KR20220163369A - Asymmetric 1,2-bis(diarylamino)benzenes, manufacturing methods and uses thereof - Google Patents

Abstract

Asymmetric 1,2-bis(diarylamino)benzenes useful as materials for organic EL devices, methods for their production, use as hole-transporting materials or blue light emitting materials, and production of asymmetric 1,2-bis(diarylamino)benzenes Ortho-phenylenediamines, which are useful intermediates for Asymmetric 1,2-bis(diarylamino)benzenes represented by the following general formula (1) and uses thereof.

Description

Asymmetric 1,2-bis(diarylamino)benzenes, manufacturing methods and uses thereof

The present invention relates to asymmetric 1,2-bis(diarylamino)benzenes useful as materials for organic EL devices, particularly hole-transporting materials or blue light-emitting materials, methods for producing the same, and uses of the hole-transporting materials, blue light-emitting materials, and the like. .

Organic EL (organic electro-luminescence: OEL) has attracted attention as a next-generation flat panel display, and those having high panel performance such as thinness and light weight, high viewing angle, high-speed response, high brightness and high energy efficiency are mentioned. For this reason, domestic and foreign companies and research institutes are developing for practical use, and application to displays for mobile phones and flat-screen TVs has begun.

In general, an organic EL device has a structure in which a hole transport material, a light emitting material (host material and dopant material), and an electron transport material are laminated between an anode and a cathode.

As a technical problem of organic EL devices, there is a need to search for materials suitable for the high panel performance described above, particularly blue light emission and hole transport materials, and to develop materials suitable for industrial applications.

Materials suitable for blue light emission are thought to affect the emission wavelength according to the energy levels of HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital). Since it affects the barrier and efficiency, it is considered a factor to be considered in the design of the compound of the hole transport material. Therefore, a material having an appropriate HOMO-LUMO level is required.

As a typical hole-transporting material, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl, denoted as NPB below, is generally known. However, since the drive voltage of the device using NPB for the hole transport layer was not sufficient and the glass transition temperature (Tg) was low, the performance was insufficient as a hole transport material.

Non-Patent Document 1 also proposes compounds represented as TCTA and mCP below, and compounds represented as L9 (N(2,3) DA-carbs below) in Patent Document 1. These cannot be said to have excellent characteristic values as a hole transporting material or a blue light emitting material from the viewpoint of ease of manufacture, and development of new compounds is desired.

Further, as an example of using 1,2-bis(diarylamino)benzenes as a hole-transporting material, Patent Document 2 is reported, for example. However, their use as hole transporting materials requires further improvement. In addition, since the compounds described in the literature are only compounds having a symmetrical structure, it is presumed to have a low glass transition temperature (Tg), and improvement as a hole-transporting material was also required.

Patent Document 1: Chinese Patent Application Publication No. 108299282 Patent Document 2: Japanese Patent Publication No. 3171755

Non-Patent Document 1: Nature Photonics, 2019, pp 678-682

In view of the above background, an object of the present invention is an asymmetric 1,2-bis(diarylamino)benzene useful as an organic EL device material such as a hole transport material or a blue light emitting material, a method for producing the same, and a hole transport material or blue light emitting material. It is to provide the use as a light emitting material.

Another object of the present invention is to provide ortho phenylenediamines which are useful intermediates for producing asymmetric 1,2-bis(diarylamino)benzenes.

As a result of intensive examination of the above problems, the inventors of the present invention have found that the specific asymmetric bis(1,2-diarylamino)benzenes shown below are suitable for use as organic EL element materials such as hole transport materials and blue light emitting materials. -LUMO level, found to have a particularly desirable Eg value. In addition, by using diarylamines having various substituents as a starting material, an efficient method for producing asymmetric 1,2-bis(diarylamino)benzenes, which had been difficult to produce, was established, and the present invention was completed.

That is, the present invention relates to the following inventions.

[1] Asymmetric 1,2-bis(diarylamino)benzenes represented by the following general formula (1).

[In equation (1),

R1 represents a methyl group, an ethyl group, a straight chain, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazole group or a phenyl group; ,

R2 represents a methyl group, an ethyl group, a straight-chain, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a phenyl group or a halogen atom;

R3 and R4 are each independently a methyl group, an ethyl group, a straight-chain, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carba represents a sol group or a phenyl group;

a, b, c and d represent 0 or 1;

A is a substituent containing a substituted or unsubstituted condensed polycyclic aromatic group or a substituent in which only one of the m-positions or a nitrogen atom is directly connected to the p-position, a substituted aryl group, a substituted or unsubstituted biphenyl group, a substituted or substituted unsubstituted indolyl group, substituted or unsubstituted benzoimidazole group, substituted or unsubstituted carbazole group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothienyl group, substituted or unsubstituted dibenzothienyl group, represents an unsubstituted fluorenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted thiophenyl group, and A is a nitrogen atom directly bonded to the nitrogen atom and a phenyl group directly bonded to the nitrogen atom to form a cyclic structure; may be.]

In addition, in the present specification, 'asymmetric 1,2-bis(diarylamino)benzenes' includes structural analogues thereof, and as described above, A is a substituted or unsubstituted furanyl group, or a substituted or substituted furanyl group. Structures that are unresolved thiophenyl groups are also included.

In the present specification, "asymmetric 1,2-bis(diarylamino)benzenes" may include compounds having a point-symmetric structure.

[2] Wherein A is an aryl group substituted with a substituent containing a nitrogen atom, asymmetric 1,2-bis(diarylamino)benzenes.

[3] The asymmetric 1,2-bis(diarylamino)benzenes described in [2] above, wherein the nitrogen atom contained in the substituent is directly bonded to an aryl group.

[4] The asymmetric 1,2-bis(diarylamino)benzenes described in [3] above, wherein the substituent is a carbazole group in which a nitrogen atom is directly bonded to an aryl group.

[5] The asymmetric 1,2-bis(diarylamino)benzenes according to the above [3], wherein the substituent has an aryl group directly bonded to a nitrogen atom.

[6] The asymmetric 1,2-bis(diarylamino)benzenes described in any one of [3] to [5] above, wherein a nitrogen atom is directly bonded to the p-position or m-position of the aryl group.

[7] The asymmetric 1,2-bis(diarylamino)benzenes described in [2] above, wherein the substituent is a substituted or unsubstituted nitrogen-containing polycyclic aromatic group.

[8] The asymmetric 1,2-bis(diarylamino)benzenes according to the above [1], which are any of the following formulas.

[9] A hole-transporting material or blue light emitting material composed of asymmetric 1,2-bis(diarylamino)benzenes represented by general formula (1) according to any one of [1] to [8] above.

In addition, in this specification, the hole transporting material includes a hole transporting host material used in the light emitting layer and a hole transporting material used in the hole transporting layer.

[10] An organic EL device comprising the hole transporting material or the blue light emitting material.

[11] A display comprising the organic EL element.

In the present invention, as an intermediate for producing the asymmetric 1,2-bis(diarylamino)benzenes of the present invention, ortho phenylenediamines represented by the following general formula (2) can be used.

[In equation (2),

R1 represents a methyl group, an ethyl group, a straight chain, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazole group or a phenyl group; ,

R2 represents a methyl group, an ethyl group, a straight-chain, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a phenyl group or a halogen atom;

R3 and R4 are each independently a methyl group, an ethyl group, a straight-chain, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carba represents a sol group or a phenyl group;

a, b, c and d represent 0 or 1.]

In the present invention, as a method for producing the asymmetric 1,2-bis (diarylamino) benzene of the present invention, the asymmetric 1,2-bis (diarylamino) benzene represented by the following general formula (1) As a method of manufacturing,

[In equation (1),

R1 represents a methyl group, an ethyl group, a straight chain, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazole group or a phenyl group; ,

R2 represents a methyl group, an ethyl group, a straight-chain, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a phenyl group or a halogen atom;

R3 and R4 are each independently a methyl group, an ethyl group, a straight-chain, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carba represents a sol group or a phenyl group;

a, b, c and d represent 0 or 1;

A is a substituent containing a substituted or unsubstituted condensed polycyclic aromatic group or a substituent in which only one of the m-positions or a nitrogen atom is directly connected to the p-position, a substituted aryl group, a substituted or unsubstituted biphenyl group, a substituted or substituted unsubstituted indolyl group, substituted or unsubstituted benzoimidazole group, substituted or unsubstituted carbazole group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothienyl group, substituted or unsubstituted dibenzothienyl group, represents an unsubstituted fluorenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted thiophenyl group, and A is a nitrogen atom directly bonded to the nitrogen atom and a phenyl group directly bonded to the nitrogen atom to form a cyclic structure; may be.]

The following general formula (3)

[In formula (3), R1, R2, a and b are each the same as in formula (1).]

Diarylamines represented by

The following general formula (4)

[In Formula (4), R3, R4, c and d are each the same as in Formula (1).]

Grignard reagent is reacted with diarylamines represented by

The following general formula (5)

[In Formula (5), R1, R2, a and b are each the same as in Formula (1), and X represents a halogen atom.]

Magnesium diarylamides (5) represented by

The following general formula (6)

[In Formula (6), R3, R4, c and d are each the same as in Formula (1), and X represents a halogen atom.]

After obtaining the magnesium diarylamides (6) represented by , the magnesium diarylamides (5) and the magnesium diarylamides (6) are reacted with a transition metal catalyst and an oxidizing agent,

The following general formula (2)

[In Formula (2), R1, R2, R3, R4, a, b, c and d are each the same as in Formula (1).]

