Aniline derivatives and uses thereof

Abstract

Aniline derivatives such as those represented by the formula shown, for example, have good solubility with respect to organic solvents, and are able to provide an organic electroluminescent element having excellent luminance characteristics when a thin film containing said aniline derivatives is used as a charge transporting substance in a hole injection layer. ##STR00001##
(In the formula, DPA represents a diphenylamino group.)

Claims

1. An aniline derivative represented by the formula (1) or (2): ##STR00214## wherein R.sup.1 and R.sup.2 independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, Ph.sup.1 represents a group represented by the formula (P1): ##STR00215## wherein R.sup.3 to R.sup.6 independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, Ar.sup.1 independently represents a group represented by any of the formulas (B1) to (B11): ##STR00216## ##STR00217## ##STR00218## wherein R.sup.7 to R.sup.27, R.sup.30 to R.sup.51 and R.sup.53 to R.sup.154 independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a diphenylamino group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, R.sup.28 and R.sup.29 independently represent an aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z.sup.1, R.sup.52 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms or alkynyl group having 2 to 20 carbon atoms which may be substituted with Z.sup.4, or an aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z.sup.1, Ar.sup.4 independently represents an aryl group having 6 to 20 carbon atoms which may be substituted with a di(aryl groups having 6 to 20 carbon atoms)amino group, Z.sup.1 represents a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms or alkynyl group having 2 to 20 carbon atoms which may be substituted with Z.sup.2, Z.sup.2 represents a halogen atom, a nitro group, a cyano group, or an aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z.sup.3, Z.sup.3 represents a halogen atom, a nitro group or a cyano group, Z.sup.4 represents a halogen atom, a nitro group, a cyano group, or an aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z.sup.5, and Z.sup.5 represents a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms or alkynyl group having 2 to 20 carbon atoms which may be substituted with Z.sup.3, Ar.sup.2 independently represents a group represented by any of the formulas (A1) to (A5) or (A7) to (A12) or (A14) to (A18): ##STR00219## ##STR00220## ##STR00221## wherein R.sup.155 represents an hydrogen atom or an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms or alkynyl group having 2 to 20 carbon atoms which may be substituted with Z.sup.4, or an aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z.sup.1, R.sup.156 and R.sup.157 independently represent an aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z.sup.1, DPA represents a diphenylamino group, and Ar.sup.4, Z.sup.1 and Z.sup.3 to Z.sup.5 have the same meanings as above, Ar.sup.3 represents a group represented by any of the formulas (C2) to (C8): ##STR00222## ##STR00223## letter k represents an integer of 1 to 10, and letter l represents 1 or 2.

2. The aniline derivative of claim 1, wherein Ar.sup.1 is a group represented by any of the formulas (B1) to (B11): ##STR00224## ##STR00225## ##STR00226## wherein R.sup.7 to R.sup.154 and Ar.sup.4 have the same meanings as above, and Ar.sup.3 is a group represented by any of the formulas (C2) to (C8): ##STR00227## ##STR00228## wherein DPA has the same meaning as above.

3. The aniline derivative of claim 1 or 2, wherein the R.sup.3 to R.sup.6, R.sup.7 to R.sup.27, R.sup.30 to R.sup.51 and R.sup.53 to R.sup.154 are each a hydrogen atom.

4. The aniline derivative of claim 1, represented by the formula (1-1): ##STR00229## wherein Ar.sup.5 simultaneously represent a group represented by any of the formulas (D1), (D2), (D4) to (D9), or (D11) to (D13), and Ph.sup.1 and letter k have the same meanings as above: ##STR00230## ##STR00231## ##STR00232## wherein R.sup.52, R.sup.156, R.sup.157, A.sup.4 and DPA have the same meanings as above.

5. The aniline derivative of claim 1, represented by the formula (1-3), (1-4), (1-9) or (1-10): ##STR00233## wherein Ar.sup.51 represents a group represented by the formula (F1-1), Ar.sup.52 represents a group represented by the formula (F2-1), Ar.sup.71 represents a group represented by the formula (F2-2), Ar.sup.72 represents a group represented by the formula (F1-2), and Ph.sup.1, Ar.sup.1 and letter k have the same meanings as above: ##STR00234## wherein Cb.sup.155 represents an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms or alkynyl group having 2 to 20 carbon atoms which may be substituted with Z.sup.4, or an aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z.sup.1, and Z.sup.1, Z.sup.4 and Ar.sup.4 have the same meanings as above.

6. The aniline derivative of claim 1, represented by the formula (1-5), (1-6), (1-11) or (1-12): ##STR00235## wherein Ar.sup.51 represents a group represented by the formula (F1-1), Ar.sup.52 represents a group represented by the formula (F2-1), Ar.sup.71 represents a group represented by the formula (F2-2), Ar.sup.72 represents a group represented by the formula (F1-2), and Ph.sup.1 and letter k have the same meanings as above: ##STR00236## wherein Cb.sup.155 represents an alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms or alkynyl group having 2 to 20 carbon atoms which may be substituted with Z.sup.4, or an aryl group having 6 to 20 carbon atoms or heteroaryl group having 2 to 20 carbon atoms which may be substituted with Z.sup.1, and Z.sup.1, Z.sup.4 and Ar.sup.4 have the same meanings as above.

7. A charge transporting substance comprising the aniline derivative of claim 1.

8. A charge transporting material comprising the charge transporting substance of claim 7.

9. A charge transporting varnish comprising the charge transporting substance of claim 7 and an organic solvent.

10. The charge transporting varnish of claim 9, further comprising a dopant substance.

11. The charge transporting varnish of claim 10, wherein the dopant substance includes at least one selected from halotetracyanoquinodimethanes and benzoquinone derivatives.

12. The charge transporting varnish of claim 11, wherein the dopant substance further includes a heteropoly-acid compound.

13. The charge transporting varnish of claim 9, further comprising an organic silane compound.

14. A charge transporting thin film produced by use of the charge transporting varnish of claim 9.

15. A charge transporting thin film produced by a vapor deposition method using the aniline derivative of claim 1.

16. An organic electroluminescence element comprising the charge transporting thin film of claim 14 or 15.

17. An organic electroluminescence element of claim 16, wherein the charge transporting thin film is a hole injection layer, a hole transport layer or a hole injection transport layer.

Description

EXAMPLES

(1) The present invention will be described more specifically below by showing Preparation Examples and Examples, but the present invention is not to be limited to the following Examples. Note that the apparatuses used are as follows. (1) MALDI-TOF-MS: autoflex III smartbeam, manufactured by Bruker Corporation. (2) .sup.1H-NMR: JNM-ECP300 FT NMR SYSTEM, manufactured by JEOL Ltd. (3) Substrate cleaning: Substrate cleaning equipment (reduced pressure plasma system), manufactured by Choshu Industry Co., Ltd. (4) Coating with varnish: Spin coater MS-A100, manufactured by Mikasa Co., Ltd. (5) Film thickness measurement: Microfigure measuring instrument SURFCORDER ET-4000, manufactured by Kosaka Laboratory Ltd. (6) Production of EL element: Multi-functional deposition apparatus system C-E2L1G1-N, manufactured by Choshu Industry Co., Ltd. (7) Measurement of luminance of EL element: I-V-L measuring system, manufactured by limited liability company Tech-world. (8) Measurement of life (measurement of half-life) of EL element: Organic El luminance life evaluation system PEL-105S, manufactured by EHC Co., Ltd.

[1] Synthesis of Compound

Preparation Example 1

(2) ##STR00175##
(In the formula, DPA represents a diphenylamino group, here and hereafter.)

(3) A flask was charged with 1.94 g of N1,N1-(1,4-phenylene)bis(N4-phenylbenzene-1,4-diamine), 4.68 g of 4-bromo-N,N-diphenylaniline, 75.3 mg of Pd(dba).sub.2, and 1.69 g of t-butoxysodium, and the atmosphere in the flask was replaced with nitrogen. Into the flask were put 30 mL of toluene and 1.3 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 40.5 g/L), followed by stirring at 50 C. for 4.5 hours.

(4) After the stirring was over, the reaction mixture was cooled to room temperature, toluene was added thereto, filtration was conducted, the resulting filtrate was mixed with saturated saline, and liquid separation treatment was conducted. To the organic layer thus obtained was added 0.2 g of activated carbon, followed by stirring at room temperature for 30 minutes.

(5) Thereafter, the activated carbon was removed by filtration, and the filtrate was condensed. Then, the thus condensed liquid was mixed with the filter cake obtained upon the filtration of the reaction mixture, the resulting mixture was mixed with toluene/tetrahydrofuran mixed solvent and ion-exchanged water, and a liquid separation treatment was performed. The organic layer thus obtained was dried with sodium sulfate and then condensed, the condensed liquid was added dropwise to methanol/ethyl acetate mixed solvent (300 mL/200 mL), and the slurry thus obtained was stirred at room temperature.

(6) Finally, the slurry was filtered, and the resulting filter cake was dried, to obtain a desired aniline derivative 1 (amount 4.72 g, yield 76%).

(7) MALDI-TOF-MS m/Z found: 1414.17 ([M].sup.+calcd: 1414.63).

Preparation Example 2

(8) ##STR00176##

(9) A flask was charged with 1.00 g of N1,N1-([1,1-biphenyl]-4,4-diyl)bis(N4-phenylbenzene-1,4-diamine), 3.13 g of 4-bromo-N,N-diphenylaniline, 44.8 mg of Pd(dba).sub.2 and 1.13 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 20 mL of toluene and 0.73 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 43 g/L), followed by stirring at 50 C. for one hour and at 40 C. for 12 hours.

(10) After the stirring was over, the reaction mixture was cooled to room temperature, the thus cooled reaction mixture was mixed with chloroform and ion-exchanged water, and a liquid separation treatment was conducted. The organic layer thus obtained was dried with sodium sulfate, and 0.5 g of activated carbon was added to the dried organic layer, followed by stirring overnight at room temperature.

(11) Thereafter, the activated carbon was removed by filtration, the filtrate was condensed, the condensed liquid obtained was added dropwise to methanol/ethyl acetate mixed solvent (400 mL/200 mL), and the resulting slurry was stirred at room temperature for three hours.

(12) Finally, the slurry was filtered, and the filter cake obtained was dried, to obtain a desired aniline derivative 2 (amount 2.69 g, yield 94%).

(13) .sup.1H-NMR (300 MHz, THF-d6) [ppm]: 7.46 (d, J=8.6 Hz, 4H), 7.18 to 7.24 (m, 19H), and 6.92 to 7.12 (m, 55H).

Preparation Example 3

(14) ##STR00177##

(15) A flask was charged with 3.00 g of N1-(4-((4-((4-diphenylamino)phenyl)amino)phenyl)amino)phenyl)-N4,N4-dihenylbenzene-1,4-diamine, 7.09 g of 4-bromo-N,N-diphenylaniline, 75.1 mg of Pd(dba).sub.2, and 2.54 g of t-butoxysodium, and the atmosphere in the flask was replaced by nitrogen. Into the flask were put 50 mL of toluene and 1.3 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 40.5 g/L), followed by stirring at 50 C. for 15 hours.

(16) After the stirring was over, the reaction mixture was cooled to room temperature, followed by filtration, then the filtrate was mixed with toluene and saturated saline, and a liquid separation treatment was conducted (twice). The organic layer thus obtained was dried with sodium sulfate, and 0.5 g of activated carbon was added to the dried organic layer, followed by stirring at room temperature for 30 minutes.

(17) Thereafter, the activated carbon was removed by filtration, the filtrate was condensed, then the condensed liquid was added dropwise to methanol/ethyl acetate mixed solvent (300 mL/200 mL), and the resulting slurry was stirred at room temperature for 30 minutes.

(18) Finally, the slurry was filtered, the filter cake obtained was dried, to obtain a desired aniline derivative 3 (amount 5.95 g, yield 96%).

(19) .sup.1H-NMR (300 MHz, THF-d6) [ppm]: 7.17 to 7.27 (m, 22H), and 6.91 to 7.05 (m, 56H).

(20) MALDI-TOF-MS m/Z found: 1414.04 ([M].sup.+calcd: 1414.63).

Preparation Example 4

(21) ##STR00178##

(22) A flask was charged with 2.00 g of N1,N1-((1,4-phenylenebis(azanediyl))bis(4,1-phenylene))-bis(N4,N4-diphenylbenzene-1,4-diamine), 4.17 g of 4-bromo-N,N-diphenylaniline, 59.3 mg of Pd(dba).sub.2 and 1.50 g of t-butoxysodium, and the atmosphere in the flask was replaced by nitrogen. Into the flask were put 20 mL of toluene and 1.0 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 43 g/L), followed by stirring at 50 C. for one hour and at 40 C. for 12 hours.

(23) After the stirring was over, the reaction mixture was cooled to room temperature, followed by filtration, the filtrate was mixed with saturated saline, and a liquid separation treatment was conducted. The organic layer thus obtained was dried with sodium sulfate, and 0.5 g of activated carbon was added to the dried organic layer, followed by stirring at room temperature for 30 minutes.

(24) Thereafter, the activated carbon was removed by filtration, the filtrate was condensed, the thus condensed liquid was added dropwise to methanol/ethyl acetate mixed solvent (300 mL/200 mL), and the resulting slurry was stirred at room temperature.

