KR20220016122A - Arylamine compounds and their use - Google Patents

Abstract

(R¹은, 각각 독립하여, 수소 원자, 할로겐 원자, 니트로기, 시아노기, 탄소수 1∼20의 알킬기, 탄소수 1∼20의 할로겐화 알킬기, 탄소수 1∼20의 알콕시기, 또는 탄소수 6∼20의 아릴기를 나타내고, R²는, 각각 독립하여, 치환되어 있어도 됨과 아울러, 헤테로 원자를 포함하고 있어도 되는 아릴기를 나타내고, Ar^s는, 각각 독립하여, 치환되어 있어도 됨과 아울러, 헤테로 원자를 포함하고 있어도 되는 아릴렌기를 나타내고, X는 치환되어 있어도 됨과 아울러, 헤테로 원자를 포함하고 있어도 되는 아릴렌기를 나타낸다.)For example, the arylamine compound represented by the formula (1) or (2) can produce a varnish with good solubility in organic solvents and good storage stability and a thin film with good optical properties. When applied to a hole injection layer or the like, an organic EL device having good characteristics can be realized.

(R ¹ each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxy group having 6 to 20 carbon atoms. represents an aryl group, R ² each independently represents an aryl group which may be substituted and may contain a hetero atom, Ar ^s are each independently may be substituted and may contain a hetero atom An arylene group is represented, and X represents an arylene group which may be substituted and may contain a hetero atom.)

Description

Arylamine compounds and their use

The present invention relates to arylamine compounds and uses thereof.

Organic electroluminescence (hereinafter referred to as organic EL) devices are expected to be put to practical use in fields such as displays and lighting. is being done

In this organic EL device, a plurality of functional thin films are used, one of which, the hole injection layer, is responsible for the transfer of charges between the anode and the hole transport layer or the light emitting layer, and plays an important role in achieving low voltage driving and high luminance of the organic EL device. carry out

The manufacturing method of this hole injection layer is roughly divided into the dry process represented by the vapor deposition method, and the wet process represented by the spin coating method. Comparing these processes, the wet process can efficiently produce a thin film with a large area and high flatness.

For this reason, the hole injection layer which can be formed by a wet process is desired now that the enlargement of an organic electroluminescent display is advancing.

In view of these circumstances, the present inventors have developed a charge-transporting material that is applicable to various wet processes and can obtain a thin film capable of realizing excellent EL device properties when applied to a hole injection layer of an organic EL device, and a charge-transporting material used therefor Compounds having good solubility in organic solvents have been developed (refer to Patent Documents 1 to 3).

On the other hand, until now, various efforts have been made to improve the performance of the organic EL device, but efforts have been made to adjust the refractive index of the functional thin film to be used for the purpose of improving light extraction efficiency or the like. Specifically, an attempt was made to increase the efficiency of the device by using a hole injection layer or a hole transport layer having a relatively high or low refractive index in consideration of the overall configuration of the device and the refractive index of other adjacent members (Patent Document 4) , see 5).

As described above, the refractive index is an important factor in the design of an organic EL device, and in the material for an organic EL device, the refractive index is also considered as an important physical property value to be considered.

In addition, the coloration of the charge-transporting thin film used in the organic EL device decreases the color purity and color reproduction of the organic EL device. It is desired to have high transparency (refer to Patent Document 6).

International Publication No. 2008/129947 International Publication No. 2015/050253 International Publication No. 2017/217457 Japanese Patent Publication No. 2007-536718 Japanese Special Publication No. 2017-501585 International Publication No. 2013/042623

The present invention has been made in view of such circumstances, and it is possible to obtain a thin film having good solubility in organic solvents and good optical properties, and an organic EL device having good properties when this thin film is applied to a hole injection layer or the like An object of the present invention is to provide an arylamine compound that can be realized.

As a result of repeated studies to achieve the above object, the present inventors have found that at least one arylcarbazole having an aryldiamine skeleton at the center and at least one arylcarbazole bonded to the two amino groups with a spacer having a predetermined arylene skeleton interposed therebetween. The compound has good solubility in organic solvents, and the varnish obtained by dissolving it in an organic solvent can produce a thin film with excellent optical properties, and when this thin film is applied to a hole injection layer, an organic EL device having good properties is obtained. Found and completed the present invention.

That is, the present invention is

1. An arylamine compound represented by any one of the following formulas (1) to (6) (however, the compound represented by the following formulas (P1) to (P4) is excluded.);

[Wherein, Ar ^c each independently represents a group represented by the formula (Q),

X each independently represents an arylene group which may be substituted and may contain a hetero atom,

Y each independently represents a phenylene group which may be substituted,

g each independently represents the integer of 1-10.

(Wherein, R ¹ is each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 carbon atoms. to 20 aryl groups, R ² each independently represents an aryl group that may be substituted and may contain a hetero atom, Ar ^s are each independently may be substituted and contain a hetero atom An arylene group which may be present is shown.)

2. Arylamine compound of 1 wherein Ar ^s is represented by any one of the following formulas (101) to (118);

(Wherein, R ³ is each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 carbon atoms. represents an aryl group of to 20, and V ¹ each independently represents C(R ⁴ ) ₂ (R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms. .), NR ⁵ (R ⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms), S, O, or SO ₂ , and V ² is NR ⁵ (R ⁵ is It represents the same meaning as above), represents S or O.)

3. Arylamine compound of 1 wherein Ar ^s is represented by any one of the following formulas (101A) to (118A);

(Wherein, R ³ , V ¹ and V ² have the same meanings as above.)

4. Arylamine compound of 3 wherein Ar ^s is represented by any one of the following formulas (101A-1) to (118A-3);

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

5. The arylamine compound of any one of 1 to 4, wherein X is represented by any one of the following formulas (201) to (207);

(Wherein, R ⁶ is each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 carbon atoms. represents an aryl group of to 20, each of W ¹ is independently a single bond, C(R ⁷ ) ₂ (R ⁷ is each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or halogenation having 1 to 20 carbon atoms) represents an alkyl group), S, O, or SO ₂ , W ² is C(R ⁷ ) ₂ (R ⁷ each independently represents the same meaning as above), NR ⁸ (R ⁸ is a hydrogen atom, represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms), S, O, or SO ₂ , W ³ is NR ⁸ (R ⁸ has the same meaning as above), S or O indicates.)

6. An arylamine compound of 5 wherein X is represented by any one of the following formulas (201A) to (207A);

(Wherein, R ⁶ , W ¹ , W ² and W ³ have the same meanings as above.)

7. An arylamine compound of 6 wherein X is represented by any one of the following formulas (201A-1) to (207A-1);

(Wherein, R ⁷ , R ⁸ and W ³ have the same meanings as above.)

8. The arylamine compound according to any one of 1 to 7, wherein Ar ^c is the same group;

9. A charge-transporting varnish comprising the arylamine compound of any one of 1 to 8 and an organic solvent;

10. The charge transporting varnish of 9 comprising a dopant material;

11. A charge-transporting thin film produced using the charge-transporting varnish of 9 or 10;

12. Electronic device having the charge-transporting thin film of 11

provides

The arylamine compound of the present invention has good solubility in organic solvents, and by using a charge-transporting varnish containing the arylamine compound, a high-transparency and high-refractive-index charge-transporting thin film can be obtained.

This charge-transporting thin film can be suitably used as a thin film for electronic devices including organic EL devices, in particular, as a thin film for electronic devices in which a thin film is laminated on an upper layer by a wet process. By applying it to an injection layer, etc., the element which has favorable characteristics can be manufactured.

1 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-1.
2 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-2.
3 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-2.
4 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-2.
5 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-3.
6 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-3.
7 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-4.
8 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-4.
9 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-5.
10 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-5.
11 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-6.
12 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-6.
13 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-7.
14 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-7.
15 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-8.
16 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-8.
17 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-9.
18 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 1-9.
19 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 2-1.
20 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 2-2.
21 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 2-2.
22 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 2-3.
23 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 2-4.
24 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 2-4.
25 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 2-5.
26 is a ¹ H-NMR spectrum diagram of the compound obtained in Preparation Example 2-5.
27 is a ¹ H-NMR spectrum diagram of the compound obtained in Example 1-1.
28 is a ¹ H-NMR spectrum diagram of the compound obtained in Example 1-2.
29 is a ¹ H-NMR spectrum diagram of the compound obtained in Example 1-3.
30 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-4.
31 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-5.
32 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-6.
33 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-7.
34 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-8.
35 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-9.
36 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-10.
37 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-11.
38 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-12.
39 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-12.
40 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-13.
41 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-13.
42 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-14.
43 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-15.
44 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-16.
45 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-17.
46 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-17.
47 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-18.
48 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-19.
49 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-20.
50 is a ¹ H-NMR spectrum diagram of the compound obtained in Example 1-21.
51 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-22.
52 is a ¹ H-NMR spectrum diagram of the compound obtained in Examples 1-23.
53 is a ¹ H-NMR spectrum diagram of the compound obtained in Comparative Example 1-1.
54 is a ¹ H-NMR spectrum diagram of the compound obtained in Comparative Example 1-2.
55 is a ¹ H-NMR spectrum diagram of the compound obtained in Comparative Example 1-3.

(Form for implementing the invention)

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

The arylamine compound according to the present invention is characterized in that it is represented by any one of the following formulas (1) to (6), but as described above, the compound represented by the formulas (P1) to (P4) is not included.

In formulas (1) to (6), Ar ^c each independently represents a group represented by the following formula (Q), and each X independently represents a group that may be substituted and may contain a hetero atom. an arylene group, Y each independently represents a phenylene group which may be substituted, g each independently represents an integer of 1 to 10, Preferably, Ar ^c is each independently The group represented by the formula (Q') or (Q'') is shown.

In the formulas (Q), (Q') and (Q''), R ¹ is each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. represents a halogenated alkyl group, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R ² is each independently an aryl group which may be substituted and may contain a hetero atom, Ar ^s is, Each independently represents the arylene group which may be substituted and may contain the hetero atom.

A fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom.

The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, a linear or branched alkyl group having 1 to 20 carbon atoms, such as n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl group; Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclo C3-C20 cyclic alkyl groups, such as a decyl group, etc. are mentioned.

In the alkoxy group having 1 to 20 carbon atoms, the alkyl group may be any of linear, branched, or cyclic, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexyloxy, n-octyloxy, n-decyloxy, 2-methylhexyloxy, 2-ethylhexyloxy, 2-n- Propylhexyloxy, 2-n-butylhexyloxy, 2-ethyldecyloxy, 3-ethylhexyloxy group, etc. are mentioned.

Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenane. a triyl, 4-phenanthryl, 9-phenanthryl group, etc. are mentioned.

A halogenated alkyl group having 1 to 20 carbon atoms is a group in which at least one hydrogen atom of the alkyl group having 1 to 20 carbon atoms is substituted with a halogen atom, and specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, bromodifluoro Methyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro- 1,1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoro Propyl, 1,1,1,3,3,3-hexafluoropropan-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl, 2- (perfluoro Hexyl) ethyl group, etc. are mentioned.

R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, all of which are more preferably a hydrogen atom do.

R ² in the formulas (Q), (Q') and (Q'') may be substituted and the aryl group which may contain a hetero atom is an arylene group which may contain a hetero atom as its constituent atom. , and a structure in which rings are condensed or a structure in which rings are linked may be sufficient. Although the carbon number is not specifically limited, Usually, it is 6-60, Preferably it is 40 or less, More preferably, it is 30 or less.

Specific examples of the substituent of the aryl group which may be substituted for R ² and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and 2 to carbon atoms. and an alkynyl group having 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. Specific examples of the alkyl group, the alkoxy group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms include the same ones as described above.

Specific examples of the alkenyl group having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3 -Butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1- pentenyl, n-1-decenyl, n-1-eicosenyl group, and the like.

Specific examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl, 1- Methyl-2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n- Butynyl, 3-methyl-n-butynyl, 1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n-1-pentadecinyl, n-1-eico A cynyl group etc. are mentioned.

R ² is preferably an aryl group having 6 to 10 carbon atoms which may be substituted and may contain a hetero atom, more preferably a phenyl group which may be substituted or a naphthyl group which may be substituted, all of which are further a phenyl group or a naphthyl group. preferred, and all of them are more preferably a phenyl group.

Hereinafter, although the specific example of group suitable as R< ² > is given, it is not limited to these.

The arylene group which may be substituted with Ar ^s in the formulas (Q), (Q') and (Q'') and may contain a hetero atom is an aryl group which may contain a hetero atom as a constituent atom thereof. It is a ren group, and a structure in which rings are condensed or a structure in which rings are linked may be sufficient. Although the carbon number is not specifically limited, Usually, it is 6-60, Preferably it is 40 or less, More preferably, it is 30 or less.

Specific examples of the substituent of the arylene group which may be substituted for Ar ^s and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, and a halogenated alkyl group having 1 to carbon atoms. and a 20 alkoxy group and an aryl group having 6 to 20 carbon atoms, and a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Examples of the group include those similar to those described above.

In one preferred embodiment, Ar ^s is a group represented by any one of the following formulas (101) to (118).

R ³ is each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms. represents a group, and V ¹ is each independently C(R ⁴ ) ₂ (R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms), NR ⁵ (R ⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.), S, O, or SO ₂ , V ² is NR ⁵ (R ⁵ has the same meaning as above) represents), S or O.

Examples of the halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and halogenated alkyl group having 1 to 20 carbon atoms for R ³ to R ⁵ include the same ones as described above. .

In particular, R ³ is each independently preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, A C1-C5 fluoroalkyl group is more preferable, and a hydrogen atom, a methyl group, and a trifluoromethyl group are still more preferable. In addition, from the viewpoint of reducing the extinction coefficient of the resulting thin film, it is preferable that at least one R ³ is an electron withdrawing group such as a halogen atom, a nitro group, a cyano group, or a fluoroalkyl group having 1 to 5 carbon atoms. Then, a trifluoromethyl group is more preferable.

R ⁴ is each independently, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group in all of them.

R ⁵ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a naphthyl group, furthermore a hydrogen atom, a methyl group, or a phenyl group desirable.

Moreover, when ^all R3 is not an electron withdrawing group, from the point of reducing the extinction coefficient of the thin film obtained, as ^for V1 _, S, O, SO2 are preferable. In addition, when V ¹ is S, O, SO ₂ , an electron withdrawing group may exist in R ³ .

Moreover, when ^all R3 is not an electron withdrawing group, from the point of reducing the extinction coefficient of the thin film obtained, as for ^V2 , S, O is preferable. ^In addition, when ^V2 is S, O, an electron withdrawing group may exist in R3.

As Ar ^s , a group represented by any one of the following formulas (101A) to (118A) is preferable.

(Wherein, R ³ , V ¹ and V ² have the same meanings as above.)

Hereinafter, although specific examples suitable as Ar ^s are given, it is not limited to these.

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁴ and R ⁵ have the same meanings as above.)

(Wherein, R ⁵ represents the same meanings as above.)

(Wherein, R ⁵ represents the same meanings as above.)

The arylene group which may be substituted and may contain the hetero atom of X in said Formula (1) and (2) is not specifically limited, A ring may be a condensed structure, or a ring-linked structure may be sufficient. Although the carbon number is not specifically limited, Usually, it is 6-60, Preferably it is 40 or less, More preferably, it is 30 or less.