Obtaining ortho phenylenediamines (2) represented by, and in the presence of a transition metal catalyst and a base,

The following general formula (7)

[In Formula (7), A is the same as in Formula (1), X represents a halogen atom, and n represents an integer of 1 to 3.]

A method for producing asymmetric 1,2-bis(diarylamino)benzenes (1) by reacting with a halogen compound represented by can be used.

In the asymmetric bis(1,2-diarylamino)benzenes represented by the general formula (1), in formula (1), R1 is a methyl group, an ethyl group, a straight-chain, branched or cyclic type having 3 to 6 carbon atoms represents an alkyl group, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazole group, or a phenyl group; represents an alkyl group, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a phenyl group or a halogen atom, and R3 and R4 are each independently a methyl group, an ethyl group, a linear or branched or cyclic alkyl group having 3 to 6 carbon atoms; A methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazole group or a phenyl group, a, b, c and d represent 0 or 1, A is substituted or substituted An aryl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted indolyl group, a substituted substituent containing a condensed polycyclic aromatic group or a substituent in which only one of the m-positions or a nitrogen atom is directly connected to the p-position A substituted or unsubstituted benzoimidazole group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted fluorenyl group , a substituted or unsubstituted furanyl group, or a substituted or unsubstituted thiophenyl group, and A may form a cyclic structure with a directly bonded nitrogen atom and a phenyl group directly bonded to the nitrogen atom.

Asymmetric 1,2-bis(diarylamino)benzenes represented by the general formula (1) are preferable as hole transporting materials or blue light emitting materials.

Among these, examples of straight-chain, branched or cyclic alkyl groups having 3 to 6 carbon atoms include n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group and i-butyl group. group, s-butyl group, t-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2- Dimethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, cyclopropyl group, A cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

As a C3-C6 alkoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert- butoxy group etc. are mentioned, for example.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned.

In addition, the substituent containing a condensed polycyclic aromatic group is a substituent containing a condensed polycyclic group having aromaticity, and the condensed polycyclic group having aromaticity may not contain a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom, may contain

Examples of the condensed polycyclic group having aromaticity include carbon condensed polycyclic groups such as naphthyl and fluorenyl groups, quinolinyl groups, indolyl groups, benzoimidazole groups, phenoxazinyl groups, phenothiazinyl groups, and 9-dimethyl Heterocondensed polycyclic groups, such as an acridinyl group, an iminostilbenyl group, 1,12-iminoperylene group, a carbazole group, a dibenzofuranyl group, a dibenzothienyl group, and an oxanthrenyl group, are mentioned.

In addition, all of R1 to R4 may be the same substituent or hydrogen atom, or may be different substituents.

When some specific examples of asymmetric bis(1,2-diarylamino)benzenes represented by the general formula (1) are shown, the following compounds: (1-1) to (1-16), (2-1) to ( 2-18), (3-1) to (3-16), (3-1) to (3-16), (4-1) to (4-7), (5-1) to (5- 2), (6-1) to (6-6), (7-1) to (7-4), (8-1) to (8-4), (9-1) to (9-3) , (10-1) to (10-2), and the like.

F-1 to F-18

Regarding the following general formula (F), the compound of F-1 - F-18 of compound No is also mentioned. These specify substituents R1 to R3 in the following general formula (F).

(F-1 is the same as (3-1), F-2 is the same as (3-2), F-17 is the same as OPDA-7,)

Among the above compounds, OPDA-1 to OPDA-11 are preferably used as a hole transport material, a blue light emitting material, or a material for organic EL, as shown in Examples described later. In addition, materials having structures of OPDA-1 to OPDA-11 as skeletons are also preferably used as hole transport materials, blue light emitting materials, and materials for organic EL.

In addition, for the compounds (1-1) to (10-2), the HOMO-LUMO levels, that is, EHOMO, ELUMO, Eg, ET, ETO, λ-, λ+, IP, EA were calculated, and the following Tables 1- Table 5 shows.

The calculation method is as follows.

All calculations are performed with the Gaussian 16 program (Revision C01) using the B3LYP density functional method in combination with the 6-31G* basis functions. The triplet energy is calculated as the difference (ET) of the electron energies of the optimized geometries of the triplet state and the singlet state. Since it was found that the triplet energy (ET0) calculated including the zero point energy correction agrees better with the experimental value, these are also calculated and compared. Reorientation energy is the change difference in electron energy associated with the geometrical change of the molecular structure in the charge transfer state and neutral state. The internal reorientation energy (l) is the energy required to change the geometry of two molecules to promote electron/hole transfer between the two molecules. It is calculated using the adiabatic potential energy surface, using the following equation.

λ=λ1+λ2=(Echarged state in neutral geometry-Echarged state in charged geometry)+(Eneutral state in charged geometry-Eneutral state in neutral geometry)

(In the equation, Echarged state in neutral geometry is the electron energy of a charged state obtained for a molecular structure in a neutral state, Echarged state in charged geometry is an electron energy of a charged state obtained for a molecular structure in a charged state, and Eneutral state in charged geometry is a charged state Eneutral state in neutral geometry represents the electron energy in a charged state obtained for a molecular structure in a neutral state.)

For the internal reorganization energies of hole transport (λ+) and electron transport (λ-), the charge states are positive and negative ions, respectively. The energy required to change the structure of the surrounding molecules surrounding the two molecules involved in the charge transfer is called external reorientation energy, and is considered to be small and is not considered in the current calculation. In addition, the adiabatic ionization potential (IP) and electron affinity (EA) are also calculated. The energy of the optimized charge state is used for this calculation and is calculated using the following equation.

IP=Ecationic state geometry-Eneutral state geometry

EA=Eanionic state geometry-Eneutral state geometry

(In the formula, IP is the ionization potential (adiabatic), EA is the electron affinity (adiabatic), Ecationic state geometry is the cation state molecular structure, Eneutral state geometry is the neutral state molecular structure, Eanionic state geometry is the anion state molecular structure, and eneutral state geometry is represents the neutral state molecular structure.)

Also, the citation reads:

(Revision C01) Gaussian 16, Revision C. 01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A.F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V.N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian, Inc., Wallingford CT, 2016.

(B3LYP functional) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.

(6-31G* basis sets) (a) Ditchfie, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54, 724-728. (b) Hehre, W. J.; Ditchfie, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257-2261. (c) Hariharan, P. C.; Pople, J. A. Theor Chim Acta 1973, 28, 213-222. (d) Francl, M. M.; Pietro, W. J.; Hehre, W. J.; Binkley, J. S.; Gordon, M. S.; Defrees, D. J.; Pople, J. A. J. Chem. Phys. 1982, 77, 3654-3665.

(formula: l) (a) Yamada, T.; Sato, T.; Tanaka, K.; Kaji, H. Organic Electronics 2010, 11, 255-265. (b) Sakanoue, K.; Motoda, M.; Sugimoto, M.; Sakaki, S. J. Phys. Chem. A 1999, 103, 5551-5556. (c) Malagoli, M.; Bredas, J. L. Chem. Phys. Lett. 2000, 327, 13-17.

In the above calculation, parameters defined below are calculated, and are summarized as Tables 1 to 5.

Procedure for calculation of different photophysical properties

Eg=ELUMO-EHOMO

ET=ETriplet-Esinglet

ET0=ETriplet(with ZPE)-ESinglet(with ZPE)

λ = (Echarged state in neutral geometry - Eneutral state geometry) + (Eneutral state in charged geometry - Echarged state geometry)

(In the formula, λ (Internal Reorganization energy) is internal reorientation energy, and the definitions of other energies are the same as the above calculation method.)

Or, in the case of λ=λ1+λ2,

λ1 = Echarged state in neutral geometry - Echarged state in charged geometry

λ2=Eneutral state in charged geometry-Eneutral state in neutral geometry

(In the formula, l1(e) and l1(h) are the l1 values of electron transport and hole transport, respectively.)

λ+ is the internal reorganization energy for hole transport, and the charged state is a cation.

λ- is the internal reorganization energy for electron transport, and the charge state is an anion.

IP is the ionization potential (adiabatic) and is calculated by Ecationic geometry-Eneutral state geometry.

EA is the electron affinity (adiabatic) and is calculated by Eanionic geometry-Eneutral state geometry.

From this calculation result, the asymmetric 1,2-bis (diarylamino) benzenes of the present invention according to the above general formula (1) have an appropriate HOMO-LUMO level, that is, EHOMO, ELUMO, Eg, ET, ET0, λ- , λ+, IP, and EA, it can be used as a hole transporting material (hole transporting host material and/or hole transporting material) or a blue light emitting material.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

In addition, in organic EL elements, for example, other factors such as compatibility with other layers may have a large influence. Therefore, it cannot be determined uniformly whether any of the compounds exemplified above is suitable for a hole transporting material or a blue light emitting material. However, in general, in the case of a hole-transporting host material, it is preferable that the compound satisfies one or more of the conditions that the HOMO is small, the condition that the Eg is high, the condition that the ET0 is high, and the λ+ condition is small do.

From the standpoint of easily satisfying the above conditions, generally in the case of a hole-transporting host material, in the above general formula (1), A is an aryl group substituted by a substituent containing a substituted or unsubstituted condensed polycyclic aromatic group, or It is preferably a substituted or unsubstituted nitrogen-containing polycyclic aromatic group, preferably an aryl group substituted by a substituent containing a substituted or unsubstituted nitrogen-containing polycyclic aromatic group, or a substituted or unsubstituted nitrogen-containing polycyclic aromatic group. it is more preferable Further, the nitrogen atom of the substituted or unsubstituted nitrogen-containing polycyclic aromatic group is more preferably directly bonded to an aryl group, and the substituent is even more preferably a carbazole group in which the nitrogen atom is directly bonded to the aryl group. In general, in the case of a hole-transporting host material, A in the general formula (1) is preferably an aryl group in which a nitrogen atom is directly bonded to the p- or m-position.