(25) Finally, the slurry was filtered, and the filter cake obtained was dried, to obtain a desired aniline derivative 4 (amount 4.37 g, yield 97%).

(26) .sup.1H-NMR (300 MHz, THF-d6) [ppm]: 7.16 to 7.21 (m, 24H), and 6.90 to 7.04 (m, 72H).

Preparation Example 5

(27) ##STR00179##

(28) A flask was charged with 3.00 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, 3.1 mL of 1-bromonaphthalene, 75.5 mg of Pd(dba).sub.2 and 2.53 g of t-butoxysodium, and the atmosphere in the flask was replaced by nitrogen. Into the flask were put 40 mL of toluene and 1.3 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 42.6 g/L), followed by stirring at 50 C. for four hours.

(29) After the stirring was over, the reaction mixture was cooled to room temperature, followed by filtration, and the filtrate was mixed with toluene and saturated saline, followed by a liquid separation treatment (twice). The organic layer thus obtained was dried with sodium sulfate, and 0.5 g of activated carbon was added to the dried organic layer, followed by stirring at room temperature for 30 minutes.

(30) Thereafter, the activated carbon was removed by filtration, the filtrate was condensed, the condensed liquid was added dropwise to methanol/ethyl acetate mixed solvent (300 mL/200 mL), and the resulting slurry was stirred at room temperature for one hour.

(31) Finally, the slurry was filtered, and the filter cake obtained was dried, to obtain a desired aniline derivative 5 (amount 4.21 g, yield 90%).

(32) .sup.1H-NMR (300 MHz, THF-d6) [ppm]: 7.95 to 8.00 (m, 4H), 7.82 to 7.86 (m, 4H), 7.69 to 7.73 (m, 4H), 7.28 to 7.46 (m, 15H), and 6.80 to 7.00 (m, 30H).

(33) MALDI-TOF-MS m/Z found: 1063.39 ([M].sup.+calcd: 1063.46).

Preparation Example 6

(34) ##STR00180##

(35) A flask was charged with 3.01 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, 5.63 g of 9-bromophenanthrene, 76.0 mg of Pd(dba).sub.2 and 2.54 g of t-butoxysodium, and the atmosphere in the flask was replaced by nitrogen. Into the flask were put 40 mL of toluene and 1.3 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 42.6 g/L), followed by stirring at 50 C. for six hours.

(36) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with tetrahydrofuran and toluene and with ion-exchanged water, and a liquid separation treatment was conducted. From the organic layer thus obtained, the solvent was distilled off at reduced pressure, the solid matter thus obtained was mixed with tetrahydrofuran/toluene/ethyl acetate mixed solvent (40 g/5 g/5 g) and 0.5 g of activated carbon, and the resulting mixture was stirred at 60 C. for 30 minutes.

(37) Thereafter, the activated carbon was removed by hot filtration, the filtrate was cooled to 0 C. with stirring, to which 25 mL of methanol and 2 mL of ethyl acetate were added sequentially, and the resulting slurry was stirred further at 0 C. for two hours.

(38) Finally, the slurry was filtered, and the filter cake obtained was dried, to obtain a desired aniline derivative 6 (amount 4.75 g, yield 89%).

(39) .sup.1H-NMR (300 MHz, THF-d6) [ppm]: 8.70 to 8.78 (m, 6H), 8.09 to 8.12 (m, 3H), 7.75 to 7.79 (m, 3H), 7.44 to 7.65 (m, 14H), 7.06 to 7.21 (m, 12H), and 6.84 to 6.99 (m, 25H).

(40) MALDI-TOF-MS m/Z found: 1213.52 ([M].sup.+calcd: 1213.51).

Preparation Example 7

(41) ##STR00181##

(42) A flask was charged with 2.00 g of N1,N1-((1,4-phenylenebis(azanediyl)bis(4,1-phenylene)bis-(N4,N4-diphenylbenzene-1,4-diamine), 3.17 g of 9-bromophenanthrene, 59.2 mg of Pd(dba).sub.2 and 1.44 g of tertiary-butoxysodium, and the atmosphere in the flask was replaced by nitrogen. Into the flask were put 20 mL of toluene and 0.880 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 47.2 g/L), followed by stirring at 50 C. for 6.5 hours.

(43) After the stirring was over, the reaction mixture was cooled to room temperature, followed by filtration, the filter cake was washed sequentially with ion-exchanged water and methanol.

(44) Finally, the washed filter cake was dried, to obtain a desired aniline derivative 7 (amount 3.24 g, yield 85%).

(45) .sup.1H-NMR (300 MHz, DMSO-d6) [ppm]: 8.75 to 8.86 (m, 7H), 7.81 to 8.00 (m, 7H), 7.47 to 7.70 (m, 18H), 7.12 to 7.28 (m, 16H), and 6.78 to 6.94 (m, 28H).

Preparation Example 8

(46) ##STR00182##

(47) A flask was charged with 2.00 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, 2.79 g of 2-bromodibenzo[b,d]thiophene, 50.3 mg of Pd(dba).sub.2, and 1.21 g of t-butoxysodium, and the atmosphere in the flask was replaced by nitrogen. Into the flask were put 20 mL of toluene and 0.750 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 47.2 g/L), followed by stirring at 50 C. for seven hours.

(48) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with toluene and saturated saline, and a liquid separation treatment was conducted. The organic layer thus obtained was dried with sodium sulfate, and then 0.2 g of activated carbon was added to the dried organic layer, followed by stirring at room temperature for 30 minutes.

(49) Thereafter, the activated carbon was removed by filtration, the solvent was distilled off from the filtrate at reduced pressure, and the thus obtained residue was dissolved in 20 mL of toluene. The solution obtained was added dropwise to methanol/ethyl acetate mixed solvent (300 mL/200 mL), the resulting slurry was stirred at room temperature, and then the slurry was filtered to recover the filter cake. By use of a solution obtained by dissolving the resulting filter cake in 20 mL of toluene, the operation from dropwise addition to the mixed solvent to the recovery of the filter cakes was performed in the same manner as above.

(50) Finally, the recovered filter cake was dried, to obtain a desired aniline derivative 8 (amount 3.23 g, yield 90%).

(51) .sup.1H-NMR (300 MHz, DMSO-d6) [ppm]: 8.19 (d, J=7.8 Hz, 3H), 8.05 (s, 3H), 7.91 to 8.00 (m, 6H), 7.42 to 7.51 (m, 6H), 7.24 to 7.29 (m, 11H), and 6.94 to 7.04 (m, 28H).

Preparation Example 9

9-1

(52) A flask was charged with 10.0 g of 3-bromocarbazole, 1.75 g of sodium hydroxide, and 100 mL of N,N-dimethylformamide, and the atmosphere in the flask was replaced by nitrogen. To the flask, 7.42 g of benzyl bromide was added dropwise, followed by stirring at room temperature for 19 hours, then the reaction mixture was added dropwise to ion-exchanged water being stirred, and stirring was further conducted at room temperature.

(53) Finally, the slurry obtained was filtered, and the filter cake was dried, to obtain the desired 9-benzyl-3-bromocarbazole (amount 13.1 g, yield 96%).

(54) .sup.1H-NMR (300 MHz, CDCl.sub.3) [ppm]: 8.23 (d, J=2.1 Hz, 1H), 8.07 (d, J=8.0 Hz, 1H), 7.49 (dd, J=8.6, 2.1 Hz, 1H), 7.42 to 7.45 (m, 1H), 7.36 (d, J=8.0 Hz, 1H), 7.21 to 7.31 (m, 5H), 7.08 to 7.11 (m, 2H), and 5.49 (s, 2H).

(55) [9-2]

(56) ##STR00183##

(57) A flask was charged with 2.00 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, 3.24 g of the above-obtained 9-benzyl-3-bromocarbazole, 50.5 mg of Pd(dba).sub.2, and 1.21 g of t-butoxysodium, and the atmosphere in the flask was replaced by nitrogen. Into the flask were put 20 mL of toluene and 0.56 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 63.4 g/L), followed by stirring at 50 C. for 24 hours.

(58) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with toluene and saturated saline, and a liquid separation treatment was conducted. To the organic layer obtained, activated carbon was added, followed by stirring at room temperature for 30 minutes, then the activated carbon was removed by filtration, and the filtrate was condensed. The condensed liquid thus obtained was added dropwise to methanol/ethyl acetate mixed solvent, and the resulting slurry was stirred at room temperature.

(59) Finally, the slurry was filtered, and the filter cake was dried, to obtain the N1,N4-bis(9-benzyl-9H-carbazol-3-yl)-N1-(4-((9-benzyl-9H-carbazol-3-yl)(4-(diphenylamino)-phenyl)amino)phenyl)-N4-(4-(diphenylamino)phenyl)benzene-1,4-diamine (amount 3.92 g, yield 93%).

(60) MALDI-TOF-MS m/Z found: 1451.52 ([M].sup.+calcd: 1450.63).

(61) [9-3]

(62) ##STR00184##

(63) A flask was charged with 2.00 g of the N1,N4-bis(9-benzyl-9H-carbazol-3-yl)-N1-(4-((9-benzyl-9H-carbazol-3-yl)(4-(diphenylamino)phenyl)amino)phenyl)-N4-(4-(diphenylamino)phenyl)benzene-1,4-diamine obtained above and 40 mL of dimethyl sulfoxide, and then the atmosphere in the flask was replaced by oxygen. To the flask, 25 mL of a preliminarily prepared tetrahydrofuran solution of t-butoxypotassium (concentration 1M) was added dropwise, followed by stirring at room temperature for 23 hours.

(64) After the stirring was over, the reaction mixture was added dropwise to ion-exchanged water/methanol mixed solvent, the resulting mixture was stirred, then 5 mL of 5 M hydrochloric acid was added dropwise thereto, and stirring was further conducted.

(65) Finally, the slurry was filtered, and the filter cake was dried, to obtain a desired aniline derivative 9 (amount 1.62 g, yield 99%).

(66) MALDI-TOF-MS m/Z found: 1180.10 ([M].sup.+calcd: 1180.49).

Preparation Example 10

(67) ##STR00185##

(68) A flask was charged with 1.50 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, 3.00 g of 3-bromo-9-ethyl-9H-carbazole, 37.9 mg of Pd(dba).sub.2, and 1.28 g of t-butoxysodium, and the atmosphere in the flask was replaced by nitrogen. Into the flask were put 15 mL of toluene and 0.64 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 41.7 g/L), followed by stirring at 50 C. for six hours.

(69) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with chloroform and saturated saline, and a liquid separation treatment was performed (twice). The organic layer thus obtained was dried with sodium sulfate, and then 0.5 g of activated carbon was added to the dried organic layer, followed by stirring at room temperature for 30 minutes.

(70) Thereafter, the activated carbon was removed by filtration, the filtrate was condensed, the condensed liquid was added dropwise to methanol, and the resulting slurry was stirred overnight at room temperature.

(71) Finally, the slurry was filtered, then column chromatography (eluent: toluene/hexane=70/30.fwdarw.90/10) was conducted using the thus obtained filter cake, and by checking the presence/absence of the target product by a thin layer chromatography (TLC) method, a fraction containing the target product was isolated. Finally, the solvent was removed from the isolated fraction at reduced pressure, to obtain a desired aniline derivative 10 (amount 1.41 g, yield 51%).

(72) MALDI-TOF-MS m/Z found: 1264.03 ([M].sup.+calcd: 1264.59).

Preparation Example 11

(73) ##STR00186##

(74) A flask was charged with 2.00 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, 3.38 g of 3-bromo-9-phenyl-9H-carbazole, 51.1 mg of Pd(dba).sub.2, and 1.21 g of t-butoxysodium, and the atmosphere in the flask was replaced by nitrogen. Into the flask were put 30 mL of toluene and 0.720 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 49.1 g/L), followed by stirring at 50 C. for six hours.

(75) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with toluene and saturated saline, and a liquid separation treatment was performed. The organic layer thus obtained was dried with sodium sulfate.

(76) Next, the solvent was distilled off from the dried organic layer at reduced pressure, and the residue was dissolved in toluene. Then, the solution obtained was added dropwise to methanol/ethyl acetate mixed solvent (200 mL/200 mL), and the resulting slurry was stirred at room temperature.

(77) Finally, the slurry was filtered, and the filter cake obtained was dried, to obtain a desired aniline derivative 11 (amount 3.35 g, yield 81%).

(78) .sup.1H-NMR (300 MHz, THF-d6) [ppm]: 7.96 to 8.07 (m, 6H), 7.57 to 7.64 (m, 11H), 7.46 to 7.48 (m, 3H), 7.14 to 7.34 (m, 24H), and 6.87 to 7.04 (m, 28H).

(79) MALDI-TOF-MS m/Z found: 1409.48 ([M].sup.+calcd: 1408.59).

Preparation Example 12

(80) [12-1]

(81) A flask was charged with 3.00 g of 3-bromocarbazole, 0.52 g of sodium hydroxide and 30 mL of N,N-dimethylformamide, and the atmosphere in the flask was replaced by nitrogen. To the flask, 1.9 mL of 4-(chloromethyl)styrene was added dropwise, followed by stirring at room temperature for 20 hours.