Specific examples of the substituent of the arylene group which may be substituted with X and may contain a hetero atom include a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. an alkoxy group and an aryl group having 6 to 20 carbon atoms; Examples of the above are the same.

In particular, when the balance of refractive index, transparency, and electrical properties is considered, the arylene group which may be substituted with X in the above formulas (1) and (2) and may contain a hetero atom is represented by the following formulas (201) to ( 207) is preferably a divalent group represented by any one of.

In the formulas (201) to (207), each R ⁶ is independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms. represents an alkoxy group or an aryl group having 6 to 20 carbon atoms, and W ¹ is each independently a single bond, C(R ⁷ ) ₂ (R ⁷ is each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms.), S, O, or SO ₂ , and W ² is C(R ⁷ ) ₂ (R ⁷ has the same meaning as above), NR ⁸ (R ⁸ ) represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms), S, O, or SO ₂ , and W ³ is NR ⁸ (R ⁸ has the same meanings as above). , S or O. Examples of the halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and halogenated alkyl group having 1 to 20 carbon atoms for R ⁶ to R ⁸ include the same ones as described above. .

In particular, R ⁶ is each independently preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, A C1-C5 fluoroalkyl group is more preferable, and a hydrogen atom, a methyl group, and a trifluoromethyl group are still more preferable. In addition, from the viewpoint of lowering the extinction coefficient of the thin film obtained, at least one R ⁶ is preferably an electron withdrawing group such as a halogen atom, a nitro group, a cyano group, or a fluoroalkyl group having 1 to 5 carbon atoms. , a trifluoromethyl group is more preferable.

R ⁷ is each independently, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group.

R ⁸ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a naphthyl group, furthermore a hydrogen atom, a methyl group, or a phenyl group desirable.

Moreover, when all R< ⁶ > is not an electron withdrawing group, from the point of reducing the extinction coefficient of the thin film obtained, S, O, SO2 _of W< ¹ > is preferable. In addition, when W ¹ is S, O, SO ₂ , an electron withdrawing group may exist in R ⁶ .

Moreover, when all R< ⁶ > is not an electron withdrawing group, S, O, SO2 are preferable at _the point ^of reducing the extinction coefficient of the thin film obtained. In addition, when W ² is S, O, SO ₂ , an electron withdrawing group may exist in R ⁶ .

Moreover, when all R< ⁶ > is not an electron withdrawing group, from the point of reducing the extinction coefficient of the thin film obtained, as for ^W3 , S, O is preferable. In addition, when W ³ is S, O, SO ₂ , an electron withdrawing group may exist in R ⁶ .

Further, in the above formulas (201) to (207), the bonding position of the amino group on the aromatic ring and the spacer W ¹ is not particularly limited, but a divalent compound represented by any one of the following formulas (201A) to (207A) group is preferred.

(Wherein, R ⁶ , W ¹ , W ² and W ³ have the same meanings as above.)

Further, from the viewpoint of improving the storage stability of the varnish using the arylamine compound of the present invention, in the formulas (201) to (207), it is preferable to have at least one substituent on the aromatic ring, and from this viewpoint, A divalent group represented by any one of the following formulas (201A') to (207A') is preferable.

(Wherein, W ¹ , W ² and W ³ have the same meanings as described above.)

In the formulas (201A') to (207A'), R ^6' is each independently a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms. represents an alkoxy group or an aryl group having 6 to 20 carbon atoms, and specific examples of a halogen atom, an alkyl group having 1 to 20 carbon atoms, halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, The same thing as above is mentioned.

Among these, R ^6' is preferably an alkyl group having 1 to 10 carbon atoms or a halogenated alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms, methyl group, trifluoro A methyl group is more preferable.

Examples of X suitable for the present invention include those represented by the following formula, but are not limited thereto.

(Wherein, R ⁷ , R ⁸ and W ³ have the same meanings as above.)

Examples of the optionally substituted phenylene group for Y in the formulas (3) to (6) include a 1,4-phenylene group, a 1,3-phenylene group which may be substituted with a halogen atom, an alkyl group, an alkenyl group, or an alkynyl group. Alternatively, a 1,2-phenylene group is mentioned, but in consideration of the balance of refractive index, transparency, and electrical properties, a 1,4-phenylene group or 1,3-phenylene group which may be substituted is preferable, and an unsubstituted 1,4 group is preferable. - A phenylene group or a 1, 3- phenylene group is more preferable.

In the above formulas (3) to (6), g each independently represents an integer of 1 to 10. In consideration of the solubility of the compound in the organic solvent and transparency of the resulting thin film, the integer of 1 to 7 is Preferably, an integer of 1 to 5 is more preferable, an integer of 1 to 3 is still more preferable, 1 or 2 is still more preferable, and 1 is optimal when the availability of the raw material compound is further considered.

In the present invention, Ar ^s is preferably a group represented by formula (107), more preferably a group represented by any one of formulas (107A) to (107C), further preferably a group represented by formulas (107A-1) to The group represented by any one of (107C-5), more preferably the group represented by the formula (107B-1) or (107C-1).

In the present invention, in each of formulas (1) to (6), from the viewpoint of easiness of synthesis, it is preferable that Ar ^c is the same group.

In particular, Ar ^c is preferably a group represented by formula (Q-1) (Ar ^c1 ), more preferably a group represented by formula (Q-2) (Ar ^c2 ) or formula (Q-3) It is a group represented (Ar ^c3 ).

In a preferred embodiment, the arylamine compound of the present invention is represented by any one of the following formulas (1-1) to (6-1), and in a more preferred embodiment, the following formulas (1-2) to (6) -2) and (1-3) to (6-3).

(Wherein, X, Y, Ar ^c1 and g have the same meanings as above.)

(Wherein, X, Y, Ar ^c2 and g have the same meanings as above.)

(Wherein, X, Y, Ar ^c3 and g have the same meanings as above.)

The arylamine compound (hereinafter also referred to as arylamine compound (1) or (2)) represented by formula (1) or (2) of the present invention is, as shown in the following scheme, an aryldiamine compound [I] and a halogenated aryl compound [II] can be reacted in the presence of a catalyst.

(Wherein, Z represents a halogen atom or a similar halogen group, and X, R ¹ , R ² and Ar ^s represent the same meanings as above.)

As a halogen atom, the thing similar to the above is mentioned.

Examples of the pseudo-halogen group include (fluoro)alkylsulfonyloxy groups such as methanesulfonyloxy, trifluoromethanesulfonyloxy and nonafluorobutanesulfonyloxy; Aromatic sulfonyloxy groups, such as a benzenesulfonyloxy group and a toluenesulfonyloxy group, etc. are mentioned.

The loading ratio of the aryldiamine compound [I] and the halogenated aryl compound [II] depends on which of the arylamine compounds (1) and (2) to be synthesized, and also taking into account the reactivity and volume of the raw material compound, etc. Usually, the amount of the halogenated aryl compound is appropriately determined in the range of about 1.2 to 0.6 equivalents of the halogenated aryl compound with respect to the total amount of NH groups in the aryldiamine compound [I], but in the case of synthesizing the arylamine compound (1), 1.0 equivalent of the halogenated aryl compound The above is preferable.

As a catalyst used for the said reaction, For example, copper catalysts, such as copper chloride, copper bromide, and copper iodide; Pd(PPh ₃ ) ₄ (tetrakis(triphenylphosphine)palladium), Pd(PPh ₃ ) ₂ Cl ₂ (bis(triphenylphosphine)dichloropalladium), Pd(dba) ₂ (bis(dibenzylideneacetone) )palladium), Pd ₂ (dba) ₃ (tris(dibenzylideneacetone)dipalladium), Pd(Pt-Bu ₃ ) ₂ (bis(tri(t-butylphosphine))palladium), Pd(OAc) ₂ Palladium catalysts, such as (palladium acetate), etc. are mentioned. These catalysts may be used independently and may be used in combination of 2 or more types. Moreover, you may use these catalysts together with a well-known suitable ligand.

Examples of such ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri-t-butylphosphine, di -t-Butyl(phenyl)phosphine, di-t-butyl(4-dimethylaminophenyl)phosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane , tertiary phosphine such as 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, trimethylphosphite, triethylphosphite, triphenylphosphite, etc. Tea phosphite, commercially available from Aldrich, JohnPhos, CyjohnPhos, DavePhos, XPhos, SPhos, tBuXPhos, RuPhos, Me4tBuXPhos, sSPhos, tBuMePhos, MePhos, tBuDavemethoxyPhos, PhDavePhos, 2'-Dinocyclohexylphos, 2'-Dinocyclohexylphos and biphenylphosphine compounds such as BrettPhos, tBuBrettPhos, AdBrettPhos, Me ₃ (OMe) t BuXPhos, (2-Biphenyl) di-1-adamantylphosphine, RockPhos, and CPhos.

The amount of the catalyst used can be about 0.01 to 0.5 mol with respect to 1 mol of the aryl halide compound [II], but about 0.05 to 0.2 mol is preferable.

Moreover, when using a ligand, although the usage-amount can be made into 0.1-5 equivalent with respect to the metal complex to be used, 1-2 equivalent is suitable.

Moreover, you may use a base in the said reaction. Examples of the base include lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium, t-butoxypotassium, sodium hydroxide, potassium hydroxide, sodium carbonate. , alkali metal simple substances such as potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, alkali metal hydride, alkali metal hydroxide, alkali alkoxy metal, alkali metal carbonate, alkali metal hydrogen carbonate; alkaline earth metals such as calcium carbonate; n-butyllithium, s-butyllithium, t-butyllithium, lithium diisopropylamide (LDA), lithium 2,2,6,6-tetramethylpiperidine (LiTMP), hexamethyldisilazane lithium (LHMDS) ), such as organolithium; and amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine.

When a base is used, the amount used can be 0.1 to 5 equivalents based on the halogenated aryl compound [II] to be used, but 1-2 equivalents are suitable.

When all of the raw material compounds are solid, or from the viewpoint of efficiently obtaining the target arylamine compound, each of the above reactions is performed in a solvent. When using a solvent, there is no restriction|limiting in particular as long as the kind does not adversely affect the reaction. Specific examples include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, nitrobenzene, Toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, etc.), ethers (diethyl ether, diisopropyl ether, t-butylmethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.), amides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), lactams and lactones (N-methylpyrrolidone, γ-butyrolactone, etc.), urea (N,N-dimethylimidazolidinone, tetramethylurea, etc.), sulfoxides (dimethyl sulfoxide, sulfolane, etc.), nitriles (acetonitrile, propionitrile, butyronitrile etc.) etc. are mentioned, These solvent may be used individually or may be used in mixture of 2 or more types.

The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent to be used. In particular, about 0 to 200°C is preferable, and 20 to 150°C is more preferable. The reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the raw material compound, and the like, but is usually about 30 minutes to 50 hours.

After completion of the reaction, a post-treatment may be carried out according to a conventional method to obtain the target arylamine compound.

The arylamine compound (hereinafter also referred to as arylamine compound (3), (4) or (5)) represented by formulas (3) to (5) of the present invention is an aryldiamine compound as shown in the following scheme. It can be prepared by reacting the compound [I'] with the halogenated aryl compound [II] in the presence of a catalyst.

(Wherein, Y, R ¹ , R ² , Z, Ar ^s and g have the same meanings as above.)

The charging ratio of the aryldiamine compound [I'] and the halogenated aryl compound [II] is not particularly limited as long as the target product is obtained, but usually, the compound to be synthesized depends on which of the arylamine compounds (3) to (5), In addition, in consideration of the reactivity and volume of the raw material compound, the halogenated aryl compound is appropriately determined in the range of 1.2 equivalents or less with respect to the total amount of NH groups in the aryldiamine compound [I'], and the arylamine compound (3) In the case of synthesizing , 1.0 equivalent or more of the halogenated aryl compound is preferable with respect to the total amount of NH groups of the aryldiamine compound [I'], and when synthesizing the arylamine compound (4), the aryldiamine compound [I'] The amount of the halogenated aryl compound can be 2.0 equivalents or more, but 2.0 to 2.4 equivalents are preferable. When synthesizing the halogenated arylamine compound (5), the aryl compound 4.0 with respect to the material amount of the aryldiamine compound [I'] Although it can be set as equivalent or more, 4.0-4.8 equivalent is preferable.

In addition, various conditions and suitable conditions for the coupling reaction with respect to the catalyst, the ligand, the base, the solvent, the temperature and time of the reaction, etc. are the same as those described for the arylamine compound represented by the formula (1) or (2).

The arylamine compound (hereinafter also referred to as arylamine compound (6)) represented by the formula (6) of the present invention can be produced by the following method.

First, the dinitro compound [I''-1] and the halogenated aryl compound [II] are reacted to obtain the dinitro compound [I''-2].

(Wherein, R ¹ , R ² , Y, Z, Ar ^s and g have the same meanings as above.)

The charging ratio of the dinitro compound [I''-1] to the halogenated aryl compound [II] is 1 to 1.2, although the amount of the halogenated aryl compound can be 1 equivalent or more with respect to the total amount of NH groups of the dinitro compound. An equivalent amount is suitable.

In addition, various conditions and suitable conditions for the reaction with respect to the catalyst, the ligand, the base, the solvent, the temperature and time of the reaction, etc. are the same as those described for the arylamine compound represented by the formula (1) or (2).

Next, the nitro group in the dinitro compound [I''-2] is reduced by hydrogenation to obtain an amine compound [I''-3]. Hydrogenation includes a hydrogenation reaction using Pd/C or the like, and can be performed by a known method.

(Wherein, Y, Ar ^c and g have the same meanings as above.)

Next, the amine compound [I''-3] and the halogenated aryl compound [II] are reacted to obtain the arylamine compound (6).

(Wherein, R ¹ , R ² , Y, Z, Ar ^c , Ar ^s and g have the same meanings as above.)

The charging ratio of the amine compound [I''-3] and the halogenated aryl compound [II] can be 2 equivalents or more of the halogenated aryl compound with respect to the amine compound, but about 2 to 2.4 equivalents is preferable.

In addition, various conditions and suitable conditions for the reaction with respect to the catalyst, the ligand, the base, the solvent, the temperature and time of the reaction, etc. are the same as those described for the arylamine compound represented by the formula (1) or (2).

The halogenated aryl compound [II], which is a raw material used in the preparation of the arylamine compound of the present invention, can be prepared by reacting the arylcarbazole compound [III] with the dihalogenated aryl compound [IV] in the presence of a catalyst.

(Wherein, R ¹ , R ² , Z and Ar ^s represent the same meanings as above.)

Z ^B each independently represents a group represented by the following formula (E1) or (E2).

Z' represents a halogen atom or a pseudo-halogen group, and examples of the halogen atom and pseudo-halogen group include those described above.

Here, both Z and Z' may be the same, but from the viewpoint of efficiently obtaining the desired aryl halide compound [II], the reactivity of the atom (group) of Z' is higher than the reactivity of the atom (group) of Z desirable. By making such a difference in reactivity, the group of Z ^B in the arylcarbazole compound [III] preferentially reacts with the atom (group) of Z' rather than the atom (group) of Z, and efficiently the desired halogenated aryl compound [ II] can be obtained.

D ¹ and D ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and D ³ is an alkanediyl group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms. , and examples of the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms include those described above.

