Asymmetrical 1,2-bis(diarylamino)benzenes, their manufacturing methods and uses

Abstract

This invention provides asymmetric 1,2-bis(diarylamino)benzenes that are useful as organic EL element materials. [Solution] A compound represented by the following general formula (1) is provided. JPEG2026048794000093.jpg56170 [In the formula, R 1 These include methyl groups, ethyl groups, and linear, branched, or cyclic alkyl groups of C3-6; R 2 These include methyl groups, ethyl groups, linear, branched, and cyclic alkyl groups of C3-6, methoxy groups, ethoxy groups, etc.; R 3 and R 4 [a, b, c, and d are 0 or 1.]

Description

[Technical Field]

[0001] This invention relates to organic EL element materials, particularly asymmetric 1,2-bis(diarylamino)benzenes useful as hole transport materials and blue light-emitting materials, methods for producing the same, and applications of hole transport materials, blue light-emitting materials, etc. [Background technology]

[0002] Organic electroluminescence (OEL) is attracting attention as a next-generation flat panel display, boasting high panel performance such as thinness, lightness, wide viewing angle, fast response, high brightness, and high energy efficiency. Therefore, development toward practical application is progressing at companies and research institutions both domestically and internationally, and applications in mobile phones and flat-screen televisions have begun.

[0003] Generally, organic EL elements have a structure in which a hole transport material, a light-emitting material (host material and dopant material), and an electron transport material are stacked between the anode and the cathode. Technical challenges for organic EL elements include the need to explore materials suitable for achieving the high panel performance mentioned above, particularly blue light emission and hole transport properties, as well as developing materials suitable for industrial applications.

[0004] For materials suitable for blue light emission, the energy levels of the HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) are thought to influence the wavelength of emission. Furthermore, since HOMO and LUMO affect the injection barrier and efficiency of holes and electrons from electrodes, they are considered factors that should be considered in the compound design of hole transport materials. Therefore, materials with appropriate HOMO-LUMO levels are required.

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

[0006] [ka]

[0007] Furthermore, as an example of using 1,2-bis(diarylamino)benzenes as hole-transporting materials, for example, Patent Document 2 is reported. However, further improvements are needed for their use as hole-transporting materials. Also, since the compounds described in the literature are all compounds with symmetrical structures, it is presumed that they have low glass transition temperatures (Tg), and therefore improvements are needed for their use as hole-transporting materials. [Prior art documents] [Patent Documents]

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

[0009] [Non-Patent Document 1] Nature Photonics,2019,pp678-682 [Overview of the project] [Problems that the invention aims to solve]

[0010] In view of the above background, the object of the present invention is to provide asymmetric 1,2-bis(diarylamino)benzenes useful as organic EL element materials such as hole transport materials and blue light-emitting materials, a method for producing the same, and applications as hole transport materials and blue light-emitting materials. Furthermore, an object of the present invention is to provide orthophenylenediamines, which are useful intermediates for producing asymmetric 1,2-bis(diarylamino)benzenes. [Means for solving the problem]

[0011] As a result of diligent research into the above-mentioned problems, the inventors have found that the following specific asymmetric bis(1,2-diarylamino)benzenes have suitable HOMO-LUMO levels for use as organic EL element materials such as hole transport materials and blue light-emitting materials, and are particularly suitable for use as E g We discovered that it possesses a value. Furthermore, by using diarylamines with various substituents as starting materials, we established an efficient method for producing asymmetric 1,2-bis(diarylamino)benzenes, which had previously been difficult to manufacture, thus completing the present invention.

[0012] In other words, the present invention relates to the following invention. [1] General formula (1) [ka] [In formula (1), R 1 This 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 These include methyl groups, ethyl groups, linear, branched, or cyclic alkyl groups having 3 to 6 carbon atoms, methoxy groups, ethoxy groups, alkoxy groups having 3 to 6 carbon atoms, and phenyl groups. orRepresents a halogen atom, R 3 and R 4 Each of these 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, 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 with a directly bonded nitrogen atom and a phenyl group directly bonded to that nitrogen atom. ] Asymmetric 1,2-bis(diarylamino)benzenes represented by ].