Further, from the standpoint of easily satisfying the above conditions, in general, in the case of a hole transporting host material, in the above general formula (1), it is preferable that R1 to R4 are electron withdrawing groups. Further, R1, R3 and R4 are preferably substituted at the p-position. In addition, even by appropriately changing the type of R1 to R4 and/or the number of R1 to R4 substituted with groups other than hydrogen atoms, the asymmetric bis(1,2 -diarylamino)benzenes.

Since the bis(1,2-diarylamino)benzenes represented by the general formula (1) have an asymmetric structure, the molecular crystallinity is lowered and the amorphousness is increased. Therefore, it is considered to have a high glass transition temperature (Tg). In particular, (1-1) to (1-15), (2-1) to (2-16), (2-18), (3-1) to (3-16), (3-1) to (3-16), (4-1) to (4-7), (5-1) to (5-2), (6-1) to (6-6), (7-1) to (7) -4), (8-1) to (8-4) and (9-1) to (9-3), OPDA-1 to OPDA-11, and F-1 to F-18 are particularly highly amorphous, It is considered to have a particularly high glass transition temperature (Tg).

As an intermediate compound for producing asymmetric bis(1,2-diarylamino)benzenes represented by the general formula (1), there are ortho phenylenediamines, which are represented by the general formula (2) in the present invention.

Some of the specific examples of the asymmetric bis(1,2-diarylamino)benzenes represented by the general formula (2) are shown in the following compounds:

(1-1a) to (1-16a), (2-1a) to (2-18a), (3-1a) to (3-16a), (3-1a) to (3-16a), (4 -1a)~(4-7a), (5-1a)~(5-2a), (6-1a)~(6-6a), (7-1a)~(7-4a), (8-1a) )~(8-4a), (9-1a)~(9-3a), (10-1a)~(10-2a), OPDA-1a~OPDA-11a

etc. can be mentioned.

The diarylamines represented by the general formula (3) may be the same as or different from the diarylamines represented by the general formula (4).

In the magnesium diarylamides represented by the general formulas (5) and (6), X represents a halogen atom. A fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned as a halogen atom.

In the halogen compound represented by the general formula (7), in formula (7), X represents a halogen atom. A fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned as a halogen atom. Moreover, if a part of a specific example is shown, the following structure etc. will be mentioned. X in the following formula represents a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned. As shown in the following formula, n (the number substituted by X) in the above general formula (7) represents an integer of 1 to 3.

If some specific examples of the halogen compound represented by the general formula (7) are shown, the following compounds:

(1-1b) to (1-16b), (2-1b) to (2-18b), (3-1b) to (3-16b), (3-1b) to (3-16b), (4 -1b)~(4-7b), (5-1b)~(5-2b), (6-1b)~(6-6b), (7-1b)~(7-4b), (8-1b) )~(8-4b), (9-1b)~(9-3b), (10-1b)~(10-2b), OPDA-1b~OPDA-11b

etc. can be mentioned.

As in the case of the above general formula (1), in the above formula (7), A is an aryl group substituted by a substituent containing a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted nitrogen-containing condensed polycyclic group It is preferably an aromatic group, and more preferably an aryl group substituted by a substituent containing a substituted or unsubstituted nitrogen-containing polycyclic aromatic group, or a substituted or unsubstituted nitrogen-containing polycyclic aromatic group. Further, the nitrogen atom of the substituted or unsubstituted nitrogen-containing polycyclic aromatic group is more preferably directly bonded to an aryl group, and the substituent is even more preferably a carbazole group in which the nitrogen atom is directly bonded to the aryl group. Further, A in the general formula (7) is preferably an aryl group in which a nitrogen atom is directly bonded to X (halogen) at the p- or m-position.

<Asymmetric 1,2-bis(diarylamino)benzenes>

Although the asymmetric 1,2-bis (diarylamino) benzene represented by General formula (1) is not specifically limited, It is possible to manufacture from the process shown below.

That is, by step 1 (OPDA synthesis step) and step 2 (synthesis step of target material such as hole transport material or blue light emitting material), asymmetric 1,2-bis(diarylamino)benzenes according to the present invention can be produced. can

(Process 1: Synthesis of OPDA)

Magnesium diarylamides represented by formulas (5) and (6) can be produced by reacting diarylamines represented by formulas (3) and (4) with a Grignard reagent.

The Grignard reagent may be an aliphatic Grignard reagent or an aromatic Grignard reagent, for example, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, isopropylmagnesium bromide, isopropylmagnesium chloride, butylmagnesium bromide , Butylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium chloride, etc. are used, and the amount used is preferably 1.0 to 100 molar equivalents relative to diarylamines (3) or diarylamines (4), more preferably It is 1.1 molar equivalent - 10.0 molar equivalent.

Grignard reagents can also be prepared from alkyllithium and magnesium salts.

Examples of the organic solvent used in the reaction include ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and dioxane. . In addition, a solvent may be used singly or may be used in mixture of two or more types.

The amount of the solvent used is usually 1 part by weight to 1000 parts by weight based on the diarylamines (3) or diarylamines (4).

The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and may be carried out under normal pressure or pressure. The reaction temperature is preferably in the range of -50°C to 300°C, more preferably in the range of 0°C to 150°C.

Since the reaction time varies depending on the type of substrate and the difference in reaction temperature, it is not particularly limited, but the reaction can usually be completed within the range of 1 hour to 48 hours.

After completion of the reaction, the solvent may be removed under vacuum or normal pressure, or may be used as it is in the next step 2.

Ortho-phenylenediamines represented by general formula (2) are transition metals to magnesium diarylamides (5) represented by general formula (5) and magnesium diarylamides (6) represented by general formula (6) It can be prepared by reacting a catalyst and an oxidizing agent.

The amount of magnesium diarylamides (5) represented by the general formula (5) is preferably 1.0 to 10 molar equivalents relative to the magnesium diarylamides (6) represented by the general formula (6), more preferably Preferably, it is 1.0 molar equivalent to 2.0 molar equivalent.

The transition metal catalyst may be an iron compound, a palladium compound, a nickel compound, a cobalt compound, or a copper compound, and examples thereof include iron (II) chloride, iron (III) chloride, iron bromide (II), iron (III) bromide, and iron acetate. (II), iron (II) fluoride, palladium chloride, palladium bromide, palladium acetate, palladium acetylacetonate, dichloro bis(triphenylphosphine)palladium, dichloro(cycloocta-1,5-diene)palladium, tris(diene) Benzylideneacetone) dipalladium, tris(dibenzylideneacetone) dipalladium chloroform complex, tetrakis(triphenylphosphine)palladium, nickel acetylacetonate, nickel(II) chloride, cobalt(II) chloride, copper acetylacetonate , copper (II) chloride, iron acetylacetonate and the like. Among these, in order to further improve the reaction yield, iron (II) chloride, iron (III) chloride, iron (II) acetate, and iron (II) fluoride are more preferable.

The addition amount of the transition metal catalyst is preferably in the range of 0.01 mol% to 100 mol% based on the magnesium diarylamides (5) or magnesium diarylamides (6). More preferably, it is the range of 0.05 mol% - 5.0 mol%.

As the oxidizing agent, 1,2-diiodoethane, 1,2-dibromoethane, 1,2-dichloroethane, 1-chloro-2-iodoethane, 1-bromo-2-chloroethane, 1-iodine- 2-bromoethane etc. are mentioned. Among these, 1,2-dichloroethane and 1,2-dibromoethane are more preferable.

The addition amount of the oxidizing agent is preferably in the range of 0.5 molar equivalent to 10 molar equivalent relative to magnesium diarylamides (5) or magnesium diarylamides (6). More preferably, it is the range of 1 molar equivalent - 5 molar equivalent.

The organic solvent used in the reaction may be either a polar solvent or a non-polar solvent, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene, diethyl ether, diisopropyl ether, dibutyl ether, and cyclopentyl methyl ether. , tertiary butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and ether solvents such as dioxane. In addition, a solvent may be used singly or may be used in mixture of two or more types.

The amount of solvent used is usually 1 part by weight to 1000 parts by weight based on magnesium diarylamides (5) or magnesium diarylamides (6).

The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and may be carried out under normal pressure or pressure. The reaction temperature is preferably in the range of 0°C to 300°C, more preferably in the range of 50°C to 150°C.

Since the reaction time varies depending on the type of substrate and the difference in reaction temperature, it is not particularly limited, but the reaction can usually be completed within the range of 1 hour to 48 hours.

After completion of the reaction, a generally known purification method can be used. For example, the organic layer is separated by separation operation, and the obtained organic layer is washed with water, brine, or aqueous alkali solution, and then column chromatography or crystallization. ) and can be isolated and purified by a general method.

Process 2 (composition process of target object)

Bis(1,2-diarylamino)benzenes represented by the general formula (1) are ortho-phenylenediamines represented by the general formula (2) in the presence of a transition metal catalyst, represented by the general formula (7) It can be manufactured by reacting with a halogen compound.