Examples of the alkanediyl group having 1 to 20 carbon atoms include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, 2,2-dimethylpropane-1,3-diyl, and 2-ethyl-2-methylpropane. -1,3-diyl, 2,2-diethylpropane-1,3-diyl, 2-methyl-2-propylpropane-1,3-diyl, butane-1,3-diyl, butane-2,3- Diyl, butane-1,4-diyl, 2-methylbutane-2,3-diyl, 2,3-dimethylbutane-2,3-diyl, pentane-1,3-diyl, pentane-1,5-diyl, Pentane-2,3-diyl, pentane-2,4-diyl, 2-methylpentane-2,3-diyl, 3-methylpentane-2,3-diyl, 4-methylpentane-2,3-diyl, 2 ,3-dimethylpentane-2,3-diyl, 3-methylpentane-2,4-diyl, 3-ethylpentane-2,4-diyl, 3,3-dimethylpentane-2,4-diyl, 3,3 -Dimethylpentane-2,4-diyl, 2,4-dimethylpentane-2,4-diyl, hexane-1,6-diyl, hexane-1,2-diyl, hexane-1,3-diyl, hexane-2 ,3-diyl, hexane-2,4-diyl, hexane-2,5-diyl, 2-methylhexane-2,3-diyl, 4-methylhexane-2,3-diyl, 3-methylhexane-2, 4-diyl, 2,3-dimethylhexane-2,4-diyl, 2,4-dimethylhexane-2,4-diyl, 2,5-dimethylhexane-2,4-diyl, 2-methylhexane-2, 5-diyl, 3-methylhexane-2,5-diyl, 2,5-dimethylhexane-2,5-diyl group, etc. are mentioned.

Examples of the arylene group having 6 to 20 carbon atoms include 1,2-phenylene, 1,2-naphthylene, 2,3-naphthylene, 1,8-naphthylene, 1,2-anthrylene, and 2,3-anthryl. Rene, 1,2-phenanthrylene, 3,4-phenanthrylene, 9,10-phenanthrylene group, etc. are mentioned.

The charging ratio of the arylcarbazole compound [III] and the dihalogenated aryl compound [IV] is, in a molar ratio, the dihalogenated aryl compound [IV] can be 1.0 or more with respect to the arylcarbazole compound [III] 1, About 1.0-1.2 are preferable.

When all of the raw material compounds are solid, or from the viewpoint of efficiently obtaining the target halogenated arylamine compound, each of the above reactions is carried out in a solvent. When using a solvent, there is no restriction|limiting in particular as long as the kind does not adversely affect the reaction. Specific examples include cyclic ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); ketones such as methyl isobutyl ketone and cyclohexanone; halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene; and aromatic hydrocarbons such as benzene, toluene and xylene. These solvents can be used individually by 1 type or in mixture of 2 or more types. Among these, 1,4-dioxane, toluene, xylene, etc. are especially preferable.

As the catalyst used in the above reaction, [1,1'-bis(diphenylphosphino)ferrocene]palladium( _II )dichloride (PdCl2(dppf)), tetrakis(triphenylphosphine)palladium(Pd(PPh)) ₃ ) ₄ ), bis(triphenylphosphine)dichloropalladium (Pd(PPh ₃ ) ₂ Cl ₂ ), bis(benzylideneacetone)palladium (Pd(dba) ₂ ), tris(benzylideneacetone)dipalladium (Pd) palladium catalysts such as ₂ (dba) ₃ ), bis(tri-t-butylphosphine)palladium (Pd(Pt-Bu ₃ ) ₂ ), and palladium(II) acetate (Pd(OAc) ₂ ); .

The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent to be used. In particular, about 0 to 200°C is preferable, and 20 to 150°C is more preferable. The reaction time is appropriately determined in consideration of the reaction temperature, the reactivity of the raw material compound, and the like, but is usually about 30 minutes to 50 hours.

After completion of the reaction, post-treatment can be carried out according to a conventional method to obtain the target halogenated arylamine compound.

Further, the dihalogenated aryl compound [IV] can be obtained by reacting the compound represented by the formula [IV'] with a halogenating agent, as shown in the following scheme.

(Wherein, Ar ^s , Z and Z' have the same meanings as above.)

A well-known thing can be used as said halogenating agent, Although N-bromosuccinimide etc. are mentioned as a specific example, It is not limited to this. The quantity of a halogenating agent is about 1-1.5 with respect to the compound represented by Formula [IV'] in molar ratio.

The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used for this type of reaction.

The reaction temperature is usually appropriately determined in the range of 0 to 140°C, and the time is usually appropriately determined in the range of 0.1 to 100 hours.

In addition, the arylcarbazole compound [III] can be obtained by reacting the compound represented by the formula [III'] with the compound represented by the formula [V], as shown in the following scheme.

(Wherein, R ¹ , R ² , Z and Z ^B have the same meanings as above.)

The charging ratio of the compound represented by the formula [III'] and the compound represented by the formula [V] is in a molar ratio, with respect to the compound 1 represented by the formula [III'], the compounds 1 to 3 represented by the formula [V] it is about

The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used for this type of reaction.

The temperature of the reaction is usually appropriately determined in the range of 0 to 140°C, and the time is usually appropriately determined in the range of 0.1 to 100 hours.

In addition, the compound represented by formula [III'] is, as shown in the following reaction scheme, after reacting the compound represented by formula [III'-2] with a halogenated aryl compound (R ² Z), treated with a halogenating agent or , It can be obtained by treating the compound represented by the formula [III'-2] with a halogenating agent and then reacting it with a halogenated aryl compound (R ² Z), but it avoids halogenation of the aryl group at the N position of the carbazole skeleton and makes it more efficient The latter reaction is preferable from the viewpoint of obtaining the target product by

(Wherein, R ¹ , R ² and Z have the same meanings as above.)

As the halogenating agent used in the above reaction, a known halogenating agent can be used, and the amount of the halogenating agent, in molar ratio, is about 1-1.5 with respect to the compound 1 represented by the formula [III'-1-1] or [III'-2]. to be.

The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used for this type of reaction.

The temperature is usually appropriately determined in the range of 0 to 140°C, and the time is usually appropriately determined in the range of 0.1 to 100 hours.

In addition, the compound represented by formula [VI] having two alkyl groups, etc. at the 9-position of the fluorene ring, which is a raw material for the spacer skeleton of Ar ^s , is a compound represented by formula [VI] in the presence of a base, as shown in the following reaction scheme, It can be obtained by reacting a compound represented by '] with a compound represented by formula [VII].

(Wherein, R ³ , Z and Z' have the same meanings as above, and R ^4' each independently represents an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group having 1 to 20 carbon atoms.)

The charging ratio of the compound represented by the formula [VI'] and the compound represented by the formula [VII] is in a molar ratio, with respect to the compound 1 represented by the formula [VI'], the compounds 1-1.5 represented by the formula [VII] it is about

The base usable in the above reaction is not particularly limited as long as it is a base used in this type of reaction, and specific examples thereof include t-BuOK, t-BuONa, CsCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , n-BuLi , t-BuLi, s-BuLi, NaOH, KOH, LiOH and the like, but t-BuOK, t-BuONa, n-BuLi, t-BuLi, s-BuLi, NaOH, and KOH are preferable.

The solvent that can be used in the above reaction is not particularly limited as long as it is a solvent used for this type of reaction.

The temperature of the reaction is usually appropriately determined in the range of 0 to 140°C, and the time is usually appropriately determined in the range of 0.1 to 100 hours.

In addition, the amine compound that can be used as a raw material of the arylamine compound of the present invention is, as shown in the following scheme, (A) an amine compound [I'''] or [I''''] and an aryl compound [ VIII] and (B) a reduction reaction of a nitro group by hydrogenation, and by repeating the reactions (A) and (B), the chain length (the number of phenylenes) is lengthened, can go

(Wherein, Y, Z and g have the same meanings as above.)

(Wherein, Y, Z and g have the same meanings as above.)

As a more specific example, the amine compound contained in the amine compound [I'] is, as shown in the following scheme, (A) a couple of m-phenylenediamine or 3-nitroaniline and 3-halonitrobenzene It can be obtained by a ring reaction and a reduction reaction of a nitro group by hydrogenation (B), and by repeating the reactions (A) and (B), the chain length (number of m-phenylenes) can be increased .

(Wherein, Z has the same meaning as above.)

Each of the above reaction and the following reaction in the above reaction scheme, because the fractional production of even and odd numbers of phenylene is possible depending on which one of the reaction is selected, it is synthetically difficult, such as protecting one amino group with a protecting group. The amine compound [I'] having a desired number of phenylenes can be freely prepared without using a high method.

In this case, the charging ratio of the raw material compounds in each reaction is about 1 to 2.4 of the raw material compound having a nitro group (the raw material compound containing a halogen atom (pseudo halogen group)) with respect to the raw material compound having an amino group in a material amount ratio. Within the range, it is appropriately determined depending on whether the number of phenylene to be added is 1 or 2.

Moreover, as a palladium catalyst used for a coupling reaction, the thing similar to the above is mentioned. Also in this case, a ligand can be used. As ligands, in addition to those exemplified above, JohnPhos, CyjohnPhos, DavePhos, XPhos, SPhos, tBuXPhos, RuPhos, Me4tBuXPhos, sSPhos, tBuMePhos, MePhos, tBuDavePhos, PhDavecyclohexylphosphino, 2'-cyclohexylphosphino Biphenylphosphine such as -2,4,6-trimethoxybiphenyl, BrettPhos, tBuBrettPhos, AdBrettPhos, Me ₃ (OMe) tBuXPhos, (2-biphenyl) di-1-adamantylphosphine, RockPhos, CPhos The compound may be suitably used.

Examples of the base used in the coupling reaction include lithium, sodium, potassium, lithium hydride, sodium hydride, lithium hydroxide, potassium hydroxide, t-butoxylithium, t-butoxysodium, t-butoxypotassium, hydroxide simple alkali metals such as sodium, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate, alkali metal hydride, alkali metal hydroxide, alkali alkoxy metal, alkali metal carbonate, alkali metal hydrogen carbonate; alkaline earth metals such as calcium carbonate; n-butyllithium, s-butyllithium, t-butyllithium, lithium diisopropylamide (LDA), lithium 2,2,6,6-tetramethylpiperidine (LiTMP), hexamethyldisilazane lithium (LHMDS) ), such as organolithium; and amines such as triethylamine, diisopropylethylamine, tetramethylethylenediamine, triethylenediamine, and pyridine.

In addition, various conditions and suitable conditions for the coupling reaction with respect to the catalyst, the solvent, the temperature and time of the reaction, etc. are the same as those described for the arylamine compound represented by Formula (1) or (2).

In addition, the hydrogenation reaction using Pd/C can be performed by a well-known method.

In addition, when a paraphenylene group or orthophenylene is introduced instead of a metaphenylene group, 4-halonitrobenzene or 2-halonitrobenzene may be used instead of 3-halonitrobenzene.

Hereinafter, although the specific example of the arylamine compound of this invention is given, it is not limited to these.

In the table, H is a hydrogen atom, Ph is a phenyl group, Me is a methyl group, n-Hex is an n-hexyl group, p-Toly is a p-tolyl group, 2-Thie is a 2-thienyl group, 1,3-Ph represents a 1,3-phenylene group, 1,4-Ph represents a 1,4-phenylene group, respectively, for example, the arylamine compounds of Nos. 1 and 865 are the following compounds, respectively.

Arylamine compound of number 1 Arylamine compound of number 865

The above-described arylamine compound of the present invention can be suitably used as a charge-transporting material. In this case, it can be used as a charge-transporting varnish comprising the arylamine compound of the present invention and an organic solvent, but in this charge-transporting varnish, depending on the use of the resulting thin film, a dopant material is added for the purpose of improving the charge-transporting ability, etc. may be included. The arylamine compound of the present invention may be used in combination with other conventionally known charge-transporting substances such as aniline derivatives and thiophene derivatives, but it is preferable to use the arylamine compound of the present invention alone as the charge-transporting substance.

In addition, in this invention, charge-transport property is synonymous with electroconductivity. A charge-transporting varnish may have charge-transporting property in itself, and the solid film obtained by it may have charge-transporting property.

The dopant substance is not particularly limited as long as it dissolves in at least one solvent used for the varnish, and either an inorganic dopant substance or an organic dopant substance can be used.

Moreover, the dopant substance of an inorganic type and an organic type may be used individually by 1 type, and may be used in combination of 2 or more types.

In addition, the dopant material functions as a dopant material in the process of obtaining a charge-transporting thin film that is a solid film from the varnish, for example, by an external stimulus such as heating during firing, for example, a part in the molecule falls off. It may be a substance which is only expressed or improved at this time, for example, an arylsulfonic acid ester compound in which a sulfonic acid group is protected by a group that is easily detached.

In particular, in the present invention, a heteropolyacid is preferable as the inorganic dopant material.

Heteropolyacid is a Keggin type represented by Formula (H1) or a Dawson type chemical structure represented by Formula (H2), and has a structure in which a hetero atom is located at the center of the molecule, vanadium (V), molybdenum (Mo ) and isopolyacid, which is an oxygen acid such as tungsten (W), and an oxygen acid of a different element are condensed to form a polyacid. As the oxygen acid of such a different element, the oxygen acid of silicon (Si), phosphorus (P), and arsenic (As) is mainly mentioned.

Specific examples of the heteropolyacid include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicic acid, phosphotungstomolybdic acid, and the like, and these may be used alone or in combination of two or more. In addition, these heteropolyacids can be obtained as a commercial item, and can also be synthesize|combined by a well-known method.

In particular, when one type of heteropolyacid is used, the one type of heteropolyacid is preferably phosphotungstic acid or phosphomolybdic acid, and phosphotungstic acid is optimal. Moreover, when using two or more types of heteropolyacid, phosphotungstic acid or phosphomolybdic acid is preferable, and, as for one of the two or more types of heteropolyacid, phosphotungstic acid is more preferable.

In addition, in quantitative analysis such as elemental analysis, the heteropolyacid is obtained as a commercial product even if the number of elements from the structure represented by the general formula is large or small, or synthesized appropriately according to a known synthesis method. As long as it is one, it can be used in the present invention.

That is, for example, in general, phosphotungstic acid is represented by the formula H ₃ (PW ₁₂ O ₄₀ )·nH ₂ O, and phosphomolybdic acid is represented by the formula H ₃ (PMo ₁₂ O ₄₀ )·nH ₂ O, respectively, but quantitative In the analysis, even if the number of P (phosphorus), O (oxygen) or W (tungsten) or Mo (molybdenum) in this formula is large or small, it is obtained as a commercial product, or in a known synthesis method. As long as it is appropriately synthesized according to the present invention, it can be used. In this case, the mass of heteropolyacid defined in the present invention is not the mass (phosphotungstic acid content) of pure phosphotungstic acid in a compound or a commercial product, but in a form available as a commercially available product and in a form that can be isolated by a known synthetic method. It means the total mass in the state including water and other impurities.

The amount of the heteropolyacid to be used is, in terms of mass ratio, about 0.001 to 50.0 with respect to the charge-transporting substance 1, but is preferably about 0.01 to 20.0, more preferably about 0.1 to 10.0.

On the other hand, as an organic dopant material, a tetracyanoquinodimethane derivative or a benzoquinone derivative can be used in particular.