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

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

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

[0016] [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 the aryl group.

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

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

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

[0020] [8] The asymmetric 1,2-bis(diarylamino)benzenes described in [1] above, which are any of the following formulas. [ka]

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

[0022]

[10] Organic EL element comprising the hole transporting material or blue light-emitting material described above.

[0023]

[11] A display including the above-mentioned organic EL elements.

[0024] In the present invention, an intermediate for producing the asymmetric 1,2-bis(diarylamino)benzenes of the present invention, wherein the following general formula (2) [Chemical formula] [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 represents 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. Ortho-phenylenediamines represented by ] can be used.

[0025] In the present invention, a method for producing the above asymmetric 1,2-bis(diarylamino)benzenes of the present invention, represented by the following general formula (1) [Chemical formula] [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 represents a halogen atom, R3 and R 4 Each of these 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, 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 with a directly bonded nitrogen atom and a phenyl group directly bonded to that 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) above. Diarylamines shown and The following general formula (4) [ka] [In formula (4), R 3 , R 4 c and d are the same as in formula (1) above. The diarylamines shown are reacted with a Grignard reagent, The following general formula (5) [ka] [In formula (5), R 1 , R 2a and b are the same as in formula (1) above, and X represents a halogen atom. Magnesium diarylamides (5) shown and The following general formula (6) [ka] [In formula (6), R 3 , R 4 c and d are the same as in formula (1) above, and X represents a halogen atom. After obtaining the magnesium diarylamides (6) shown, 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) [ka] [In formula (2), R 1 , R 2 , R 3 ,R 4 ,a, b, c, and d are the same as in formula (1) above. Orthophenylenediamines (2) shown are obtained, and further in the presence of a transition metal catalyst and a base, The following general formula (7) [ka] [In equation (7), A is the same as in equation (1), X represents a halogen atom, and n represents an integer from 1 to 3.] A method for producing asymmetric 1,2-bis(diarylamino)benzenes (1) by reacting them with a halogen compound shown can be used.

[0026] In the asymmetric bis(1,2-diarylamino)benzenes represented by the above general formula (1), in formula (1), R 1 R 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. 2These include methyl groups, ethyl groups, linear, branched, or cyclic alkyl groups having 3 to 6 carbon atoms, methoxy groups, ethoxy groups, alkoxy groups having 3 to 6 carbon atoms, and phenyl groups. or Represents a halogen atom, R 3 and R 4 Each of the following 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 including a substituted or unsubstituted condensed polycyclic aromatic group or a substituent in which a nitrogen atom is directly attached to only one of the m positions or to 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 with a directly bonded nitrogen atom and a phenyl group directly bonded to that nitrogen atom. It is suitable as a hole-transporting material or a blue light-emitting material consisting of asymmetric 1,2-bis(diarylamino)benzenes represented by the above general formula (1).

[0027] Examples of linear, 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, i-butyl 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, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Examples of alkoxy groups having 3 to 6 carbon atoms include n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy groups. Examples of halogen atoms include fluorine, chlorine, bromine, or iodine. Furthermore, a substituent containing a condensed polycyclic aromatic group is a substituent containing an aromatic condensed polycyclic group, and the aromatic condensed polycyclic group may or may not contain heteroatoms such as nitrogen atoms, oxygen atoms, or sulfur atoms. Examples of aromatic condensed polycyclic groups include carbon condensed polycyclic groups such as naphthyl and fluorenyl groups, and heterocondensed polycyclic groups such as quinolinyl, indolyl, benzimidazole, phenoxazinyl, phenothiazinyl, 9-dimethylacridinyl, iminostylbenyl, 1,12-iminoperylene, carbazole, dibenzofuranyl, dibenzothienyl, and oxantrenyl groups. Also, R 1 ~R 4 These substituents or hydrogen atoms may all be the same, or they may be different substituents.

