Asymmetric 1,2-bis(diarylamino)benzenes, their production method and use

Abstract

To provide compounds useful as organic EL element materials, particularly hole-transporting materials or blue light-emitting materials.SOLUTION: The present invention provides an optical material, which is a 1,2-bis(diarylamino)benzene represented by any of the following formulae.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to asymmetric 1,2-bis(diarylamino)benzenes useful as materials for organic EL devices, particularly hole transport materials and blue light emitting materials, a method for producing the same, and uses thereof as hole transport materials and blue light emitting materials. [Background technology]

[0002] Organic electroluminescence (OEL) has attracted attention as a next-generation flat panel display, due to its excellent panel performance, including thinness and light weight, wide viewing angle, fast response, high brightness, and high energy efficiency. For this reason, development toward practical use is being promoted by companies and research institutes both in Japan and overseas, and OEL has begun to be applied to displays for mobile phones and flat-screen televisions.

[0003] In general, an organic EL element 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 challenge for organic EL devices, there is a need to find materials suitable for the above-mentioned high panel performance, particularly blue light emission and hole transporting materials, as well as to develop materials suitable for industrial applications.

[0004] For materials suitable for blue light emission, the wavelength of emitted light is thought to be affected by the energy levels of the HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital). The HOMO and LUMO also affect the barrier and efficiency of injection of holes and electrons from the electrodes, so these are factors that must be taken into consideration when designing hole-transporting materials. Therefore, materials with appropriate HOMO-LUMO levels are required.

[0005] A typical hole-transporting material is 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl, shown below as NPB. However, the driving voltage of devices using NPB in the hole-transporting layer was insufficient, and its glass transition temperature (Tg) was low, so its performance as a hole-transporting material was insufficient. In addition, Non-Patent Document 1 discloses compounds shown below as TCTA and mCP, and Patent Document 1 discloses L9 (referred to below as N (2,3) Compounds designated as DA-carbs have also been proposed. However, these compounds are not easy to manufacture and do not have excellent properties as hole transport materials or blue light-emitting materials, so the development of new compounds is desired.

[0006] [ka]

[0007] Furthermore, for example, Patent Document 2 reports an example of using 1,2-bis(diarylamino)benzenes as hole transport materials. However, further improvement is required for use as a hole transport material. In addition, the compounds described in the document are all compounds with symmetric structures, and therefore are presumed to have low glass transition temperatures (Tg), and therefore improvement is also required for their use as hole transport materials. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Chinese Patent Application Publication No. 108299282 [Patent Document 2] Patent No. 3171755 [Non-patent literature]

[0009] [Non-Patent Document 1] Nature Photonics,2019,pp678-682 Summary of the Invention [Problem to be solved by the invention]

[0010] In view of the above background, an object of the present invention is to provide asymmetric 1,2-bis(diarylamino)benzenes useful as organic EL device materials such as hole transport materials and blue light-emitting materials, a method for producing the same, and uses thereof as hole transport materials and blue light-emitting materials. It is a further object of the present invention to provide ortho-phenylenediamines which are useful intermediates for the preparation of unsymmetrical 1,2-bis(diarylamino)benzenes. [Means for solving the problem]

[0011] As a result of extensive research into the above-mentioned problems, the present inventors have found that the specific asymmetric bis(1,2-diarylamino)benzenes shown below have suitable HOMO-LUMO levels, particularly suitable E g Furthermore, by using diarylamines having various substituents as starting materials, the inventors have established an efficient method for producing asymmetric 1,2-bis(diarylamino)benzenes, which have been difficult to produce until now, and have completed the present invention.

[0012] That is, the present invention relates to the following inventions. [1] The following general formula (1) [ka] [In formula (1), R 1 represents a methyl group, an ethyl group, a linear, 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, R 2 represents a methyl group, an ethyl group, a linear, 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, R 3 and R 4 each independently represents a methyl group, an ethyl group, a linear, 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 represents an aryl group substituted with a substituent containing a substituted or unsubstituted fused polycyclic aromatic ring or a substituent having a nitrogen atom directly bonded to only one of the m-positions or the p-position, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzimidazole 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 together with the nitrogen atom directly bonded to it and the phenyl group directly bonded to the nitrogen atom.

[0013] In this specification, the term "asymmetric 1,2-bis(diarylamino)benzenes" also includes structural analogues thereof, and as described above, also includes structures in which A is a substituted or unsubstituted furanyl group or a substituted or unsubstituted thiophenyl group. In addition, in this specification, the term "asymmetric 1,2-bis(diarylamino)benzenes" may include compounds with a point-symmetric structure.

[0014] [2] Asymmetric 1,2-bis(diarylamino)benzenes, in which A is an aryl group substituted with a nitrogen atom-containing substituent.

[0015] [3] The asymmetric 1,2-bis(diarylamino)benzene according to [2] above, wherein the nitrogen atom contained in the substituent is directly bonded to the aryl group.

[0016] [4] The asymmetric 1,2-bis(diarylamino)benzene according to [3] above, wherein the substituent is a carbazole group in which a nitrogen atom is directly bonded to the aryl group.

[0017] [5] The asymmetric 1,2-bis(diarylamino)benzenes according to [3] above, wherein the substituent has an aryl group directly bonded to the nitrogen atom.

[0018] [6] The asymmetric 1,2-bis(diarylamino)benzene according to any one of the above [3] to [5], wherein a nitrogen atom is directly bonded to the p-position or m-position of the aryl group.

[0019] [7] The asymmetric 1,2-bis(diarylamino)benzene according to [2] above, wherein the substituent is a substituted or unsubstituted nitrogen-containing condensed polycyclic aromatic group.

[0020] [8] The asymmetric 1,2-bis(diarylamino)benzene according to the above [1], which is any one of the following formulae: [ka]

[0021] [9] A hole transporting material or a blue light emitting material comprising an asymmetric 1,2-bis(diarylamino)benzene represented by the general formula (1) described in any one of [1] to [8] above. 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 transport layer.

[0022]

[10] An organic electroluminescent device comprising the hole transporting material or blue light-emitting material described above.

[0023]

[11] A display including the organic EL element.

[0024] In the present invention, an intermediate for producing the asymmetric 1,2-bis(diarylamino)benzene of the present invention is represented by the following general formula (2): [ka] [In formula (2), R 1 represents a methyl group, an ethyl group, a linear, 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, R 2 represents a methyl group, an ethyl group, a linear, 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, R 3 and R 4 each independently represents a methyl group, an ethyl group, a linear, 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 each represent 0 or 1. Orthophenylenediamines represented by the formula: can be used.