Specific examples of the tetracyanoquinodimethane derivative include 7,7,8,8-tetracyanoquinodimethane (TCNQ) and halotetracyanoquinodimethane represented by the formula (H3).

Specific examples of the benzoquinone derivative include tetrafluoro-1,4-benzoquinone (F4BQ), tetrachloro-1,4-benzoquinone (chloranyl), tetrabromo-1,4-benzoquinone, 2,3 -dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) etc. are mentioned.

In the formula, R ⁵⁰⁰ to R ⁵⁰³ each independently represent a hydrogen atom or a halogen atom, but at least one is a halogen atom, preferably at least two are halogen atoms, and more preferably at least three are halogen atoms. and most preferably all are halogen atoms.

Examples of the halogen atom include those described above, but a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.

Specific examples of such halotetracyanoquinodimethane include 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2-chloro-7,7,8,8-tetracyanoquinodimethane; 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane, 2,5-dichloro-7,7,8,8-tetracyanoquinodimethane, 2,3,5, 6-tetrachloro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), etc. can be heard

The amount of the tetracyanoquinodimethane derivative and the benzoquinone derivative to be used is preferably 0.0001 to 100 equivalents, more preferably 0.01 to 50 equivalents, and still more preferably 1 to 20 equivalents based on the charge-transporting substance.

Further, as the organic dopant material, an electrically neutral onium borate salt comprising a monovalent or divalent anion represented by the following formula (a1) and a counter cation represented by the formulas (c1) to (c5) may be used. .

(Wherein, Ar each independently represents an optionally substituted aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may have a substituent, L is an alkylene group having 1 to 20 carbon atoms, - NH-, oxygen atom, sulfur atom or -CN ⁺ -)

In formula (a1), linear, branched or cyclic any may be sufficient as a C1-C20 alkylene group, As the specific example, methylene, methylmethylene, dimethylmethylene, ethylene, trimethylene, propylene, tetramethylene, penta A methylene group, a hexamethylene group, etc. are mentioned. Moreover, as an aryl group and a heteroaryl group, the thing similar to the above is mentioned.

Preferable examples of the anion of the formula (a1) include those represented by the formula (a2), but are not limited thereto.

The usage-amount of an onium borate salt can be about 0.1-10 with respect to a charge-transporting substance in a substance amount (mol) ratio.

In addition, the said onium borate salt can be synthesize|combined with reference to the well-known method described in Unexamined-Japanese-Patent No. 2005-314682 etc., for example.

Moreover, an arylsulfonic acid compound and an arylsulfonic acid ester compound can also be used suitably as an organic dopant substance.

Specific examples of the arylsulfonic acid compound include benzenesulfonic acid, tosylic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzenesulfonic acid, dihexylbenzenesulfonic acid, 2,5- Dihexylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, 6,7-dibutyl-2-naphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, 3-dodecyl-2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 4-hexyl-1-naphthalenesulfonic acid, 7-hexyl-1-naphthalenesulfonic acid, 6-hexyl-2-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, 2,7-dinonyl-4-naphthalenesulfonic acid, dinonyl Naphthalenedisulfonic acid, 2,7-dinonyl-4,5-naphthalenedisulfonic acid, 1,4-benzodioxanedisulfonic acid compound described in International Publication No. 2005/000832, Arylsulfonic acid described in International Publication No. 2006/025342 The compound, the arylsulfonic acid compound of International Publication No. 2009/096352, etc. are mentioned.

As an example of a preferable arylsulfonic acid compound, the arylsulfonic acid compound represented by a formula (H4) or (H5) is mentioned.

A ¹ represents O or S, but O is preferred.

^Although A2 represents a naphthalene ring or an anthracene ring, a naphthalene ring is preferable.

A ³ represents a divalent to tetravalent perfluorobiphenyl group, p represents the number of bonds between A ¹ and A ³ and is an integer satisfying 2≤p≤4, but A ³ is a perfluorobiphenyldiyl group, preferably It is preferably a perfluorobiphenyl-4,4'-diyl group, and p is preferably 2.

q represents the number of sulfonic acid groups bonded to A ² , and is an integer satisfying 1≤q≤4, but 2 is optimal.

A ⁴ to A ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated alkenyl group having 2 to 20 carbon atoms, but A ⁴ at least 3 of -A ⁸ are halogen atoms.

Examples of the halogenated alkyl group having 1 to 20 carbon atoms include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4 ,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluoro A butyl group etc. are mentioned.

Examples of the halogenated alkenyl group having 2 to 20 carbon atoms include perfluorovinyl, perfluoropropenyl (perfluoroallyl), and perfluorobutenyl group.

Other examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms include the same ones as described above, but the halogen atom is preferably a fluorine atom.

Among these, A ⁴ to A ⁸ is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms, and A ⁴ to A At least 3 of ⁸ are preferably a fluorine atom, a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorinated alkenyl group having 2 to 5 carbon atoms, and At least three of A ⁴ to A ⁸ are more preferably a fluorine atom, a hydrogen atom, a fluorine atom, a cyano group, a perfluoroalkyl group having 1 to 5 carbon atoms, or a perfluoroalkenyl group having 1 to 5 carbon atoms, Moreover, ^it is further more preferable that A4, ^A5 , and ^A8 are a fluorine atom.

In addition, the perfluoroalkyl group is a group in which all the hydrogen atoms of an alkyl group are substituted with fluorine atoms, and the perfluoroalkenyl group is a group in which all the hydrogen atoms of an alkenyl group are substituted with fluorine atoms.

r represents the number of sulfonic acid groups bonded to the naphthalene ring, and is an integer satisfying 1≤r≤4, but 2 to 4 are preferable and 2 is optimal.

The molecular weight of the arylsulfonic acid compound used as the dopant material is not particularly limited, but considering solubility in organic solvents when used together with the arylamine compound of the present invention, it is preferably 2000 or less, more preferably 1500 or less.

Hereinafter, although the specific example of a suitable arylsulfonic acid compound is given, it is not limited to these.

The amount of the arylsulfonic acid compound used is preferably about 0.01 to 20.0, more preferably about 0.4 to 5.0, relative to the charge-transporting substance 1 in terms of the amount (mol) of the substance.

Commercially available arylsulfonic acid compounds may be used, but International Publication No. 2006/025342, International Publication No. 2009/096352, International Publication No. 2015/111654, International Publication No. 2015/053320, International Publication No. 2015/115515, etc. It can also be synthesize|combined by the described well-known method.

On the other hand, as an arylsulfonic acid ester compound, an arylsulfonic acid ester compound disclosed in International Publication No. 2017/217455, an arylsulfonic acid ester compound disclosed in International Publication No. 2017/217457, and Japanese Patent Application No. 2017-243631 (International Publication No. 2019/124412) and the arylsulfonic acid ester compounds described above. Specifically, those represented by any of the following formulas (H6) to (H8) are preferable.

(Wherein, m is an integer satisfying 1≤m≤4, preferably 2. n is an integer satisfying 1≤n≤4, but 2 is preferable.)

In the formula (H6), A ¹¹ is an m-valent group derived from perfluorobiphenyl.

A ¹² is -O- or -S-, but -O- is preferable.

A ¹³ is a (n+1) valent group derived from naphthalene or anthracene, but a group derived from naphthalene is preferred.

R ^s1 to R ^s4 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ^s5 is an optionally substituted monovalent hydrocarbon group having 2 to 20 carbon atoms.

Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-hexyl group, but having 1 to 3 carbon atoms An alkyl group of

The monovalent hydrocarbon group having 2 to 20 carbon atoms may be any of linear, branched or cyclic, and specific examples thereof include alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl; Aryl groups, such as a phenyl, a naphthyl group, and a phenanthryl group, etc. are mentioned.

In particular, among R ^s1 to R ^s4 , R ^s1 or R ^s3 is a linear alkyl group having 1 to 3 carbon atoms, the remainder is a hydrogen atom, or R ^s1 is a straight chain alkyl group having 1 to 3 carbon atoms, and R ^s2 to R ^s4 is a hydrogen atom It is preferable to be In this case, a methyl group is preferable as a C1-C3 linear alkyl group.

Moreover, as R ^<s5> , a C2-C4 linear alkyl group or a phenyl group is preferable.

In the formula (H7), A ¹⁴ is an optionally substituted hydrocarbon group having 6 to 20 carbon atoms including one or more aromatic rings, and this hydrocarbon group is a hydrocarbon group having 6 to 20 carbon atoms including one or more aromatic rings. It is a group obtained by removing m hydrogen atoms from a hydrocarbon compound.

Examples of such hydrocarbon compounds include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, and phenanthrene.

In the hydrocarbon group, some or all of the hydrogen atoms may be further substituted with a substituent, and examples of such substituents include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, nitro, cyano, hydroxy, amino, silanol, thiol. , carboxy, sulfonic acid ester, phosphoric acid, phosphoric acid ester, ester, thioester, amide, organooxy, organoamino, organosilyl, organothio, acyl, sulfo, monovalent hydrocarbon group and the like.

Among these, as A ¹⁴ , a group derived from benzene, biphenyl, or the like is preferable.

Moreover, although A ¹⁵ is -O- or -S-, -O- is preferable.

A ¹⁶ is a C6-C20 (n+1) aromatic hydrocarbon group, and this aromatic hydrocarbon group is a group obtained by removing (n+1) hydrogen atoms from the aromatic ring of a C6-C20 aromatic hydrocarbon compound.

Benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene etc. are mentioned as such an aromatic hydrocarbon compound.

Among them, as A ¹⁶ , a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.

R ^s6 and R ^s7 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group, and R ^s8 is a linear or branched monovalent aliphatic hydrocarbon group. However, the sum total of carbon number of ^Rs6 , ^Rs7 , and ^Rs8 is 6 or more. Although the upper limit of the sum total of carbon number of ^Rs6 , ^Rs7 , and ^Rs8 is not specifically limited, 20 or less are preferable and 10 or less are more preferable.

Specific examples of the linear or branched monovalent aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, C1-C20 alkyl groups, such as a decyl group; Vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, hexenyl group having 2 to 20 carbon atoms An alkenyl group etc. are mentioned.

Among these, a hydrogen atom is preferable for R ^s6 , and R ^s7 and R ^s8 are each independently and a C1-C6 alkyl group is preferable.

In formula (H8), R ^s9 to R ^s13 are each independently a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkyl group having 2 to 10 carbon atoms. is a halogenated alkenyl group of

The alkyl group having 1 to 10 carbon atoms may be any of linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n -pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl group, etc. are mentioned.

The halogenated alkyl group having 1 to 10 carbon atoms is not particularly limited as long as some or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms are substituted with halogen atoms, and specific examples thereof include trifluoromethyl, 2,2,2- Trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1, 2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4 ,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group, and the like.

The halogenated alkenyl group having 2 to 10 carbon atoms is not particularly limited as long as some or all of the hydrogen atoms of the alkenyl group having 2 to 10 carbon atoms are substituted with halogen atoms, and specific examples thereof include perfluorovinyl, perfluoro-1 -propenyl, perfluoro-2-propenyl, perfluoro-1-butenyl, perfluoro-2-butenyl, perfluoro-3-butenyl group, and the like.

Among these, R ^s9 is preferably a nitro group, a cyano group, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms, a nitro group, a cyano group, a halogenated alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 2 to 4 carbon atoms. A halogenated alkenyl group of is more preferable, and a nitro group, a cyano group, a trifluoromethyl group and a perfluoropropenyl group are still more preferable.

As R ^s10 to R ^s13 , a halogen atom is preferable, and a fluorine atom is more preferable.

A ¹⁷ is -O-, -S- or -NH-, but -O- is preferable.

A ¹⁸ is an (n+1) valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and this aromatic hydrocarbon group is a group obtained by removing (n+1) hydrogen atoms from the aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms.

Benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene etc. are mentioned as such an aromatic hydrocarbon compound.

Among these, as A ¹⁸ , a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.

R ^s14 to R ^s17 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of the monovalent aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n- an alkyl group having 1 to 20 carbon atoms such as heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl; Vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, hexenyl group having 2 to 20 carbon atoms Although an alkenyl group etc. are mentioned, A C1-C20 alkyl group is preferable, A C1-C10 alkyl group is more preferable, A C1-C8 alkyl group is still more preferable.

R ^s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or OR ^s19 . R ^s19 is an optionally substituted monovalent hydrocarbon group having 2 to 20 carbon atoms.

Examples of the linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms for R ^s18 include the same ones as described above.

When R ^s18 is a monovalent aliphatic hydrocarbon group, R ^s18 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 8 carbon atoms.

Examples of the monovalent hydrocarbon group having 2 to 20 carbon atoms for R ^s19 include aryl groups such as phenyl, naphthyl and phenanthryl groups other than the methyl group among the monovalent aliphatic hydrocarbon groups described above.

Among these, R ^s19 is preferably a linear alkyl group having 2 to 4 carbon atoms or a phenyl group.

Moreover, as a substituent which the said monovalent|monohydric hydrocarbon group may have, a fluorine atom, a C1-C4 alkoxy group, a nitro group, a cyano group, etc. are mentioned.

Although those shown below are mentioned as a specific example of a suitable arylsulfonic acid ester compound, It is not limited to these.

The amount of the arylsulfonic acid ester compound to be used is preferably about 0.01 to 20, more preferably about 0.05 to 10, relative to the charge-transporting substance 1 in terms of the amount (mol) of the substance.

The arylsulfonic acid ester compound may be a commercially available product, but may also be synthesized by a known method described in International Publication Nos. 2017/217455, 2017/217457, and International Publication No. 2019/124412.

In the present invention, it is preferable to use an arylsulfonic acid compound or an arylsulfonic acid ester compound as a dopant material in consideration of producing a charge-transporting thin film having excellent transparency and high refractive index, and solubility in a solvent and extinction coefficient Considering obtaining a smaller thin film, it is more preferable to use an arylsulfonic acid ester compound.

In addition, when the thin film obtained is used as a hole injection layer of an organic EL device, the charge transporting varnish may contain an organosilane compound for the purpose of improving the injection property into the hole transport layer and the lifetime characteristics of the device. The content is usually about 1 to 30 mass% with respect to the total mass of the charge-transporting substance and the dopant substance.

As an organic solvent used when preparing the charge-transporting varnish of this invention, the highly polar solvent which can melt|dissolve the arylamine compound of this invention favorably can be used. The arylamine compound of the present invention can be dissolved in a solvent regardless of the polarity of the solvent. Moreover, you may use a low-polarity solvent at the point which is excellent in process suitability rather than a high-polarity solvent as needed. In the present invention, the low-polarity solvent is defined as having a relative permittivity of less than 7 at a frequency of 100 kHz, and the high-polarity solvent is defined as having a relative permittivity of 7 or more at a frequency of 100 kHz.

As a low-polarity solvent, for example,

chlorine-based solvents such as chloroform and chlorobenzene;

aromatic hydrocarbon solvents such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene;

aliphatic alcohol solvents such as 1-octanol, 1-nonanol, and 1-decanol;

Tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether solvents such as ether;

Methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. of ester solvents.

Moreover, as a highly polar solvent, for example,

amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone;

ketone solvents such as ethyl methyl ketone, isophorone and cyclohexanone;

cyano solvents such as acetonitrile and 3-methoxypropionitrile;

polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol;

Diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, monohydric alcohol solvents other than aliphatic alcohols such as tetrahydrofurfuryl alcohol;

Sulfoxide-based solvents such as dimethyl sulfoxide

and the like.