The transition metal compound constituting the transition metal catalyst may be a palladium compound, a nickel compound, a copper compound, or an iron compound, and examples thereof include sodium hexachloropalladate tetrahydrate, potassium hexachloropalladate, palladium chloride, palladium bromide, and acetic acid Palladium, palladium acetylacetonate, dichloro bis(benzonitrile)palladium, dichloro bis(acetonitrile)palladium, dichloro bis(triphenylphosphine)palladium, dichlorotetraammine palladium, dichloro(cycloocta-1,5-diene)palladium , palladium trifluoroacetate, tris(dibenzylideneacetone)dipalladium, tris(dibenzylideneacetone)dipalladium chloroform complex, tetrakis(triphenylphosphine)palladium, nickel acetylacetonate, nickel chloride, copper acetylaceto nate, copper chloride, iron acetylacetonate, iron chloride and the like. In addition, this transition metal compound can also use various ligands together, and as a method of adding a ligand, a method of adding a transition metal compound and a ligand after reacting outside the system may be used, or a transition metal compound and a ligand are added to the reaction system. A method of adding and preparing in the system may be used.

The addition amount of the transition metal compound is preferably in the range of 0.01 mol% to 100 mol% with respect to 1 mol of ortho-phenylenediamine represented by the general formula (2). In order to further improve the reaction selectivity, the range of 0.1 mol% to 5 mol% is more preferable.

As the ligand, any ligand may be used as long as it coordinates with a transition metal compound, and examples thereof include phosphine compounds, nitrogen-based compounds, and olefin-based compounds. For example, alkyl phosphines such as triethylphosphine, tricyclohexylphosphine, and tri(tert-butyl)phosphine, triphenylphosphine, 1,1'-bis(diphenylphosphino)ferrocene [dppf ], 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene [XANTphos] and other aryl phosphines, other 1,5-cyclooctadiene [COD], 2,2'-bipyridine Dill etc. are mentioned. Among these, tricyclohexylphosphine or tri(tert-butyl)phosphine is preferable in order to improve the reaction selectivity.

The added amount of the ligand is preferably in the range of 0.1 to 100 times the mole of the transition metal compound. In order to further improve the reaction selectivity, the range of 1 to 10 moles is more preferable.

The organic solvent used in the reaction may be either a polar solvent or a non-polar solvent, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, diethyl ether, diisopropyl ether, cyclopentyl methyl ether, Ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran, and dioxane, hydrocarbon solvents such as hexane, heptane, pentane, octane, nonane, and decane, acetonitrile, N,N-dimethylformamide (DMF), 1 -Methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), hexamethylphosphotri Amide (HMPA), triethyl phosphite (TEP), trimethyl phosphite (TMP), acetic acid, etc. are mentioned. In addition, a solvent may be used singly or may be used in mixture of two or more types.

The amount of solvent to be used is usually 1 part by weight to 10000 parts by weight with respect to 100 parts by weight of ortho phenylenediamine represented by the general formula (2).

Bases used in the reaction include metal hydroxides, metal carbonates, metal phosphates, metal sulfates, and metal alkoxylates. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tripotassium phosphate, sodium sulfate, sodium hydrogen sulfate, sodium-methoxide, sodium-ethoxide, potassium -Methoxide, potassium-ethoxide, lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert-butoxide, etc. are mentioned. Among these, potassium hydroxide, potassium carbonate, tripotassium phosphate, and sodium-tert-butoxide are preferred. The amount of these used is preferably in the range of 1 to 50 moles with respect to 1 mole of the halogen compound represented by the general formula (7). In order to further improve the reaction selectivity, a range of 1.5 to 5 moles is more preferable. In addition, a base can also be used singly or in combination of two or more types.

The amount of halogen compound (7) used is preferably in the range of 0.1 to 10 moles relative to 1 mole of ortho phenylenediamine represented by the general formula (2). In order to further improve the reaction selectivity, the range of 0.3 to 5 moles is more preferable.

The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and may be carried out under normal pressure or pressure. The reaction temperature is preferably in the range of 0°C to 300°C, more preferably in the range of 50°C to 150°C.

Since the reaction time varies depending on the type of substrate and the difference in reaction temperature, it is not particularly limited, but the reaction can usually be completed within the range of 1 hour to 48 hours.

After completion of the reaction, a generally known purification method can be used. For example, the organic layer is separated by separation operation, and the obtained organic layer is washed with water, brine, or aqueous alkali solution, and then a general method such as column chromatography or crystallization. It can be isolated and purified by

According to the present invention, since the asymmetric bis(1,2-diarylamino)benzenes represented by the general formula (1) have an appropriate HOMO-LUMO level, organic EL device materials such as hole transport materials and blue light emitting materials can be used as

According to the present invention, asymmetric bis(1,2-diarylamino)benzenes, which have hitherto been difficult to manufacture, can be efficiently produced. Furthermore, this manufacturing method makes it easy to introduce various substituents position-selectively, and it is possible to design molecules having energy levels suitable for organic EL element materials such as hole transport materials and blue light emitting materials.

1 is a diagram showing the energy level of HOMO-LUMO calculated from the absorption edge and oxidation potential of the solution for the materials used in the present invention and conventional materials, the horizontal axis (X axis) is the material used for calculating the energy level, and the vertical axis (Y-axis) is the energy level (unit: eV).
Fig. 2 is a diagram showing a laminated structure for evaluating devices, and in the OPDA layer, m-CBP as a control and OPDA-3 and OPDA-4 according to the present invention were evaluated. For reference, we also compared the data presented in the paper.
3 is data obtained by evaluating devices, and is a diagram showing voltage-current characteristics, the horizontal axis (X axis) is voltage (Voltage, unit is V (volt)), and the vertical axis (Y axis) is current density (Current Density, Unit is mA/cm ² ). In the figure, the materials used are m-CBP as a control and OPDA-3 and OPDA-4 according to the present invention.
FIG. 4 is device evaluation data, and is a diagram showing an EL (Electroluminescence) spectrum, the horizontal axis (X-axis) is the wavelength (Wavelength, unit is nm), and the vertical axis (Y-axis) is the EL intensity (normalized). In the figure, the materials used are m-CBP as a control and OPDA-3 and OPDA-4 according to the present invention.

Example

Hereinafter, the present invention will be described in more detail using examples, but these examples show the outline of the present invention, and the present invention is not limited to these examples.

Identification of the target compound is 1H NMR (1H nuclear magnetic resonance spectrum), 13C NMR (13C nuclear magnetic resonance spectrum), 19F NMR (19F nuclear magnetic resonance spectrum), MS (mass spectrometry spectrum), IR analysis, HRMS analysis, melting point analysis and determined by elemental analysis. The purity and isomer ratio were determined by GC analysis, and the yield was determined by NMR analysis using dibromoethane as an internal standard. Further, for purification of the target material, recycled preparative GPC was used as needed. The devices used are as follows.

Nuclear Magnetic Resonance Spectrum: JEOL ECS-400NR, Bruker AVANCE III 800US Plus

IR Device: PerkinElmer Spectrum One FT-IR Spectrometer

HR-MS device: JEOL JMS-700 massspectrometer

Melting point measuring device: Yanaco MP-500D

GC device: Shimadzu GC-2010 (FID)

Column: ZB-1MS (10 m × 0.10 mm I. D. df: 0.1 μm) (manufactured by Phenomenex)

Detector: Hydrogen flame ionization detector

Recycle preparative GPC: Japan Analytical Industry LC-9204 instrument

Column: JAIGEL-1H-40/JAIGEL-2H-40

Example 1 Synthesis of OPDA(1-1a)

Diphenylamine (18.0 g, 110 mmol) and Et2O (108 mL) were added to a 500 mL flask under an argon atmosphere, and EtMgBr (39.0 mL, 3.0 M in Et2O, 121 mmol) was added under ice-cooling. , heating and stirring were performed at 40° C. for 2 hours.

Thereafter, Et2O was removed under reduced pressure, FeCl2 (0.67 g, 5.5 mmol), dibromoethane (18.0 mL, 220 mmol), and 108 mL of Bu2O were added, heated and stirred at 80° C. for 24 hours, and room temperature Underneath, 108 mL of 1N HCl was added, followed by extraction with 108 mL of AcOEt x 3 and washing with 108 mL of brine.

MgSO4 was added to the obtained organic layer, and after filtration using 90 g of Florisil, the mixture was concentrated with an evaporator. To 22 g of the obtained crude, 53 mL of EtOH was added and dissolved by heating, and after stirring at room temperature for 1 hour, a beige powder was obtained by filtering the precipitate.

Since this powder contained a small amount of impurities, 48 mL of EtOH was added again to heat and dissolve, and after stirring at room temperature for 1 hour, filtration and drying were performed to obtain 14.8 g of white powdery OPDA in 83% yield.

The analysis results are as follows.

1H NMR (DMSO-d6 392 MHz) δ 6.76-6.79 (m, 1H), 6.91-6.97 (m, 9H), 7.08-7.29 (m, 10H)

Example 2 Synthesis of OPDA(2-8a)

Diarylamine (14.0 g, 70.8 mmol) and Bu O (94 mL) were added to a 500 mL flask under an argon atmosphere, and BuMgBr (100 mL, 0.779 M in Bu O, 77.9 mmol) was added at room temperature (25 ° C). , heating and stirring were performed at 100° C. for 1 hour.

Thereafter, FeCl 2 (0.45 g, 3.54 mmol) and dibromoethane (26.6 g, 142 mmol) were added at room temperature (25° C.), and heating and stirring were performed at 80° C. for 24 hours. 1N HCl (200 mL) was added to the reaction solution, followed by celite filtration, followed by extraction with AcOEt 100 mL x 3.

After filtering the obtained organic layer with a filter paper, it was concentrated with an evaporator to obtain 15.6 g of crude. Silica gel column purification was performed using 500 g of silica gel and hexane as developing solvents to obtain 8.97 g of OPDA with GC purity>99%, 64% yield, and 4.80 g of OPDA with 92% GC purity, 34% yield. respectively obtained with

The analysis results are as follows.