[0025] In the present invention, there is provided a method for producing the asymmetric 1,2-bis(diarylamino)benzene of the present invention, which comprises: [ka] [In formula (1), R 1 represents a methyl group, an ethyl group, a linear, 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, R 2 represents a methyl group, an ethyl group, a linear, 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, R 3 and R 4each independently represents a methyl group, an ethyl group, a linear, 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 represents an aryl group substituted with a substituent containing a substituted or unsubstituted fused polycyclic aromatic group or a substituent having a nitrogen atom directly bonded to only one of the m-positions or the p-position, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzimidazole 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 together with the nitrogen atom directly bonded to A and the phenyl group directly bonded to the nitrogen atom. The following general formula (3) [ka] [In formula (3), R 1 , R 2 , a and b are the same as in formula (1). and diarylamines represented by the formula: The following general formula (4) [ka] [In formula (4), R 3 , R 4 , c and d are the same as in formula (1). By reacting the diarylamine represented by the formula with a Grignard reagent, The following general formula (5) [ka] [In formula (5), R 1 , R 2a and b are the same as in the formula (1), and X represents a halogen atom. Magnesium diarylamides (5) represented by The following general formula (6) [ka] [In formula (6), R 3 , R 4 , c and d are the same as in the formula (1), and X represents a halogen atom.] After obtaining magnesium diarylamide (6) represented by the formula: The following general formula (2) [ka] [In formula (2), R 1 , R 2 , R 3 ,R 4 , a, b, c and d are the same as in formula (1). and further, in the presence of a transition metal catalyst and a base, The following general formula (7) [ka] [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 an asymmetric 1,2-bis(diarylamino)benzene (1) can be used, in which the compound (1) is reacted with a halogen compound represented by the formula:

[0026] In the asymmetric bis(1,2-diarylamino)benzenes represented by the general formula (1), 1 represents a methyl group, an ethyl group, a linear, 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; R 2represents a methyl group, an ethyl group, a linear, 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; R 3 and R 4 each independently represent a methyl group, an ethyl group, a linear, 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 represents an aryl group substituted with a substituent containing a substituted or unsubstituted fused polycyclic aromatic group or a substituent in which a nitrogen atom is directly bonded to only one of the m-positions or the p-position, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzimidazole 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; A may form a cyclic structure together with the nitrogen atom to which it is directly bonded and the phenyl group directly bonded to the nitrogen atom. The asymmetric 1,2-bis(diarylamino)benzenes represented by the general formula (1) are suitable as hole transporting materials or blue light emitting materials.

[0027] Among these, examples of the linear, branched, or cyclic alkyl group having 3 to 6 carbon atoms include an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an i-propyl group, an i-butyl group, an s-butyl group, a t-butyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a 1,1,2-trimethylpropyl group, a 1,2,2-trimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the alkoxy group having 3 to 6 carbon atoms include an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Furthermore, the substituent containing a fused polycyclic aromatic group is a substituent containing a fused polycyclic group having aromaticity, and the fused polycyclic group having aromaticity may or may not contain a heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom. Examples of aromatic fused polycyclic groups include fused carbon polycyclic groups such as naphthyl groups and fluorenyl groups, and fused heterocyclic polycyclic groups such as quinolinyl groups, indolyl groups, benzimidazole groups, phenoxazinyl groups, phenothiazinyl groups, 9-dimethylacridinyl groups, iminostilbenyl groups, 1,12-iminoperylene groups, carbazole groups, dibenzofuranyl groups, dibenzothienyl groups, and oxanthrenyl groups. Also, R 1 ~R 4 may all be the same substituent or hydrogen atom, or may be different substituents.

[0028] Specific examples of the asymmetric bis(1,2-diarylamino)benzenes represented by the general formula (1) include 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), and (10-1) to (10-2).

[0029] (1-1)~(1-16) [ka]

[0030] (2-1)~(2-18) [ka]

[0031] [ka]

[0032] (3-1)~(3-16) [ka]

[0033] (4-1)~(4-7) [ka]

[0034] (5-1)~(5-2) [ka]

[0035] (6-1)~(6-6) [ka]

[0036] (7-1)~(7-4) [ka]

[0037] (8-1)~(8-4) [ka]

[0038] (9-1)~(9-3) [ka]

[0039] (10-1)~(10-2) [ka]

[0040] OPDA-1 to OPDA-11 (OPDA-1 is the same as (1-15), OPDA-2 is the same as (2-1), OPDA-3 is the same as (3-1), OPDA-4 is the same as (3-2)) [ka]

[0041] F-1~F-18 With respect to the following general formula (F), compounds Nos. F-1 to F-18 are also included, which specify the 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.) [ka] [ka] [ka] [ka]

[0042] Among the above compounds, OPDA-1 to OPDA-11 are preferably used as hole transport materials, blue light emitting materials, and organic EL materials, as will be shown in the examples described later. Materials having the structure of OPDA-1 to OPDA-11 as a skeleton are also preferably used as hole transport materials, blue light emitting materials, and organic EL materials.

[0043] In addition, for the above compounds (1-1) to (10-2), the HOMO-LUMO levels, i.e., E HOMO , E LUMO , E g , E T , E TO , λ - , λ + , IP, and EA were calculated and are shown in Tables 1 to 5 below. The calculation method is as follows: All calculations were performed with the Gaussian 16 program (revision C01) using the B3LYP density functional method in combination with the 6-31G* basis set. Triplet energies were calculated as the difference in electronic energy between the triplet and singlet states in the optimized geometry (E T ) is calculated as the triplet energy (E T0 ) were found to be in better agreement with the experimental values, so these are also calculated and compared. The reorganization energy is the differential change in electronic energy associated with the geometric change in molecular structure between the charge transfer state and the neutral state. The internal reorganization energy (l) is the energy required for the geometric change of two molecules to facilitate the electron / hole transfer between them. It is calculated using an adiabatic potential energy surface using the following equation: l = l1+ l2= (E charged state in neutral geometry -E charged state in charged geometry ) + (E neutral state in charged geometry -E neutral state in neutral geometry ) (In the formula, E charged state in neutral geometry is the electron energy of the charged state calculated for the neutral molecular structure, E charged state in charged geometry is the electron energy of the charged state calculated for the molecular structure in the charged state, E neutral state in charged geometry is the neutral electron energy calculated for the molecular structure in the charged state, E neutral state in neutral geometry indicates the electronic energy of the charged state calculated for the molecular structure in the neutral state.)

[0044] Hole transport (λ + ) and electron transport (λ - ), the charge states are cation and anion, respectively. The energy required for the structural change of the surrounding molecules surrounding the two molecules involved in the charge transfer is called the external reorganization energy, which is considered small and is not considered in the current calculation. In addition, the adiabatic ionization potential (IP) and electron affinity (EA) are also calculated. The optimized charge state energies are used for this calculation and are calculated using the following formula: IP = E cationic state geometry -E neutral state geometry EA = E anionic state geometry -E neutral state geometry (where IP is the adiabatic ionization potential, EA is the adiabatic electron affinity, and E cationic state geometry is the molecular structure in the cationic state, E neutral state geometry is the neutral molecular structure, E anionic state geometry is the anionic molecular structure, E neutral state geometry indicates the neutral molecular structure.)