Although the viscosity of a charge-transporting varnish is suitably determined according to the thickness of the thin film to produce, and solid content concentration, it is 1-50 mPa*s at 25 degreeC normally. In addition, in this invention, solid content means components other than the solvent contained in the charge-transporting varnish of this invention.

In addition, the solid content concentration of the charge-transporting varnish is appropriately set in consideration of the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, etc. Considering this, Preferably it is about 0.5-10.0 mass %, More preferably, it is about 1.0-5.0 mass %.

Although it does not specifically limit as a preparation method of a charge-transporting varnish, For example, a method of dissolving all solid content, such as a charge-transporting substance containing the arylamine compound of this invention, in an organic solvent at once, and a part of solid content in an organic solvent and the method of dissolving the remaining solid content after that, etc. are mentioned.

In particular, when preparing a charge-transporting varnish, from the viewpoint of obtaining a thin film with a higher flatness with good reproducibility, it is recommended to dissolve a charge-transporting material, a dopant material, etc. in an organic solvent, and then filter it using a sub-micrometer-sized filter or the like. desirable.

Since the charge-transporting varnish demonstrated above can manufacture a charge-transporting thin film easily by using this, when manufacturing an electronic element, especially an organic electroluminescent element, it can be used suitably.

In this case, the charge-transporting thin film may be formed by applying the above-described charge-transporting varnish on a substrate and firing.

The method for applying the varnish is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an inkjet method, a spray method, a slit coating method, and the like. It is desirable to control the viscosity and surface tension.

In addition, the firing atmosphere of the charge-transporting varnish after application is not particularly limited, and a thin film having a uniform film-forming surface and high charge-transporting properties can be obtained not only in an atmospheric atmosphere but also in an inert gas such as nitrogen or in a vacuum. Depending on the type of substance, a thin film having higher charge transport properties may be obtained with good reproducibility by firing the varnish in an atmospheric atmosphere.

The firing temperature is appropriately set within the range of about 100 to 260° C. in consideration of the purpose of the resulting thin film, the degree of charge transport properties imparted to the resulting thin film, the kind and boiling point of the solvent, and the like, and the resulting thin film is subjected to the hole hole in the organic EL device. When used as an injection layer, the temperature is preferably about 140 to 250 ° C, and more preferably about 145 to 240 ° C. However, when the arylamine compound of the present invention is used as a charge-transporting material, even in low-temperature calcination of 200 ° C. or less, A thin film having good charge transport properties can be formed.

In addition, at the time of baking, for the purpose of expressing higher uniformity of film formation or advancing a reaction on a base material, you may give two or more steps of temperature change, and heating is suitable apparatus, such as a hotplate and oven, for example. This can be done using

Although the film thickness of a charge-transporting thin film is not specifically limited, When using as a hole injection layer, a hole transport layer, or a hole injection and transport layer of an organic electroluminescent element, 5-300 nm is preferable. As a method of changing a film thickness, there exist methods, such as changing the solid content concentration in a varnish, and changing the amount of solution (varnish amount) on the board|substrate at the time of application|coating.

The charge-transporting thin film of the present invention described above usually exhibits a refractive index (n) of 1.60 or more and an extinction coefficient (k) of 0.100 or less at an average value of a wavelength region of 400 to 800 nm, but in some embodiments, a refractive index of 1.65 or more, In some other aspect, a refractive index of 1.70 or more is shown, and in some aspect, it shows an extinction coefficient of 0.050 or less, and in some other aspect, it shows an extinction coefficient of 0.010 or less.

When the charge-transporting thin film is applied to an organic EL device, the above-described charge-transporting thin film can be provided between a pair of electrodes constituting the organic EL device.

Although the following (a)-(f) is mentioned as a typical structure of organic electroluminescent element, It is not limited to these. In addition, in the following configuration, if necessary, an electron blocking layer or the like may be provided between the light emitting layer and the anode, and a hole (hole) blocking layer or the like may be provided between the light emitting layer and the cathode. Further, the hole injection layer, the hole transport layer or the hole injection transport layer may have a function as an electron blocking layer or the like, and the electron injection layer, the electron transport layer or the electron injection transport layer may have a function as a hole (hole) blocking layer or the like . Moreover, it is also possible to provide arbitrary functional layers between each layer as needed.

(a) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(b) anode/hole injection layer/hole transport layer/light emitting layer/electron injection transport layer/cathode

(c) anode/hole injection transport layer/light emitting layer/electron transport layer/electron injection layer/cathode

(d) anode/hole injection transport layer/light emitting layer/electron injection transport layer/cathode

(e) anode/hole injection layer/hole transport layer/light emitting layer/cathode

(f) anode/hole injection transport layer/light emitting layer/cathode

"Hole injection layer", "hole transport layer", and "hole injection transport layer" are layers formed between the light emitting layer and the anode, and have a function of transporting holes from the anode to the light emitting layer, and between the light emitting layer and the anode, hole transportability When only one layer of material is provided, it is a "hole injection transport layer", and when two or more layers of hole transport material are provided between the light emitting layer and the anode, the layer close to the anode is a "hole injection layer", A layer other than that is a "hole transport layer." In particular, as the hole injection (transport) layer, a thin film excellent not only in accepting holes from the anode but also in hole injection to the hole transporting (light emitting) layer is used.

"Electron injection layer", "electron transport layer", and "electron injection transport layer" are layers formed between the light emitting layer and the cathode, and have a function of transporting electrons from the cathode to the light emitting layer, and between the light emitting layer and the cathode, electron transport properties When only one layer of material is provided, it is an "electron injection transport layer", and when two or more layers of an electron transport material are provided between the light emitting layer and the cathode, the layer close to the cathode is an "electron injection layer", A layer other than that is an "electron transport layer".

A "light-emitting layer" is an organic layer having a light-emitting function, and contains a host material and a dopant material when a doping system is employed. In this case, the host material mainly promotes recombination of electrons and holes and has a function of confining excitons in the light emitting layer, and the dopant material has a function of efficiently emitting excitons obtained from recombination. In the case of a phosphorescent device, the host material mainly has a function of confining excitons generated from the dopant in the light emitting layer.

The charge-transporting thin film produced from the charge-transporting varnish of the present invention can be used as a functional layer, such as a hole injection layer, a hole transport layer, a hole injection and transport layer, provided between the anode and the light emitting layer of the organic EL device. , suitable as a hole injection layer in which the upper layer is formed by a coating method.

Although the following are mentioned as a material used in the case of producing an organic electroluminescent element using the charge-transporting varnish of this invention, and a manufacturing method, It is not limited to these.

An example of the manufacturing method of the OLED element which has a hole injection layer which consists of a thin film obtained from the said charge-transporting varnish is as follows. In addition, it is preferable that the electrode is previously cleaned with alcohol, pure water, etc., or surface-treated by UV ozone treatment, oxygen-plasma treatment, or the like within a range that does not adversely affect the electrode.

On the anode substrate, a hole injection layer is formed by the above method using the charge transporting varnish. This is introduced into a vacuum vapor deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer/hole block layer, an electron injection layer, and a cathode metal are sequentially deposited. Alternatively, in this method, instead of forming the hole transport layer and the light emitting layer by vapor deposition, a composition for forming a hole transport layer comprising a hole transport polymer and a composition for forming a light emitting layer comprising a light emitting polymer are used to form these layers by a wet process to form Moreover, you may provide an electron blocking layer between a light emitting layer and a positive hole transport layer as needed.

Examples of the anode material include a transparent electrode typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and a metal anode made of a metal typified by aluminum, or an alloy thereof. do. Polythiophene derivatives or polyaniline derivatives having high charge transport properties can also be used.

Moreover, although gold, silver, copper, indium, these alloys, etc. are mentioned as another metal which comprises a metal anode, it is not limited to these.

As a material for forming the hole transport layer, (triphenylamine) dimer derivative, [(triphenylamine) dimer] spirodimer, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)- Benzidine (α-NPD), 4,4',4''-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA), 4,4',4''-tris[1-naphthyl triarylamines such as (phenyl)amino]triphenylamine (1-TNATA), 5,5''-bis-{4-[bis(4-methylphenyl)amino]phenyl}-2,2':5'; Oligothiophenes, such as 2''-terthiophene (BMA-3T), etc. are mentioned.

Examples of the material for forming the light emitting layer include a metal complex such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo[h]quinoline, a bisstyrylbenzene derivative, a bisstyrylarylene derivative, (2-hydroxy low molecular weight light emitting materials such as metal complexes of phenyl) benzothiazole and silol derivatives; Poly(p-phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], poly(3-alkylthiophene), polyvinylcar Although the system etc. which mixed the light emitting material and the electron transfer material with high molecular compounds, such as basol, are mentioned, It is not limited to these.

Moreover, when forming a light emitting layer by vapor deposition, you may co-evaporate with a light emitting dopant, As a light emitting dopant, metal complexes, such as tris (2-phenylpyridine) iridium (III) (Ir(ppy) ₃ ), rubrene, etc. Condensed polycyclic aromatic rings, such as a naphthacene derivative of, a quinacridone derivative, and perylene, etc. are mentioned, However, It is not limited to these.

Examples of the material for forming the electron transport layer/hole blocking layer include, but are not limited to, oxydiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxyline derivatives, benzimidazole derivatives, and pyrimidine derivatives.

Examples of the material for forming the electron injection layer include metal oxides such as lithium oxide (Li ₂ O), magnesium oxide (MgO), and alumina (Al ₂ O ₃ ), and metal fluorides such as lithium fluoride (LiF) and sodium fluoride (NaF). , but is not limited thereto.

Examples of the negative electrode material include, but are not limited to, aluminum, magnesium-silver alloy, and aluminum-lithium alloy.

Examples of the material for forming the electron blocking layer include, but are not limited to, tris(phenylpyrazole)iridium.

As the hole-transporting polymer, poly[(9,9-dihexylfluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene)] , poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}-1,1'-biphenylene-4,4- diamine)], poly[(9,9-bis{1'-penten-5'-yl}fluorenyl-2,7-diyl)-co-(N,N'-bis{p-butylphenyl}- 1,4-diaminophenylene)], poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine]-and capped with polysilsesquioxane, poly[ (9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine)] etc. are mentioned.

Examples of the luminescent polymer include polyfluorene derivatives such as poly(9,9-dialkylfluorene) (PDAF), poly(2-methoxy-5-(2'-ethylhexoxy)-1,4-phenylenevinylene, etc. ) polyphenylenevinylene derivatives such as (MEH-PPV), polythiophene derivatives such as poly(3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).

The charge-transporting thin film obtained from the charge-transporting varnish of the present invention can be used as a functional layer such as a hole injection layer, a hole transport layer, and a hole injection and transport layer provided between the anode and the light emitting layer of an organic EL device. Organic thin film solar cell, organic perovskite photoelectric conversion element, organic integrated circuit, organic field effect transistor, organic thin film transistor, organic light emitting transistor, organic optical tester, organic photoreceptor, organic electric field quenching element, light emitting electrochemical cell, quantum It can also be used as a charge-transporting thin film in electronic devices, such as a dot light emitting diode, a quantum laser, an organic laser diode, and an organic plasmon light emitting device.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, the apparatus and reagent used are as follows.

[Device]

(1) MALDI-TOF-MS: manufactured by Bruker, autoflex III smartbeam

(2) ¹ H-NMR: JNM-ECP300 FT NMRSYSTEM manufactured by JEOL Co., Ltd.

(3) Substrate cleaning: Choshu Sangyo Co., Ltd. substrate cleaning apparatus (pressure-reduced plasma method)

(4) Varnish application: Mikasa Co., Ltd. spin coater MS-A100

(5) Film thickness measurement: Kosaka Kenkyusho Co., Ltd. micro-shape measuring instrument Surf Corda ET-4000

(6) Fabrication of element: Choshu Sangyo Co., Ltd. multi-function vapor deposition system system C-E2L1G1-N

(7) Measurement of device current density and luminance: Multi-channel IVL measuring device manufactured by EHC Co., Ltd.

(8) Lifetime measurement of EL element (luminance half-life measurement): EHC Co., Ltd. organic EL luminance lifetime evaluation system PEL-105S

(9) Measurement of refractive index (n) and extinction coefficient (k): Multi-incident angle spectroscopic ellipsometer VASE manufactured by J.A. Ulam Japan

[reagent]

RuPhos Aldrich company

t-BuXPhos made by Aldrich

t-Bu ₃ PHBF ₄ Fujifilm Wako Chemical Co., Ltd.

Copper (I) iodide manufactured by FUJIFILM Wako Chemical Co., Ltd.

Ethylenediamine manufactured by Fujifilm Wako Chemical Co., Ltd.

Pd(DBA) ₂ manufactured by Tokyo Kasei High School Co., Ltd.

Pd(OAc) ₂ manufactured by Tokyo Kasei Kogyo Co., Ltd.

Pd[P(C ₆ H ₅ ) ₃ )] ₄ manufactured by Tokyo Kasei Kogyo Co., Ltd.

Pd(dppf)Cl ₂ manufactured by Tokyo Kasei Kogyo Co., Ltd.

3-Bromo-9-phenylcarbazole manufactured by Tokyo Kasei Kogyo Co., Ltd.

3-Bromocarbazole Tokyo Kasei Kogyo Co., Ltd. product

4-iodotoluene manufactured by Tokyo Kasei High School Co., Ltd.

4-Iodo anisole manufactured by Tokyo Kase High School Co., Ltd.

18-Crown-6 Tokyo Kasei High School Co., Ltd.

Bis (Pina Collaito) Diboron Tokyo Kasei High School Co., Ltd.

3,3',5,5'-tetramethylbenzidine manufactured by Tokyo Chemical Industry Co., Ltd.

Lithium hexamethyldisilazide (LHMDS) 1.3 mol/L tetrahydrofuran solution manufactured by Tokyo Kasei Kogyo Co., Ltd.

2-Bromo-7-iodofluorene manufactured by Tokyo Kasei Kogyo Co., Ltd.

Benzyltriethylammonium chloride manufactured by Tokyo Kasei Kogyo Co., Ltd.

3-Nitroaniline manufactured by Tokyo Kasei Kogyo Co., Ltd.

1-Bromo-3-nitrobenzene manufactured by Tokyo Kasei Kogyo Co., Ltd.

Hydrogen chloride (about 1 mol/L ethyl acetate solution) manufactured by Tokyo Kasei Kogyo Co., Ltd.

4,4'-diaminodiphenylamine manufactured by Tokyo Kasei Kogyo Co., Ltd.

t-BuONa Tokyo Kasei High School Co., Ltd.

(9-phenyl-9H-carbazol-3-yl) boronic acid manufactured by Tokyo Chemical Industry Co., Ltd.

1,4-dioxane manufactured by Kanto Chemical Co., Ltd.

2,2'-bis(trifluoromethyl)benzidine manufactured by Kanto Chemical Co., Ltd.

Bis(4-aminophenyl)sulfone manufactured by Kanto Chemical Co., Ltd.

1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene manufactured by Kanto Chemical Co., Ltd.

Silica gel N60 manufactured by Kanto Chemical Co., Ltd.

Dimethyl sulfoxide Junsei Chemicals Co., Ltd.