(82) Thereafter, the reaction mixture thus obtained was added dropwise to ion-exchanged water being stirred, and stirring was conducted further at room temperature.

(83) Finally, the resulting slurry was filtered, and the filter cake was dried, to obtain the desired N-(4-vinylbenzyl)-3-bromocarbazole (amount 3.97 g, yield 90%).

(84) .sup.1H-NMR (300 MHz, CDCl.sub.3) [ppm]: 8.23 (d, J=2.1 Hz, 1H), 8.07 (d, J=7.7 Hz, 1H), 7.20 to 7.51 (m, 7H), 7.05 (d, J=8.1 Hz, 2H), 6.64 (dd, J=17.7, 10.8 Hz, 1H), 5.67 (d, J=17.7 Hz, 1H), 5.47 (s, 2H), and 5.20 (d, J=10.8 Hz, 1H).

(85) [12-2]

(86) ##STR00187##

(87) A flask was charged with 2.18 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, 3.80 g of 3-bromo-9-(4-vinylbenzyl)carbazole, 1110 mg of Pd(dba).sub.2, and 1.32 g of t-butoxysodium, and the atmosphere in the flask was replaced by nitrogen. Into the flask were put 20 mL of toluene and 1.1 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 70.9 g/L), followed by stirring at 50 C. for five hours.

(88) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with toluene and saturated saline, and a liquid separation treatment was conducted. Activated carbon was added to the thus obtained organic layer, followed by stirring at room temperature for 30 minutes, then the activated carbon was removed by filtration, and the filtrate was condensed. The condensed liquid thus obtained was added dropwise to methanol/ethyl acetate mixed solvent, and the resulting slurry was stirred at room temperature.

(89) Finally, the slurry was filtered, and the filter cake was dried, to obtain a desired aniline derivative 12 (amount 4.51 g, yield 93%).

(90) MALDI-TOF-MS m/Z found: 1527.85 ([M].sup.+calcd: 1528.68).

Preparation Example 13

(91) [13-1]

(92) A flask was charged with 2.00 g of 3-bromocarbazole, 0.349 g of sodium hydroxide, and 20 mL of N,N-dimethylformamide, and then the atmosphere in the flask was replaced by nitrogen. To the flask, 1.10 mL of 4-(bromomethyl)-1,2-difluorobenzene was added dropwise, followed by stirring at room temperature for three days.

(93) Thereafter, the reaction mixture obtained was added dropwise to ion-exchanged water being stirred, and the resulting slurry was stirred further at room temperature.

(94) Finally, the slurry was filtered, and the filter cake was dried, to obtain 3-bromo-9-(3,4-difluorobenzyl)carbazole (amount 2.91 g, yield 96%).

(95) .sup.1H-NMR (300 MHz, CDCl.sub.3) [ppm]: 8.23 (d, J=2.1 Hz, 1H), 8.07 (d, J=7.7 Hz, 1H), 7.43 to 7.52 (m, 2H), 7.28 to 7.32 (m, 2H), 7.17 (d, J=8.6 Hz, 1H), 7.00 to 7.09 (m, 1H), 6.80 to 6.91 (m, 2H), and 5.41 (s, 2H).

(96) [13-2]

(97) ##STR00188##

(98) A flask was charged with 1.03 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, 1.84 g of 3-bromo-9-(3,4-difluorobenzyl)carbazole, 26.3 mg of Pd(dba).sub.2, and 0.635 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 10 mL of toluene and 0.20 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 93.2 g/L), followed by stirring at 50 C. for nine hours.

(99) After the stirring was over, the resulting reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with toluene and saturated saline, and a liquid separation treatment was conducted. The organic layer obtained was dried with sodium sulfate, and then activated carbon was added to the dried organic layer, followed by stirring at room temperature for three hours.

(100) Thereafter, the activated carbon was removed by filtration, the filtrate was condensed, and the condensed liquid thus obtained was added dropwise to methanol/ethyl acetate mixed solvent, and the resulting slurry was stirred at room temperature.

(101) Finally, the slurry was filtered, and the filter cake obtained was dried, to obtain a desired aniline derivative 13 (amount 2.18 g, yield 93%).

(102) MALDI-TOF-MS m/Z found: 1559.48 ([M].sup.+calcd: 1558.58).

Preparation Example 14

(103) [14-1]

(104) A flask was charged with 2.00 g of 3-bromocarbazole, 0.352 g of sodium hydroxide, and 20 mL of N,N-dimethylformamide, and the atmosphere in the flask was replaced by nitrogen. To the flask, 2.05 g of 1-(bromomethyl)-4-(trifluoromethyl)benzene was added dropwise, followed by stirring at room temperature for 15 hours.

(105) Thereafter, the reaction mixture was added dropwise to ion-exchanged water being stirred, and the resulting slurry was stirred further at room temperature.

(106) Finally, the slurry was filtered, and the filter cake was dried, to obtain the desired 3-bromo-9-(4-(trifluoro-methyl)benzyl)carbazole (amount 3.20 g, yield 97%).

(107) .sup.1H-NMR (300 MHz, CDCl.sub.3) [ppm]: 8.24 (d, J=1.5 Hz, 1H), 8.08 (d, J=8.0 Hz, 1H), 7.43 to 7.53 (m, 4H), 7.16 to 7.32 (m, 5H), and 5.53 (s, 2H).

(108) [14-2]

(109) ##STR00189##

(110) A flask was charged with 1.03 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, 2.00 g of 3-bromo-9-(4-(trifluoromethyl)benzyl)carbazole, 26.0 mg of Pd(dba).sub.2, and 0.637 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 10 mL of toluene and 0.20 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 93.2 g/L), followed by stirring at 50 C. for 2.5 hours.

(111) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with toluene and saturated saline, and a liquid separation treatment was performed. The organic layer obtained was dried with sodium sulfate, and then activated carbon was put into the dried organic layer, followed by stirring at room temperature for 30 minutes.

(112) Thereafter, the activated carbon was removed by filtration, the filtrate was condensed, the condensed liquid was added dropwise to methanol/ethyl acetate mixed solvent, and the resulting slurry was stirred at room temperature.

(113) Finally, the slurry was filtered, and the resulting filter cake was dried, to obtain a desired aniline derivative 14 (amount 2.25 g, yield 91%).

(114) MALDI-TOF-MS m/Z found: 1655.44 ([M].sup.+calcd: 1654.60).

Preparation Example 15

(115) ##STR00190##

(116) A flask was charged with 1.00 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, 2.08 g of 2-bromo-9,9-spirobi[fluorene], 25 mg of Pd(dba).sub.2, and 0.607 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 10 mL of toluene and 0.35 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 0.050 g/L), followed by stirring at 50 C. for four hours.

(117) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with toluene and ion-exchanged water, and a liquid separation treatment was conducted. The organic layer obtained was dried with sodium sulfate, and 0.2 g of activated carbon was added to the organic layer, followed by stirring at room temperature for 30 minutes.

(118) Thereafter, the activated carbon was removed by filtration, the solvent was distilled off from the filtrate at reduced pressure, and the residue was dissolved in 15 mL of toluene. The solution obtained was added dropwise to methanol/ethyl acetate mixed solvent (200 mL/50 mL), the resulting slurry was stirred at room temperature, and then the slurry was filtered, to recover the filter cake.

(119) Then, the filter cake obtained was again dissolved in 10 mL of toluene, the resulting solution was added dropwise to methanol/ethyl acetate mixed solvent (200 mL/200 mL), and the slurry thus obtained was stirred at room temperature.

(120) Finally, the slurry was filtered, and the resulting filter cake was dried, to obtain a desired aniline derivative 15 (amount 1.86 g, yield 78%).

(121) MALDI-TOF-MS m/Z found: 1628.01 ([M].sup.+calcd: 1627.65).

Preparation Example 16

(122) [16-1]

(123) ##STR00191##

(124) A flask was charged with 20 g of 4-bromo-4-iodo-1,1-biphenyl, 3.2 g of Pd(PPh.sub.3).sub.4, and 6.4 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 200 mL of toluene and 6.1 g of aniline, followed by stirring for 6.5 hours under reflux conditions.

(125) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with chloroform and ion-exchanged water, and a liquid separation treatment was performed. The solvent was distilled off from the separated organic layer at reduced pressure, column chromatography was conducted using a solution obtained by dissolving the residue in chloroform, and, by checking the presence/absence of the target product by a thin layer chromatography (TLC) method, a fraction containing the target product was isolated.

(126) The isolated fraction was condensed, and the condensed liquid was mixed with 100 g of methanol/toluene mixed solvent (3/1 (w/w)). The mixture thus obtained was stirred under reflux conditions to dissolve the solid matter, followed by stirring for 30 minutes under the reflux conditions, then by cooling to room temperature, and by stirring further at room temperature for one hour.

(127) Finally, the precipitated solid matter was filtered, and the filter cake was dried, to obtain 4-bromo-N-phenyl-[1,1-biphenyl]-4-amine (amount 11.20 g, yield 62%).

(128) .sup.1H-NMR (300 MHz, CDCl.sub.3) [ppm]: 7.53 to 7.40 (m, 6H), 7.32 to 7.26 (m, 2H), 7.11 (d, J=8.6 Hz, 4H), 6.99 to 6.94 (t, J=7.4 Hz, 1H), and 5.78 (s, 1H).

(129) [16-2]

(130) ##STR00192##
(In the formula, BOC means a t-butoxycarbonyl group, here and hereafter.)

(131) A flask was charged with 5.0 g of 4-bromo-N-phenyl-[1,1-biphenyl]-4-amine, 0.09 g of N,N-dimethyl-4-aminopyridine, and 50 mL of tetrahydrofuran, then the mixture was refluxed by heating, 10 g of di-t-butyl dicarbonate was added dropwise thereto, and the resulting mixture was stirred under reflux conditions for 1.5 hours.

(132) Thereafter, the reaction mixture was let cool to room temperature, the solvent was distilled off from the reaction mixture thus let cool at reduced pressure, and the residue was dissolved in chloroform. Column chromatography was conducted using the resulting solution, and, by checking the presence/absence of the target product by a thin layer chromatography (TLC) method, a fraction containing the target product was isolated, and the solvent was distilled off from the isolated fraction at reduced pressure.

(133) Finally, the residue obtained was mixed with 20 mL of n-hexane, the precipitated solid matter was recovered by filtration and dried, to obtain the desired t-butyl(4-bromo-[1,1-biphenyl]-4-yl)(phenyl)carbamate (amount 5.4 g, yield 83%).

(134) .sup.1H-NMR (300 MHz, CDCl.sub.3) [ppm]: 7.54 (d, J=6.3 Hz, 2H), 7.41 to 7.49 (m, 4H), 7.18 to 7.36 (m, 7H), and 1.47 (s, 9H).

(135) [16-3]

(136) ##STR00193##

(137) A flask was charged with 2.00 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl)-N4,N4-diphenylbenzene-1,4-diamine, 4.09 g of t-butyl(4-bromo-[1,1-biphenyl]-4-yl)(phenyl)carbamate, 50 mg of Pd(dba).sub.2, and 1.40 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 20 mL of toluene and 0.88 mL of a toluene solution of tri-t-butylphosphine (concentration 0.040 g/L), followed by stirring at 50 C. for seven hours.

(138) After the stirring was over, the reaction mixture was let cool to room temperature, the reaction mixture thus let cool was mixed with chloroform and ion-exchanged water, and a liquid separation treatment was performed. The organic layer thus obtained was dried with sodium sulfate, and then 0.2 g of activated carbon was added to the dried organic layer, followed by stirring at room temperature for 30 minutes.

(139) Thereafter, the activated carbon was removed by filtration, the filtrate was condensed, the condensed liquid was mixed with 30 mL of toluene, the resulting mixture was added dropwise to methanol/ethyl acetate mixed solvent (300 mL/200 mL), the resulting slurry was stirred at room temperature, and then the slurry was filtered to recover the filter cake (filter cake A). Then, the filtrate obtained was again condensed, the condensed liquid was mixed with 15 mL of toluene, the resulting mixture was added dropwise to methanol/ethyl acetate mixed solvent (180 mL/60 mL), the resulting slurry was stirred at room temperature, and the slurry was filtered to recover the filter cake (filter cake B).

(140) The filter cake A and the filter cake B recovered were washed with methanol, then dissolved in toluene, the solvent was distilled off from the resulting solution at reduced pressure, and the residue was dried to obtain a solid matter.

(141) The solid matter thus obtained, 21 mL of toluene and 6.29 g of trifluoroacetic acid were mixed, the resulting mixture was stirred at room temperature for four hours, and then 100 mL of saturated aqueous solution of sodium hydrogen carbonate and 300 mL of toluene were added thereto, followed by stirring further at room temperature.

(142) After the stirring was over, the reaction mixture was filtered, the filter cake was washed with methanol, then dissolved in 200 mL of tetrahydrofuran, and the resulting solution was put to celite filtration. The solvent was distilled off from the resulting filtrate at reduced pressure, the residue obtained was dissolved in 20 mL of tetrahydrofuran, the resulting solution was added dropwise to methanol/ethyl acetate mixed solvent (300 mL/200 mL), and the slurry obtained was stirred at room temperature.