[0045] And the citation is as follows: (Revision C01) Gaussian 16, Revision C.01, Frisch, MJ; Trucks, GW; Schlegel, HB; Scuseria, GE; Robb, MA; Cheeseman, JR; Scalmani, G.; Barone, V.; Petersson, GA; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, AV; Bloino, J.; Janesko, BG; Gomperts, R.; Mennucci, B.; Hratchian, HP; Ortiz, JV; Izmailov, AF; Sonnenberg, JL; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, VG; 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, JA, Jr.; Peralta, JE; Ogliaro, F.; Bearpark, MJ; Heyd, JJ; Brothers, EN; Kudin, KN; Staroverov, VN; Keith, TA; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, AP; Burant, JC; Iyengar, SS; Thomas, J.; Cossi, M.; Millam, JM; Klene, M.; Adamo, J.; Cammi, R.; Ochterski , JW ; Martin , RL ; Morokuma, K.; Farkas, O.; Foresman , JB ; Fox, DJ Gaussian, Inc., Wallingford CT, 2016. (B3LYP functional) Becke, ADJ Chem. Phys. Rev. 1993, 98, 5648–5652. (6-31G * basis sets) (a) Ditchfie, R.; Hehre , WJ ; Pople , JJ Chem. Phys. 1971, 54, 724–728. (b) Hehre, WJ; Ditchfie, R.; Pople , JJ Chem. Phys. Rev. 1972, 56, 2257–2 (c) Hariharan, PC; Pople, JA Theor Chem Acta 1973, 28, 213-222. (d) Francl, MM; Pietro , WJ ; Hehre , WJ ; Binkley , JS ; Gordon, MS; Defrees, DJ; Pople , JJ Chem. Phys. Rev. 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, SJ Phys. Chem. A 1999, 103, 5551–5556. (c) Malagoli, M.; Bredas , JL Chem. Phys. Lett. 2000, 327, 13–17.

[0046] If you are looking for a suitcase, you will be able to do it It is available in pages 1~5. Procedure for calculation of different photophysical properties E g = E LUMO -E HOMO E T = E Triplet -E singlet E T0 = E Triplet (with ZPE) -E Singlet (with ZPE) l = (E charged state in neutral geometry -E neutral state geometry ) + (E neutral state in charged geometry -E charged state geometry ) (In the formula, l (Internal Reorganization energy) is the internal reorganization energy, and the definitions of the other various energies are the same as those in the calculation method described above.) Or, if l = l1 + l2, l1= E charged state in neutral geometry -E charged state in charged geometry l2= E neutral state in charged geometry -E neutral state in neutral geometry (where l1(e) and l1(h) are the l1 values ​​for electron transport and hole transport, respectively.) λ + is the internal reorganization energy for hole transport, and the charge state is positive ion. λ - is the internal reorganization energy for electron transport, and the charge state is anion. IP is the ionization potential (adiabatic), E cationic geometry -E neutral state geometry It is calculated as follows. EA is the electron affinity (adiabatic), and E anionic geometry -E neutral state geometry It is calculated as follows.

[0047] From the calculation results, it is clear that the asymmetric 1,2-bis(diarylamino)benzenes of the present invention according to the general formula (1) have an appropriate HOMO-LUMO level, i.e., E HOMO , E LUMO , E g , E T , E T0 , λ - , λ + , IP, and EA, and can be used as a hole transporting material (hole transporting host material and / or hole transporting material) or a blue light emitting material.

[0048] [Table 1]

[0049] [Table 2]

[0050] [Table 3]

[0051] [Table 4]

[0052] [Table 5]

[0053] In addition, for example, in an organic EL device, other factors such as compatibility with other layers may have a large effect. Therefore, it is not possible to determine whether any of the compounds listed 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, the compound must satisfy the conditions that the HOMO is small, the Eg is large, and the E T0 The condition that λ is large +It is preferable that one or more of the following conditions be satisfied:

[0054] From the viewpoint of easily satisfying the above conditions, in the case of a hole-transporting host material, in the above general formula (1), A is preferably an aryl group substituted with a substituent containing a substituted or unsubstituted fused polycyclic aromatic group, or a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group, and more preferably an aryl group substituted with a substituent containing a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group, or a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group. Furthermore, it is more preferable that the nitrogen atom of the substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group is directly bonded to the aryl group, and it is even more preferable that the substituent is a carbazole group in which the nitrogen atom is directly bonded to the aryl group. Furthermore, in the case of a hole-transporting host material, A in the above general formula (1) is preferably an aryl group in which the nitrogen atom is directly bonded to the p-position or m-position.

[0055] In addition, from the viewpoint of easily satisfying the above condition, in general, in the case of a hole transporting host material, R 1 ~R 4 is preferably an electron withdrawing group. 1 , R 3 , R 4 is preferably substituted at the p-position. 1 ~R 4 Type of and / or R 1 ~R 4 By appropriately changing the number of groups substituted with groups other than hydrogen atoms in A, it is possible to obtain an asymmetric bis(1,2-diarylamino)benzene that easily satisfies the above-mentioned conditions, as in the case of changing A.

[0056] The bis(1,2-diarylamino)benzenes represented by the general formula (1) have an asymmetric structure, which results in low molecular crystallinity and high amorphousness. Therefore, they are believed 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 believed to have particularly high amorphousness and therefore a particularly high glass transition temperature (Tg).

[0057] Ortho-phenylenediamines are intermediate compounds for producing the asymmetric bis(1,2-diarylamino)benzenes represented by the above general formula (1), and in the present invention, they are represented by the general formula (2). [ka] Specific examples of the asymmetric bis(1,2-diarylamino)benzenes represented by the above general formula (2) include the following compounds: (1-1a)~(1-16a), (2-1a)~(2-18a), (3-1a)~(3-16a), (3-1a)~(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 Examples include:

[0058] (1-1a)~(1-16a) [ka]

[0059] (2-1a)~(2-18a) [ka]

[0060] (3-1a)~(3-16a) [ka]

[0061] (4-1a)~(4-7a) [ka]

[0062] (5-1a)~(5-2a) [ka]

[0063] (6-1a)~(6-6a) [ka]

[0064] (7-1a)~(7-4a) [ka]

[0065] (8-1a)~(8-4a) [ka]

[0066] OPDA-1a to OPDA-11a [ka]

[0067] The diarylamine represented by the general formula (3) may be the same as or different from the diarylamine represented by the general formula (4). In the magnesium diarylamides represented by the general formula (5) and the general formula (6), X represents a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0068] In the halogen compound represented by the general formula (7), X in formula (7) represents a halogen atom. Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples include the following structures. X in the formula below represents a halogen atom. Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As shown in the formula below, in the general formula (7), n (the number of atoms substituted by X) represents an integer of 1 to 3.

[0069] [ka]

[0070] Specific examples of the halogen compound represented by the general formula (7) include the following compounds: (1-1b)~(1-16b), (2-1b)~(2-18b), (3-1b)~(3-16b), (3-1b)~(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 Examples include:

[0071] (1-1b)~(1-16b) [ka]

[0072] (2-1b)~(2-18b) [ka]

[0073]

change

[0074] (3-1b)~(3-16b)

change

[0075] (4-1b)~(4-7b)

change

[0076] (5-1b)~(5-2b)

change

[0077] (6-1b)~(6-6b)

change

[0078] (7-1b)~(7-4b)

change

[0079] (8-1b)~(8-4b)

change

[0080] OPDA-1b~OPDA-11b

change

[0081] As in the case of the general formula (1), in the above formula (7), A is preferably an aryl group substituted with a substituent containing a substituted or unsubstituted fused polycyclic aromatic group, or a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group, and more preferably an aryl group substituted with a substituent containing a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group, or a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group. Furthermore, it is more preferable that the nitrogen atom of the substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group is directly bonded to the aryl group, and even more preferably that the substituent is a carbazole group in which the nitrogen atom is directly bonded to the aryl group. Furthermore, in the above general formula (7), A is preferably an aryl group in which the nitrogen atom is directly bonded to the p-position or m-position relative to X (halogen).