Iodomethane Junseikagaku Co., Ltd. product

Potassium carbonate Junseikagaku Co., Ltd. product

Potassium acetate Tokyo Kasei Kogyo Co., Ltd. product

Toluene Junseikagaku Co., Ltd. product

Tetrahydrofuran Junsei Chemicals Co., Ltd.

Ethyl acetate Junse Chemicals Co., Ltd. product

Methanol Jun Sei Chemicals Co., Ltd.

Hexane Jun Sei Chemicals Co., Ltd. product

m-tollidine manufactured by Wakayama Seika High School Co., Ltd.

N,N'-bis(4-aminophenyl)terephthalamide manufactured by Wakayama Seika Kogyo Co., Ltd.

Pd/C CGS-10DR[H2O]=54.40% N.E. Made by Chemcat

3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole manufactured by Beijing aglaia technology development co., ltd

[1] Synthesis of compounds

[Production Example 1-1]

In a 100 mL reaction flask, 30 mmol (11.1 g) of 2-bromo-7-iodofluorene and 3 mmol (683.3 mg) of benzyltriethylammonium chloride were weighed and placed, and then 60 mL of dimethyl sulfoxide was added, followed by nitrogen substitution for 10 stirred for minutes.

After adding 14 g of the 50 mass % sodium hydroxide aqueous solution prepared separately there and stirring for 10 minutes, 72.5 mmol (10.3 g) of iodomethane was dripped and it stirred at room temperature overnight. In addition, a trace amount of the solution in the flask was taken along the way, and the reaction was tracked using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target increased. At that time, no prominent peaks such as those corresponding to by-products were identified.

The obtained reaction mixture was added to 800 mL of a mixed solvent of methanol and water (3/1 (v/v)), and the precipitated solid was separated by filtration with a membrane filter.

Finally, the recovered solid was dried under reduced pressure at 60°C to obtain 6.26 g (78.4%) of 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene. ¹ H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG.

[Production Example 1-2]

In a 200 mL two-neck flask, 3-bromocarbazole 20 mmol (4.93 g), 4-iodotoluene 44 mmol (9.61 g), copper (I) 16 mmol (3.05 g), cesium carbonate 50 mmol (16.3 g), toluene 100 mL was added, and after stirring at room temperature for 5 minutes under nitrogen stream, 30 mmol (1.82 g) of ethylenediamine was added there, and it stirred under heating and refluxing overnight.

After the obtained reaction mixture was cooled to room temperature, insoluble matter was removed by celite filtration, the obtained filtrate was concentrated, the concentrate was purified by column chromatography, and 3-bromo-9-(4-tolyl) 2.84 g (42.2%) of carbazole was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 2 to 4 .

[Production Example 1-3]

Reaction and purification were performed in the same manner as in Preparation Example 1-2, except that 88 mmol (20.6 g) of 4-iodoanisole was used instead of 44 mmol of 4-iodotoluene, and the equivalents of other reagents were doubled. , to obtain 11.1 g (78.7%) of 3-bromo-9-(4-methoxyphenyl)carbazole. ¹ H-NMR spectrum of the obtained compound is shown in FIGS. 5 and 6 .

[Production Example 1-4]

In a 200 mL two-neck flask, 3-bromocarbazole 60 mmol (14.76 g), copper (I) iodide 4.5 mmol (0.86 g), potassium carbonate 63 mmol (8.71 g), 18-crown-6 61.5 mmol (16.2 g) was added and the inside of the flask was purged with nitrogen, and then 100 mL of N,N-dimethylacetamide was added thereto, followed by stirring at room temperature for 10 minutes. Then, after heating up to 160 degreeC and stirring for 2 hours, 63 mmol (13.23 g) of 2-iodothiophene was added, and it stirred for further 70 hours.

After the reaction mixture was cooled to room temperature, insoluble matter was removed by celite filtration, the resulting filtrate was concentrated, and the concentrate was subjected to column chromatography (developing solvent: n-hexane/ethyl acetate = 100/0→95/ 5) to obtain 5.80 g (29.5%) of 3-bromo-9-(thiophen-2-yl)carbazole. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 7 and 8 .

[Production Example 1-5]

Reaction and purification were carried out in the same manner as in Production Example 1-4 except that 60 mmol (14.76 g) of 2-bromocarbazole was used instead of 3-bromocarbazole, and 2-bromo-9- (thiophene- 2-yl) carbazole 7.36 g (37.2%) was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 9 and 10 .

[Production Example 1-6]

In a 100 mL reaction flask, 3-bromo-9- (p-tolyl) carbazole 5 mmol (1.68 g), bis (pinacolato) diboron 5.05 mmol (1.28 g), potassium acetate 15 mmol (1.47 g), Pd (dppf)Cl ₂ 0.15 mmol (0.125 g) and 50 mL of N,N-dimethylformamide were added, and after nitrogen substitution for 10 minutes while stirring at room temperature, the temperature was raised to 90° C., and the mixture was further stirred overnight.

The reaction mixture, 75 mL of water, and 75 mL of methylene chloride were mixed, extraction was performed, and the organic layer was collect|recovered. The collected organic layer was dried over magnesium sulfate, and magnesium sulfate was removed by filtration. The resulting filtrate was concentrated, and the concentrate was purified by column chromatography to obtain 1.42 g (74.3%) of 9-(p-tolyl)carbazole-3-boronic acid pinacolaito. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 11 and 12 .

[Production Example 1-7]

Instead of 5 mmol of 3-bromo-9-(p-tolyl)carbazole, 10 mmol (3.522 g) of 3-bromo-9-(p-methoxyphenyl)carbazole was used, and the equivalent used for other reagents was 2 The reaction and purification were carried out in the same manner as in Production Example 1-6, except that it was doubled to obtain 1.53 g (38.3%) of 9-(p-methoxyphenyl)carbazole-3-boronic acid pinacolato. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 13 and 14 .

[Production Example 1-8]

15 mmol (4.92 g) of 3-bromo-9-(thiophen-2-yl)carbazole was used instead of 5 mmol of 3-bromo-9-(p-tolyl)carbazole, and the equivalent used for other reagents was The reaction and purification were carried out in the same manner as in Production Example 1-6, except that it was tripled, to obtain 2.53 g (44.9%) of pinacolato 9-(thiophen-2-yl)carbazole-3-boronic acid. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 15 and 16 .

[Production Example 1-9]

The same as in Preparation Example 1-6, except that 5 mmol (1.64 g) of 2-bromo-9-(thiophen-2-yl)carbazole was used instead of 3-bromo-9-(p-tolyl)carbazole. The reaction and purification were carried out according to the above method to obtain 1.26 g (67.2%) of 9-(thiophen-2-yl)carbazole-2-boronic acid pinacolato. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 17 and 18 .

[Production Example 2-1]

In a 100 mL reaction flask, (9-phenyl-9H-carbazol-3-yl) boronic acid 5 mmol (1.44 g), 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene 5.25 mmol (2.95 g), sodium hydroxide 15 mmol (600 mg), tetrahydrofuran and water mixed solvent (2/1 (v/v)) 75 mL and Pd[P(C ₆ H ₅ ) ₃ )] ₄ 0.15 mmol (173.5 mg) was added and stirred at room temperature for 10 minutes while purging with nitrogen, followed by stirring at 60° C. for 5 hours. In addition, a trace amount of the solution in the flask was taken along the way, and the reaction was tracked using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target increased. At that time, no prominent peaks such as those corresponding to by-products were identified.

The obtained reaction mixture was added to 400 mL of a mixed solvent of methanol and water (3/1 (v/v)), the precipitated solid was filtered off with a membrane filter, and the filtered solid was dried under reduced pressure at 60°C.

Further, the dried solid was dissolved in 20 mL of tetrahydrofuran, the resulting solution was added to 200 mL of n-hexane, the precipitated solid was filtered off with a membrane filter, and the filtered solid was dried under reduced pressure at 60°C.

Finally, the dried solid was dissolved in 20 mL of tetrahydrofuran, and the resulting solution was added to 200 mL of a mixed solvent of methanol and water (3/1 (v/v)), and the precipitated solid was separated by filtration with a membrane filter. The obtained solid was dried under reduced pressure at 60°C to obtain 1.28 g (49.8%) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole. . ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 19 .

[Production Example 2-2]

In a 100 mL reaction flask, 9-(p-tolyl) carbazole-3-boronic acid pinacolato 2.5 mmol (0.958 g), 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene 2.63 mmol (1.05 g), sodium hydroxide 7.5 mmol (300 mg), 37.5 mL of a mixed solvent of tetrahydrofuran and water (2/1 (v/v)) and Pd[P(C ₆ H ₅ ) ₃ )] ₄ 0.075 mmol (86.7 mg) was added, followed by stirring at room temperature for 10 minutes while purging with nitrogen, followed by stirring at 60°C overnight.

After the obtained reaction mixture was cooled to room temperature, the aqueous layer was removed. The obtained organic layer was added dropwise to a mixed solvent of methanol and water (3/1 (v/v)), the precipitated solid was filtered off with a membrane filter, and the filtered solid was dried under reduced pressure at 60°C.

Further, the dried solid was dissolved in 20 mL of tetrahydrofuran, the resulting solution was added to 200 mL of n-hexane, the precipitated solid was filtered off with a membrane filter, and the filtered solid was dried under reduced pressure at 60°C. 1.10 g (83.3%) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(p-tolyl)-9H-carbazole was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 20 and 21 .

[Production Example 2-3]

Instead of 9-(p-tolyl) carbazole-3-boronic acid pinacolato, 15 mmol (5.99 g) of 9-(p-methoxyphenyl) carbazole-3-boronic acid pinacolato was used, and other The reaction and purification were carried out in the same manner as in Production Example 2-2, except that the equivalent used of the reagent was increased to 6, and 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)- 5.80 g (70.4%) of 9-(p-methoxyphenyl)-9H-carbazole was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 22 .

[Production Example 2-4]

5 mmol (1.79 g) of 9-(thiophen-2-yl) carbazole-3-boronic acid pinacolato was used instead of 9-(p-tolyl) carbazole-3-boronic acid pinacolato, and the The reaction and purification were carried out in the same manner as in Production Example 2-2, except that the equivalent used of the external reagent was doubled, and 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl) 1.86 g (76.8%) of -9-(thiophen-2-yl)-9H-carbazole was obtained. ¹ H-NMR spectra of the obtained compound are shown in FIGS. 23 and 24 (measurement solvent: heavy THF).

[Production Example 2-5]

Instead of 9-(p-tolyl) carbazole-3-boronic acid pinacolato, 5 mmol (1.88 g) of 9-(thiophen-2-yl)carbazole-2-boronic acid pinacolato was used, and the The reaction and purification were carried out in the same manner as in Production Example 2-2, except that the equivalent used of the external reagent was doubled, and 2-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl) 2.0 g (77.7%) of -9-(thiophen-2-yl)-9H-carbazole was obtained. ¹ H-NMR spectra of the obtained compound are shown in FIGS. 25 and 26 (measurement solvent: heavy THF).

[Production Example 3]

In a 1000 mL reaction flask equipped with a reflux tower, Pd (DBA) ₂ 5 mmol (2.88 g), t-BuXPhos 10 mmol (4.25 g), potassium carbonate 300 mmol (41.46 g), 3-nitroaniline 100 mmol (13.82 g), 1 -Bromo-3-nitrobenzene 110mmol (22.22g) and toluene 1000mL were put, the inside of a flask was nitrogen-substituted, and it stirred overnight in an 80 degreeC bath. In addition, a trace amount of the solution in the flask was taken along the way, and the reaction was tracked using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target increased. At that time, no prominent peaks such as those corresponding to by-products were identified.

The reaction solution was cooled to room temperature, filtered through a filter filled with 200 g of silica gel N60, and the resulting filtrate was concentrated to a weight of 100 g, the concentrate was added dropwise to 1000 mL of toluene, and the resulting solid was separated by filtration. The obtained solid was dried to obtain 24.1 g of bis(3-nitrophenyl)amine (yield 93.1%).

[Production Example 4]

In a 300 mL reaction flask equipped with a reflux column, 77.15 mmol (20 g) of bis(3-nitrophenyl)amine and 2 g of Pd/CCGS-10DR[H2O]=54.40% were weighed and placed, and the inside of the flask was replaced with hydrogen. After adding 200 mL of tetrahydrofuran thereto, the mixture was stirred at 50°C overnight. The mixture was cooled to room temperature, filtered through a filter loaded with 200 g of Celite, and the solvent was distilled off from the filtrate under reduced pressure. After taking a small amount of the residue and confirming the production of 3,3'-diaminodiphenylamine using ¹ H-NMR, 100 g of tetrahydrofuran was added to the residue, and the resulting solution was cooled to 0 ° C. in an ice bath; After confirming that the temperature was stable, 50 mL of a hydrogen chloride solution (about 1 mol/L ethyl acetate solution) was added, and the precipitated solid was separated by filtration. The obtained solid was dried to obtain 19.8 g (99.0%) of 3,3'-diaminodiphenylamine dihydrochloride.

[Example 1-1]

In a 30 mL reaction flask equipped with a reflux column, Pd(DBA) ₂ 0.1 mmol (57.6 mg), RuPhos 0.15 mmol (70.0 mg), 3,3',5,5'-tetramethylbenzidine 0.5 mmol (120.2 mg) , 2.1 mmol (1080.4 mg) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole (1080.4 mg) was weighed, followed by nitrogen substitution. .

10 mL of dioxane was added thereto, stirred at room temperature for 5 minutes, then 1.69 mL of a 1.3 mol/L LHMDS solution in tetrahydrofuran (equivalent to 2.2 mmol of LHMDS) was added, stirred at room temperature for 5 minutes, and then 8 in a 110°C bath It heated and stirred for hours (internal temperature 92 degreeC). In addition, a trace amount of the solution in the flask was taken along the way, and the reaction was tracked using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target increased. At that time, no prominent peaks such as those corresponding to by-products were identified.

After the reaction mixture was cooled to room temperature, the cooled reaction mixture was put into a separatory funnel together with 50 mL of a saturated aqueous ammonium chloride solution and 50 mL of a mixed solvent of ethyl acetate and tetrahydrofuran (2/1 (v/v)) to perform extraction, The organic layer was left in the separatory funnel, and the aqueous layer was collect|recovered. 50 mL of saturated brine was placed in a separatory funnel, the remaining organic layer was washed, and the aqueous layer and the organic layer were respectively recovered. Then, all the recovered aqueous layers were combined and placed in a separatory funnel, 20 mL of ethyl acetate was added thereto for extraction, the organic layer was recovered, all the recovered organic layers were combined, and this was dried over magnesium sulfate.

Magnesium sulfate was removed by filtration, and the solvent was distilled off with the rotary evaporator from the filtrate obtained. The obtained residue was dissolved in 3 mL of toluene, and column chromatography (developing solvent: n-hexane/methylene chloride = 60/40→0/100) was performed using the obtained solution, and fractions containing the target substance were fractionated.

Finally, the solvent was removed from the fractions collected, and after drying under reduced pressure at 70°C, 0.56 g (>99%) of an arylamine compound C2d was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 27 .

[Example 1-2]

The operation was carried out in the same manner as in Example 1-1 except that 0.5 mmol (123.2 mg) of N,N'-bis(4-aminophenyl)terephthalamide was used instead of 3,3',5,5'-tetramethylbenzidine. was carried out to obtain 0.43 g (70.9%) of arylamine compound D2d. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 28 .