1H NMR (CDCl3, 392 MHz) δ 2.20 (s, 3H), 2.24 (s, 3H), 2.26 (s, 6H), 5.66 (s, 1H), 6.78 (d, 2H, J = 8.2Hz), 6.89 -6.94 (m, 6H), 6.97-7.06 (m, 6H), 7.16 (d, 1H, J = 8.6 Hz)

Example 3 Synthesis of OPDA-biphenyl

Under an argon atmosphere, diarylamine (5.00 g, 15.6 mmol) and Et2O (50 mL) were added to a 300 mL flask, EtMgBr (5.73 mL, 3.0 M in Et2O, 17.2 mmol) was added at room temperature, and at 40°C. Heat stirring was performed for 2 hours. Then, Et2O was removed under reduced pressure, FeCl2 (98.8 mg, 0.78 mmol), dibromoethane (5.8 g, 31.2 mmol), and Bu2O (50 mL) were added, followed by heating and stirring at 80°C for 12 hours. , and heating and stirring were performed again at 140° C. for 24 hours. At room temperature, 1N HCl (50 mL) was added, extraction was performed with AcOEt (30 mL x 3), MgSO4 was added to the resulting organic layer, filtered using filter paper, and concentrated with an evaporator. For 4.21 g of the obtained crude, OPDA-biphenyl was obtained in a yield of 0.78 g and <16% by silica gel column purification.

The analysis results are as follows.

1H NMR (CDCl3, 392 MHz) δ 5.99 (s, 1H), 7.01-7.03 (m, 2H), 7.21-7.31 (m, 7H), 7.36-7.56 (m, 26H)

Example 4 Synthesis of 4-Br-N,N-dimethylaniline substituents

Under an argon atmosphere, OPDA (4.68 g, 13.9 mmol) obtained in Example 1 and 4-bromo-N, N-dimethylaniline (4.12 g, 20.6 mmol), Pd(OAc) 2 (62.9 mg, 0.28 mmol), tBu3P ( 228 mg, 1.12 mmol), NaOtBu (2.67 g, 27.8 mmol), and toluene (70 mL) were added to a 300 mL flask, dissolved at room temperature (25 ° C), followed by heating and stirring at 120 ° C for 4 hours. 1N HCl (50 mL) was added to the reaction solution at room temperature (25°C), followed by extraction with AcOEt (20 mL x 3) and concentration using an evaporator. The target product was obtained in 5.63 g, <89% yield by reprecipitation using a toluene/hexane solvent system.

The analysis results are as follows.

1H NMR (CDCl3, 392 MHz) δ 3.02 (s, 6H), 6.70 (d, 4H, J = 7.8 Hz), 6.76 (t, 4H, J = 9.6 Hz), 6.86 (t, 2H, J = 7.4 Hz) ), 6.94-7.01 (m, 1H), 7.08 (t, 4H, J = 7.8 Hz), 7.14-7.15 (m, 6H), 7.32-7.44 (m, 2H)

GC purity 100.0%

Example 5 Synthesis of 4-Br-N,N-dimethylaniline substituents

Under argon atmosphere, OPDA_Tol (4.55 g, 11.6 mmol) and 4-bromo-N, N-dimethylaniline (4.64 g, 23.2 mmol), Pd(OAc) 2 (51.6 mg, 0.230 mmol), tBu3P (186 mg, 0.92 mmol) ), NaOtBu (2.23 g, 23.2 mmol), and toluene (58 mL) were added to a 300 mL flask, dissolved at room temperature (25 ° C), and heated and stirred at 120 ° C for 6 hours. 1N HCl (50 mL) was added to the reaction solution at room temperature (25°C), followed by extraction with AcOEt (50 mL × 3). The resulting organic layer was dried over MgSO4, filtered through Florisil, and then concentrated with an evaporator to obtain 6.71 g of crude. I tried to purify 3.00 g of crude with GPC (toluene), but it is thought that oxidation occurred due to tailing of the peak. 3.71 g of the remaining crude was reprecipitated using a toluene/hexane solvent system to obtain 2.88 g of the target product with GC purity >99% in 49% yield.

The analysis results are as follows.

1H NMR (CDCl3, 392 MHz) δ 2.22 (s, 6H), 2.25 (s, 3H), 2.26 (s, 3H), 3.05 (s, 6H), 6.56-6.58 (m, 4H), 6.67 (d, 2H, J = 8.8 Hz), 6.73 (d, 2H, J = 9.0 Hz), 6.87-6.98 (m, 9H), 7.32 (d, 2H, J = 8.6 Hz)

GC purity 100.0%

Example 6 Synthesis of 4-Br-N,N-dimethylaniline substituents

Under argon atmosphere, OPDA_biphenyl (0.78 g, 1.22 mmol) and 4-bromo-N, N-dimethylaniline (366 mg, 1.83 mmol), Pd(OAc)2 (5.5 mg, 0.024 mmol), tBu3P (19.6 mg, 0.096 mmol) ), NaOtBu (177 mg, 1.83 mmol), and toluene (12 mL) were added to a 100 mL flask and dissolved at room temperature (25 ° C), followed by heating and stirring at 120 ° C for 4 hours. 1N HCl (30 mL) was added to the reaction solution at room temperature (25°C), followed by extraction with CHCl3 (20 mL x 3), drying over MgSO4, filtering with filter paper, and concentrating with an evaporator. It was obtained in crude 885 mg, <95% yield by reprecipitation using a toluene/hexane solvent system.

The analysis results are as follows.

1H NMR (CDCl3, 392 MHz) δ 3.00 (s, 6H), 6.91-6.96 (m, 4H), 7.16-7.46 (m, 18H), 7.48-7.55 (m, 8H)

Example 7 Synthesis of 3-Br-9-phenyl-9H-carbazole substituents

Under argon atmosphere, OPDA_Ph (2.91 g, 8.66 mmol) and 3-bromo-9-phenyl-9H-carbazole (4.19 g, 12.99 mmol), Pd(OAc) 2 (38.7 mg, 0.17 mmol), tBu3P (140 mg, 0.692 mmol), NaOtBu (1.25 g, 12.99 mmol), and xylene (43 mL) were added to a 100 mL flask and dissolved at room temperature (25 ° C), followed by heating and stirring at 130 ° C for 14 hours. Again, Pd(OAc) 2 (141 mg, 0.63 mmol) and tBu3P (141 mg, 0.70 mmol) were added at room temperature (25°C), followed by heating and stirring at 130°C for 5 hours. 1N HCl (50 mL) was added to the reaction solution at room temperature (25°C), followed by extraction with AcOEt (30 mL x 3) and concentration using an evaporator. It was obtained in 3.67 g, <73% yield by reprecipitation using a toluene/hexane solvent system.

The analysis results are as follows.

1H NMR (CDCl3, 392 MHz) δ 6.77-6.90 (m, 5H), 7.07-7.61 (m, 25H), 7.91 (d, 1 H,J = 7.6 Hz)

GC purity 94.3%

Example 8 Synthesis of OPDA-1

Under an inert atmosphere, OPDA (336 mg, 1 mmol), 2-bromo-9-phenylcarbazole (322 mg, 1 mmol), Pd (OAc) 2 (4.5 mg, 0.02 mmol), tBu3P (16.2 mg, 0.08 mmol) and NaOtBu (144 mg, 1.5 mmol) in mesitylene (2.7 mL) were stirred at 150 °C for 4 hours. The reaction was quenched with 1 M HCl at room temperature (to stop the reaction) and extracted with ethyl acetate. The organic layer was washed with brine (brine), dried over MgSO4 and filtered through a pad of Florisil. The solvent was removed under reduced pressure to obtain a crude product. The crude product was recrystallized from EtOH and toluene to give the desired product OPDA-1 (0.43 g, 74% yield) as a white solid.

The target substance was analyzed by 1 H-NMR, and the following results were obtained.

1H NMR (DMSO-d6 392MHz) δ 6.56-6.59 (m, 5H), 6.64-6.68 (m, 3H), 6.79-6.86 (m, 3H), 7.00-7.04 (m, 5H), 7.07-7.12 (m , 3H), 7.15–7.17 (m, 2H), 7.20–7.23 (m, 2H), 7.31–7.35 (m, 1H), 7.42 (d, J = 7.2 Hz, 2H), 7.50 (t, J = 7.4 Hz, 1H), 7.63 (t, J = 7.9 Hz, 2H), 8.00 (d, J = 8.5 Hz, 1H), 8.47 (d, J = 8.5 Hz, 1H); Anal. Calcd for C42H31N3 C, 87.32; H, 5.41; n, 7.27. Found C, 87.42; H, 5.52; N, 7.16.

Example 9 Synthesis of OPDA-2

Under inert atmosphere, OPDA (336 mg, 1 mmol), 3-bromo-9-phenylcarbazole (322 mg, 1 mmol), Pd(OAc)2 (4.5 mg, 0.02 mmol), tBu3P (16.2 mg, 0.08 mmol) and NaOtBu (144 mg, 1.5 mmol) in mesitylene (5 mL) were stirred at 150 °C for 4 h. The reaction was quenched with 1 M HCl at room temperature (to stop the reaction) and extracted with 4 ml of ethyl acetate. Filtered through a pad of 1.5 g fluorisil. The solvent (hexane : ethyl acetate = 30 : 1) was removed under reduced pressure to obtain a crude product. The crude product was recrystallized from EtOH and toluene to give the desired product OPDA-2 (0.50772 g, 88% yield) as a white solid.

The target substance was analyzed by 1H-NMR, and the following results were obtained.