[0082] <Unsymmetric 1,2-bis(diarylamino)benzenes> The asymmetric 1,2-bis(diarylamino)benzenes represented by the general formula (1) can be produced by the following steps, although there are no particular limitations on the process.

[0083] [ka]

[0084] That is, the asymmetric 1,2-bis(diarylamino)benzenes according to the present invention can be produced by step 1 (OPDA synthesis step) and step 2 (synthesis step of target products such as hole transporting materials and blue light-emitting materials).

[0085] (Step 1: OPDA synthesis) The magnesium diarylamide compounds represented by the general formula (5) and the general formula (6) can be produced by reacting the diarylamine compounds represented by the general formula (3) and the general formula (4) with a Grignard reagent.

[0086] The Grignard reagent may be an aliphatic Grignard reagent or an aromatic Grignard reagent, such as methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, isopropylmagnesium bromide, isopropylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, phenylmagnesium bromide, or phenylmagnesium chloride. The amount of the Grignard reagent used is preferably 1.0 to 100 molar equivalents, more preferably 1.1 to 10.0 molar equivalents, relative to the diarylamine (3) or diarylamine (4). Grignard reagents may also be prepared from alkyllithium and magnesium salts.

[0087] 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, dioxane, etc. The solvent may be used alone or in combination of two or more. The amount of the solvent used is usually 1 to 1000 parts by weight based on the diarylamine (3) or diarylamine (4).

[0088] The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and can be carried out under normal pressure or elevated pressure. The reaction temperature is preferably in the range of -50°C to 300°C, more preferably 0°C to 150°C. The reaction time is not particularly limited as it differs depending on the type of substrate and the reaction temperature, but the reaction can usually be completed within a range of 1 hour to 48 hours. After the reaction is complete, the solvent may be removed under vacuum or normal pressure, or the reaction mixture may be used in the next step 2 as is.

[0089] Ortho-phenylenediamines represented by general formula (2) can be produced by reacting magnesium diarylamides (5) represented by general formula (5) and magnesium diarylamides (6) represented by general formula (6) with a transition metal catalyst and an oxidizing agent.

[0090] The amount of magnesium diarylamide (5) represented by general formula (5) used is preferably 1.0 to 10 molar equivalents, more preferably 1.0 to 2.0 molar equivalents, relative to the amount of magnesium diarylamide (6) represented by general formula (6).

[0091] The transition metal catalyst may be an iron compound, a palladium compound, a nickel compound, a cobalt compound, or a copper compound, such as iron chloride (II), iron chloride (III), iron bromide (II), iron bromide (III), iron acetate (II), iron fluoride (II), palladium chloride, palladium bromide, palladium acetate, palladium acetylacetonate, dichlorobis(triphenylphosphine)palladium, dichloro(cycloocta-1,5-diene)palladium, tris(dibenzylideneacetone)dipalladium, tris(dibenzylideneacetone)dipalladium chloroform complex, tetrakis(triphenylphosphine)palladium, nickel acetylacetonate, nickel chloride (II), cobalt chloride (II), copper acetylacetonate, copper chloride (II), iron acetylacetonate, etc. Among these, in order to further improve the reaction yield, iron chloride (II), iron chloride (III), iron acetate (II), and iron fluoride (II) are more preferable. The amount of the transition metal catalyst added is preferably in the range of 0.01 mol % to 100 mol % relative to the magnesium diarylamide (5) or magnesium diarylamide (6), and more preferably in the range of 0.05 mol % to 5.0 mol %.

[0092] Examples of the oxidizing agent include 1,2-diiodoethane, 1,2-dibromoethane, 1,2-dichloroethane, 1-chloro-2-iodoethane, 1-bromo-2-chloroethane, 1-iodo-2-bromoethane, etc. Among these, 1,2-dichloroethane and 1,2-dibromoethane are more preferred. The amount of the oxidizing agent added is preferably in the range of 0.5 to 10 molar equivalents, more preferably 1 to 5 molar equivalents, relative to the magnesium diarylamide (5) or magnesium diarylamide (6).

[0093] 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, etc., and ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tertiary butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, dioxane, etc. The solvent may be used alone or in combination of two or more. The amount of the solvent used is usually 1 to 1000 parts by weight based on the magnesium diarylamide (5) or magnesium diarylamide (6).

[0094] The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon, and can be carried out under normal pressure or under 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. The reaction time is not particularly limited as it differs depending on the type of substrate and the reaction temperature, but the reaction can usually be completed within a range of 1 hour to 48 hours.

[0095] After completion of the reaction, a generally known purification method can be used. For example, the organic layer can be separated by a liquid separation operation, and the obtained organic layer can be washed with water, saline, an alkaline aqueous solution, or the like, and then isolated and purified by a general method such as column chromatography or crystallization.

[0096] Step 2 (synthesis of the target product) The bis(1,2-diarylamino)benzenes represented by the general formula (1) can be produced by reacting the orthophenylenediamines represented by the general formula (2) with the halogen compound represented by the general formula (7) in the presence of a transition metal catalyst.

[0097] 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, palladium acetate, palladium acetylacetonate, dichlorobis(benzonitrile)palladium, dichlorobis(acetonitrile)palladium, dichlorobis(triphenylphosphine)palladium, dichlorotetraamminepalladium, dichloro(cycloocta-1,5-diene)palladium, palladium trifluoroacetate, tris(dibenzylideneacetone)dipalladium, tris(dibenzylideneacetone)dipalladium chloroform complex, tetrakis(triphenylphosphine)palladium, nickel acetylacetonate, nickel chloride, copper acetylacetonate, copper chloride, iron acetylacetonate, and iron chloride. The transition metal compound may be used in combination with various ligands, and the ligand may be added by reacting the transition metal compound and the ligand outside the system beforehand, or by adding the transition metal compound and the ligand to the reaction system and preparing the ligand inside the system. The amount of the transition metal compound added is preferably in the range of 0.01 mol % to 100 mol % relative to 1 mol of orthophenylenediamine represented by general formula (2), and more preferably in the range of 0.1 mol % to 5 mol % to further improve the reaction selectivity.

[0098] The ligand may be any compound that coordinates with a transition metal compound, including phosphine compounds, nitrogen-based compounds, and olefin-based compounds. Examples include alkylphosphines such as triethylphosphine, tricyclohexylphosphine, and tri(tert-butyl)phosphine; arylphosphines such as triphenylphosphine, 1,1'-bis(diphenylphosphino)ferrocene [dppf], and 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene [XANTphos]; and 1,5-cyclooctadiene [COD] and 2,2'-bipyridyl. Among these, tricyclohexylphosphine or tri(tert-butyl)phosphine is preferred for improving reaction selectivity. The amount of the ligand added is preferably in the range of 0.1 to 100 times by mole relative to the transition metal compound, and more preferably in the range of 1 to 10 times by mole in order to further improve the reaction selectivity.