[Example 1-3]

The operation was carried out in the same manner as in Example 1-1 except that 0.5 mmol (160.12 mg) of 2,2'-bis(trifluoromethyl)benzidine was used instead of 3,3',5,5'-tetramethylbenzidine. was carried out to obtain 0.46 g (44.8%) of arylamine compound A3d. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 29 .

[Example 1-4]

The arylamine compound E3d was carried out in the same manner as in Example 1-1 except that 0.5 mmol (124.5 mg) of bis(4-aminophenyl)sulfone was used in place of 3,3',5,5'-tetramethylbenzidine. 0.35 g (35.3%) was obtained. ¹ H-NMR spectrum (measurement solvent: CDCl ₃ ) of the obtained compound is shown in FIG. 30 .

[Example 1-5]

3-(7-bromo-9,9-dihexyl-9H instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole -Fluoren-2-yl)-9-phenyl-9H-carbazole 0.71 g (55.8%) of arylamine compound E3i in the same manner as in Example 1-4 except that 2.1 mmol (1.375 mg) of carbazole was used. got ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 31 .

[Example 1-6]

Example 1- Except that 0.5 mmol (219.2 mg) of 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene was used instead of 3,3',5,5'-tetramethylbenzidine The operation was carried out in the same manner as in 1 to obtain 0.35 g (32.4%) of an arylamine compound F3d. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 32 .

[Example 1-7]

3-(4-bromophenyl)-9-phenyl-9H- instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole The operation was carried out in the same manner as in Example 1-3 except that 2.1 mmol (836.4 mg) of carbazole was used to obtain 0.32 g (40.3%) of an arylamine compound A3b. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 33 .

[Example 1-8]

3-(4'-bromo-[1,1'-bi instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole) Phenyl]-4-yl)-9-phenyl-9H-carbazole 0.57 g (60.2%) of arylamine compound A3c was obtained in the same manner as in Example 1-3 except that 2.1 mmol (996.2 mg) of carbazole was used. got it ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 34 .

[Example 1-9]

The procedure was repeated in the same manner as in Example 1-1 except that 0.5 mmol (106.1 mg) of m-tolidine was used in place of 3,3',5,5'-tetramethylbenzidine, and 0.17 g of arylamine compound G3d (17.5 mg). %) was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 35 .

[Example 1-10]

In a 200 mL reaction flask equipped with a reflux column, Pd(OAc) _{2 2} mmol (0.45 g), t-Bu3PHBF _{4 4} mmol (1.16 g), t-BuONa 40 mmol (3.84 g), 4,4'-diaminodiphenyl Weighed 4 mmol (797.0 mg) of amine, 20.6 mmol (10.61 g) of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, The inside of the flask was replaced with nitrogen. Toluene (50 mL) was added thereto, and the mixture was stirred overnight in a bath at 110°C. In addition, a trace amount of the solution in the flask was taken along the way, and the reaction was tracked using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target increased. At that time, no prominent peaks such as those corresponding to by-products were identified.

The reaction mixture was cooled to room temperature and filtered through a membrane filter. The filtrate was concentrated, and the resulting concentrate was diluted with 10 mL of toluene and subjected to column chromatography using the resulting solution (developing solvent: n-hexane/methylene chloride = 70/30 (v/v) → 55/45 (v/) v)), the target product fractions were collected, the collected fractions were concentrated, the obtained concentrate was diluted with 10 mL of toluene, and the resulting solution was used again for column chromatography under the same conditions, and the target product fractions were collected. The collected fractions were concentrated, the concentrate was dissolved in 30 mL of tetrahydrofuran, and the resulting solution was added dropwise to a mixed solvent of ethyl acetate and methanol (1/1 (v/v)), and the precipitated solid was collected with a membrane filter. . The obtained solid was dried to obtain 2.67 g (28.2%) of an arylamine compound H3d. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 36 .

[Example 1-11]

In a 30 mL reaction flask equipped with a reflux tower, Pd(OAc) ₂ 2.5 mmol (0.56 g), t-Bu ₃ PHBF ₄ 5 mmol (1.45 g), t-BuONa 25 mmol (2.40 g), 3,3'-dia Minodiphenylamine dihydrochloride 2.5 mmol (80.4 mg), 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole 12.6 mmol (6.49 g) ) was weighed, and the inside of the flask was replaced with nitrogen. Toluene (50 mL) was added thereto, and the mixture was stirred overnight in a bath at 110°C. In addition, a trace amount of the solution in the flask was taken along the way, and the reaction was tracked using liquid chromatography. As the area of the peak attributable to the raw material decreased, the area of the peak attributable to the target increased. At that time, no prominent peaks such as those corresponding to by-products were identified.

The reaction mixture was cooled to room temperature and filtered through a membrane filter. The filtrate was concentrated, the resulting concentrate was diluted with 5 mL of toluene, and column chromatography was performed using the resulting solution (developing solvent: n-hexane/methylene chloride = 70/30 (v/v) → 55/45 (v/) v)), the target product fractions were collected, the collected fractions were concentrated, the obtained concentrate was diluted with 5 mL of toluene, and the resulting solution was used again for column chromatography under the same conditions, and the target product fractions were collected. The collected fractions were concentrated, the concentrate was dissolved in 30 mL of tetrahydrofuran, and the resulting solution was added dropwise to a mixed solvent of ethyl acetate and methanol (1/1 (v/v)), and the precipitated solid was collected with a membrane filter. . The obtained solid was dried to obtain 2.34 g (39.5%) of arylamine compound I3d. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 37 .

[Example 1-12]

In a 50 mL flask, 3,3'-diaminodiphenylamine dihydrochloride 0.4 mmol (108.9 mg), 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9- (p-Tolyl)-9H-carbazole 2.02 mmol (1067.5 mg), Pd(OAc) ₂ 0.4 mmol (89.8 mg), t-Bu ₃ PHBF ₄ 0.8 mmol (232.1 mg), t-BuONa 4 mmol (384.4 mg) After nitrogen substitution, 8 mL of toluene was added, stirred for 10 minutes, and then stirred overnight under heating and reflux conditions.

After the reaction mixture was cooled to room temperature, the aqueous layer was removed from the cooled reaction mixture, and the obtained organic layer was added dropwise to a mixed solvent of methanol and water (methanol/water = 3/1 (v/v)). The precipitated solid was collect|recovered by filtration, the obtained solid was dissolved in tetrahydrofuran, and this solution was dripped at n-hexane. The obtained solid was collected by filtration and dried under reduced pressure to obtain 210 mg (21.5%) of arylamine compound I3e. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 38 and 39 .

[Example 1-13]

2-(7-bromo-9,9- instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-(p-tolyl)-9H-carbazole The operation was carried out in the same manner as in Example 1-12, except that 2.02 mmol (1051.4 mg) of dimethyl-9H-fluoren-2-yl)-9-(thiophen-2-yl)-9H-carbazole was used. 157.0 mg (16.4%) of arylamine compound I3h was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 40 and 41 .

[Example 1-14]

3-(7-bromo-9,9-dimethyl-9H- instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole The procedure was repeated in the same manner as in Example 1-3 except that 2.1 mmol (1109.8 mg) of fluoren-2-yl)-9-(p-tolyl)-9H-carbazole was used, and 323.8 mg of arylamine compound A3e ( 38.3%) was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 42 .

[Example 1-15]

3-(7-bromo-9,9-dimethyl-9H- instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole Arylamine compound A3f 552.6 in the same manner as in Example 1-3, except that 2.1 mmol (1143.4 mg) of fluoren-2-yl)-9-(p-methoxyphenyl)-9H-carbazole was used. mg (50.8%) was obtained. Fig. 43 shows a ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound.

[Example 1-16]

3-(7-bromo-9,9-dimethyl-9H- instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole Arylamine compound A3g in the same manner as in Example 1-3, except that 2.1 mmol (1093.0 mg) of fluoren-2-yl)-9-(thiophen-2-yl)-9H-carbazole was used. 499.9 mg (48.1%) was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 44 .

[Example 1-17]

2-(7-bromo-9,9-dimethyl-9H- instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole Arylamine compound A3h in the same manner as in Example 1-3, except that 2.1 mmol (1093.0 mg) of fluoren-2-yl)-9-(thiophen-2-yl)-9H-carbazole was used. 664.9 mg (64.0%) was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIGS. 45 and 46 .

[Example 1-18]

In a 50 mL reaction flask, 0.5 mmol (164 mg) of octafluorobiphenyl-4,4'-diamine, 2.1 mmol (836 mg) of 3-(4-bromophenyl)-9-phenylcarbazole, Pd (OAc) ₂ 0.2 mmol (45 mg), t-Bu ₃ PHBF ₄ 0.4 mmol (166 mg), and t-BuONa 4 mmol (385 mg) were added and nitrogen substituted, and then 10 mL of toluene was added, followed by stirring at room temperature for 5 minutes, followed by stirring at 100° C. for 6 hours. did.

After the reaction mixture was cooled to room temperature, the cooled reaction mixture was filtered through a membrane filter, and activated carbon was added to the resulting filtrate, followed by stirring for 1 hour. Activated carbon was removed by filtration, the resulting filtrate was concentrated, and the concentrate was purified by silica gel chromatography (developing solvent: n-hexane/dichloromethane = 3/2 (v/v)), and 311.8 mg of arylamine compound B3b (44.6%) was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 47 .

[Example 1-19]

3-(4'-bromo-[1,1'-biphenyl]-4-yl)-9-phenyl-9H-carbazole instead of 3-(4-bromophenyl)-9-phenylcarbazole 2.1 391 mg (41.1%) of arylamine compound B3c was obtained in the same manner as in Example 1-18 except that mmol (996.2 mg) was used. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 48 .

[Example 1-20]

3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole instead of 3-(4-bromophenyl)-9-phenylcarbazole 2.1 535 mg (51.9%) of arylamine compound B3d was obtained in the same manner as in Example 1-18 except that mmol (1080.4 mg) was used. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG.

[Example 1-21]

In a 50 mL reaction flask, 0.5 mmol (164 mg) of octafluorobiphenyl-4,4'-diamine, 2.1 mmol (836 mg) of 3-(4-bromophenyl)-9-phenylcarbazole, Pd (DBA) ₂ 0.1 mmol (57.5 mg), t-Bu ₃ PHBF ₄ 0.2 mmol (84 mg), and t-BuONa 2 mmol (193 mg) were added and nitrogen substituted, and then 10 mL of toluene was added, followed by stirring at room temperature for 5 minutes, and then at 100° C. for 6 hours. stirred.

After the reaction mixture was cooled to room temperature, the cooled reaction mixture was filtered through a membrane filter, and activated carbon was added to the resulting filtrate, followed by stirring for 1 hour. Activated carbon was removed by filtration, the resulting filtrate was concentrated, and the concentrate was purified by silica gel chromatography (developing solvent: n-hexane/dichloromethane = 3/2 (v/v)), and 419.0 mg of arylamine compound B2b (87.0%) was obtained. ¹ H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG. 50 .

[Example 1-22]

3-(4'-bromo-[1,1'-biphenyl]-4-yl)-9-phenyl-9H-carbazole in place of 3-(4-bromophenyl)-9-phenylcarbazole 2.1 72.9 mg (13.1%) of arylamine compound B2c was obtained in the same manner as in Example 1-21 except that mmol (996.2 mg) was used. ¹ H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG. 51 .

[Example 1-23]

3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole instead of 3-(4-bromophenyl)-9-phenylcarbazole 2.1 114.0 mg (19.1%) of arylamine compound B2d was obtained in the same manner as in Example 1-21 except that mmol (1080.4 mg) was used. ¹ H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG. 52 .

[Comparative Example 1-1]

Instead of 3-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazole, 2.1 mmol of 3-bromo-N-phenylcarbazole (676.6 mg ) was used, and the operation was carried out in the same manner as in Example 1-3 to obtain 0.45 g (70.0%) of an arylamine compound A3a. Fig. 53 shows a ¹ H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound.

[Comparative Example 1-2]

The operation was carried out in the same manner as in Example 1-18, except that 2.1 mmol (677 mg) of 3-bromo-N-phenylcarbazole was used instead of 3-(4-bromophenyl)-9-phenylcarbazole. 236.2 mg (36.6%) of the amine compound B3a was obtained. ¹ H-NMR spectrum (measurement solvent: heavy THF) of the obtained compound is shown in FIG. 54 .

[Comparative Example 1-3]

The operation was performed in the same manner as in Example 1-21 except that 2.1 mmol (677 mg) of 3-bromo-9-phenylcarbazole was used instead of 3-(4-bromophenyl)-9-phenylcarbazole, and the aryl 272.3 mg (67.2%) of amine compound B2a was obtained. ¹ H-NMR spectrum (measurement solvent: heavy DMSO) of the obtained compound is shown in FIG. 55 .

[2] Preparation of varnish for hole injection layer

[Comparative Example 2-1]

To chloroform (10 g), the arylamine compound A3a (0.025 g) and the arylsulfonic acid ester A (0.025 g) represented by the following formula were added, stirred at room temperature to dissolve, and the resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm. A charge-transporting varnish A3a-1 was obtained.

[Example 2-1]

A solution obtained by adding arylamine compound A3b (0.028 g) and arylsulfonic acid ester A (0.022 g) to chloroform (10 g) and stirring at room temperature to dissolve it was filtered through a syringe filter having a pore diameter of 0.2 μm, and then charge-transporting varnish A3b -1 was obtained.

