JP2003238558A - Amine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new amine compound. <P>SOLUTION: This amine compound is represented by formula (1) (wherein, Ar<SB>1</SB>and Ar<SB>3</SB>denote each independently a substituted or an unsubstituted biphenyl group; and Ar<SB>2</SB>and Ar<SB>4</SB>denote each independently a substituted or an unsubstituted naphthyl group). <P>COPYRIGHT: (C)2003,JPO

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel amine compound. [0002] Conventionally, amine compounds have been used as intermediates for producing various dyes or as various functional materials. As a functional material, for example, it has been used as a charge transport material of an electrophotographic photosensitive member. Furthermore, recently, it has been proposed to be useful as a hole injection / transport material for an organic electroluminescent device (organic electroluminescence device: organic EL device) using an organic material as a light emitting material [for example, App.
l. Phys. Lett., 51 , 913 (1987)]. It has been proposed to use 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl as a hole injecting and transporting material for an organic electroluminescent device [Jpn. J. Appl. Ph
ys., 27 , L269 (1988)]. Further, as a hole injecting and transporting material for an organic electroluminescent element, for example, 2,5-bis [4 ′
-(N, N-diarylamino) phenyl] -3,4-
Diphenylthiophene derivative [for example, 2,5-bis [4 ′-[N-phenyl-N- (2 ″ -naphthyl) amino] phenyl] -3,4-diphenylthiophene;
It has been proposed to use 5-bis [4 ′-[N-phenyl-N- (4 ″ -phenylphenyl) amino] phenyl] -3,4-diphenylthiophene]
0-125468). However, an organic electroluminescent device using these amine compounds as a hole injecting / transporting material has disadvantages such as poor stability and durability. At present, to obtain a more improved organic electroluminescent device,
New amine compounds are desired. [0003] An object of the present invention is to provide a novel amine compound. More specifically, it is an object of the present invention to provide a novel amine compound suitable for a hole injection / transport material of an organic electroluminescent device. [0004] The present inventors have made intensive studies on various amine compounds, and as a result, have completed the present invention. That is, the present invention is an amine compound represented by the general formula (1). [0005] [0006] (wherein, Ar ₁ and Ar ₃ each independently represent a substituted or unsubstituted biphenyl group, Ar ₂
And Ar ₄ each independently represent a substituted or unsubstituted naphthyl group. DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below. The present invention is an amine compound represented by the general formula (1). [0008] [0009] (wherein, Ar ₁ and Ar ₃ each independently represent a substituted or unsubstituted biphenyl group, Ar ₂
And Ar ₄ each independently represent a substituted or unsubstituted naphthyl group. In the general formula (1), Ar ₁ and Ar 4
₃ represents a substituted or unsubstituted biphenyl group. Ar ₁ and Ar ₃ are preferably unsubstituted or, as a substituent, for example, a total of 12 to 26 carbon atoms which may be mono- or polysubstituted by a halogen atom, an alkyl group, an alkoxy group, or an aryl group. Is a biphenyl group,
More preferably, it may be unsubstituted or mono- or polysubstituted by a halogen atom, an alkyl group having 1 to 14 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or an aryl group having 6 to 10 carbon atoms. A biphenyl group having 12 to 26 carbon atoms in total, more preferably an unsubstituted or halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl having 6 to 10 carbon atoms A biphenyl group having a total of 12 to 22 carbon atoms which may be mono- or polysubstituted. In the general formula (1), Ar ₂ and Ar
₄ represents a substituted or unsubstituted naphthyl group. Ar ₂ and Ar ₄ are preferably unsubstituted or, as a substituent, for example, a halogen atom, an alkyl group, an alkoxy group or an aryl group, which has a total of 10 to 24 carbon atoms which may be mono- or polysubstituted. A naphthyl group, which is unsubstituted or a halogen atom, an alkyl group having 1 to 14 carbon atoms, an alkoxy group having 1 to 14 carbon atoms or 6 carbon atoms;