(143) Finally, the slurry was filtered, and the filter cake was dried, to obtain the desired N4-(4-(diphenylamino)phenyl)-N4(4-((4-((4-(diphenylamino)phenyl)(4-(phenylamino)-[1,1-biphenyl]-4-yl)amino)phenyl)(4-(phenylamino)-[1,1-biphenyl]-4-yl)amino)phenyl)-N4-phenyl-[1,1-biphenyl]-4,4-diamine (amount 2.18 g, yield 63%).

(144) MALDI-TOF-MS m/Z found: 1414.23 ([M].sup.+calcd: 1414.63).

(145) [16-4]

(146) ##STR00194##

(147) A flask was charged with 2.00 g of N4-(4-(diphenylamino)phenyl)-N4(4-((4-((4-(diphenylamino)-phenyl)(4-(phenylamino)-[1,1-biphenyl]-4-yl)amino)phenyl)-(4-(phenylamino)-[1,1-biphenyl]-4-yl)amino)phenyl)-N4-phenyl-[1,1-biphenyl]-4,4-diamine, 1.65 g of 4-bromo-N,N-diphenylaniline, 24.9 mg of Pd(dba).sub.2, and 0.584 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 20 mL of toluene and 0.43 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 40.1 g/L), followed by stirring at 50 C. for four hours, then the temperature was raised to 80 C., and after the temperature rise, stirring was conducted for 12 hours.

(148) After the stirring was over, the reaction mixture was let cool to room temperature, the reaction mixture thus let cool was mixed with chloroform and saturated saline, and a liquid separation treatment was conducted. The organic layer obtained was dried with sodium sulfate, and then 0.2 g of activated carbon was added to the dried organic layer, followed by stirring at room temperature for 30 minutes.

(149) Thereafter, the activated carbon was removed by filtration, the filtrate was condensed, the condensed liquid was mixed with 30 mL of toluene, the resulting mixture was added dropwise to methanol/ethyl acetate mixed solvent (300 mL/200 mL), and the resulting slurry was stirred at room temperature.

(150) Finally, the slurry was filtered, and the filter cake was dried, to obtain a desired aniline derivative 16 (amount 2.34 g, yield 77%).

(151) MALDI-TOF-MS m/Z found: 2144.64 ([M].sup.+calcd: 2143.95).

Preparation Example 17

(152) [17-1]

(153) ##STR00195##

(154) A flask was charged with 0.500 g of bis(4-aminophenyl)amine, 2.18 g of 2-bromo-9,9-spirobi[fluorene], 0.117 g of Pd(PPh.sub.3).sub.4, and 0.579 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask was put 20 mL of xylene, followed by stirring for five hours under heating and reflux conditions.

(155) Thereafter, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with toluene and ion-exchanged water, a liquid separation treatment was conducted, and the organic layer obtained was washed with ion-exchanged water and further washed with saturated saline.

(156) Next, the organic layer after washed was dried with sodium sulfate and then condensed, silica gel column chromatography (eluent: toluene) was conducted using the condensed liquid, and, by checking the presence/absence of the target product by a thin layer chromatography (TLC) method, a fraction containing the target product was isolated.

(157) Finally, the solvent was removed from the isolated fraction at reduced pressure, to obtain the desired N1-(9,9-spirobi[fluorene]-2-yl)-N4-(4-(9,9-spirobi-[fluorene]-2-ylamino)phenyl)benzene-1,4diamine (amount 0.926 g, yield 46%).

(158) MALDI-TOF-MS m/Z found: 826.45 ([M].sup.+calcd: 827.33).

(159) [17-2]

(160) ##STR00196##

(161) A flask was charged with 0.500 g of N1-(9,9-spirobi[fluorene]-2-yl)-N4-(4-(9,9-spirobi-[fluorene]-2-ylamino)phenyl)benzene-1,4diamine, 0.700 g of 3-bromo-9-phenylcarbazole, 10.7 mg of Pd(dba).sub.2, and 0.259 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 10 mL of toluene and 0.11 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 65.6 g/L), followed by stirring at 50 C. for five hours.

(162) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with toluene and saturated saline, and a liquid separation treatment was conducted. The organic layer obtained was dried with sodium sulfate, and activated carbon was added to the dried organic layer, followed by stirring at room temperature for 30 minutes.

(163) Next, the activated carbon was removed by filtration, the filtrate was condensed, the condensed liquid was added dropwise to methanol/ethyl acetate mixed solvent being stirred, and the resulting slurry was stirred further at room temperature.

(164) Finally, the slurry was filtered, and the filter cake was dried, to obtain an aniline derivative 17 (amount 0.772 g, yield 83%).

(165) MALDI-TOF-MS m/Z found: 1551.41 ([M].sup.+calcd: 1550.60).

Preparation Example 18

(166) ##STR00197##

(167) A flask was charged with 1.00 g of N1-(4-aminophenyl)benzene-1,4-diamine, 8.89 g of 3-bromo-9-phenyl-9H-carbazole, 112 mg of palladium acetate, and 3.47 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 30 mL of toluene and 2.75 mL of a preliminarily prepared toluene solution of di-t-butyl(phenyl)phosphine (concentration 81.0 g/L), followed by stirring at 90 C. for six hours.

(168) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with toluene and ion-exchanged water, and a liquid separation treatment was conducted. The organic layer obtained was dried with sodium sulfate, and condensed. The condensed liquid was filtered using silica gel, and 0.2 g of activated carbon was added to the thus obtained filtrate, followed by stirring at room temperature for 30 minutes.

(169) Thereafter, the activated carbon was removed by filtration, and the filtrate was condensed. The condensed liquid was added dropwise to methanol/ethyl acetate mixed solvent (500 mL/500 mL), the resulting slurry was stirred overnight at room temperature, and then the slurry was filtered to recover the filter cake. The filter cake obtained was dried, to obtain a desired aniline derivative 18 (amount 5.88 g, yield 83%).

(170) .sup.1H-NMR (300 MHz, THF-d8) [ppm]: 8.08 (d, J=7.7 Hz, 2H), 7.99 (d, J=7.7 Hz, 8H), 7.60 to 7.64 (m, 19H), 7.42 to 7.47 (m, 6H), 7.28 to 7.36 (m, 19H), 7.09 to 7.21 (m, 6H), and 7.00 (m, 8H).

(171) MALDI-TOF-MS m/Z found: 1404.68 ([M].sup.+calcd: 1404.56).

Preparation Example 19

(172) [19-1]

(173) ##STR00198##

(174) A flask was charged with 5.00 g of N1-(4-aminophenyl)benzene-1,4-diamine, 8.09 g of 9-benzyl-3-bromo-9H-carbazole, 252 mg of Pd(dba).sub.2, and 3.03 g of tertiary-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 50 mL of toluene and 2.02 mL of a preliminarily prepared toluene solution of di-t-butyl(phenyl)phosphine (concentration 96.4 g/L), followed by stirring at 90 C. for three hours.

(175) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture was mixed with 200 mL of toluene and 150 mL of saturated saline, and a liquid separation treatment was performed. To the thus obtained organic layer was added 0.5 g of activated carbon, followed by stirring at room temperature for one hour.

(176) Thereafter, the activated carbon was removed by filtration, and the filtrate was condensed. The condensed liquid was added dropwise to methanol/ethyl acetate mixed solvent (200 mL/200 mL), the resulting slurry was stirred at room temperature for one hour, and then the slurry was filtered to recover a filter cake. The filter cake obtained was dried, to obtain the desired N1,N1,N4-tris(9-benzyl-9H-carbazol-3-yl)-N4-(4-(bis(9-benzyl-9H-carbazol-3-yl)amino)-phenyl)benzene-1,4-diamine (amount 8.46 g, yield 80%).

(177) .sup.1H-NMR (300 MHz, THF-d8) [ppm]: 7.91 to 8.00 (m, 10H), 7.52 to 7.58 (m, 10H), 7.34 to 7.39 (m, 6H), 7.17 to 7.26 (m, 29H), 7.03 to 7.11 (m, 5H), 6.83 (d, J=9.0 Hz, 4H), 6.76 (d, J=9.0 Hz, 4H), and 5.58 (s, 10H).

(178) [19-2]

(179) ##STR00199##

(180) A flask was charged with 5.05 g of t-butoxypotassium, 18 mL of dimethyl sulfoxide, and 6 mL of tetrahydrofuran, and the atmosphere in the flask was replaced by oxygen. A solution prepared by mixing 3.00 g of the N1,N1,N4-tris(9-benzyl-9H-carbazol-3-yl)-N4-(4-(bis(9-benzyl-9H-carbazol-3-yl)amino)phenyl)benzene-1,4-diamine obtained above and 9 mL of tetrahydrofuran was added dropwise to the flask at 10 C., and the resulting mixture was heated up to room temperature and then stirred for four hours.

(181) After the stirring was over, the reaction mixture was added dropwise to 120 mL of ion-exchanged water, then 9 mL of hydrochloric acid (5 M) was added dropwise thereto, and the resulting slurry was stirred at room temperature for one hour. Then, the slurry was filtered, to recover a filter cake. The filter cake obtained was mixed well with 90 mL of tetrahydrofuran, the resulting mixture was filtered using silica gel, and the filtrate obtained was condensed. The condensed liquid was added dropwise to 150 mL of methanol, and the resulting slurry was stirred at room temperature for one hour.

(182) Finally, the slurry was filtered to recover a filter cake, and the filter cake obtained was dried, to obtain a desired aniline derivative 19 (amount 2.20 g, yield 90%).

(183) MALDI-TOF-MS m/Z found: 1024.13 ([M].sup.+calcd: 1024.40).

Preparation Example 20

(184) [20-1]

(185) ##STR00200##

(186) A flask was charged with 0.30 g of bis(aminophenyl)amine, 3.51 g of t-butyl(4-bromo-[1,1-biphenyl]-4-yl(phenyl)-carbamate, 44 mg of Pd(dba).sub.2, and 1.05 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 30 mL of toluene and 510 L of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 60 g/L), followed by stirring at 50 C. for 26 hours.

(187) After the stirring was over, the reaction mixture was let cool to room temperature, the reaction mixture thus let cool was mixed with toluene and saturated saline, and a liquid separation treatment was conducted. The organic layer obtained was dried with sodium sulfate, and activated carbon was added to the dried organic layer, followed by stirring at room temperature for one hour.

(188) Next, the activated carbon was removed by filtration, and the filtrate was condensed. The condensed liquid was added dropwise to methanol being stirred, and the resulting slurry was stirred further at room temperature.

(189) Finally, the slurry was filtered, and the resulting filter cake was dried, to obtain a desired intermediate (amount 2.40 g, yield 83%).

(190) .sup.1H-NMR (300 MHz, DMSO-d6) [ppm]: 7.56 to 7.58 (m, 20H), 7.33 to 7.38 (m, 11H), 7.19 to 7.24 (m, 24H), 7.06 to 7.11 (m, 18H), and 1.38 (s, 45H).

(191) [20-2]

(192) ##STR00201##

(193) A flask was charged with 2.20 g of the intermediate obtained above, 15 mL of toluene, and 2.5 mL of trifluoroacetic acid, followed by stirring at room temperature for six hours. After the stirring was over, toluene and saturated aqueous solution of sodium hydrogen carbonate were added to the reaction mixture, and the resulting slurry was stirred.

(194) Next, the slurry was filtered, the filter cake obtained was dissolved in tetrahydrofuran, the resulting solution was added dropwise to methanol/ethyl acetate mixed solvent being stirred, and the resulting slurry was stirred further at room temperature.

(195) Finally, the slurry was filtered, and the filter cake obtained was dried, to obtain an aniline derivative 20 (amount 1.24 g, yield 74%).

(196) .sup.1H-NMR (300 MHz, THF-d8) [ppm]: 7.46 to 7.51 (m, 23H), 7.39 (s, 5H), 7.07 to 7.22 (m, 44H), and 6.78 to 6.83 (m, 6H).

(197) MALDI-TOF-MS m/Z found: 1414.17 ([M].sup.+calcd: 1414.63).

Preparation Example 21

(198) ##STR00202##

(199) A flask was charged with 1.00 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl) N4,N4-diphenylbenzene-1,4-diamine, 1.96 g of N-(4-bromophenyl)-N-phenylnaphthalene-1-amine, 51.0 mg of Pd(dba).sub.2, and 0.61 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 10 mL of toluene and 410 L of a preliminarily prepared toluene solution of di-t-butyl(phenyl)phosphine (concentration 96 g/L), followed by stirring at 100 C. for 2.5 hours.

(200) After the stirring was over, the reaction mixture was let cool to room temperature, the reaction mixture thus let cool was mixed with toluene and saturated saline, and a liquid separation treatment was performed. Activated carbon was added to the organic layer obtained, followed by stirring at room temperature for 30 minutes.

(201) Next, the activated carbon was removed by filtration, and the filtrate was condensed. The condensed liquid was added dropwise to methanol/ethyl acetate mixed solvent being stirred, and the resulting slurry was stirred further at room temperature.

(202) Finally, the slurry was filtered, and the filter cake obtained was dried, to obtain an aniline derivative 21 (amount 1.58 g, yield 69%).

(203) MALDI-TOF-MS m/Z found: 1565.38 ([M].sup.+calcd: 1564.68).