[0099] The organic solvent used in the reaction may be either a polar solvent or a nonpolar solvent, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, 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), hexamethylphosphotriamide (HMPA), triethyl phosphite (TEP), trimethyl phosphite (TMP), and acetic acid. The solvent may be used alone or in combination. The amount of the solvent used is usually 1 to 10,000 parts by weight per 100 parts by weight of the orthophenylenediamine represented by the general formula (2).

[0100] Examples of bases used in the reaction include metal hydroxides, metal carbonates, metal phosphates, metal sulfates, and metal alkoxylates. Examples include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, tripotassium phosphate, sodium sulfate, sodium hydrogen sulfate, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide. Among these, potassium hydroxide, potassium carbonate, tripotassium phosphate, and sodium tert-butoxide are preferred. The amount of these bases used is preferably in the range of 1 to 50 moles per mole of the halogen compound represented by formula (7). To further improve reaction selectivity, a range of 1.5 to 5 times the molar amount is more preferred. The base may be used alone or in combination of two or more types.

[0101] The amount of the halogen compound (7) used is preferably in the range of 0.1 to 10 moles per mole of the orthophenylenediamine represented by the general formula (2), and more preferably in the range of 0.3 to 5 moles to further improve the reaction selectivity.

[0102] The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon, and can be carried out under normal pressure or under 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. The reaction time is not particularly limited as it differs depending on the type of substrate and the reaction temperature, but the reaction can usually be completed within a range of 1 hour to 48 hours.

[0103] After completion of the reaction, a generally known purification method can be used. For example, the organic layer can be separated by a liquid separation operation, and the obtained organic layer can be washed with water, saline, an alkaline aqueous solution, or the like, and then isolated and purified by a general method such as column chromatography or crystallization. [Effects of the Invention]

[0104] According to the present invention, the asymmetric bis(1,2-diarylamino)benzenes represented by the general formula (1) have appropriate HOMO-LUMO levels and can therefore be used as organic EL device materials such as hole transport materials and blue emitting materials. According to the present invention, asymmetric bis(1,2-diarylamino)benzenes, which have been difficult to produce until now, can be efficiently produced. Furthermore, this production method facilitates the regioselective introduction of various substituents, enabling molecular design to have energy levels suitable for organic EL device materials such as hole transport materials and blue emitting materials. [Brief explanation of the drawings]

[0105] [Figure 1] FIG. 1 is a diagram showing the HOMO-LUMO energy levels calculated from the absorption edge and oxidation potential of the solution for the materials used in the present invention and conventional materials, in which the horizontal axis (X axis) represents the material used to calculate the energy level, and the vertical axis (Y axis) represents the energy level (unit: eV). [Figure 2] The OPDA layer was evaluated using m-CBP as a control and OPDA-3 and OPDA-4 according to the present invention. For reference, data from a paper was also compared. [Figure 3] This figure shows the voltage-current characteristics of the device, with the horizontal axis (X axis) representing voltage (Volts) and the vertical axis (Y axis) representing current density (mA / cm). The materials used in the figure are m-CBP as a control and OPDA-3 and OPDA-4 according to the present invention. [Figure 4] This figure shows the electroluminescence (EL) spectrum of the device, where the horizontal axis (X axis) is wavelength (unit: nm) and the vertical axis (Y axis) is 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]

[0106] The present invention will be described in more detail below using examples. However, these examples are merely an outline of the present invention and the present invention is not limited to these examples.

[0107] Identification of the target compound 1 H NMR( 1 H nuclear magnetic resonance spectrum), 13 C NMR( 13 C nuclear magnetic resonance spectrum), 19 F NMR( 19 The purity and isomer ratio were determined by GC analysis, and the yield was determined by NMR analysis using dibromoethane as an internal standard. Recycling preparative GPC was used as needed to purify the target product. The following equipment was used: Nuclear magnetic resonance spectrum: JEOL ECS-400NR, Bruker AVANCE III 800US Plus IR device: PerkinElmer Spectrum One FT-IR Spectrometer HR-MS equipment: JEOL JMS-700 mass spectrometer Melting point measurement device: Yanaco MP-500D GC device: Shimadzu GC-2010(FID) Column: ZB-1MS (10 m x 0.10 mm I.D. df: 0.1 μm) (Phenomenex) Detector: Hydrogen flame ionization detector Recycled Preparative GPC: Japan Analytical Industry LC-9204 instrument Column: JAIGEL-1H-40 / JAIGEL-2H-40

[0108] Example 1 Synthesis of OPDA (1-1a) [ka] [ka]

[0109] Under an argon atmosphere, diphenylamine (18.0 g, 110 mmol) and EtO (108 mL) were added to a 500 mL Kolben, and EtMgBr (39.0 mL, 3.0 M in EtO, 121 mmol) was added under ice cooling, followed by heating and stirring at 40°C for 2 hours. After that, Et2O was removed under reduced pressure, and FeCl2 (0.67 g, 5.5 mmol), dibromoethane (18.0 mL, 220 mmol), and 108 mL of Bu2O were added. The mixture was heated and stirred at 80°C for 24 hours, and then 108 mL of 1N HCl was added at room temperature. The mixture was extracted with 108 mL of AcOEt three times and washed with 108 mL of brine.

[0110] MgSO4 was added to the obtained organic layer, and after filtering using 90 g of Florisil, it was concentrated in an evaporator. 22 g of the obtained Crude was added to 53 mL of EtOH and dissolved by heating. After stirring at room temperature for 1 hour, the precipitate was filtered to obtain a beige powder. Since this powder contained a small amount of impurities, 48 ​​mL of EtOH was added again, and the mixture was heated and dissolved. After stirring at room temperature for 1 hour, the mixture was filtered and dried to obtain 14.8 g of OPDA as a white powder in 83% yield.

[0111] The analysis results were as follows: 1 H NMR (DMSO-d6392 MHz) δ6.76-6.79 (m, 1H), 6.91-6.97 (m, 9H), 7.08-7.29 (m, 10H)

[0112] Example 2 Synthesis of OPDA (2-8a) [ka] [ka]

[0113] Under an argon atmosphere, diarylamine (14.0 g, 70.8 mmol) and BuO (94 mL) were added to a 500 mL Kolben, and BuMgBr (100 mL, 0.779 M in BuO, 77.9 mmol) was added at room temperature (25 °C), followed by heating and stirring at 100 °C for 1 hour.

[0114] Then, FeCl2 (0.45 g, 3.54 mmol) and dibromoethane (26.6 g, 142 mmol) were added at room temperature (25 °C), and the mixture was heated and stirred at 80 °C for 24 hours. After adding 1N HCl (200 mL), the reaction solution was filtered through Celite and extracted with 100 mL of AcOEt three times. The resulting organic layer was filtered and concentrated in an evaporator to give 15.6 g of crude. Purification was performed on a silica gel column using 500 g of silica gel and hexane as a developing solvent to give 8.97 g of OPDA with a GC purity of >99% in a 64% yield, and 4.80 g of OPDA with a GC purity of 92% in a 34% yield.