1H NMR (CDCl3, 392 MHz) δ 6.83-6.97 (m, 10H), 7.12-7.17 (m, 9H), 7.22-7.27 (m, 8H), 7.33 (dd, 2H, J = 1.3, 1.3 Hz), 8.1 (d, 2H, J = 7.6 Hz); Anal. Calcd for C42H31N3 C, 87.32; H, 5.41; n, 7.27. Found C, 87.09; H, 5.57; N, 7.09.

Example 10 Synthesis of OPDA-3

Under an inert atmosphere, OPDA (336 mg, 1 mmol), 2-bromo-9-phenylcarbazole (322 mg, 1 mmol), Pd (OAc) 2 (4.5 mg, 0.02 mmol), tBu3P (16.2 mg, 0.08 mmol) and NaOtBu (144 mg, 1.5 mmol) in mesitylene (2.5 mL) were stirred at 150 °C for 5.5 h. The reaction was quenched (reaction stopped) with 1.5 ml of 1 M HCl at room temperature and extracted with 10 ml of ethyl acetate. Filtered through a pad of 1.5 g fluorisil. The solvent was removed under reduced pressure to obtain a crude product. The crude product was recrystallized from EtOH and toluene to give the desired product OPDA-3 (0.51068 g, 88% yield) as a white solid.

The target substance was analyzed by 1H-NMR, and the following results were obtained.

1H NMR (DMSO-d6, 392 MHz) δ 6.59 (s, 1H), 6.63 (d, 4H, J = 8.0 Hz), 6.82 (m, 5H), 6.92 (dd, 1H, J = 7.6, 7.6 Hz) , 6.99–7.09 (m, 6H), 7.16–7.26 (m, 9H), 7.35–7.43 (m, 3H), 8.19 (d, 2H, J = 7.6 Hz); Anal. Calcd for C42H31N3 C, 87.32; H, 5.41; n, 7.27. Found C, 87.53; H, 5.48; N, 7.48.

Example 11 Synthesis of Me-OPDA-4 (methyl substituent)

Under argon atmosphere, Me-OPDA-4a (393 mg), mesitylene (2.7 ml), Me-OPDA-4b (Br derivative) (487 mg), Pd (OAc) 2 (4.5 mg, 0.02 mmol), tBu3P ( 16.2 mg) and NaOtBu (144 mg) were added to the reaction vessel and dissolved at room temperature (25°C), followed by heating and stirring at 150°C for 4 hours. 1N HCl (1.5 mL) was added to the reaction solution at room temperature (25 ° C), followed by extraction with AcOEt (2 mL × 2), passage through 1.34 g of Florisil (60-100 mesh), and AcOEt (2 mL). washed and evaporated. It was in the state of brown oil. This was purified by silica gel column chromatography and filtered. 0.48 g of the target product (Me-OPDA-4) was obtained. The target object was a white powder.

The target substance was analyzed by 1H-NMR, and the following results were obtained.

1H NMR (DMSO-d6, 392 MHz) δ 2.02 (s, 6H), 2.14 (s, 3H), 2.19 (s, 3H), 6.46 (d, J = 8.5 Hz, 4H), 6.64 (d, J = 8.1 Hz, 4H), 6.74-6.77 (m, 3H), 6.95-7.02 (m, 3H), 7.1 (d, J = 8.5 Hz, 2H), 7.27-7.31 (m, 6H), 7.39-7.47 (m , 8H), 8.23 (d, J = 8.1 Hz, 4H); Anal. Calcd for C58H46N4 C, 87.19; H, 5.80; N, 7.01. Found C, 87.25; H, 5.88; N, 6.75.

Example 12 Synthesis of F-OPDA-4 (fluorine-substituted)

Under argon atmosphere, F-OPDA-4a (408.40 mg, 1.00 mmol) and F-OPDA-4b (Br derivative) (487.40 mg, 1.00 mmol), Pd(OAc) 2 (4.5 mg, 0.02 mmol), tBu3P (144.2 mg, 1.50 mmol), NaOtBu (144 mg, 1.5 mmol), and mesitylene (5.0 ml) were added to a reaction vessel and dissolved at room temperature (25° C.), followed by heating and stirring at 150° C. for 8 hours. The reaction was stopped at room temperature (25°C), extracted with AcOEt (20 mL x 3), and dried over MgSO4. Purification by column chromatography gave 467 mg of the desired product (F-OPDA-4). The yield was 57.3%. The object was a light brown solid.

The target substance was analyzed by 1H-NMR, and the following results were obtained.

1H NMR (DMSO-d6, 392 MHz) δ 6.64-6.68 (m, 3H), 6.71-6.78 (m, 5H), 7.09 (td, 1H, J = 8.2, 2.7 Hz), 7.11 (d, 3H, J = 2.7 Hz), 7.15–7.30 (m, 7H), 7.40–7.56 (m, 10H), 8.21–8.26 (m, 5H); Anal. Calcd for C54H34F4N4 C, 79.59; H, 4.21; N, 6.88. Found C, 80.97; H, 4.39; N, 6.63.

Example 13 Synthesis of OPDA-5

Under argon atmosphere, OPDA(OPDA-5a) (336.44 mg, 1.00 mmol) and OPDA-5b (Br derivative) (322.21 mg, 1.00 mmol), Pd(OAc)2 (4.5 mg, 0.02 mmol), tBu3P (16.2 mg) , 0.08 mmol), NaOtBu (144 mg, 1.5 mmol), and mesitylene (5.0 ml,) were added to a reaction vessel and dissolved at room temperature (25° C.), followed by heating and stirring at 150° C. for 8 hours. 1N-HCl was added at room temperature (25°C) to stop the reaction, the solution was passed through 1.5 g of Florisil, and purified with 20 g of silica gel (solvent: hexane: AcOEt = 30: 1) to obtain 507.72 mg of the target product ( OPDA-5) was obtained. The yield was 88%. The target object was a white solid.

The target substance was analyzed by 1H-NMR, and the following results were obtained.

1H NMR (DMSO-d6, 392 MHz) δ 6.68-6.77 (m, 8H), 6.86-6.93 (m, 3H), 7.10-7.22 (m, 12H), 7.29 (dd, 1H, J = 7.3, 7.3 Hz ), 7.37–7.44 (m, 2H), 7.55–7.71 (m, 7H), 8.30 (d, 1H, J = 7.6), 8.45 (s, 1H); Anal. Calcd for C48H35N3 C, 88.18; H, 5.39; N, 6.43. Found C, 88.33; H, 5.44; N, 6.23.

Example 14 Synthesis of OPDA-6

Under argon atmosphere, OPDA (OPDA-6a) (336.44 mg, 1.00 mmol) and OPDA-6b (Br derivative) (372.27 mg, 1.00 mmol), Pd (OAc) 2 (4.5 mg, 0.02 mmol), tBu3P (16.2 mg) , 0.08 mmol), NaOtBu (144 mg, 1.5 mmol), and mesitylene (5.0 ml,) were added to a reaction vessel and dissolved at room temperature (25° C.), followed by heating and stirring at 150° C. for 7 hours. 1N-HCl was added at room temperature (25°C) to stop the reaction, followed by extraction with AcOEt (20 mL x 3) and drying over MgSO4. The solution was passed through 1.5 g of Florisil and recrystallized after solvent extraction to obtain 566.91 mg of the desired product (OPDA-6). The yield was 90.3%. The target object was a white solid.

The target substance was analyzed by 1H-NMR, and the following results were obtained.

1H NMR (DMSO-d6, 392 MHz) δ 6.66 (d, 6H, J = 7.6 Hz), 6.76 (s, 3H), 6.84-6.88 (m, 4H), 7.08 (dd, 7H, J = 14.7, 7.6 Hz), 7.18-7.24 (m, 4H), 7.31 (dd, 2H, J = 14.1, 7.4 Hz), 7.44 (s, 1H), 7.59 (dd, 1H, J = 7.6, 7.6 Hz), 7,70 -7.79 (m, 2H), 8.07 (d, 1H, J = 7.6 Hz), 8.16 (dd, 2H, J = 18.1, 8.2 Hz); Anal. Calcd for C46H33N3 C, 88.01; H, 5.30; N, 6.69. Found C, 87.77; H, 5.36; N, 6.55.

Example 15 Synthesis of OPDA-7

Under argon atmosphere, OPDA (OPDA-7a) (670 mg, 2.0 mmol), mesitylene (4 ml), OPDA-7b (Br derivative, 1,3-Dibromobenzene) (240 mg, 1.0 mmol), Pd (OAc) 2 (9 mg, 0.04 mmol), tBu3P (32.4 mg), and NaOtBu (290 mg) were added to a reaction vessel and dissolved at room temperature (25° C.), followed by heating and stirring at 150° C. for 6 hours. 1N HCl (3 mL) was added to the reaction solution at room temperature (25°C), followed by extraction with AcOEt (5 mL, 3 mL), washing with brine (brine), passing through 3.5 g of silica gel and evaporation. . It was a brown candy. This was solidified, filtered and dried to obtain 0.65 g of the desired product (OPDA-7). The target product was a pale beige powder.

The target substance was analyzed by ¹ H-NMR, and the following results were obtained.

¹ H NMR (DMSO-d6, 392 MHz) δ 6.23 (dd, J = 8.1, 2.2 Hz, 2H), 6.27-6.28 (m, 1H), 6.43 (d, J = 7.6 Hz, 4H), 6.57-6.59 (m, 8H), 6.76-6.89 (m, 8H), 6.93-7.17 (m, 19H); Anal. Calcd for C54H42N4 C, 86.83; H, 5.67; N, 7.50. Found C, 86.62; H, 5.67; n, 7.39.