A naphthyl group having a total of 10 to 24 carbon atoms, which may be monosubstituted or polysubstituted with an aryl group of 10 to 10, more preferably an unsubstituted or halogen atom, a carbon atom of 1
A naphthyl group having a total carbon number of 10 to 20, which may be mono- or polysubstituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Specific examples of the substituted or unsubstituted biphenyl group in Ar ₁ and Ar ₃ include, for example, 4-
Phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4′-methylphenyl) phenyl group, 4- (3′-methylphenyl) phenyl group,
-(4'-ethylphenyl) phenyl group, 4- (4'-
Isopropylphenyl) phenyl group, 4- (4′-tert
-Butylphenyl) phenyl group, 4- (4'-n-hexylphenyl) phenyl group, 4- (4'-n-octylphenyl) phenyl group, 4- (4'-n-dodecylphenyl) phenyl group, -(4'-methylphenyl) phenyl group, 2- (4'-methylphenyl) phenyl group, 2
-(4'-ethylphenyl) phenyl group, 4- (4'-
Methoxyphenyl) phenyl group, 4- (3′-methoxyphenyl) phenyl group, 4- (4′-ethoxyphenyl) phenyl group, 4- (4′-n-butoxyphenyl)
Phenyl group, 4- (4'-n-hexyloxyphenyl) phenyl group, 4- (4'-n-octyloxyphenyl) phenyl group, 4- (4'-n-decyloxyphenyl) phenyl group, 3- (4′-methoxyphenyl) phenyl group, 2- (4′-methoxyphenyl) phenyl group, 2- (2′-methoxyphenyl) phenyl group, 4-
(4′-fluorophenyl) phenyl group, 4- (4′-
Chlorophenyl) phenyl group, 4- (3′-fluorophenyl) phenyl group, 4- (2′-fluorophenyl)
Phenyl group, 2- (4′-fluorophenyl) phenyl group, 3-methyl-4-phenylphenyl group, 4-methyl-3-phenylphenyl group, 4-methyl-2-phenylphenyl group, 5-methyl-2 -Phenylphenyl group, 6
-Methyl-3-phenylphenyl group, 2-ethyl-4-
Phenylphenyl group, 4-ethyl-2-phenylphenyl group, 2-methoxy-4-phenylphenyl group, 3-methoxy-4-phenylphenyl group, 4-methoxy-2-
Phenylphenyl group, 4-fluoro-2-phenylphenyl group, 3-fluoro-4-phenylphenyl group, 3-
Fluoro-2-phenylphenyl group, 5-fluoro-2
-Phenylphenyl group, 2,4-diphenylphenyl group, 2-phenyl-4- (4'-methylphenyl) phenyl group, 3,4-diphenylphenyl group, 3,5-diphenylphenyl group, and the like. However, the present invention is not limited to these. Specific examples of the substituted or unsubstituted naphthyl group in Ar ₂ and Ar ₄ include, for example, 1-naphthyl group, 2-naphthyl group, 2-methyl-1-naphthyl group, 4-methyl-1- Naphthyl group, 4-ethyl-1-naphthyl group, 4-n-butyl-1-naphthyl group, 4-n-
Hexyl-1-naphthyl group, 4-n-decyl-1-naphthyl group, 5-methyl-1-naphthyl group, 1-methyl-2
-Naphthyl group, 6-methyl-2-naphthyl group, 6-ethyl-2-naphthyl group, 6-n-butyl-2-naphthyl group, 6-n-octyl-2-naphthyl group, 2-methoxy-1- Naphthyl group, 4-methoxy-1-naphthyl group, 4
-N-butoxy-1-naphthyl group, 5-ethoxy-1-
Naphthyl group, 6-methoxy-2-naphthyl group, 6-ethoxy-2-naphthyl group, 6-n-butoxy-2-naphthyl group, 6-n-hexyloxy-2-naphthyl group, 7-
A methoxy-2-naphthyl group, a 7-n-butoxy-2-naphthyl group, a 4-phenyl-1-naphthyl group, a 6-phenyl-2-naphthyl group, a 4-fluoro-1-naphthyl group,
2-fluoro-1-naphthyl group, 4-chloro-1-naphthyl group, 4-chloro-2-naphthyl group, 6-chloro-2
-Naphthyl group, 6-bromo-2-naphthyl group, 2,4-
Examples thereof include, but are not limited to, a dichloro-1-naphthyl group and a 1,6-dichloro-2-naphthyl group. Specific examples of the amine compound represented by the general formula (1) include, for example, the following compounds, but the present invention is not limited thereto. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image The amine compound represented by the general formula (1) is
It can be produced by a method known per se. That is, the amine compound represented by the general formula (1) is, for example,
A compound represented by the general formula (2), a compound represented by the general formula (3), a compound represented by the general formula (4), a compound represented by the general formula (5), and a compound represented by the general formula (6) Reaction in the presence of a copper compound (Ullmann reaction)