[0115] The analysis results were as follows: 1 H 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)

[0116] Example 3 Synthesis of OPDA-biphenyl [ka] [ka]

[0117] Under an argon atmosphere, diarylamine (5.00 g, 15.6 mmol) and EtO (50 mL) were added to a 300 mL Kolben flask. EtMgBr (5.73 mL, 3.0 M in EtO, 17.2 mmol) was added at room temperature, and the mixture was heated and stirred at 40 °C for 2 h. Then, EtO was removed under reduced pressure, and FeCl (98.8 mg, 0.78 mmol), dibromoethane (5.8 g, 31.2 mmol), and BuO (50 mL) were added. The mixture was heated and stirred at 80 °C for 12 h, followed by further heating and stirring at 140 °C for 24 h. 1N HCl (50 mL) was added at room temperature, and the mixture was extracted with AcOEt (30 mL x 3). MgSO was added to the resulting organic layer, which was then filtered using filter paper and concentrated on an evaporator. The crude obtained (4.21 g) was purified using a silica gel column to give 0.78 g of OPDA-biphenyl in a yield of <16%.

[0118] The analysis results were as follows: 1 H 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)

[0119] Example 4 Synthesis of substituted 4-Br-N,N-dimethylaniline [ka]

[0120] Under an argon atmosphere, OPDA (4.68 g, 13.9 mmol) obtained in Example 1, 4-bromo-N,N-dimethylaniline (4.12 g, 20.6 mmol), Pd(OAc) (62.9 mg, 0.28 mmol), tBuP (228 mg, 1.12 mmol), NaOtBu (2.67 g, 27.8 mmol), and toluene (70 mL) were added to a 300 mL Kolben tube and dissolved at room temperature (25 °C). The mixture was then heated and stirred 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. Reprecipitation using a toluene / hexane solvent system afforded 5.63 g of the target product in <89% yield.

[0121] The analysis results were as follows: 1 H 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%

[0122] Example 5 Synthesis of substituted 4-Br-N,N-dimethylaniline [ka]

[0123] Under an argon atmosphere, OPDA_Tol (4.55 g, 11.6 mmol), 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 and dissolved at room temperature (25 °C). The mixture was then heated and stirred at 120 °C for 6 h. 1N HCl (50 mL) was added to the reaction solution at room temperature (25 °C), followed by extraction with AcOEt (50 mL x 3). The resulting organic layer was dried over MgSO4, filtered through Florisil, and concentrated using an evaporator to give 6.71 g of crude. An attempt was made to purify 3.00 g of the crude product by GPC (toluene), but the peak tailing was suspected to be due to oxidation. The remaining 3.71 g of crude product was reprecipitated using a toluene / hexane solvent system to obtain 2.88 g of the desired product in 49% yield with a GC purity of >99%.

[0124] The analysis results were as follows: 1 H 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%

[0125] Example 6 Synthesis of substituted 4-Br-N,N-dimethylaniline [ka]

[0126] Under an argon atmosphere, OPDA_biphenyl (0.78 g, 1.22 mmol), 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). The mixture was then heated and stirred at 120 °C for 4 h. 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 through a filter paper, and concentrating on an evaporator. Reprecipitation using a toluene / hexane solvent system afforded 885 mg of crude product in <95% yield.

[0127] The analysis results were as follows: 1 H 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)

[0128] Example 7 Synthesis of substituted 3-Br-9-phenyl-9H-carbazole [ka]

[0129] Under an argon atmosphere, OPDA_Ph (2.91 g, 8.66 mmol), 3-bromo-9-phenyl-9H-carbazole (4.19 g, 12.99 mmol), Pd(OAc) (38.7 mg, 0.17 mmol), tBuP (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). The mixture was then heated and stirred at 130 °C for 14 h. Pd(OAc) (141 mg, 0.63 mmol) and tBuP (141 mg, 0.70 mmol) were then added at room temperature (25 °C), and the mixture was heated and stirred at 130 °C for 5 h. After adding 1N HCl (50 mL) to the reaction mixture at room temperature (25°C), the mixture was extracted with AcOEt (30 mL x 3) and concentrated using an evaporator. Reprecipitation using a toluene / hexane solvent system afforded 3.67 g in a <73% yield.

[0130] The analysis results were as follows: 1 H 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%

[0131] Example 8 Synthesis of OPDA-1 [ka]

[0132] Under an inert atmosphere, OPDA (336 mg, 1 mmol), 2-bromo-9-phenylcarbazole (322 mg, 1 mmol), Pd(OAc) (4.5 mg, 0.02 mmol), tBuP (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 h. The reaction was quenched with 1 M HCl at room temperature and extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSO, and filtered through a pad of Florisil. The solvent was removed under reduced pressure to give the 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.

[0133] The object 1 Analysis by H-NMR gave the following results: 1 H NMR (DMSO-d6392MHz) δ6.56-6.59 (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.

[0134] Example 9 Synthesis of OPDA-2 [ka]

[0135] Under an 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 and extracted with 4 mL of ethyl acetate. The mixture was filtered through a 1.5 g pad of fluorisil. The solvent (hexane:ethyl acetate = 30:1) was removed under reduced pressure to give the 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.

[0136] The object 1 Analysis by H-NMR gave the following results: 1 H NMR (CDCl3, 392 MHz) δ6.83-6.97 (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.

[0137] Example 10 Synthesis of OPDA-3 [ka]

[0138] Under an inert atmosphere, OPDA (336 mg, 1 mmol), 2-bromo-9-phenylcarbazole (322 mg, 1 mmol), Pd(OAc) (4.5 mg, 0.02 mmol), tBuP (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 with 1.5 mL of 1 M HCl at room temperature and extracted with 10 mL of ethyl acetate. The mixture was filtered through a 1.5 g pad of fluorisil. The solvent was removed under reduced pressure to give the 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.

[0139] The object 1 Analysis by H-NMR gave the following results: 1 H 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.

[0140] Example 11 Synthesis of Me-OPDA-4 (methyl group substituted) [ka]

[0141] Under an argon atmosphere, Me-OPDA-4a (393 mg), mesitylene (2.7 mL), Me-OPDA-4b (Br derivative) (487 mg), Pd(OAc) (4.5 mg, 0.02 mmol), tBuP (16.2 mg), and NaOtBu (144 mg) were added to a reaction vessel and dissolved at room temperature (25 °C). The mixture was then heated and stirred 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 x 2). The mixture was passed through 1.34 g of Florisil (60-100 mesh), washed with AcOEt (2 mL), and evaporated. The resulting product was a brown oil. It was purified by silica gel column chromatography and filtered to obtain 0.48 g of the desired product (Me-OPDA-4). The product was a white powder.

[0142] The object 1 Analysis by H-NMR gave the following results: 1 H 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, Anal. Calcd for C58H46N4 C, 87.19; H, 5.80; N, 7.01. Found C, 87.25; H, 5.88; N, 6.75.

[0143] Example 12 Synthesis of F-OPDA-4 (fluorine-substituted) [ka]

[0144] Under an argon atmosphere, F-OPDA-4a (408.40 mg, 1.00 mmol), F-OPDA-4b (Br derivative) (487.40 mg, 1.00 mmol), Pd(OAc) (4.5 mg, 0.02 mmol), tBuP (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). The mixture was then heated and stirred at 150 °C for 8 hours. The reaction was quenched at room temperature (25 °C), extracted with AcOEt (20 mL x 3), and dried over MgSO. Purification by column chromatography afforded 467 mg of the desired product (F-OPDA-4) in a 57.3% yield. The desired product was a light brown solid.