Preparation Example 22

(204) ##STR00203##

(205) A flask was charged with 0.50 g of the aniline derivative 19, 0.67 g of potassium carbonate, and 5 mL of N,N-dimethylformamide, and then the atmosphere in the flask was replaced by nitrogen. To the flask, 330 L of pentafluorobenzonitrile was added dropwise, followed by stirring at room temperature for 15 hours.

(206) After the stirring was over, the reaction mixture was added dropwise to ion-exchanged water, and the resulting slurry was stirred at room temperature for 30 minutes. Next, the slurry was filtered, the filter cake was dried, silica gel column chromatography (eluent: toluene) was conducted using a solution obtained by dissolving the thus obtained powder in toluene, and, by checking the presence/absence of the target product by a thin layer chromatography (TLC) method, a fraction containing the target product was isolated. The solvent was distilled off from the isolated fraction at reduced pressure, and the resulting solid matter was dried, to obtain an aniline derivative 22 (amount 0.37 g, yield 40%).

(207) MALDI-TOF-MS m/Z found: 1890.54 ([M].sup.+calcd: 1889.34).

Preparation Example 23

(208) [23-1]

(209) A flask was charged with 1.59 g of sodium hydride (60%/fluid paraffin), and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 20 mL of N,N-dimethylformamide and 7.46 g of 1,2,3,4,5-pentafluoro-6-methylbenzene, and then 40 mL of a preliminarily prepared N,N-dimethylformamide solution of 3-bromo-9H-carbazole (concentration 123 g/L) was added dropwise thereto, followed by stirring at room temperature for one hour.

(210) After the stirring was over, the reaction mixture, ion-exchanged water, and chloroform were mixed, a liquid separation treatment was conducted, and the solvent was distilled off from the resulting organic layer at reduced pressure. Next, the residue obtained, n-hexane, and ion-exchanged water were mixed, a liquid separation treatment was performed, and the solvent was distilled off from the resulting organic layer at reduced pressure. Further, the residue thus obtained, hexane/ethyl acetate mixed solvent (1/1 (v/v)), and ion-exchanged water were mixed, a liquid separation treatment was conducted, the resulting organic layer was mixed with saturated saline, and a liquid separation treatment was again conducted.

(211) The organic layer thus obtained was dried with sodium sulfate, the solvent was distilled off from the dried organic layer at reduced pressure, and the resulting residue was dissolved in hexane/ethyl acetate mixed solvent (1/1 (v/v)). Silica gel column chromatography (eluent: hexane/ethyl acetate) was conducted using the thus obtained solution, and, by checking the presence/absence of the target product by a thin layer chromatography (TLC) method, a fraction containing the target product was isolated.

(212) The solvent was distilled off from the isolated fraction at reduced pressure, and the solid matter obtained was dried, to obtain 3-bromo-9-(2,3,5,6-tetrafluoro-4-methylphenyl)-9H-carbazole (amount 6.21 g, yield 76%).

(213) .sup.1H-NMR (300 MHz, CDCl.sub.2) [ppm]: 8.24 (d, J=2.0 Hz, 1H), 8.08 (d, J=7.8 Hz, 1H), 7.52 (dd, J=8.9, 2.0 Hz, 1H), 7.47 (td, J=7.8, 1.4 Hz, 1H), 7.34 (t, J=7.8 Hz, 1H), 7.13 (d, J=7.8 Hz, 1H), 7.02 (d, J=8.9 Hz, 1H), and 1.55 (s, 3H).

(214) [23-2]

(215) ##STR00204##

(216) A flask was charged with 1.37 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl) N4,N4-diphenylbenzene-1,4-diamine, 3.32 g of 3-bromo-9-(2,3,5,6-tetrafluoro-4-methylphenyl)-9H-carbazole, 211 mg of Pd(dba).sub.2, and 2.48 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 15 mL of toluene and 2.1 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 70 g/L), followed by stirring at 50 C. for 51 hours.

(217) After the stirring was over, the reaction mixture was let cool to room temperature, the reaction mixture thus let cool, ethyl acetate, and ion-exchanged water were mixed, and a liquid separation treatment was conducted. The organic layer thus obtained was dried with magnesium sulfate, and activated carbon was added to the dried organic layer, followed by stirring at room temperature for 30 minutes.

(218) Next, the activated carbon was removed by filtration, the filtrate was condensed, a solution obtained by dissolving the thus obtained residue in tetrahydrofuran was added dropwise to acetonitrile being stirred, and the resulting slurry was stirred further at room temperature.

(219) Finally, the slurry was filtered, and the filter cake obtained was dried to obtain an aniline derivative 23 (amount 1.18 g, yield 35%).

(220) .sup.1H-NMR (300 MHz, THF-d8) [ppm]: 8.08 (d, J=7.7 Hz, 3H), 8.02 (d, J=1.5 Hz, 3H), 6.88 to 7.42 (m, 51H), and 2.50 (s, 9H).

(221) MALDI-TOF-MS m/Z found: 1667.79 ([M].sup.+calcd: 1667.53).

Preparation Example 24

(222) [24-1]

(223) A flask was charged with 1.43 g of sodium hydride (60%/fluid paraffin), and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 9 mL of N,N-dimethylformamide and 20.2 g of 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene, and 18 mL of a preliminarily prepared N,N-dimethylformamide solution of 3-bromo-9H-carbazole (concentration 123 g/L) was added dropwise thereto, followed by stirring at room temperature for one hour.

(224) After the stirring was over, the reaction mixture, ion-exchanged water, and ethyl acetate were mixed, a liquid separation treatment was conducted, the organic layer obtained was washed sequentially with ion-exchanged water and saturated saline, and the washed organic layer was dried with sodium sulfate. The solvent was distilled off from the dried organic layer at reduced pressure, silica gel column chromatography (eluent: hexane/ethyl acetate) was conducted using a solution obtained by dissolving the thus obtained residue in hexane/ethyl acetate mixed solvent (1/1 (v/v)), and, by checking the presence/absence of the target product by a thin layer chromatography (TLC) method, a fraction containing the target product was isolated.

(225) The solvent was distilled off from the isolated fraction at reduced pressure, and the solid matter thus obtained was dried, to obtain 3-bromo-9-(2,3,5,6-tetrafluoro-4-(trifluoro-methyl)phenyl)-9H-carbazole (amount 4.10 g, yield 98%).

(226) .sup.1H-NMR (300 MHz, CDCl.sub.3) [ppm]: 8.10 (d, J=1.7 Hz, 1H), 7.91 (d, J=7.5 Hz, 1H), 7.41 (dd, J=8.9, 1.7 Hz, 1H), 7.37 (t, J=7.5 Hz, 1H), 7.24 (t, J=7.5 Hz, 1H), 7.08 (d, J=7.5 Hz, 1H), and 6.92 (d, J=8.9 Hz, 1H).

(227) [24-2]

(228) ##STR00205##

(229) A flask was charged with 1.37 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl) N4,N4-diphenylbenzene-1,4-diamine, 3.16 g of 3-bromo-9-(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl)-9H-carbazole, 70.4 mg of Pd(dba).sub.2, and 0.83 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 15 mL of toluene and 750 L of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 65 g/L), followed by stirring at 50 C. for five hours.

(230) After the stirring was over, the reaction mixture was let cool to room temperature, the reaction mixture thus let cool, ethyl acetate, and ion-exchanged water were mixed, and a liquid separation treatment was conducted. The organic layer obtained was washed sequentially with ion-exchanged water and saturated saline, and the washed organic layer was dried with magnesium sulfate. The solvent was distilled off from the dried organic layer at reduced pressure, the resulting condensed liquid was added dropwise to methanol being stirred, and the resulting slurry was stirred at room temperature.

(231) Finally, the slurry was filtered, and the filter cake obtained was dried, to obtain an aniline derivative 24 (amount 3.24 g, yield 89%).

(232) .sup.1H-NMR (300 MHz, THF-d8) [ppm]: 8.09 (d, J=8.0 Hz, 3H), 8.03 (d, J=1.8 Hz, 3H), and 6.90 to 7.46 (m, 51H).

(233) MALDI-TOF-MS m/Z found: 1829.52 ([M].sup.+calcd: 1829.44).

Preparation Example 25

(234) [25-1]

(235) A flask was charged with 3.97 g of sodium hydride (60%/fluid paraffin), and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 25 mL of N,N-dimethylformamide and 10.7 g of 2,3,4,5,6-pentafluorostyrene, and then 50 mL of a preliminarily prepared N,N-dimethylformamide solution of 3-bromo-9H-carbazole (concentration 246 g/L) was added dropwise thereto, followed by stirring at room temperature for two hours.

(236) After the stirring was over, the reaction mixture, ion-exchanged water, and chloroform were mixed, and a liquid separation treatment was conducted. The organic layer obtained was washed sequentially with ion-exchanged water and saturated saline, and the washed organic layer was dried with magnesium sulfate. Then, the solvent was distilled off from the dried organic layer at reduced pressure, silica gel column chromatography (eluent: hexane/ethyl acetate) was conducted using a solution obtained by dissolving the thus obtained residue in hexane/ethyl acetate mixed solvent (1/1 (v/v)), and, by checking the presence/absence of the target product by a thin layer chromatography (TLC) method, a fraction containing the target product was isolated.

(237) The solvent was distilled off from the isolated fraction at reduced pressure, and the solid matter obtained was dried, to obtain 3-bromo-9-(2,3,5,6-tetrafluoro-4-vinylphenyl)-9H-carbazole (amount 12.7 g, yield 59%).

(238) .sup.1H-NMR (300 MHz, CDCl.sub.3) [ppm]: 8.40 (d, J=2.0 Hz, 1H), 8.17 (d, J=7.8 Hz, 1H), 7.66 (dd, J=8.9, 2.0 Hz, 1H), 7.59 (t, J=7.8 Hz, 1H), 7.45 (t, J=7.8 Hz, 1H), 7.36 (d, J=7.8 Hz, 1H), 7.21 (d, J=8.9 Hz, 1H), 6.91 (dd, J=18.1, 11.9 Hz, 1H), 6.37 (d, J=18.1 Hz, 1H), and 5.90 (d, J=11.9 Hz, 1H).

(239) [25-2]

(240) ##STR00206##

(241) A flask was charged with 1.37 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl) N4,N4-diphenylbenzene-1,4-diamine, 69.7 mg of Pd(dba).sub.2, and 0.83 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 8.4 mL of a preliminarily prepared toluene solution of 3-bromo-9-(2,3,5,6-tetrafluoro-4-vinylphenyl)-9H-carbazole (concentration 31 g/L), 0.70 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 12 g/L), and 6.5 mL of toluene, followed by stirring at 50 C. for three hours.

(242) After the stirring was over, the reaction mixture was let cool to room temperature, the reaction mixture thus let cool, ethyl acetate, and ion-exchanged water were mixed, and a liquid separation treatment was conducted. The organic layer thus obtained was washed sequentially with ion-exchanged water and saturated saline, and the washed organic layer was dried with magnesium sulfate. Then, the solvent was distilled off from the dried organic layer at reduced pressure, a solution obtained by dissolving the resulting residue in tetrahydrofuran was added dropwise to acetonitrile being stirred, and the resulting slurry was stirred at room temperature.

(243) Finally, the slurry was filtered, and the filter cake obtained was dried, to obtain an aniline derivative 25 (amount 2.88 g, yield 85%).

(244) .sup.1H-NMR (300 MHz, THF-d8) [ppm]: 8.07 (d, J=7.8 Hz, 3H), 8.03 (d, J=1.7 Hz, 3H), 6.83 to 7.43 (m, 54H), 6.24 (d, J=17.7 Hz, 3H), and 5.87 (d, J=11.9 Hz, 3H).

(245) MALDI-TOF-MS m/Z found: 1703.84 ([M].sup.+calcd: 1703.53).

Preparation Example 26

(246) ##STR00207##

(247) A flask was charged with 2.36 g of the aniline derivative 9, 20 mL of N,N-dimethylformamide, and 1.66 g of potassium carbonate, and then the atmosphere in the flask was replaced by nitrogen. Next, while cooling the flask on ice bath, 1.29 g of pentafluorobenzonitrile was added dropwise thereto, the temperature was gradually raised to room temperature with stirring, and the stirring was continued at room temperature for 24 hours.

(248) After the stirring was over, the reaction mixture was filtered, and the solvent was distilled off from the resulting filtrate at reduced pressure. Silica gel column chromatography (eluent: toluene/hexane) was conducted using a solution obtained by dissolving the thus obtained residue in toluene/n-hexane mixed solvent (3/2 (v/v)), and, by checking the presence/absence of the target product by a thin layer chromatography (TLC) method, a fraction containing the target product was isolated.

(249) The solvent was distilled off from the isolated fraction at reduced pressure, and the solid matter obtained was dried, to obtain an aniline derivative 26 (amount 1.34 g, yield 40%).

(250) .sup.1H-NMR (300 MHz, THF-d8) [ppm]: 8.02 to 8.10 (m, 6H), and 6.90 to 7.46 (m, 51H).

(251) MALDI-TOF-MS m/Z found: 1699.75 ([M].sup.+calcd: 1700.46).