It can be manufactured by doing. Embedded image [In the above formula, X _{1 to} X ₄ represent a halogen atom, and Ar _{1 to} Ar ₄ represent the same meaning as in the general formula (1).] The amine compound is obtained, for example, by reacting a compound represented by the general formula (7) with a compound represented by the general formula (8) and a compound represented by the general formula (9) in the presence of a copper compound ( (Ullmann reaction). Embedded image [In the above formula, X ₅ and X ₆ represent a halogen atom, and Ar _{1 to} Ar ₄ have the same meaning as in the general formula (1).] The amine compound is, for example, a compound represented by the general formula (7):
The compound represented by the general formula (8) is reacted (Ullman reaction) in the presence of a copper compound to produce a compound represented by the general formula (10), and further represented by the general formula (9). Can also be produced by reacting a compound (Ullmann reaction) in the presence of a copper compound. Of course, the amine compound represented by the general formula (1) is, for example, a compound represented by the general formula (7):
The compound represented by the general formula (9) is reacted (Ullman reaction) in the presence of a copper compound to produce a compound represented by the general formula (11), and further represented by the general formula (8). Can also be produced by reacting a compound (Ullmann reaction) in the presence of a copper compound. Embedded image [In the above formula, X ₅ and X ₆ represent a halogen atom, and Ar _{1 to} Ar ₄ have the same meaning as in the general formula (1).] In the general formulas (3) to (7), In the formula (10) and the general formula (11), X _{1 to} X ₆ represent a halogen atom, preferably represent a chlorine atom, a bromine atom or an iodine atom, and more preferably represent a bromine atom or an iodine atom. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but it is needless to say that the present invention is not limited to these examples. Example 1 Preparation of Compound of Exemplified Compound No. 1 In a nitrogen atmosphere, 6.4 g of 2,5-bis (4'-iodophenyl) -3,4-diphenylthiophene,
6.5 g of (1-naphthyl) -N- (4′-phenylphenyl) amine, 2 g of metallic copper powder, and 10 g of anhydrous potassium carbonate in o-dichlorobenzene (50 g) at 190 ° C.
For 15 hours. After cooling the reaction mixture to 100 ° C.,
After hot filtration, methanol (200 g) was added to the filtrate,
The precipitated pale yellow solid was filtered and dried. This solid is subjected to alumina column chromatography (eluent: toluene)
After further purification by sublimation (300 ° C.) under reduced pressure (10 ⁻⁶ torr), 6.3 g of the compound of Exemplified Compound No. 1 was obtained as a pale yellow solid. Glass transition temperature 157
° C and did not show a clear melting point. Example 2 Preparation of Compound of Exemplified Compound No. 2 In Example 1, N- (1-naphthyl) -N- (4 '
Instead of using (-phenylphenyl) amine, N-
The compound of Exemplified Compound No. 2 was produced as a pale yellow solid according to the method described in Example 1 except that (1-naphthyl) -N- [4 ′-(3 ″ -methylphenyl) phenyl] amine was used. The glass transition temperature was 155 ° C.
It did not show a clear melting point. Example 3 Preparation of Compound of Exemplified Compound No. 7 In Example 1, N- (1-naphthyl) -N- (4 '
Instead of using (-phenylphenyl) amine, N-
The compound of Exemplified Compound No. 7 was produced as a pale yellow solid according to the method described in Example 1 except that (1-naphthyl) -N- (3′-methyl-4′-phenylphenyl) amine was used. . The glass transition temperature was 151 ° C., and no clear melting point was exhibited. Example 4 Preparation of Compound of Exemplified Compound No. 9 In a nitrogen atmosphere, 64 g of 2,5-bis (4′-iodophenyl) -3,4-diphenylthiophene and N- (2
-Naphthyl) -N- (4'-phenylphenyl) amine 30 g, metallic copper powder 10 g, and anhydrous potassium carbonate 20
g was stirred in o-dichlorobenzene (200 g) at 190 ° C. for 8 hours. After the reaction mixture was cooled to 100 ° C. and filtered hot, methanol (400 g) was added to the filtrate, and the precipitated pale yellow solid was filtered and dried. This solid was treated by alumina column chromatography (eluent: toluene) to give 2- [4 '-[N- (2 "-naphthyl) -N-
(4 "'-phenylphenyl) amino] phenyl] -5