[0145] The object 1 Analysis by H-NMR gave the following results: 1 H NMR (DMSO-d6, 392 MHz) δ6.64-6.68 (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.

[0146] Example 13 Synthesis of OPDA-5 [ka]

[0147] Under an argon atmosphere, OPDA (OPDA-5a) (336.44 mg, 1.00 mmol), 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). The mixture was then heated and stirred at 150 °C for 8 hours. The reaction was quenched by adding 1N HCl at room temperature (25 °C). The mixture was then passed through 1.5 g of Florisil and purified on 20 g of silica gel (solvent: hexane:AcOEt = 30:1) to obtain 507.72 mg of the desired product (OPDA-5). The yield was 88%. The desired product was a white solid.

[0148] The object 1 Analysis by H-NMR gave the following results: 1 H NMR (DMSO-d6, 392 MHz) δ6.68-6.77 (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.

[0149] Example 14 Synthesis of OPDA-6 [ka]

[0150] Under an argon atmosphere, OPDA (OPDA-6a) (336.44 mg, 1.00 mmol), 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). The mixture was then heated and stirred at 150 °C for 7 h. The reaction was quenched by adding 1N HCl at room temperature (25 °C). The mixture was extracted with AcOEt (20 mL x 3) and dried over MgSO4. The mixture was passed through 1.5 g of Florisil, extracted with the solvent, and recrystallized to obtain 566.91 mg of the desired product (OPDA-6). The yield was 90.3%. The target product was a white solid.

[0151] The object 1 Analysis by H-NMR gave the following results: 1 H 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.

[0152] Example 15 Synthesis of OPDA-7 [ka]

[0153] Under an 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). The mixture was then heated and stirred at 150 °C for 6 h. 1N HCl (3 mL) was added to the reaction solution at room temperature (25 °C), followed by extraction with AcOEt (5 mL, 3 mL). The mixture was washed with brine, passed through 3.5 g of silica gel, and evaporated. The resulting product was a brown syrup. It was solidified, filtered, and dried to yield 0.65 g of the desired product (OPDA-7), a light beige powder.

[0154] The object 1 Analysis by H-NMR gave the following results: 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.

[0155] Example 16 Synthesis of OPDA-8 [ka]

[0156] Under an 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) (9 mg, 0.04 mmol), tBuP (32.4 mg), and NaOtBu (290 mg) were added to a reaction vessel and dissolved at room temperature (25 °C). The mixture was then heated and stirred at 150 °C for 6 h. 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 to give a crude product (0.8 g) as a gray powder. This product was dissolved in CHCl, passed through 7.5 g of silica gel, and evaporated. The product was green and foamy. This was dissolved, filtered, and dried to obtain 0.69 g of the target product (OPDA-8), which was a pale gray white powder.

[0157] The object 1 Analysis by H-NMR gave the following results: 1 H NMR (DMSO-d6, 392 MHz) δ6.50-6.60 (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.

[0158] Example 17 Synthesis of OPDA-9 [ka]

[0159] Under an argon atmosphere, OPDA (OPDA-9a) (472.88 mg, 1.50 mmol), 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). The mixture was then heated and stirred at 150 °C for 6 h. The reaction was quenched by adding 1N HCl at room temperature (25 °C). The mixture was extracted with AcOEt (20 mL x 3) and dried over MgSO4. The mixture was passed through 25 g of silica gel, extracted with a solvent (hexane: EtOAc = 25:1), and recrystallized to give 782.62 mg of the desired product (OPDA-9). The yield was 85.8%. The target product was a white solid.

[0160] The object 1 Analysis by H-NMR gave the following results: 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.

[0161] Example 18 Synthesis of OPDA-10 [ka]

[0162] Under an 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). The mixture was then heated and stirred at 150 °C for 4 h. 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 to give a crude product (0.83 g) as a beige powder. This product was purified by column chromatography, dissolved in CHCl3, passed through 8 g of silica gel, and evaporated. 0.93 g of the crude target product was obtained as reddish purple bubbles. This was dissolved in a solvent, filtered, and dried to obtain 0.67 g of the target product (OPDA-10), which was a white powder.

[0163] The object 1 Analysis by H-NMR gave the following results: 1 H NMR (CDCl3, 392 MHz) δ6.95-6.99 (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.

[0164] Example 19 Synthesis of OPDA-11 [ka]

[0165] Under an 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). The mixture was then heated and stirred at 150 °C for 4 h. 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 to give a brown foamy crude product (0.97 g). This product was purified by column chromatography on silica gel (9 g) and turned purple foamy upon addition of CHCl3. Adding 10 ml of IpA to this resulted in a clay-like substance that turned into a powder. Filtration yielded a pale brownish white powder (0.76 g). Further purification by column chromatography using silica gel (11 g) and extraction with a solvent (hexane: EtOAc = 10:1 → 4:1) yielded a yellow-orange foamy substance (0.72 g). 5 mL of ethanol was added to this, and the mixture was filtered and dried to yield 0.64 g of the target product (OPDA-11) as a pale brownish white powder.

[0166] The object 1 Analysis by H-NMR gave the following results: 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;

[0167] 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 according to the following reaction scheme and used for evaluation. [ka] [ka] [ka]

[0168] Example 21 Measurement of basic physical properties The glass transition temperature, absorption maximum wavelength, log ε, absorption edge, fluorescence maximum wavelength, fluorescence quantum yield, and oxidation potential vs. Ag / Ag+ were measured for OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, Me-OPDA-4, F-OPDA-4, OPDA-7, and OPDA-9, and the results are shown in Table 6.

[0169] Each measurement was carried out under the following conditions. Glass transition temperature Differential scanning calorimetry (DSC / TG-DTA 6200, Hitachi High-Tech Science) was used. Measurement conditions were as follows: sample size: 5 mg, temperature increase rate: 10°C / min, temperature decrease rate between the first and second runs: 20°C / min. The glass transition temperature was determined from the second run. Maximum absorption wavelength The measurement was performed using a spectrometer SEC2020 (manufactured by BAS Co., Ltd.). The measurement conditions were as follows: -5 A solution of about 100 mol / L was prepared, and the wavelength of the maximum point of the absorption band on the longest wavelength side in the absorption spectrum observed with the above-mentioned measuring device was determined as the maximum absorption wavelength. log ε is the logarithm of the molar extinction coefficient at the wavelength of long absorption. The absorption edge is the wavelength at the long wavelength end of the absorption spectrum where a straight line approximation of the curve intersects with the x-axis (absorbance 0). Fluorescence maximum wavelength Fluorescence spectroscopy was performed using a JASCO F8200 instrument under the following conditions: excitation wavelength 310 nm, excitation light band 2.5 nm, and fluorescence band 2.5 nm. Fluorescence quantum yield It was determined by the relative method against a cyclohexane solution of 9,10-diphenylanthracene. Oxidation potential vs Ag / Ag+ The measurement was performed by cyclic voltammetry under the following conditions: 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 0.01 M CH3CN solution, sweep rate: 50 mV / sec.