Example 16 Synthesis of OPDA-8

Under argon atmosphere, OPDA (OPDA-8a) (670 mg, 2.0 mmol), mesitylene (4 ml), OPDA-8b (Br derivative, 1,3-Dibromobenzene) (240 mg, 1.0 mmol), Pd (OAc) 2 (9 mg, 0.04 mmol), tBu3P (32.4 mg), and NaOtBu (290 mg) were added to a reaction vessel and dissolved at room temperature (25° C.), followed by heating and stirring at 150° C. for 6 hours. 1N HCl (3 mL) was added to the reaction solution at room temperature (25°C), followed by extraction with AcOEt (5 mL, 3 mL) and washing with brine (brine) to obtain a crude product as a gray powder (0.8 g). After dissolving this in CHCl3, the solution was passed through 7.5 g of silica gel and evaporated. It was a green bubble. This was dissolved, filtered and dried to obtain 0.69 g of the desired product (OPDA-8). The target product was a pale gray white powder.

The target substance was analyzed by ¹ H-NMR, and the following results were obtained.

¹ H NMR (DMSO-d6, 392 MHz) δ 6.50-6.60 (m, 4H), 6.76-6.78 (m, 10H), 6.87-6.99 (m, 5H), 7.00-7.11 (m, 20H), 7.25- 7.26 (m, 3H); Anal. Calcd for C54H42N4 C, 86.83; H, 5.67; N, 7.50. Found C, 86.64; H, 5.72; N, 7.46.

Example 17 Synthesis of OPDA-9

Under argon atmosphere, OPDA (OPDA-9a) (472.88 mg, 1.50 mmol) and OPDA-9b (Br derivative) (401.1 mg, 1.00 mmol), Pd (OAc) 2 (9 mg, 0.04 mmol), tBu3P (32.4 mg) , 0.16 mmol), NaOtBu (288.3 mg, 3 mmol), and mesitylene (5.0 ml,) were added to a reaction vessel and dissolved at room temperature (25° C.), followed by heating and stirring at 150° C. for 6 hours. 1N-HCl was added at room temperature (25°C) to stop the reaction, followed by extraction with AcOEt (20 mL x 3) and drying over MgSO4. The solution was passed through 25 g of silica gel, extracted with a solvent (hexane:EtOAc = 25:1) and recrystallized to obtain 782.62 mg of the desired product (OPDA-9). The yield was 85.8%. The target object was a white solid.

The target substance was analyzed by ¹ H-NMR, and the following results were obtained.

¹ H NMR (DMSO-d6, 392 MHz) δ 5.92 (s, 2H), 6.56-6.63 (m, 13H), 6.74 (dd, 3H, J = 7.4, 7.4 Hz), 6.83-7.20 (m, 27H) , 7.31 (dd, 2H, J = 7.4, 7.4 Hz), 8.12 (d, 2H, J = 7.6 Hz); Anal. Calcd for C66H49N5 C, 86.91; H, 5.41; N, 7.68. Found C, 86.91; H, 5.56; N, 7.72.

Example 18 Synthesis of OPDA-10

Under argon atmosphere, OPDA-10a (640 mg, 1.0 mmol), mesitylene (2.7 ml), OPDA-10b (Br derivative, 1,3-Dibromobenzene) (230 mg, 1.0 mmol), Pd(OAc)2 (4.5 mg, 0.02 mmol), tBu3P (16.2 mg, 0.08 mmol), and NaOtBu (144 mg, 1.5 mmol) were added to a reaction vessel and dissolved at room temperature (25° C.), followed by heating and stirring at 150° C. for 4 hours. 1N HCl (1.5 mL) was added to the reaction solution at room temperature (25°C), followed by extraction with AcOEt (5 mL, 3 mL) and washing with brine (brine) to obtain a crude product as a beige powder (0.83 g). . This was purified by column chromatography, dissolved in CHCl3, passed through 8 g of silica gel, and evaporated. 0.93 g of crude target product was obtained in the form of reddish-purple foam. This was dissolved in a solvent, filtered and dried to obtain 0.67 g of the desired product (OPDA-10). The target object was a white powder.

The target substance was analyzed by ¹ H-NMR, and the following results were obtained.

¹ H NMR (CDCl3, 392 MHz) δ 6.95-6.99 (m, 8H), 7.27-7.34 (m, 5H), 7.36-7.42 (m, 19H), 7.49-7.54 (m, 12H); Anal. Calcd for C60H44N2 C, 90.87; H, 5.59; N, 3.53. Found C, 91.06; H, 5.69; n, 3.25.

Example 19 Synthesis of OPDA-11

Under argon atmosphere, OPDA-11a (640 mg, 1.0 mmol), mesitylene (2.7 ml), OPDA-11b (Br derivative) (320 mg, 1.0 mmol), Pd(OAc)2 (4.5 mg, 0.02 mmol), tBu3P (16.2 mg, 0.08 mmol) and NaOtBu (144 mg, 1.5 mmol) were added to a reaction vessel and dissolved at room temperature (25°C), followed by heating and stirring at 150°C for 4 hours. 1N HCl (1.5 mL) was added to the reaction solution at room temperature (25°C), followed by extraction with AcOEt (5 mL, 3 mL) and washing with brine (brine) to obtain a brown foamy crude product (0.97 g). . When this was purified by column chromatography with silica gel (9 g) and CHCl3 was added, it became a purple foam. When 10 ml of IpA was added to this, it became clay and powdered. Filtration gave a light brown white powder (0.76 g). Further purification was performed by column chromatography using silica gel (11 g), followed by extraction with a solvent (hexane:EtOAc = 10:1→4:1) to obtain a yellow-orange foam (0.72 g). 5 mL of ethanol was added to this, followed by filtration and drying to obtain 0.64 g of the target product (OPDA-11) as a pale brown white powder.

The target substance was analyzed by ¹ H-NMR, and the following results were obtained.

¹ H NMR (DMSO-d6, 392 MHz) δ 6.72 (t, J = 2.0 Hz, 1H), 6.90 (d, J = 8.5 Hz, 4 H), 7.04 (d, J = 9.0 Hz, 3H), 7.70 −7.45 (m, 29H), 7.49–7.63 (m, 8H), 8.22 (d, J = 7.2, 1.3 Hz, 2H); Anal. Calcd for C66H47N3 C, 89.87; H, 5.37; N, 4.76. Found C, 89.66; H, 5.48; N, 4.61.

Example 20 Synthesis of OPDA-7-X, OPDA-7-cbz and OPDA-8-X

In the same manner as above, OPDA-7-X, OPDA-7-cbz and OPDA-8-X were synthesized under the following reaction scheme and used for evaluation.

Example 21 Measurement of basic physical properties

For OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, Me-OPDA-4, F-OPDA-4, OPDA-7 and OPDA-9, the glass transition temperature, absorption maximum wavelength, logε, absorption edge, maximum fluorescence wavelength, fluorescence quantum yield, and oxidation potential vs. Ag/Ag+ were measured, and the results are shown in Table 6.

Each measurement was performed under the following conditions.

glass transition temperature

Differential scanning calorimetry (apparatus: Hitachi High-Tech Science Corporation DSC/TG-DTA 6200) was used. Measurement conditions were carried out at a sample amount of ~5 mg, a temperature increase rate of 10°C/min, and a temperature decrease rate of 20°C/min between the 1st run and the 2nd run, and the value of the 2nd run was adopted as the glass transition temperature.

maximum absorption wavelength

As a measuring device, a spectrometer SEC2020 (manufactured by BAS Inc.) was used. The measurement conditions were to dissolve the material in tetrahydrofuran to prepare a solution of about 10-5 mol/l, and the wavelength at the maximum point of the absorption band on the longest wavelength side in the absorption spectrum observed with the measuring device was determined as the absorption maximum wavelength.

logε is the logarithm of the molar extinction coefficient at the absorption wavelength.

The absorption edge is the wavelength at the point where a straight line approximation of the curve intersects the x-axis (absorbance 0) on the long-wavelength short-term side of the absorption spectrum.

maximum fluorescence wavelength

The fluorescence spectrum was measured using (Apparatus: JASCO Corporation F8200). Measurement conditions were performed with an excitation wavelength of 310 nm, an excitation light band of 2.5 nm, and a fluorescence band of 2.5 nm.

fluorescence quantum yield

It was determined by a relative method with respect to a solution of 9,10-diphenylanthracene in cyclohexane.

Oxidation potential vs Ag/Ag+

by cyclic voltammetry. The measurement conditions were solvent: dichloromethane, compound concentration: 10-3 mol/l, supporting electrolyte: TBAP 0.1 M, working electrode: platinum disk, counter electrode: platinum wire, reference electrode: Ag/AgNO3 0.01M CH3CN solution, sweep ) rate: 50 mV/sec.

[Table 6] Basic physical properties 1

Example 22 Measurement of basic physical properties

For OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, Me-OPDA-4, F-OPDA-4, OPDA-7 and OPDA-9, the optical energy gap, HOMO and LUMO of The levels were calculated, and the results are shown in Table 7.

[Table 7] Basic physical properties 2

In Table 7 above,

HOMO levels were obtained from cyclic voltammetry. Measurement conditions were based on NPD oxidation potential of 477 mV vs Ag/Ag+ and HOMO of 5.43 eV.

The optical energy gap was calculated from the long wavelength end of the absorption spectrum.

The LUMO level was calculated from the difference between the optical energy gap and the HOMO level.

Example 23 HOMO-LUMO diagram calculated from the absorption edge and oxidation potential of the solution

Energy levels were calculated for OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, OPDA-6, OPDA-7 and OPDA-9, and the results are shown in FIG.