38 g of-(4 "'-iodophenyl) -3,4-diphenylthiophene was obtained. Further, under a nitrogen atmosphere, 8.0 g of this compound and N- (1-naphthyl) -N- (4'-
Phenylphenyl) amine 3.0 g, metallic copper powder 2 g, and anhydrous potassium carbonate 5 g were added to o-dichlorobenzene (5
In 0 g), the mixture was stirred at 190 ° C. for 8 hours. Reaction mixture 1
After cooling to 00 ° C and hot filtration, the filtrate was added with methanol (2
00g) was added, and the precipitated pale yellow solid was filtered and dried. This solid was purified by alumina column chromatography (eluent: toluene), and further purified under reduced pressure (10
Sublimation purification (300 ° C.) at ^-6 torr) afforded 5.6 g of compound of Exemplified Compound No. 9 as a pale yellow solid. The glass transition temperature was 158 ° C, and did not show a clear melting point. Example 5 Production of Compound of Exemplified Compound No. 10 In Example 4, N- (1-naphthyl) -N- (4 '
Instead of using (-phenylphenyl) amine, N-
The compound of Exemplified Compound No. 10 was produced as a pale yellow solid according to the method described in Example 4 except that (1-naphthyl) -N- [4 ′-(3 ″ -methylphenyl) phenyl] amine was used. The glass transition temperature was 155 ° C. and did not show a clear melting point Example 6 Preparation of Compound of Exemplified Compound No. 13 In Example 1, N- (1-naphthyl) -N- (4 ′) was prepared.
Instead of using (-phenylphenyl) amine, N-
According to the method described in Example 1 except that (2-naphthyl) -N- (4′-phenylphenyl) amine was used,
The compound of Exemplified Compound No. 13 was produced as a pale yellow solid. The glass transition temperature was 158 ° C, and did not show a clear melting point. Example 7 Preparation of Compound of Exemplified Compound No. 16 In Example 1, N- (1-naphthyl) -N- (4 '
Instead of using (-phenylphenyl) amine, N-
The compound of Exemplified Compound No. 16 was produced as a pale yellow solid according to the method described in Example 1 except that (2-naphthyl) -N- (3 ′, 4′-diphenylphenyl) amine was used. The glass transition temperature was 171 ° C. and did not show a clear melting point. Example 8 Preparation of Compound of Exemplified Compound No. 21 In a nitrogen atmosphere, 64 g of 2,5-bis (4′-iodophenyl) -3,4-diphenylthiophene and N- (1
-Naphthyl) -N- (4'-phenylphenyl) amine 30 g, metallic copper powder 10 g, and anhydrous potassium carbonate 20
g was stirred in o-dichlorobenzene (200 g) at 190 ° C. for 8 hours. After the reaction mixture was cooled to 100 ° C. and filtered hot, methanol (400 g) was added to the filtrate, and the precipitated pale yellow solid was filtered and dried. This solid was treated by alumina column chromatography (eluent: toluene) to give 2- [4 '-[N- (1 "-naphthyl) -N-
(4 "'-phenylphenyl) amino] phenyl] -5
42 g of-(4 ""-iodophenyl) -3,4-diphenylthiophene was obtained. Further, under a nitrogen atmosphere, 8.0 g of this compound and N- (2-naphthyl) -N- (3′-
Phenylphenyl) amine 3.0 g, metallic copper powder 2 g, and anhydrous potassium carbonate 5 g were added to o-dichlorobenzene (5
In 0 g), the mixture was stirred at 190 ° C. for 8 hours. Reaction mixture 1
After cooling to 00 ° C and hot filtration, the filtrate was added with methanol (2
00g) was added, and the precipitated pale yellow solid was filtered and dried. This solid was purified by alumina column chromatography (eluent: toluene), and further purified under reduced pressure (10
Sublimation purification (300 ° C.) at ^-6 torr) gave 5.4 g of the compound of Exemplified Compound No. 21 as a pale yellow solid. The glass transition temperature was 152 ° C, and did not show a clear melting point. Example 9 Preparation of Compound of Exemplified Compound No. 27 In Example 4, N- (1-naphthyl) -N- (4 '
Instead of using (-phenylphenyl) amine, N-
The compound of Exemplified Compound No. 27 was produced as a pale yellow solid according to the method described in Example 4 except that (2-naphthyl) -N- [3 ′-(4 ″ -methylphenyl) phenyl] amine was used. The glass transition temperature was 148 ° C. and no clear melting point was obtained Example 10 Preparation of Compound of Exemplified Compound No. 41 In Example 1, N- (1-naphthyl) -N- (4 ′) was prepared.