[Example 2-2]

To chloroform (10 g), arylamine compound A3c (0.030 g) and arylsulfonic acid ester A (0.020 g) were added, stirred at room temperature to dissolve, and the resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm, and then a charge-transporting varnish A3c- got 1

[Example 2-3]

To chloroform (10 g), arylamine compound A3d (0.031 g) and arylsulfonic acid ester A (0.019 g) were added, stirred at room temperature to dissolve, and the resulting solution was filtered through a syringe filter having a pore diameter of 0.2 µm, and charge-transporting varnish A3d- got 1

[Example 2-4]

To chloroform (10 g), arylamine compound A3e (0.031 g) and arylsulfonic acid ester A (0.019 g) were added, stirred at room temperature to dissolve, and the resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm, and then charge-transporting varnish A3e- got 1

[Example 2-5]

In chloroform (10 g), arylamine compound A3f (0.032 g) and arylsulfonic acid ester A (0.018 g) were added and dissolved by stirring at room temperature. The resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm, followed by charge-transporting varnish A3f- got 1

[Example 2-6]

To chloroform (10 g), arylamine compound A3 g (0.031 g) and arylsulfonic acid ester A (0.019 g) were added, stirred at room temperature to dissolve, and the resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm, and charge-transporting varnish A3g- got 1

[Example 2-7]

To chloroform (10 g), arylamine compound A3h (0.031 g) and arylsulfonic acid ester A (0.019 g) were added, stirred at room temperature to dissolve, and the resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm, and then charge-transporting varnish A3h- got 1

[Comparative Example 2-2]

To chloroform (10 g), arylamine compound B3a (0.026 g) and arylsulfonic acid ester A (0.024 g) were added, stirred at room temperature to dissolve, and the resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm, and then a charge-transporting varnish B3a- got 1

[Example 2-8]

To chloroform (10 g), arylamine compound B3b (0.029 g) and arylsulfonic acid ester A (0.021 g) were added, stirred at room temperature to dissolve, and the resulting solution was filtered through a syringe filter having a pore diameter of 0.2 µm, and then a charge-transporting varnish B3b- got 1

[Example 2-9]

To chloroform (10 g), arylamine compound B3c (0.030 g) and arylsulfonic acid ester A (0.020 g) were added and dissolved by stirring at room temperature. The resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm, and then a charge-transporting varnish B3c- got 1

[Example 2-10]

To chloroform (10 g), arylamine compound B3d (0.031 g) and arylsulfonic acid ester A (0.019 g) were added, stirred at room temperature to dissolve, and the resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm, and charge-transporting varnish B3d- got 1

[Comparative Example 2-3]

To chloroform (10 g), arylamine compound B2a (0.020 g) and arylsulfonic acid ester A (0.030 g) were added and dissolved by stirring at room temperature. The resulting solution was filtered through a syringe filter having a pore diameter of 0.2 µm, and then a charge-transporting varnish B2a- got 1

[Example 2-11]

To chloroform (10 g), arylamine compound B2b (0.022 g) and arylsulfonic acid ester A (0.028 g) were added, stirred at room temperature to dissolve, and the resulting solution was filtered through a syringe filter having a pore diameter of 0.2 µm, and then a charge-transporting varnish B2b- got 1

[Example 2-12]

To chloroform (10 g), arylamine compound B2c (0.024 g) and arylsulfonic acid ester A (0.026 g) were added and dissolved by stirring at room temperature. The resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm, and then a charge-transporting varnish B2c- got 1

[Example 2-13]

To chloroform (10 g), arylamine compound B2d (0.025 g) and arylsulfonic acid ester A (0.025 g) were added and dissolved by stirring at room temperature. The resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm, and then a charge-transporting varnish B2d- got 1

[Example 2-14]

To chloroform (10 g), arylamine compound H3d (0.033 g) and arylsulfonic acid ester A (0.017 g) were added and dissolved by stirring at room temperature. The resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm, and then a charge-transporting varnish H3d- got 1

[Example 2-15]

To chloroform (10 g), arylamine compound I3d (0.033 g) and arylsulfonic acid ester A (0.017 g) were added, stirred at room temperature to dissolve, and the resulting solution was filtered through a syringe filter having a pore diameter of 0.2 μm, and then a charge-transporting varnish I3d- got 1

[3] Preparation of varnish for hole transport layer

[Comparative Example 3-1]

A solution obtained by adding arylamine compound A3a (0.040 g) to chloroform (10 g) and stirring at room temperature to dissolve it was filtered through a syringe filter having a pore diameter of 0.2 µm to obtain a charge-transporting varnish A3a-2.

[Examples 3-1 to 3-11]

Charge-transporting varnish was carried out in the same manner as in Comparative Example 3-1 except that arylamine compounds A3b, A3c, A3d, A3e, A3f, A3g, A3h, B3d, B2d, H3d, or I3d were respectively used instead of the arylamine compound A3a. A3b-2, A3c-2, A3d-2, A3e-2, A3f-2, A3g-2, A3h-2, B3d-2, B2d-2, H3d-2, or I3d-2 were obtained.

[4] Thin film production and film properties evaluation

[Comparative Example 4-1, Examples 4-1 to 4-3]

Charge-transporting varnishes A3a-1, A3b-1, A3c-1, and A3d-1 were respectively applied to a quartz substrate using a spin coater, and then dried under atmospheric firing at 120°C for 1 minute. Next, the dried quartz substrate was fired at 200 DEG C for 15 minutes in an atmospheric atmosphere to form a uniform 50 nm thin film on the quartz substrate.

Using the obtained quartz substrate with a film, the average refractive index (n) in the visible region and the average extinction coefficient (k) in the visible region at a wavelength of 400 to 800 nm were measured. A result is shown in Table 23.

As shown in Table 23, the thin film obtained from the charge-transporting varnish of the present invention has the same or higher refractive index and the same or lower extinction coefficient than the thin film obtained from the charge-transporting varnish of Comparative Example 4-1. It can be seen that .

[5] Fabrication and Characterization of Hall-Only Devices (HODs)

[Comparative Example 5-1]

As the ITO substrate, a glass substrate of 25 mm × 25 mm × 0.7 t on which indium tin oxide (ITO) was patterned to a film thickness of 150 nm was used, and impurities on the surface were removed before use by an O ₂ plasma cleaning device (150 W, 30 seconds). Removed. Subsequently, the composition for forming a hole injection layer obtained by the method described below is applied by spin coating, heated to 80° C. in the air, on a hot plate, dried for 1 minute, and further fired at 230° C. for 15 minutes, the hole injection layer ( film thickness: 30 nm) was formed.

Next, the charge-transporting varnish A3a-2 was applied on the hole injection layer using a spin coater, and then baked at 130°C for 10 minutes in an atmospheric atmosphere to form a hole transport layer (film thickness: 40 nm).

On this, an aluminum thin film of 80 nm was formed at 0.2 nm/sec using a vapor deposition apparatus (vacuum degree of 1.0×10 ⁻⁵ Pa) to obtain a Hall-only device (HOD).

In addition, the composition for hole injection layer formation was prepared in the following procedure. 0.137 g of an aniline derivative represented by Formula (3) synthesized according to the method described in International Publication No. 2013/084664 and an arylsulfonic acid represented by Formula (4) synthesized according to the method described in International Publication No. 2006/025342 0.271 g was dissolved in 6.7 g of 1,3-dimethyl-2-imidazolidinone under a nitrogen atmosphere. To the obtained solution, 10 g of cyclohexanol and 3.3 g of propylene glycol were sequentially added and stirred to obtain a composition for forming a hole injection layer (hereinafter the same).

[Examples 5-1 to 5-11]

Instead of the charge-transporting varnishes A3a-2, the charge-transporting varnishes A3b-2, A3c-2, A3d-2, A3e-2, A3f-2, A3g-2, A3h-2, B3d-2, B2d-2, H3d- 2 or I3d-2 was used, respectively, and HOD was produced in the same manner as in Example 5-1.

For each HOD produced in the above examples and comparative examples, the current density at a driving voltage of 4 V was measured. A result is shown in Table 24.

As shown in Table 24, it is understood that the thin film produced from the charge-transporting varnish of the present invention exhibits better charge-transporting properties than the thin film produced from the charge-transporting varnish of the comparative example. It is thought that this improvement of charge transport property is accompanied by the increase of the effective conjugate length of the electrically-conductive site|part in the arylamine compound of this invention.

[6] Fabrication of single-layer devices (SLD) and HOD and evaluation of relative intensity of current density of HOD with respect to current density of SLD

[Comparative Example 6-1]

As the ITO substrate, a glass substrate of 25 mm × 25 mm × 0.7 t on which indium tin oxide (ITO) was patterned to a film thickness of 150 nm was used, and impurities on the surface by an O ₂ plasma cleaning device (150 W, 30 seconds) before use. has been removed

A charge-transporting varnish A3a-1 is applied on an ITO substrate by spin coating, dried at 120° C. under atmospheric conditions for 1 minute, and then fired at 200° C. for 15 minutes to form a hole injection layer (film thickness: 50 nm) on the ITO substrate. did.

On this, an aluminum thin film of 80 nm was formed at 0.2 nm/sec using a vapor deposition apparatus (vacuum degree of 1.0×10 ⁻⁵ Pa) to obtain a single-layer device (SLD).

[Examples 6-1 to 6-12, Comparative Example 6-2]

Instead of the charge-transporting varnishes A3a-1, the charge-transporting varnishes A3b-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3h-1, B3b-1, B3d-1, B2d- An SLD was produced in the same manner as in Comparative Example 6-1 except that 1, H3d-1, I3d-1, or B3a-1 was used, respectively.

[Comparative Example 7-1]

Charge-transporting varnish A3a-1 was applied to an ITO substrate using a spin coater, dried at 120° C. for 1 minute in the atmosphere, and then fired at 200° C. for 15 minutes to form a 50 nm thin film on the ITO substrate. In addition, as an ITO board|substrate, the ITO board|substrate similar to Comparative Example 6-1 was used.

On it, using a vapor deposition apparatus (vacuum degree 2.0x10 ^-5 Pa), α-NPD and thin films of aluminum were sequentially laminated to obtain HOD. Vapor deposition was performed on condition of the deposition rate of 0.2 nm/sec. The film thicknesses of the α-NPD and aluminum thin films were set to 30 nm and 80 nm, respectively.

[Examples 7-1 to 7-12, Comparative Example 7-2]

Instead of the charge-transporting varnishes A3a-1, respectively, the charge-transporting varnishes A3b-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3h-1, B3b-1, B3d-1, B2d An HOD was produced in the same manner as in Comparative Example 7-1 except that -1, H3d-1, I3d-1, or B3a-1 was used.

The SLD prepared in Examples 6-1 to 6-12 and Comparative Examples 6-1 to 6-2, and the HOD prepared in Examples 7-1 to 7-12 and Comparative Examples 7-1 to 7-2 were applied to voltage The current density in the case of driving at 4 V was measured. A result is shown in Table 25. In addition, the relative intensity of the current density of the HOD to the current density of the SLD, calculated using these measured values, is also shown. In addition, the high relative strength indicates that hole supply to the hole transport layer is efficiently realized.

As shown in Table 25, it was found that the device using the hole injection layer prepared from the charge-transporting varnish of the present invention had a higher relative intensity of the HOD current density to the SLD current density compared to the device manufactured in the comparative example. .

[7] Fabrication and characteristic evaluation of organic EL devices

[Comparative Example 8-1]

The charge-transporting varnish A3a-1 was applied to the ITO substrate using a spin coater, dried at 120° C. for 1 minute under the atmosphere, and then fired at 200° C. for 15 minutes to form a 50 nm thin film on the ITO substrate. In addition, as an ITO board|substrate, the ITO board|substrate similar to Comparative Example 6-1 was used.

Next, with respect to the ITO substrate on which the thin film was formed, 30 nm of α-NPD was formed into a film at 0.2 nm/sec using a vapor deposition apparatus (vacuum degree of 1.0×10 ⁻⁵ Pa). Next, an electron block material HTEB-01 manufactured by Kanto Chemical Co., Ltd. was formed into a film to a thickness of 10 nm. Next, the light emitting layer host material NS60 and the light emitting layer dopant material Ir(ppy) ₃ manufactured by Nippon Steel Chemicals Co., Ltd. were co-evaporated. For co-deposition, the deposition rate was controlled so that the concentration of Ir(ppy) ₃ was 6%, and 40 nm was laminated. Then, thin films of Alq ₃ , lithium fluoride, and aluminum were sequentially laminated to obtain an organic EL device. At this time, the deposition rate was 0.2 nm/sec for Alq ₃ and aluminum, and 0.02 nm/sec for lithium fluoride, respectively, and the film thicknesses were 20 nm, 0.5 nm, and 80 nm, respectively.

In addition, in order to prevent the characteristic deterioration by the influence of oxygen in air, water, etc., the organic electroluminescent element was sealed with the sealing substrate, and the characteristic was evaluated. Sealing was performed in the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76° C. or less, an organic EL element was placed between sealing substrates, and the sealing substrate was bonded with an adhesive (MORESCO Co., Ltd., Moresco Moisture Cut WB90US(P)). . At this time, a desiccant (HD-071010W-40 manufactured by Dynic Co., Ltd.) was put together with the organic EL element in the sealing substrate. After irradiating UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ/cm ² ) to the bonded sealing substrate, annealing was performed at 80° C. for 1 hour to harden the adhesive.

[Examples 8-1 to 8-12]

Instead of the charge-transporting varnishes A3a-1, respectively, the charge-transporting varnishes A3b-1, A3c-1, A3d-1, A3e-1, A3f-1, A3g-1, A3h-1, B3b-1, B3d-1, B2d An organic EL device was produced in the same manner as in Comparative Example 8-1 except that -1, H3d-1, or I3d-1 was used.

Driving voltage, current density, current efficiency, luminous efficiency, external emission quantum yield (EQE), and LT90 (initial luminance of 5,000 cd/m ² ) when the obtained organic EL device was emitted with a luminance of 5,000 cd/m ² time required) was measured. A result is shown in Table 26.

As shown in Table 26, compared with the organic EL device of Comparative Example 8-1, all of the organic EL devices of the present invention exhibited the same or less driving voltage, and had a half-life equal to or higher than that of the organic EL device.

Claims (12)

An arylamine compound represented by any one of the following formulas (1) to (6) (however, the compound represented by the following formulas (P1) to (P4) is excluded).

[Wherein, Ar ^c each independently represents a group represented by the formula (Q),
X each independently represents an arylene group which may be substituted and may contain a hetero atom,
Y each independently represents a phenylene group which may be substituted,
g each independently represents the integer of 1-10.

(Wherein, R ¹ is each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 carbon atoms. to 20 aryl groups, R ² each independently represents an aryl group that may be substituted and may contain a hetero atom, Ar ^s are each independently may be substituted and contain a hetero atom An arylene group which may be present is shown.)]

The method of claim 1,
An arylamine compound wherein Ar ^s is represented by any one of the following formulas (101) to (118).

(Wherein, R ³ is each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 carbon atoms. represents an aryl group of to 20, V ¹ each independently represents C(R ⁴ ) ₂ (R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms) .), NR ⁵ (R ⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms), S, O, or SO ₂ , and V ² is NR ⁵ (R ⁵ is It represents the same meaning as above), represents S or O.) The method of claim 1,
An arylamine compound wherein Ar ^s is represented by any one of the following formulas (101A) to (118A).

(Wherein, R ³ , V ¹ and V ² have the same meanings as above.) 4. The method of claim 3,
An arylamine compound wherein Ar ^s is represented by any one of the following formulas (101A-1) to (118A-3).

(Wherein, R ⁴ and R ⁵ have the same meanings as above.) 5. The method according to any one of claims 1 to 4,
An arylamine compound wherein X is represented by any one of the following formulas (201) to (207).

(Wherein, R ⁶ is each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 carbon atoms. represents an aryl group of to 20, each of W ¹ is independently a single bond, C(R ⁷ ) ₂ (R ⁷ is each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or halogenation having 1 to 20 carbon atoms) represents an alkyl group), S, O, or SO ₂ , W ² is C(R ⁷ ) ₂ (R ⁷ each independently represents the same meaning as above), NR ⁸ (R ⁸ is a hydrogen atom, represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms), S, O, or SO ₂ , W ³ is NR ⁸ (R ⁸ has the same meaning as above), S or O indicates.) 6. The method of claim 5,
An arylamine compound wherein X is represented by any one of the following formulas (201A) to (207A).

(Wherein, R ⁶ , W ¹ , W ² and W ³ have the same meanings as above.) 7. The method of claim 6,
An arylamine compound wherein X is represented by any one of the following formulas (201A-1) to (207A-1).

(Wherein, R ⁷ , R ⁸ and W ³ have the same meanings as above.) 8. The method according to any one of claims 1 to 7,
An arylamine compound wherein Ar ^c is the same group. A charge-transporting varnish comprising the arylamine compound according to any one of claims 1 to 8 and an organic solvent. 10. The method of claim 9,
A charge transporting varnish comprising a dopant material. A charge-transporting thin film produced using the charge-transporting varnish of claim 9 or 10. An electronic device comprising the charge-transporting thin film according to claim 11 .

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