Calculations were made for NPD and TPD as conventional materials and added to FIG. 1 . In addition, NPD used herein is N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (N,N'-Di( 1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine), TPD is N,N'-diphenyl-N,N'-bis(3- Abbreviation for methylphenyl)-(1,1'-biphenyl)-4,4'-diamine.

From these results, each material of OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, OPDA-6, OPDA-7 and OPDA-9 according to the present invention is a difference in HOMO-LUMO level It can be seen that the energy level has an appropriate intensity and is preferable as a light emitting material.

Example 24 Measurement of basic physical properties

The energy levels of OPDA-3 and OPDA-9 as well as NPD, CBP and m-CBP as comparison objects were calculated, and the results are shown in Table 8.

[Table 8] Basic physical properties 3 (calculated values)

In Table 8, the S1 level was calculated from the short wavelength end of the fluorescence spectrum, and the T1 level was calculated from the short wavelength end of the phosphorescence spectrum.

From Table 8, it was found that the T1 levels of OPDA-3 and OPDA-9 are higher in energy than those of NPD and CBP, and that the ΔEST of OPDA-3 and OPDA-9 is smaller than any of NPD, CBP and m-CBP. . From this, OPDA-3 and OPDA-9 are thought to have an advantageous energy level as a host for triplet blue or as an exciton diffusion barrier layer.

In addition, m-CBP used herein is 3,3'-Di (9H-carbazol-9-yl) -1,1'-biphenyl (3,3'-di (9H-carbazol-9-yl) - It is an abbreviation of 1,1'-biphenyl).

Example 25 Examination of method for purifying products by sublimation

For OPDA-1, OPDA-2, OPDA-5, OPDA-6, Me-OPDA-4 and F-OPDA-4, a purification method by sublimation was examined, and the results are shown in Table 9.

[Table 9] Review of product purification method by sublimation 1

Example 26 Examination of method for purifying products by sublimation

For OPDA-3, OPDA-4, OPDA-7, OPDA-9, OPDA-10 and OPDA-11, a purification method by sublimation was examined, and the results are shown in Table 10.

[Table 10] Review of product purification method by sublimation 2

From the above Tables 9 and 10, it was found that the material according to the present invention can be highly purified by the sublimation method, which is useful as a purification method.

Example 27 Evaluation of refractive index (difficulty in total reflection)

The refractive indices of F-OPDA-4, OPDA-4, and NPD as a comparison object were measured, and the results are shown in Table 11.

[Table 11] Evaluation of refractive index (difficulty in total reflection)

Measurements in Table 11 were performed by ellipsometry.

The measurement is obtained by observing a change in the polarization state of the outgoing light with respect to the polarization state of the incident light, and measuring ψ(tanψ=|rp│/│rs│) and Δ(=δrp-δrs), as is usually performed. Further, an optical model was created, and the model and actual measured values were matched by fitting to determine the refractive index.

From Table 11, it was found that the material according to the present invention is less prone to total reflection than NPD of the conventional material, especially on the low wavelength side of 400 nm, as low as on the high wavelength side.

Example 28 device evaluation

For OPDA-3 and OPDA-4, and m-CBP as a comparison and contrast, an element configuration for evaluation (laminated structure made of organic layers) was prepared in FIG. 2, and driving voltage, luminance, luminous efficiency and chromaticity CIE1931 were measured, Table 12 shows the results.

The configuration of the laminated structure is as follows.

In addition, the organic borane used as a light emitting material is a material shown below, and Nat. Photon. 8, 326-332 (2014).

Organic borane: N7,N7,N13,N13,5,9,11,15-octaphenyl-5,9,11,15-tetrahydro-5,9,11,15-tetraaza-19b,20b-diboradinaphtho[3,2 ,1-de:1',2',3'-jk]pentacene-7,13-diamine

Composition of m-CBP:

ITO/HAT-CN (5 nm)/NPD (40 nm)/TCTA (15 nm)/m-CBP (15 nm)/m-CBP+1wt% organic borane (20 nm)/NBPhen (40 nm)/Al

Composition of OPDA-3:

ITO/HAT-CN (5 nm)/NPD (50 nm)/TCTA (20 nm)/OPDA-3+1wt% organic borane (20 nm)/NBPhen (40 nm)/Al

OPDA-4 consists of:

ITO/HAT-CN (5 nm)/NPD (50 nm)/TCTA (20 nm)/OPDA-4+1wt% organic borane (20 nm)/NBPhen (40 nm)/Al

[Table 12] Device evaluation

In Table 12, driving voltage measurement was performed by I-V measurement, and luminance measurement was performed by a color luminance meter. Also, the luminous efficiency is the luminance current efficiency.

From Table 12, the driving voltage of the laminated structure using OPDA-3 and the laminated structure using OPDA-4 according to the present invention is lower than that of the laminated structure using the conventional material m-CBP, and is inferior in terms of luminance, luminous efficiency, and chromaticity. It was found that there was no such thing, and it was found that it was preferable as a light emitting material.

Example 29 Voltage-current characteristics

Voltage-current characteristics were measured in FIG. 3 for OPDA-3 and OPDA-4, and for the laminated structures using m-CBP as a comparison and contrast, respectively, and the results are shown. The configuration of the laminated structure was the same as that of the laminated structure of FIG. 2 .

3, the OPDA device having a stacked structure using OPDA-3 and the stacked structure using OPDA-4 according to the present invention can reduce the driving voltage compared to the m-CBP device having a stacked structure using m-CBP. I was able to confirm that there is

Example 30 EL spectrum

EL spectra were measured in FIG. 4 for the laminated structure using OPDA-3 and the laminated structure using OPDA-4, and the laminated structure using m-CBP as a comparison and contrast, and the results are shown. The configuration of the laminated structure was the same as that of the laminated structure of FIG. 2 .

4, the OPDA device having a stacked structure using OPDA-3 and a stacked structure using OPDA-4 according to the present invention has a spectrum having almost the same maximum value as the m-CBP device, and having a stacked structure using OPDA-4 It was found that the OPDA device has a shoulder on the low-wavelength side.

Example 31 Cyclic Voltammetry of Dichloromethane Solutions

OPDA-1, OPDA-2, OPDA-5, OPDA-6, Me-OPDA-4, F-OPDA-4, OPDA-7, OPDA-9, OPDA-10 and OPDA-11 in dichloromethane solution. Cyclic voltammetry was measured and the results are shown in Tables 13 and 14.

The measurement condition is

Solvent: Dichloromethane,

Compound concentration: 10-3 mol/l,

Supporting Electrolyte: TBAP 0.1 M;

Working electrode: Platinum disc;

Counter electrode: platinum wire,

Reference electrode: Ag/AgNO3 0.01M CH3CN solution;

Sweep rate: 50 mV/sec

However, NPD oxidation potential 477 mV vs Ag/Ag+,

Based on HOMO 5.43 eV

performed with

[Table 13] Cyclic voltammetry of dichloromethane solution

[Table 14] Cyclic voltammetry of dichloromethane solution

It is industrially useful as a material for an organic EL device such as a hole transporting material or a blue light emitting material.

Claims (11)

Asymmetric 1,2-bis (diarylamino) benzenes represented by the following general formula (1).

[In equation (1),
R1 represents a methyl group, an ethyl group, a straight chain, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carbazole group or a phenyl group; ,
R2 represents a methyl group, an ethyl group, a straight-chain, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a phenyl group or a halogen atom;
R3 and R4 are each independently a methyl group, an ethyl group, a straight-chain, branched or cyclic alkyl group having 3 to 6 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 6 carbon atoms, a halogen atom, a substituted or unsubstituted carba represents a sol group or a phenyl group;
a, b, c and d represent 0 or 1;
A is a substituent containing a substituted or unsubstituted condensed polycyclic aromatic group or a substituent in which only one of the m-positions or a nitrogen atom is directly connected to the p-position, a substituted aryl group, a substituted or unsubstituted biphenyl group, a substituted or substituted unsubstituted indolyl group, substituted or unsubstituted benzoimidazole group, substituted or unsubstituted carbazole group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothienyl group, substituted or unsubstituted dibenzothienyl group, represents an unsubstituted fluorenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted thiophenyl group, and A is a nitrogen atom directly bonded to the nitrogen atom and a phenyl group directly bonded to the nitrogen atom to form a cyclic structure; may be.] According to claim 1,
Wherein A is an aryl group substituted by a substituent containing a nitrogen atom, asymmetric 1,2-bis (diarylamino) benzenes. According to claim 2,
Asymmetric 1,2-bis (diarylamino) benzenes in which the nitrogen atom included in the substituent is directly bonded to an aryl group. According to claim 3,
The substituent is a carbazole group in which a nitrogen atom is directly bonded to an aryl group, asymmetric 1,2-bis (diarylamino) benzenes. According to claim 3,
The substituent has an aryl group directly bonded to a nitrogen atom, asymmetric 1,2-bis (diarylamino) benzenes. According to any one of claims 3 to 5,
Asymmetric 1,2-bis (diarylamino) benzenes in which a nitrogen atom is directly bonded to the p-position or m-position of the aryl group. According to claim 2,
The substituent is a substituted or unsubstituted nitrogen-containing polycyclic aromatic group, asymmetric 1,2-bis (diarylamino) benzenes. According to claim 1,
Any one of the following formulas, asymmetric 1,2-bis (diarylamino) benzenes.

A hole-transporting material or a blue light emitting material comprising an asymmetric 1,2-bis(diarylamino)benzene represented by the general formula (1) according to any one of claims 1 to 8. An organic EL device comprising the hole transporting material or the blue light emitting material according to claim 9. A display comprising the organic EL element according to claim 10 .

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