Preparation Example 27

(252) ##STR00208##

(253) A flask was charged with 2.84 g of the aniline derivative 9, 420 mg of Pd(dba).sub.2, 1.45 g of 5-bromopicolinonitrile, and 1.40 g of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 120 mL of toluene and 2.5 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 175 g/L), followed by stirring at 120 C. for two hours.

(254) After the stirring was over, the reaction mixture was let cool to room temperature, and the reaction mixture thus let cool was filtered. Then, the filtrate was condensed, a solution obtained by dissolving the resulting residue in tetrahydrofuran was added dropwise to methanol being stirred, and the resulting slurry was stirred further at room temperature.

(255) Next, the slurry was filtered, silica gel column chromatography (eluent: toluene/ethyl acetate) was conducted using a solution obtained by dissolving the resulting filter cake in toluene, and, by checking the presence/absence of the target product by a thin layer chromatography (TLC) method, a fraction containing the target product was isolated.

(256) The solvent was distilled off from the isolated fraction at reduced pressure, and the solid matter obtained was dried, to obtain an aniline derivative 27 (amount 1.59 g, yield 45%).

(257) .sup.1H-NMR (300 MHz, THF-d8) [ppm]: 9.06 (d, J=2.7 Hz, 3H), 8.28 (dd, J=8.5, 2.7 Hz, 3H), 8.11 (d, J=8.5 Hz, 3H), 8.08 (d, J=7.8 Hz, 3H), 8.01 (d, J=2.1 Hz, 3H), 7.38 to 7.51 (m, 9H), 7.16 to 7.31 (m, 14H), and 6.89 to 7.04 (m, 28H).

(258) MALDI-TOF-MS m/Z found: 1487.02 ([M].sup.+calcd: 1487.56).

Preparation Example 28

(259) ##STR00209##

(260) A flask was charged with 0.25 g of bis(aminophenyl)amine, 2.58 g of N-(4-bromophenyl)-N-phenylnaphthalene-1-amine, 72.2 mg of Pd(dba).sub.2 and 0.87 g of tertiary-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 15 mL of toluene and 530 L of a preliminarily prepared toluene solution of di-t-butyl(phenyl)phosphine (concentration 96 g/L), followed by stirring at 100 C. for 3.5 hours.

(261) After the stirring was over, the reaction mixture was cooled to room temperature, the cooled reaction mixture, toluene, and saturated saline were mixed, and a liquid separation treatment was conducted. Activated carbon was added to the resulting organic layer, followed by stirring at room temperature for one hour.

(262) Next, the activated carbon was removed by filtration, the filtrate was condensed, the condensed liquid was added dropwise to methanol/ethyl acetate mixed solvent being stirred, and the resulting slurry was stirred further at room temperature.

(263) Finally, the slurry was filtered, and the filter cake obtained was dried, to obtain an aniline derivative 28 (amount 1.70 g, yield 81%).

(264) MALDI-TOF-MS m/Z found: 1665.40 ([M].sup.+calcd: 1664.71).

Preparation Example 29

(265) [29-1]

(266) A flask was charged with 790 mg of sodium hydroxide, 50 mL of N,N-dimethylformamide, and 4.43 g of 3-bromo-9H-carbazole, and 5.04 g of pentafluorobenzyl bromide was added dropwise thereto with stirring under ice bath conditions. After the dropwise addition was over, the resulting mixture was returned to room temperature, and was stirred further for four days.

(267) After the stirring was over, the reaction mixture was poured into ion-exchanged water, the resulting mixture was mixed with ethyl acetate, and a liquid separation treatment was conducted. The organic layer thus obtained was washed with ion-exchanged water, the solvent was distilled off from the washed organic layer at reduced pressure, and recrystallization was conducted by use of the resulting residue and hexane/ethyl acetate.

(268) Finally, the solid matter obtained was dried, to obtain 3-bromo-9-pentafluorobenzylcarbazole (amount 3.31 g, yield 43%).

(269) .sup.1H-NMR (300 MHz, CDCl.sub.3) [ppm]: 8.15 (d, J=1.4 Hz, 1H), 7.99 (d, J=7.8 Hz, 1H), 7.44 to 7.55 (m, 3H), 7.23 to 7.35 (m, 2H), and 5.46 (s, 2H).

(270) [29-2]

(271) ##STR00210##

(272) A flask was charged with 1.37 g of N1-(4-((4-((4-(diphenylamino)phenyl)amino)phenyl)amino)phenyl) N4,N4-diphenylbenzene-1,4-diamine, 2.81 g of 3-bromo-9-pentafluorobenzylcarbazole, 69.6 mg of Pd(dba).sub.2, and 861 mg of t-butoxysodium, and then the atmosphere in the flask was replaced by nitrogen. Into the flask were put 1.0 mL of a preliminarily prepared toluene solution of tri-t-butylphosphine (concentration 47 g/L) and 15 mL of toluene, followed by stirring at 50 C. for seven hours.

(273) After the stirring was over, the reaction mixture was let cool to room temperature, the reaction mixture thus let cool, ethyl acetate, ion-exchanged water, and saturated saline were mixed, and a liquid separation treatment was conducted. The organic layer thus obtained was dried with magnesium sulfate, and then activated carbon was added to the dried organic layer, followed by stirring at room temperature for 0.5 hour.

(274) Thereafter, the activated carbon was removed by filtration, the filtrate was condensed, the condensed liquid was dissolved in ethyl acetate, the resulting solution was added dropwise to methanol/ethyl acetate mixed solvent being stirred, and the resulting slurry was stirred at room temperature.

(275) Finally, the slurry was filtered, and the filter cake obtained was dried, to obtain an aniline derivative 29 (amount 2.14 g, yield 62%).

(276) .sup.1H-NMR (300 MHz, THF-d8) [ppm]: 7.94 to 7.99 (m, 6H), 6.87 to 7.55 (m, 51H), and 5.67 (s, 6H).

(277) MALDI-TOF-MS m/Z found: 1719.19 ([M].sup.+calcd: 1721.50).

[2] Preparation of Charge Transporting Varnish

Example 1-1

(278) 0.105 g of the aniline derivative 1 as a charge transporting substance, 0.202 g of phosphotungstic acid (PTA) as a dopant substance, and 0.097 g of tetrafluorotetracyanoquinodimethane (F4TCNQ) were dissolved in 20 g of cyclohexanone. To the resulting solution were added 0.007 g of 3,3,3-trifluoropropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) and 0.013 g of phenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.), followed by stirring, and the resulting solution was filtered using a PTFE-made filter having a pore diameter of 0.2 m, to prepare a charge transporting varnish.

Examples 1-2 to 1-64

(279) Charge transporting varnishes were prepared in the same manner as in Example 1-1, except for changing the kind of aniline derivative and the amounts of constituents blended together according to Tables 19 to 21.

(280) Note that in the tables, F4BQ means tetrafluoro-1,4-benzoquinone, PMA means phosphomolybdic acid, DDQ means 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, SAC means an arylsulfonic acid compound represented by the formula (H4-1), silane A means 3,3,3-trifluoropropyltrimethoxysilane, silane B means phenyltrimethoxysilane, CHN means cyclohexanone, DMI means 1,3-dimethyl-2-imidazolidinone, 2,3-B,D means 2,3-butanediol, PGME means propylene glycol monomethyl ether, PG means propylene glycol, ECA means diethylene glycol monoethyl ether acetate, CHA means cyclohexanol, DPM means dipropylene glycol monomethyl ether, DMIB means N,N-dimethylisobutylamide, and the parenthesized numerals means the amounts used (unit: g). Note that the arylsulfonic acid compound represented by the formula (H4-1) was synthesized according to the method described in PCT Patent Publication No. WO 2006/025342, here and hereinafter.

(281) ##STR00211##

(282) TABLE-US-00019 TABLE 19 Exam- Charge transporting Dopant Organic ple substance substance Organosilane solvent 1-1 Aniline derivative 1 PTA (0.202) Silane A (0.007) CHN (20) (0.105) F4TCNQ (0.097) Silane B (0.013) 1-2 Aniline derivative 2 PTA (0.202) Silane A (0.007) CHN (20) (0.102) F4TCNQ (0.100) Silane B (0.013) 1-3 Aniline derivative 3 PTA (0.202) Silane A (0.007) CHN (20) (0.102) F4TCNQ (0.100) Silane B (0.013) 1-4 Aniline derivative 4 PTA (0.202) Silane A (0.007) CHN (20) (0.113) F4TCNQ (0.089) Silane B (0.013) 1-5 Aniline derivative 5 PTA (0.202) Silane A (0.007) CHN (20) (0.088) F4TCNQ (0.114) Silane B (0.013) 1-6 Aniline derivative 6 PTA (0.202) Silane A (0.007) CHN (20) (0.095) F4TCNQ (0.107) Silane B (0.013) 1-7 Aniline derivative 7 PTA (0.202) Silane A (0.007) CHN (20) (0.105) F4TCNQ (0.097) Silane B (0.013) 1-8 Aniline derivative 7 PTA (0.202) Silane A (0.007) CHN (20) (0.071) F4TCNQ (0.131) Silane B (0.013) 1-9 Aniline derivative 8 PTA (0.202) Silane A (0.007) CHN (20) (0.062) F4TCNQ (0.140) Silane B (0.013) 1-10 Aniline derivative 9 PTA (0.202) Silane A (0.007) CHN (20) (0.061) F4TCNQ (0.140) Silane B (0.013) 1-11 Aniline derivative 10 PTA (0.202) Silane A (0.007) CHN (20) (0.063) F4TCNQ (0.139) Silane B (0.013) 1-12 Aniline derivative 11 PTA (0.102) Silane A (0.003) CHN (5) (0.052) F4TCNQ (0.050) Silane B (0.007) 1-13 Aniline derivative 11 PTA (0.263) Silane A (0.009) CHN (5) (0.133) F4TCNQ (0.130) Silane B (0.018) 1-14 Aniline derivative 12 PTA (0.101) Silane A (0.003) CHN (10) (0.053) F4TCNQ (0.048) Silane B (0.007) 1-15 Aniline derivative 12 PTA (0.309) Silane A (0.010) CHN (10) (0.113) F4TCNQ (0.147) Silane B (0.021) 1-16 Aniline derivative 13 PTA (0.202) Silane A (0.007) CHN (20) (0.063) F4TCNQ (0.139) Silane B (0.013) 1-17 Aniline derivative 13 PTA (0.619) Silane A (0.021) CHN (20) (0.223) F4TCNQ (0.395) Silane B (0.041) 1-18 Aniline derivative 14 PTA (0.202) Silane A (0.007) CHN (20) (0.076) F4TCNQ (0.126) Silane B (0.013) 1-19 Aniline derivative 14 PTA (0.619) Silane A (0.021) CHN (20) (0.232) F4TCNQ (0.387) Silane B (0.041) 1-20 Aniline derivative 15 PTA (0.202) Silane A (0.007) CHN (20) (0.075) F4TCNQ (0.127) Silane B (0.013) 1-21 Aniline derivative 16 PTA (0.202) Silane A (0.007) CHN (20) (0.088) F4TCNQ (0.114) Silane B (0.013) 1-22 Aniline derivative 17 PTA (0.202) Silane A (0.007) CHN (20) (0.073) F4TCNQ (0.129) Silane B (0.13) 1-23 Aniline derivative 18 PTA (0.619) Silane A (0.021) DMI (14) (0.321) F4TCNQ (0.306) Silane B (0.041) 2,3-B,D (4) PGME (2) 1-24 Aniline derivative 18 PTA (0.309) Silane A (0.010) DMI (7) (0.171) F4TCNQ (0.138) Silane B (0.021) 2,3-B,D (2) PGME (1)