[0170] [Table 6]

[0171] Example 22 Measurement of basic physical properties The optical energy gap, HOMO and LUMO levels were calculated for OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, Me-OPDA-4, F-OPDA-4, OPDA-7 and OPDA-9, and the results are shown in Table 7.

[0172] [Table 7]

[0173] In Table 7 above, The HOMO level was obtained by cyclic voltammetry. The measurement conditions were an NPD oxidation potential of 477 mV vs. Ag / Ag+ and a 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.

[0174] Example 23 HOMO-LUMO diagram calculated from the absorption edge and oxidation potential of the solution The energy levels of OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, OPDA-6, OPDA-7, and OPDA-9 were calculated and the results are shown in Figure 1. Calculations were performed for NPD and TPD as conventional materials and added to Figure 1. Note that in this specification, NPD is an abbreviation for N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine, and TPD is an abbreviation for N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine. These results demonstrate that the materials OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, OPDA-6, OPDA-7, and OPDA-9 according to the present invention have an appropriate energy level difference between the HOMO and LUMO levels, making them suitable as light-emitting materials.

[0175] Example 24 Measurement of basic physical properties The energy levels of OPDA-3 and OPDA-9, as well as NPD, CBP, and m-CBP for comparison, were calculated, and the results are shown in Table 8.

[0176] [Table 8]

[0177] In Table 8 above, 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.

[0178] From Table 8, the T1 levels of OPDA-3 and OPDA-9 are higher in energy than NPD and CBP, and the ΔE STIt was found that the dc-dc peak density was smaller than that of NPD, CBP, and m-CBP. This suggests that OPDA-3 and OPDA-9 possess advantageous energy levels as hosts for triplet blue and exciton diffusion blocking layers. As used herein, m-CBP is an abbreviation for 3,3'-Di(9H-carbazol-9-yl)-1,1'-biphenyl.

[0179] Example 25: Investigation of a method for purifying the product by sublimation The purification method by sublimation was investigated for OPDA-1, OPDA-2, OPDA-5, OPDA-6, Me-OPDA-4 and F-OPDA-4, and the results are shown in Table 9.

[0180] [Table 9]

[0181] Example 26: Investigation of a method for purifying the product by sublimation The purification method by sublimation was investigated for OPDA-3, OPDA-4, OPDA-7, OPDA-9, OPDA-10 and OPDA-11, and the results are shown in Table 10. [Table 10] OPDA-10: Purity after sublimation: 99.1% OPDA-11: Purity after sublimation: 97.1%

[0182] From Tables 9 and 10 above, it is clear that the materials according to the present invention can be highly purified by sublimation, and that this method is useful as a purification method.

[0183] Example 27 Evaluation of refractive index (difficulty of total reflection) The refractive indexes of F-OPDA-4 and OPDA-4, as well as NPD for comparison, were measured, and the results are shown in Table 11. [Table 11]

[0184] In Table 11, measurements were made by ellipsometry. Measurements are typically performed by observing the change in the polarization state of the output light relative to the polarization state of the input light, and calculating Ψ(tanΨ=│r p │ / │r s │) and Δ(=δ rp -δ rs ) was obtained from the measurement. Then, an optical model was created and the refractive index was calculated by fitting the model to the actual measurement.

[0185] From Table 11, it can be seen that the material according to the present invention is less prone to total reflection than the conventional NPD material, and that the reflection is particularly low even at low wavelengths such as 400 nm, which is about the same as the reflection at high wavelengths.

[0186] Example 28: Element evaluation For OPDA-3 and OPDA-4, and for comparison, m-CBP, the device configuration (layered structure consisting of organic layers) for evaluation was created as shown in Figure 2, and the driving voltage, luminance, luminous efficiency, and chromaticity CIE1931 were measured. The results are shown in Table 12. The laminated structure is configured as follows. The organoborane used as the luminescent material is the material shown below, which can be prepared with reference to Nat. Photon. 8, 326-332 (2014). Organoborane: 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 m-CBP consists of: ITO / HAT-CN(5nm) / NPD(40nm) / TCTA(15nm) / m-CBP(15nm) / m-CBP+1wt%Organoborane(20nm) / NBPhen(40nm) / Al OPDA-3 consists of: ITO / HAT-CN(5nm) / NPD(50nm) / TCTA(20nm) / OPDA-3+1wt%Organoborane(20nm) / NBPhen(40nm) / Al OPDA-4 consists of: ITO / HAT-CN(5nm) / NPD(50nm) / TCTA(20nm) / OPDA-4+1wt%Organoborane(20nm) / NBPhen(40nm) / Al

[0187] [Table 12]

[0188] In Table 12, the driving voltage was measured by IV measurement, the luminance was measured by a color luminance meter, and the luminous efficiency is luminance current efficiency.

[0189] Table 12 shows that the driving voltages of the stacked structures using OPDA-3 and OPDA-4 according to the present invention are lower than those of the stacked structure using the conventional material m-CBP, and that they are comparable in terms of luminance, luminous efficiency, and chromaticity. This demonstrates that they are suitable as light-emitting materials.

[0190] Example 29: Voltage-current characteristics The voltage-current characteristics of the laminated structures using OPDA-3 and OPDA-4, and m-CBP as a control, were measured and the results are shown in Figure 3. The configuration of the laminated structure was the same as that shown in Figure 2. From Figure 3, it was confirmed that the OPDA devices having a stacked structure using OPDA-3 and 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.

[0191] Example 30 EL Spectrum The EL spectra of the stacked structures using OPDA-3 and OPDA-4, and the stacked structure using m-CBP as a control, were measured and the results are shown in Figure 4. The configuration of the stacked structures was the same as that of Figure 2. As can be seen from Figure 4, the OPDA devices having a stacked structure using OPDA-3 according to the present invention and a stacked structure using OPDA-4 have spectra with almost the same maximum value as the m-CBP device, and the OPDA device having a stacked structure using OPDA-4 has a shoulder on the low wavelength side.

[0192] Example 31 Cyclic voltammetry of dichloromethane solution Cyclic voltammetry was measured in dichloromethane solution for OPDA-1, OPDA-2, OPDA-5, OPDA-6, Me-OPDA-4, F-OPDA-4, OPDA-7, OPDA-9, OPDA-10, and OPDA-11, and the results are shown in Tables 13 and 14. The measurement conditions are: Solvent: dichloromethane, Compound concentration: 10-3 mol / l, Supporting electrolyte: TBAP 0.1 M, Work electrode: platinum disc, Counter electrode: platinum wire, Reference electrode: Ag / AgNO30.01M CH3CN solution, Sweep speed: 50mV / sec However, the NPD oxidation potential is 477 mV vs Ag / Ag+. HOMO 5.43 eV reference, I went there.

[0193] [Table 13]

[0194] [Table 14] [Industrial Applicability]

[0195] The compound is industrially useful as a hole transport material or a blue light emitting material for organic EL devices.

Claims

1. 1,2-bis(diarylamino)benzenes of any of the following formulae: 【Chemistry 80】

2. A hole transporting material or a blue light emitting material comprising the 1,2-bis(diarylamino)benzene compound according to claim 1.

3. An organic EL element comprising the hole transport material or blue light-emitting material described in claim 2.

4. A display comprising the organic EL element described in claim 3.

Images