second to a film thickness of 50 nm to form an electron transport / light emitting layer. Next, magnesium and silver were co-evaporated on tris (8-quinolinolato) aluminum at an atomic ratio of 10: 1 (= Mg: Ag) to a film thickness of 150 nm, a cathode was formed, and an organic electroluminescence device was produced. Each thin film was laminated at a vacuum degree of 1.0 × 10 ⁻⁵ Torr by a vacuum deposition method.

The organic EL device fabricated in this manner exhibited a luminance of 500 cd / m ² at a current density of 8 mA / cm ² and a voltage of 7 V. The device was held at 90 ° C. for 100 hours under vacuum, and the current-luminance characteristics were measured. As a result, almost no change was observed.

Comparative Example 4
An organic electroluminescence device was produced in the same manner as in Example 22 except that the compounds of Comparative Examples 1 to 3 were used in the hole transport layer instead of the compound 1 synthesized in Example 1. The device was held at 90 ° C. for 100 hours under vacuum, and then the current-luminance characteristics were measured. As a result, the luminance deteriorated faster than the device of Example 22 for the same current.

It is a chart of the suggestion thermal analysis of the compound obtained in Example 1 and Comparative Examples 1-3.

Claims (12)

An amine compound represented by the general formula (1).

(Wherein R ^{1 to} R ² each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group, an aryl group, an aryloxy group, or a halogen atom, and Ar ^{1 to} Ar ² each represents Independently represents a heteroaryl group , or an aromatic group having 6 to 24 carbon atoms which may have a methyl group, a phenyl group or a diphenylamino group , and forms a nitrogen-containing heterocycle together with the nitrogen atom to which it is bonded. Ar ³ each independently has a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a phenyl group, a phenoxy group, and a pyridyl group. Or a phenyl group, a naphthyl group, a biphenylyl group, a terphenyl group, an anthryl group, a fluorenyl group, or a pyridyl group (excluding an amino-substituted product). M represents a single bond, an arylene group, or a heteroarylene group.) The general formula (1), wherein at least one of Ar ¹ and Ar ² is a naphthyl group, a phenanthryl group, a fluorenyl group, an anthryl group, a pyrenyl group, a chrysenyl group, a picenyl group, or a perylenyl group. The amine compound according to 1. In general formula (1), Ar < ¹ > and Ar < ² > are respectively independently a phenyl group, 4-methylphenyl group, or 4-biphenylyl group, The amine compound of Claim 1 characterized by the above-mentioned. In the general formula (1), Ar ³ is a phenyl group, 3,5-diphenylphenyl group, 1-naphthyl group, 4-biphenylyl group, 4-terphenylyl group, 9-anthryl group, 10-phenyl-9-anthryl group, Or an amine compound according to any one of claims 1 to 3, which is a 10- (3,5-diphenylphenyl) -9-anthryl group. In the general formula (1), M is a phenylene group, 1,4-naphthalenediyl group, 2,6-naphthalenediyl group, 4,4′-biphenyldiyl group, 4,4′-terphenyldiyl group, 9,10 The amine compound according to any one of claims 1 to 4, which is an anthracenediyl group or a 2,7-9,9'-dialkylfluorenediyl group. In general formula (1), M is the following general formula (2a)-(2f), The amine compound of any one of Claims 1 thru | or 4 characterized by the above-mentioned.

(In the formula, R ³ represents a hydrogen atom, an alkyl or alkoxy group having 1 to 18 carbon atoms, or an aryl group having 6 to 12 carbon atoms. L, m, and n are positive integers satisfying 1 ≦ l + m + n ≦ 4. Represents.) The amine compound according to any one of claims 1 to 6, wherein R ¹ and R ² are hydrogen atoms. An amine compound represented by the following general formula (3).

(In the formula, Ar ¹ and Ar ² each independently represent a phenyl group, a 4-methylphenyl group, a 4-biphenylyl group, or a 1-naphthyl group, and Ar ¹ and Ar ² are contained together with the nitrogen atom to which they are bonded. A nitrogen heterocycle may be formed, Ar is a phenyl group, 4-methylphenyl group, 3,5-diphenylphenyl group, 1-naphthyl group, 4-biphenylyl group, 4-terphenylyl group, 9-anthryl group, 10 -Represents a phenyl-9-anthryl group or a 10- (3,5-diphenylphenyl) -9-anthryl group.) The amine compound according to claim 1, which has an amorphous structure. 8. The fluorene derivative represented by the following general formula (4) and the arylboronic acid represented by the following general formula (5) are reacted in the presence of a palladium catalyst. A method for producing an amine compound according to 1.

(Wherein R ^{1 and} R ² each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group, an aryl group, an aryloxy group, or a halogen atom, and Ar ¹ and Ar ² each represent Independently represents a heteroaryl group or an aryl group having 6 to 24 carbon atoms, and Ar ¹ and Ar ² may form a nitrogen-containing heterocycle together with the nitrogen atom to which M is bonded, M is an arylene group or heteroarylene; And Tf represents a trifluoromethanesulfonyl group.)

(In the formula, Ar ³ is a phenyl group which may have a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a phenyl group, a phenol group and a phenoxy group; A naphthyl group, a biphenylyl group, a terphenyl group, an anthryl group, a fluorenyl group, or a pyridyl group (however, an amino-substituted product is excluded). The fluorene derivative represented by the following general formula (4) and the arylboronic acid represented by the following general formula (5) are reacted in the presence of a palladium catalyst. A method for producing an amine compound according to 1.

(Wherein R ^{1 and} R ² each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group or alkoxy group, an aryl group, an aryloxy group, or a halogen atom, and Ar ¹ and Ar ² each represent Independently represents a heteroaryl group or an aryl group having 6 to 24 carbon atoms, Ar ¹ and Ar ² may form a nitrogen-containing heterocycle together with the nitrogen atom to which M is bonded, M represents a single bond, and Tf Represents a trifluoromethanesulfonyl group.)

(In the formula, Ar ³ is a phenyl group which may have a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a phenyl group, a phenol group and a phenoxy group; A naphthyl group, a biphenylyl group, a terphenyl group, an anthryl group, a fluorenyl group, or a pyridyl group (however, an amino-substituted product is excluded). 10. An organic electroluminescence device using the amine compound according to claim 1 in any one of a light emitting layer, a hole transport layer, and a hole injection layer.

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