(283) TABLE-US-00020 TABLE 20 Exam- Charge transporting Dopant Organic ple substance substance Organosilane solvent 1-25 Aniline derivative 9 SAC (0.107) DMI (3.3) (0.093) CHA (4.9) PG (1.6) 1-26 Aniline derivative 9 SAC (0.107) Silane A (0.007) DMI (3.3) (0.093) Silane B (0.013) CHA (4.9) PG (1.6) 1-27 Aniline derivative 9 PTA (0.101) Silane A (0.003) DMI (4.0) (0.047) F4TCNQ (0.054) Silane B (0.007) 2,3-BD (4.5) ECA (1.5) 1-28 Aniline derivative 11 PTA (0.101) Silane A (0.003) CHN (10) (0.056) DDQ (0.045) Silane B (0.007) 1-29 Aniline derivative 11 PTA (0.101) Silane A (0.003) CHN (10) (0.062) F4BQ (0.039) Silane B (0.007) 1-30 Aniline derivative 11 PMA (0.101) Silane A (0.003) CHN (10) (0.051) F4TCNQ (0.039) Silane B (0.007) 1-31 Aniline derivative 11 PTA (0.202) Silane A (0.007) DMI (8.0) (0.102) F4TCNQ (0.100) Silane B (0.013) 2,3-BD (9.0) ECA (3.0) 1-32 Aniline derivative 13 PTA (0.101) Silane A (0.003) DMI (4.0) (0.054) F4TCNQ (0.047) Silane B (0.007) 2,3-BD (4.5) ECA (1.5) 1-33 Aniline derivative 14 PTA (0.101) Silane A (0.003) DMI (4.0) (0.055) F4TCNQ (0.046) Silane B (0.007) 2,3-BD (4.5) ECA (1.5) 1-34 Aniline derivative 18 PMA (0.202) Silane A (0.003) CHN (20) (0.102) F4TCNQ (0.100) Silane B (0.007) 1-35 Aniline derivative 18 PTA (0.202) Silane A (0.007) DMI (8.0) (0.102) F4TCNQ (0.100) Silane B (0.013) 2,3-BD (9.0) ECA (3.0) 1-36 Aniline derivative 18 PTA (0.093) Silane A (0.003) DMI (2.1) (0.051) DDQ (0.041) Silane B (0.006) 2,3-BD (0.6) PGME (0.3) 1-37 Aniline derivative 18 PTA (0.309) Silane A (0.010) DMI (7.0) (0.157) DDQ (0.152) Silane B (0.021) 2,3-BD (2.0) PGME (1.0) 1-38 Aniline derivative 18 PTA (0.309) Silane A (0.010) DMI (7.0) (0.145) DDQ (0.164) Silane B (0.021) 2,3-BD (2.0) PGME (1.0) 1-39 Aniline derivative 18 PTA (0.309) Silane A (0.010) DMI (7.0) (0.135) DDQ (0.174) Silane B (0.021) 2,3-BD (2.0) PGME (1.0) 1-40 Aniline derivative 18 DDQ (0.091) Silane A (0.007) DMI (7.0) (0.113) Silane B (0.014) 2,3-BD (2.0) PGME (1.0) 1-41 Aniline derivative 18 PTA (0.102) Silane A (0.007) DMI (7.0) (0.113) DDQ (0.091) Silane B (0.014) 2,3-BD (2.0) PGME (1.0) 1-42 Aniline derivative 18 PTA (0.306) Silane A (0.007) DMI (7.0) (0.113) DDQ (0.091) Silane B (0.014) 2,3-BD (2.0) PGME (1.0) 1-43 Aniline derivative 18 PTA (0.408) Silane A (0.007) DMI (7.0) (0.113) DDQ (0.091) Silane B (0.014) 2,3-BD (2.0) PGME (1.0) 1-44 Aniline derivative 18 PTA (0.204) Silane A (0.007) DMI (7.0) (0.113) DDQ (0.091) Silane B (0.014) 2,3-BD (2.0) PGME (1.0) 1-45 Aniline derivative 19 SAC (0.138) DMI (3.3) (0.062) CHA (4.9) PG (1.6) 1-46 Aniline derivative 19 SAC (0.138) Silane A (0.007) DMI (3.3) (0.062) Silane B (0.013) CHA (4.9) PG (1.6) 1-47 Aniline derivative 19 PTA (0.101) Silane A (0.003) DMI (4.0) (0.043) F4TCNQ (0.058) Silane B (0.007) 2,3-BD (4.5) ECA (1.5) 1-48 Aniline derivative 19 SAC (0.128) DMI (4.0) (0.117) CHA (6.0) PG (2.0)

(284) TABLE-US-00021 TABLE 21 Exam- Charge transporting Dopant Organic ple substance substance Organosilane solvent 1-49 Aniline derivative 21 PTA (0.155) Silane A (0.005) DMI (3.5) (0.082) F4TCNQ (0.072) Silane B (0.010) 2,3-BD (1.0) PGME (0.5) 1-50 Aniline derivative 21 PTA (0.0155) Silane A (0.005) DMI (3.5) (0.090) DDQ (0.065) Silane B (0.010) 2,3-BD (1.0) PGME (0.5) 1-51 Aniline derivative 23 PTA (0.101) Silane A (0.003) DMI (4.0) (0.055) F4TCNQ (0.046) Silane B (0.007) 2,3-BD (4.5) ECA (1.5) 1-52 Aniline derivative 24 PTA (0.101) Silane A (0.003) DMI (4.0) (0.058) F4TCNQ (0.043) Silane B (0.007) 2,3-BD (4.5) ECA (1.5) 1-53 Aniline derivative 25 PTA (0.101) Silane A (0.003) DMI (4.0) (0.056) F4TCNQ (0.045) Silane B (0.007) 2,3-BD (4.5) ECA (1.5) 1-54 Aniline derivative 25 PTA (0.416) Silane A (0.014) DMI (14.0) (0.230) F4TCNQ (0.187) Silane B (0.028) 2,3-BD (4.0) DPM (2.0) 1-55 Aniline derivative 25 PTA (0.416) Silane A (0.014) DMI (14.0) (0.250) DDQ (0.167) Silane B (0.028) 2,3-BD (4.0) DPM (2.0) 1-56 Aniline derivative 28 PTA (0.155) Silane A (0.005) DMI (3.5) (0.085) F4TCNQ (0.070) Silane B (0.010) 2,3-BD (1.0) PGME (0.5) 1-57 Aniline derivative 28 PTA (0.155) Silane A (0.005) DMI (3.5) (0.085) DDQ (0.063) Silane B (0.010) 2,3-BD (1.0) PGME (0.5) 1-58 Aniline derivative 29 PTA (0.101) Silane A (0.003) DMI (4.0) (0.056) F4TCNQ (0.045) Silane B (0.007) 2,3-BD (4.5) ECA (1.5) 1-59 Aniline derivative 18 PTA (0.833) Silane A (0.028) DMI (28.0) (0.421) F4TCNQ (0.412) Silane B (0.056) 2,3-BD (8.0) DPM (4.0) 1-60 Aniline derivative 18 PTA (1.666) Silane A (0.056) DMI (56.0) (0.842) F4TCNQ (0.824) Silane B (0.111) 2,3-BD (16.0) PGME (8.0) 1-61 Aniline derivative 18 PTA (0.151) Silane A (0.005) DMI (8.0) (0.076) F4TCNQ (0.075) Silane B (0.010) 2,3-BD (9.0) ECA (3.0) 1-62 Aniline derivative 24 CHN (10) (0.204) 1-63 Aniline derivative 22 DMIB (10) (0.208) 1-64 Aniline derivative 26 DMIB (10) (0.208)

[3] Production of Organic EL Elements and Evaluation of their Characteristics

[3-1] Use as Hole Injection Layer

Example 2-1

(285) The varnish obtained in Example 1-1 was applied to an ITO substrate by use of a spin coater, and then dried at 80 C. for one minute. Further, the varnish was baked in the atmospheric air at 150 C. for five minutes, to form a 30 nm-thick uniform thin film on the ITO substrate. As the ITO substrate, a glass substrate measuring 25 mm by 25 mm and 0.7 thick provided thereon with a pattern of 150 nm-thick film of indium tin oxide (ITO) was used, by removing impurities on its surface by an O.sub.2 plasma cleaning apparatus (150 W, 30 minutes) before use.

(286) Next, on the ITO substrate thus formed with the thin film, a 30 nm-thick film of a-NPD (N,N-di(1-naphthyl)-N,N-diphenylbenzidine) was formed at 0.2 nm/second by use of a vapor deposition system (vacuum degree 1.010.sup.5 Pa). Subsequently, CBP and Ir(PPy).sub.3 were co-evaporated. The co-evaporation was conducted while controlling the vapor deposition rates in such a manner as to obtain an Ir(PPy).sub.3 concentration of 6%, the film thickness being 40 nm. Next, thin films of BAlq, lithium fluoride, and aluminum were sequentially formed, to obtain an organic EL element. In this case, the vapor deposition rate was 0.2 nm/second for BAlq and aluminum, and 0.02 nm/second for lithium fluoride, and the thicknesses of the thin films were each set to be 20 nm, 0.5 nm, and 120 nm.

(287) Note that in order to prevent characteristics from being degraded under influences of oxygen and water in air, the organic EL element was sealed with sealing substrates, before evaluation of the characteristics thereof. The sealing was conducted by the following procedure. The organic EL element was placed between the sealing substrates in a nitrogen atmosphere with an oxygen concentration of up to 2 ppm and a dew point of up to 85 C., and the sealing substrates were adhered to each other using an adhesive (XNR5516Z-B1, manufactured by Nagase ChemteX Corporation). In this instance, a water capturing agent (HD-071010W-40, manufactured by Dynic Corporation) was placed inside the sealing substrates together with the organic EL element. After the thus adhered sealing substrates were irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ/cm.sup.2), an annealing treatment was conducted at 80 C. for one hour, to cure the adhesive.

(288) ##STR00212##

Examples 2-2 to 2-12, 2-14, 2-16, 2-18, and 2-20 to 2-24

(289) Organic EL elements were produced by the same method as in Example 2-1, except for each using the varnishes obtained in Examples 1-2 to 1-12, 1-14, 1-16, 1-18, and 1-20 to 1-24 in place of the varnish obtained in Example 1-1.

Examples 2-13, 2-15, 2-17 and 2-19

(290) Organic EL elements were produced by the same method as in Example 2-1, except for each using the varnishes obtained in Examples 1-13, 1-15, 1-17, and 1-19 in place of the varnish obtained in Example 1-1 and setting the thickness of the thin film formed on the ITO substrate to 100 nm.

Examples 2-25 to 2-38

(291) Organic EL elements were produced by the same method as in Example 2-1, except for setting the aluminum film thickness to 100 nm, each using the varnishes obtained in Examples 1-27 to 1-35, 1-47, 1-51 to 1-53, and 1-58 in place of the varnish obtained in Example 1-1.

Examples 2-39 to 2-53

(292) Organic EL elements were produced by the same method as in Example 2-1, except for setting the aluminum film thickness to 100 nm, each using the varnishes obtained in Examples 1-23, 1-36 to 1-43, 1-49, 1-50, and 1-54 to 1-57 in place of the varnish obtained in Example 1-1, and setting the baking time at 150 C. to 10 minutes.

Example 2-54

(293) An organic EL element was produced by the same method as in Example 2-1, except for setting the aluminum film thickness to 100 nm, using the varnish obtained in Example 1-44 in place of the varnish obtained in Example 1-1, setting the baking time at 150 C. to 10 minutes, and setting the thickness of the thin film formed on the ITO substrate to 90 nm.

Example 2-55

(294) An organic EL element was produced by the same method as in Example 2-1, except for setting the aluminum film thickness to 100 nm, using the varnish obtained in Example 1-23 in place of the varnish obtained in Example 1-1, setting the baking time at 150 C. to 10 minutes, and setting the thickness of the thin film formed on the ITO substrate to 100 nm.

Example 2-56

(295) An organic EL element was produced by the same method as in Example 2-1, except for setting the aluminum film thickness to 100 nm, using the varnish obtained in Example 1-52 in place of the varnish obtained in Example 1-1, and baking in vacuum instead of baking in the atmospheric air.

Example 2-57

(296) An organic EL element was produced by the same method as in Example 2-1, except for setting the aluminum film thickness to 100 nm, using the varnish obtained in Example 1-23 in place of the varnish obtained in Example 1-1, setting the baking time at 150 C. to 10 minutes, and baking in vacuum instead of baking in the atmospheric air.

Example 2-58

(297) An organic EL element was produced by the same method as in Example 2-1, except for setting the aluminum film thickness to 100 nm, using the varnish obtained in Example 1-23 in place of the varnish obtained in Example 1-1, setting the baking time at 150 C. to 10 minutes, baking in vacuum instead of baking in the atmospheric air, and setting the thickness of the thin film formed on the ITO substrate to 100 nm.

Examples 2-59 to 2-67

(298) Organic EL elements were produced by the same method as in Example 2-1, except for setting the aluminum film thickness to 100 nm, each using the varnishes obtained in Examples 1-23, 1-25, 1-26, 1-44 to 1-46, 1-48, 1-54, and 1-55 in place of the varnish obtained in Example 1-1, and baking at 230 C. for 15 minutes instead of baking at 150 C. for five minutes.

Example 2-68

(299) An organic EL element was produced by the same method as in Example 2-1, except for setting the aluminum film thickness to 100 nm, using the varnish obtained in Example 1-44 in place of the varnish obtained in Example 1-1, baking at 230 C. for 15 minutes instead of baking at 150 C. for five minutes, and setting the thickness of the thin film formed on the ITO substrate to 90 nm.

Examples 2-69 and 2-70

(300) Organic EL elements were produced by the same method as in Example 2-1, except for setting the aluminum film thickness to 100 nm, each using the varnishes obtained in Examples 1-63 and 1-64 in place of the varnish obtained in Example 1-1, and setting the baking time at 150 C. to 10 minutes.

(301) Driving voltage, luminance, and luminous efficiency at a driving current of 0.7 mA as well as luminance half-life (the time required for the luminance to reach one half the initial value in the case where the element is continuously driven with a driving current kept at 0.7 mA) were measured, for the elements obtained in Examples 2-1 to 2-22, 2-25 to 2-39, 2-55 to 2-61, and 2-63 to 2-65.

(302) In addition, driving voltage, current density, and luminous efficiency in the case of driving at a luminance of 5,000 cd/m.sup.2 as well as luminance half-life (the time required for luminance to reach one half the initial luminance of 5,000 cd/m.sup.2) were measured, for the elements obtained in Examples 2-23, 2-24, 2-40 to 2-54, 2-62, and 2-66 to 2-68. The results are set forth in Tables 22 to 25.