Instead of using (-phenylphenyl) amine, N-
According to the method described in Example 1, except that (1-naphthyl) -N- (3′-phenylphenyl) amine was used,
The compound of Exemplified Compound No. 41 was produced as a pale yellow solid. The glass transition temperature was 142 ° C, and did not show a clear melting point. Example 11 Preparation of Compound of Exemplified Compound No. 44 In Example 1, N- (1-naphthyl) -N- (4 '
Instead of using (-phenylphenyl) amine, N-
The compound of Exemplified Compound No. 44 was produced as a pale yellow solid according to the method described in Example 1 except that (1-naphthyl) -N- (3 ′, 5′-diphenylphenyl) amine was used. The glass transition temperature was 167 ° C., and no clear melting point was exhibited. Example 12 Preparation of Compound of Exemplified Compound No. 50 In Example 1, N- (1-naphthyl) -N- (4 '
Instead of using (-phenylphenyl) amine, N-
The compound of Exemplified Compound No. 50 was produced as a pale yellow solid according to the method described in Example 1, except that (2-naphthyl) -N- (3 ′, 5′-diphenylphenyl) amine was used. The glass transition temperature was 163 ° C., and no clear melting point was exhibited. Application Example 1 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, the compound of Exemplified Compound No. 1 was deposited on the ITO transparent electrode to a thickness of 75 nm at a deposition rate of 0.2 nm / sec to form a hole injection transport layer. Then tris (8-quinolinolato) aluminum was deposited thereon with a deposition rate of 0,1.
Evaporation was performed at a thickness of 50 nm at a rate of 2 nm / sec to form a light emitting layer also serving as an electron injection transport layer. Further, magnesium and silver were further deposited thereon as a cathode at a deposition rate of 0.2 nm / sec.
A cathode was formed by co-evaporation to a thickness of 00 nm (weight ratio: 10: 1) to produce an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. A direct current voltage is applied to the produced organic electroluminescent device, and at 50 ° C. in a dry atmosphere,
The device was continuously driven at a constant current density of 0 mA / cm ² . Initially, green light emission of 6.5 V and a luminance of 470 cd / m ² was confirmed. The half-life of the luminance was 750 hours. Application Examples 2 to 5 In Application Example 1, instead of using the compound of Exemplified Compound No. 1 in forming the hole injecting and transporting layer, the compound of Exemplified Compound No. 7 (Application Example 2) and the Exemplified Compound No. 10 (Application Example 3), the compound of Exemplified Compound No. 27 (Application Example 4), and the compound of Exemplified Compound No. 44 (Application Example 5), except that the organic electroluminescent device was fabricated by the method described in Application Example 1. Produced. Green light emission was confirmed from each element. The characteristics were further examined, and the results are shown in Table 1. Comparative Examples 1 to 3 In Application Example 1, instead of using the compound of Exemplified Compound No. 1 in forming the hole injecting and transporting layer,
-Bis [N-phenyl-N- (3 "-methylphenyl)
Amino] biphenyl (Comparative Example 1), 2,5-bis [4 ′
-[N-phenyl-N- (2 "-naphthyl) amino] phenyl] -3,4-diphenylthiophene (Comparative Example 2), 2,5-bis [4 '-[N-phenyl-N-
(4 "-phenylphenyl) amino] phenyl] -3,
An organic electroluminescent device was produced by the method described in Application Example 1 except that 4-diphenylthiophene (Comparative Example 3) was used. Green light emission was confirmed from each element. The characteristics were further examined, and the results are shown in Table 1. [Table 1] According to the present invention, it has become possible to provide a novel amine compound. In particular, it has become possible to provide an amine compound having excellent properties as a hole injection / transport material for an organic electroluminescent device.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Yoshimitsu Tanabe             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             In the formula company (72) Inventor Yoshiyuki Toya             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             In the formula company F-term (reference) 2H068 AA20 BA16 BA64                 3K007 AB02 AB11 DB03                 4C023 CA07

Claims (1)

Claims: 1. An amine compound represented by the general formula (1). Embedded image (Wherein, Ar ₁ and Ar ₃ each independently represent a substituted or unsubstituted biphenyl group, and Ar ₂ and Ar ₄
Each independently represents a substituted or unsubstituted naphthyl group)