(303) TABLE-US-00022 TABLE 22 Thickness of Lumi- charge trans- Driving Lumi- nous Exam- porting thin film voltage nance efficiency Half-life ple (nm) (V) (cd/m.sup.2) (cd/A) (hours) 2-1 30 8.9 4820 27.5 301 2-2 30 9.6 5040 28.8 173 2-3 30 9.1 5070 29.0 280 2-4 30 8.9 4970 28.4 307 2-5 30 9.3 4920 28.1 276 2-6 30 8.8 4550 26.0 263 2-7 30 8.3 3660 20.9 351 2-8 30 9.0 4810 27.5 295 2-9 30 8.8 4290 24.6 419 2-10 30 8.9 4724 27.0 239 2-11 30 9.0 4880 27.9 351 2-12 30 9.2 5100 29.2 380 2-13 100 9.5 5350 30.6 227 2-14 30 9.3 5180 29.6 307 2-15 100 9.2 5460 31.2 278 2-16 30 9.2 5095 29.1 404 2-17 100 9.0 5328 30.5 323 2-18 30 9.2 5146 29.4 412 2-19 100 9.2 5336 30.5 291 2-20 30 9.2 4470 25.6 358 2-21 30 9.2 4970 28.4 195 2-22 30 9.4 4708 26.9 258

(304) TABLE-US-00023 TABLE 23 Thickness of Lumi- charge trans- Driving Current nous Exam- porting thin film voltage density efficiency Half-life ple (nm) (V) (mA/cm.sup.2) (cd/A) (hours) 2-23 30 9.39 17.6 28.4 242 2-24 30 9.43 17.9 27.9 388

(305) TABLE-US-00024 TABLE 24 Thickness of Lumi- charge trans- Driving Lumi- nous Exam- porting thin film voltage nance efficiency Half-life ple (nm) (V) (cd/m.sup.2) (cd/A) (hours) 2-25 30 9.10 5060 24.4 129 2-26 30 9.38 4643 26.5 362 2-27 30 10.30 4530 25.9 283 2-28 30 9.43 4770 27.3 365 2-29 30 9.41 5020 28.9 145 2-30 30 9.38 5000 28.8 182 2-31 30 9.38 5100 29.2 183 2-32 30 9.87 4994 28.5 230 2-33 30 9.40 4920 28.4 226 2-34 30 9.31 5020 27.3 165 2-35 30 9.61 5169 29.5 204 2-36 30 9.45 5149 29.4 189 2-37 30 9.61 4842 27.7 261 2-38 30 9.31 5080 27.8 170 2-39 30 9.26 4925 28.1 369 2-55 100 9.26 5042 28.8 310 2-56 30 9.58 5132 29.3 231 2-57 30 9.50 5063 28.9 347 2-58 100 9.29 5014 28.7 270 2-59 30 9.8 4987 28.5 376 2-60 30 9.6 4906 28.0 466 2-61 30 9.3 4865 27.8 504 2-63 30 9.5 4647 26.6 220 2-64 30 9.6 4807 27.5 209 2-65 30 9.8 4739 27.1 300 2-69 30 11.1 18.9 26.5 375 2-70 30 11.2 20.6 24.2 398

(306) TABLE-US-00025 TABLE 25 Thickness of Lumi- charge trans- Driving Current nous Exam- porting thin film voltage density efficiency Half-life ple (nm) (V) (mA/cm.sup.2) (cd/A) (hours) 2-40 30 9.52 18.0 27.8 271 2-41 30 9.49 18.0 27.8 289 2-42 30 9.39 18.2 27.6 313 2-43 30 9.42 18.6 26.9 300 2-44 30 9.76 17.4 28.8 2-45 30 9.70 17.9 27.9 206 2-46 30 9.49 18.4 27.1 270 2-47 30 9.40 18.3 27.4 194 2-48 30 9.43 17.9 27.9 388 2-49 30 9.39 17.6 28.4 242 2-50 30 9.40 18.3 27.3 294 2-51 30 9.31 18.4 27.1 388 2-52 30 9.41 17.8 28.1 382 2-53 30 9.44 17.9 28.0 220 2-54 90 9.48 17.4 28.8 188 2-62 30 9.50 18.9 26.5 413 2-66 30 9.40 18.6 26.9 378 2-67 30 9.34 19.1 26.1 596 2-68 90 9.50 17.8 28.0 443

(307) As shown in Tables 22 to 25, it is seen that the organic EL elements having a charge transporting thin film obtained from the charge transporting varnish of the present invention as a hole injection layer show high luminance and are excellent in durability not only when the film thickness is comparatively small (30 nm) but also when the film thickness is comparatively large (90 nm, 100 nm).

Example 3-1

(308) The varnish obtained in Example 1-59 was applied to an Al/Nd substrate by use of a spin coater, dried at 80 C. for one minute, and further baked in the atmospheric air at 150 C. for five minutes, to form a 30 nm-thick uniform thin film on the Al/Nd substrate. Note that the Al/Nd substrate was produced by sputtering Al and Nd by 150 nm onto a glass substrate, and impurities on the surface of the Al/Nd substrate were removed by use of an O.sub.2 plasma cleaning apparatus (150 W, 30 minutes) before use.

(309) Next, on the Al/Nd substrate formed thereon with the thin film, a 30 nm-thick film of a-NPD was formed at 0.2 nm/second by use of a vapor deposition system (vacuum degree 1.010.sup.5 Pa). Subsequently, CBP and Ir(PPy).sub.3 were co-evaporated. Note that the co-evaporation was conducted by controlling the vapor deposition rates in such a manner as to obtain an Ir(PPy).sub.3 concentration of 6%, the film thickness being 40 nm.

(310) Next, thin films of BAlq and lithium fluoride were sequentially formed. In this case, the vapor deposition rate was 0.2 nm/second for BAlq and 0.02 nm/second for lithium fluoride, and the thicknesses of the thin films were each 20 nm and 0.5 nm.

(311) Finally, magnesium and silver were co-evaporated, to obtain an organic EL element. Note that the co-evaporation was conducted by controlling the vapor deposition rates in such a manner as to obtain a magnesium concentration of 90%, the film thickness being 20 nm.

(312) Note that the element was sealed by the same method as in Example 2-1, before put to evaluation of characteristics thereof.

Examples 3-2 and 3-3

(313) Organic EL elements were produced by the same method as in Example 3-1, except for each using the varnishes obtained in Examples 1-60 and 1-61 in place of the varnish obtained in Example 1-59.

(314) Driving voltage, current density, and luminous efficiency in the case of driving at a luminance of 3,000 cd/m.sup.2 as well as luminance half-life (the time required for luminance to reach one half the initial luminance of 3,000 cd/m.sup.2) were measured, for the elements obtained in Examples 3-1 to 3-3. The results are set forth in Table 26.

(315) TABLE-US-00026 TABLE 26 Thickness of Lumi- charge trans- Driving Current nous Exam- porting thin film voltage density efficiency Half-life ple (nm) (V) (mA/cm.sup.2) (cd/A) (hours) 3-1 30 11.5 13.5 22.2 1287 3-2 30 11.5 13.1 23.0 1291 3-3 30 11.5 12.3 24.4 1063

(316) As shown in Table 26, it is seen that the charge transporting thin films obtained from the charge transporting varnishes of the present invention can be used also as a hole injection layer in an organic EL element of a top emission structure.

Example 4-1

(317) 0.165 g of a triphenylamine derivative represented by the formula (H6-1) and 0.325 g of an arylsulfonic acid compound represented by the formula (H4-1) were dissolved in 8 g of 1,3-dimethyl-2-imidazolidinone in a nitrogen atmosphere. To the resulting solution were added 12 g of cyclohexanol and 4 g of propylene glycol, followed by stirring, and 0.016 g of 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.033 g of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were further added thereto, followed by stirring, to obtain a hole injection layer forming composition. Note that the triphenylamine derivative represented by the formula (H6-1) was synthesized according to the method described in PCT Patent Publication No. WO 2013/084664, here and hereafter.

(318) ##STR00213##

(319) Next, the hole injection layer forming composition was applied to an ITO substrate by use of a spin coater, then dried at 80 C. for one minute, and further baked at 230 C. for 15 minutes in the atmospheric air, to form a 30 nm-thick uniform thin film on the ITO substrate as a hole injection layer. As the ITO substrate, a glass substrate measuring 25 mm by 25 mm and 0.7 thick formed thereon with a pattern of a 150 nm-thick film of indium tin oxide (ITO) was used, and impurities on the surface thereof were removed by an O.sub.2 plasma cleaning apparatus (150 W, 30 minutes) before use.

(320) Subsequently, on the ITO substrate thus formed with the thin film, vapor deposition method (vapor deposition rate 0.2 nm/second) using the aniline derivative 6 as a vapor source was conducted, to form a 30 nm-thick uniform thin film composed only of the aniline derivative 6 on the hole injection layer.

(321) Then, CBP and Ir(PPy).sub.3 were co-evaporated by use of a vapor deposition system (vacuum degree 1.010.sup.5 Pa). The co-evaporation was conducted by controlling the vapor deposition rates in such a manner as to obtain an Ir(PPy).sub.3 concentration of 6%, the film thickness being 40 nm.

(322) Finally, thin films of BAlq, lithium fluoride and aluminum were sequentially formed, to obtain an organic EL element. In this case, the vapor deposition rate was 0.2 nm/second for BAlq and aluminum and 0.02 nm/second for lithium fluoride, and the thicknesses of the thin films were each 20 nm, 0.5 nm and 100 nm.

(323) Note that the element was sealed by the same method as in Example 2-1, before put to evaluation of characteristics thereof.

(324) Driving voltage, luminance and luminous efficiency at a driving current of 0.7 mA were measured, for the element obtained in Example 4-1. The results are set forth in Table 27.

(325) TABLE-US-00027 TABLE 27 Thickness of Lumi- charge trans- Driving Current nous Exam- porting thin film voltage density efficiency Half-life ple (nm) (V) (mA/cm.sup.2) (cd/A) (hours) 4-1 30 11.1 54.2 9.2

(326) As shown in FIG. 27, it was found that the charge transporting thin film composed of the vapor-deposited film of the aniline derivative of the present invention is also excellent in charge transporting properties and is preferable as a hole injection layer in an organic EL element.

[3-2] Use of Thin Film as Hole Transport Layer or Hole Injection Transport Layer

Example 5-1

(327) An organic EL element was produced by the same method as in Example 4-1, except that instead of forming a vapor-deposited film of the aniline derivative 6 on the hole injection layer, the varnish obtained in Example 1-62 was applied by use of a spin coater, dried at 80 C. for one minute, and further baked in the atmospheric air at 150 C. for five minutes, to form a 30 nm-thick uniform thin film on the hole injection layer.

Example 5-2

(328) An organic EL element was produced by the same method as in Example 5-1, except that the baking time was 10 minutes.

Example 5-3

(329) An organic EL element was produced by the same method as in Example 5-1, except that the baking temperature was 230 C.

Example 6-1

(330) The varnish obtained in Example 1-62 was applied to an ITO substrate by use of a spin coater, dried at 80 C. for one minute, and further baked in the atmospheric air at 150 C. for five minutes, to form a 30 nm-thick uniform thin film on the ITO substrate. As the ITO substrate, a glass substrate measuring 25 mm by 25 mm and 0.7 thick formed thereon with a pattern of a 150 nm-thick film of indium tin oxide (ITO) was used, and impurities on the surface thereof were removed by an O.sub.2 plasma cleaning apparatus (150 W, 30 minutes) before use.

(331) Next, on the ITO substrate thus formed with the thin film, CBP and Ir(PPy).sub.3 were co-evaporated by use of a vapor deposition system (vacuum degree 1.010.sup.5 Pa). The co-evaporation was conducted by controlling the vapor deposition rates in such a manner as to obtain an Ir(PPy).sub.3 concentration of 6%, the film thickness being 40 nm. Subsequently, thin films of BAlq, lithium fluoride, and aluminum were sequentially formed, to obtain an organic EL element. In this case, the vapor deposition rate was 0.2 nm/second for BAlq and aluminum and 0.02 nm/second for lithium fluoride, and the thicknesses of the thin films were each 20 nm, 0.5 nm, and 100 nm.

(332) Note that the element was sealed by the same method as in Example 2-1, before put to evaluation of characteristics thereof.

(333) Driving voltage, current density, and luminous efficiency in the case of driving at a luminance of 1,000 cd/m.sup.2 as well as luminance half-life at a driving current of 0.7 mA (the time required for luminance to reach one half the initial value in the case where the element is continuously driven with the driving current kept at 0.7 mA) were measured, for the elements obtained in Examples 5-1 to 5-3, and 6-1. The results are set forth in Table 28.

(334) TABLE-US-00028 TABLE 28 Thickness of Lumi- charge trans- Driving Current nous Exam- porting thin film voltage density efficiency Half-life ple (nm) (V) (mA/cm.sup.2) (cd/A) (hours) 5-1 30 8.8 6.3 15.9 314 5-2 30 8.8 6.4 15.6 320 5-3 30 8.5 5.1 19.5 266 6-1 30 9.0 5.6 17.8 255

(335) As shown in Table 28, it is seen that the charge transporting thin films obtained from the charge transporting varnishes of the present invention can be preferably used also as a hole transport layer and a hole injection transport layer, and by use of the thin films, organic EL elements excellent in luminance characteristics and durability can be obtained.