[0028] Some specific examples of asymmetric bis(1,2-diarylamino)benzenes represented by the general formula (1) above include the following compounds: (1-1)~(1-16), (2-1)~(2-18), (3-1)~(3-16), (3-1)~(3-16), (4-1)~(4-7), (5-1)~(5-2), (6-1)~(6-6), (7-1)~(7-4), (8-1)~(8-4), (9-1)~(9-3), (10-1)~(10-2), etc.

[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), and OPDA-4 is the same as (3-2)) [ka]

[0041] F-1 to F-18 The following general formula (F) also includes compounds F-1 to F-18. These identify 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 compounds described above, OPDA-1 to OPDA-11 are preferably used as hole transport materials, blue light-emitting materials, and materials for organic EL, as shown in the examples described later. Materials having the structure of OPDA-1 to OPDA-11 as a framework are also preferably used as hole transport materials, blue light-emitting materials, and materials for organic EL.

[0043] Furthermore, 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 + The IP and EA are calculated and shown in Tables 1 to 5 below. The calculation method is as follows: All calculations are performed using the B3LYP density functional method in combination with the 6-31G* basis set, and run in the Gaussian 16 program (revision C01). The triplet energy is the difference in electron energies (E) between the triplet state and the singlet state with optimized geometry. T It is calculated as (E). The triplet energy (E) calculated including the zero-point energy correction. T0 These values ​​were found to agree better with experimental values, so they are also calculated and compared. Reorientation energy is the difference in electron energy change associated with the geometric changes in the molecular structure of the charge transfer state and the neutral state. Internal reorientation energy (l) is the energy required for the geometric changes of two molecules to facilitate electron / hole transfer between them. It is calculated using the adiabatic potential energy surface with the following equation. λ = λ1 + λ2 = (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 E is the electron energy of the charged state determined for a neutral molecular structure. charged state in charged geometry E is the electron energy in the charged state, which is determined for the molecular structure in the charged state. neutral state in charged geometry E is the electron energy of the neutral state, which is determined for the molecular structure in the charged state. neutral state in neutral geometry This indicates the electron energy of the charged state, determined relative to the molecular structure in the neutral state.

[0044] Hole transport (λ + ) and electron transport (λ - In the case of the internal rearrangement energy, the charged states are cation and anion, respectively. The energy required for the structural changes of the surrounding molecules surrounding the two molecules involved in charge transfer is called the external rearrangement energy, and is considered small and is not considered in the current calculation. Furthermore, the adiabatic ionization potential (IP) and electron affinity (EA) are also calculated. The optimized energies of the charged states are used in this calculation and are calculated using the following equation. IP = E cationic state geometry - E neutral state geometry EA = E anionic state geometry - E neutral state geometry (In the formula, IP is the ionization potential (adiabatic), EA is the electron affinity (adiabatic), E cationic state geometry This is the molecular structure of the cation state, E neutral state geometry This is the neutral state molecular structure, E anionic state geometry This is the anionic state molecular structure, E neutral state geometry (This shows the molecular structure in a neutral state.)

[0045] The citation will be 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:λ) (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 calculating various photophysical properties E g = E LUMO - E HOMO E T = E Triplet - E singlet E T0 = E Triplet (with ZPE) - E Singlet (with ZPE) λ = (E charged state in neutral geometry - E neutral state geometry ) + (E neutral state in charged geometry - E charged state geometry ) (In the formula, λ (Internal Reorganisation energy) is the internal reorganization energy, and the definitions of the other energies are the same as those calculated above.) Alternatively, if λ = λ1 + λ2, λ1 = E charged state in neutral geometry - E charged state in charged geometry λ² = E neutral state in charged geometry - E neutral state in neutral geometry (In the equation, λ1(e) and λ1(h) are the λ1 values ​​for electron transport and hole transport, respectively.) λ + This is the internal reorganization energy for hole transport, and the charged state is a positive ion. λ - This is the internal reorganization energy for electron transport, and its charged state is anion. IP is the ionization potential (adiabatic), E cationic geometry - E neutral state geometry It is calculated by [this method]. EA is electron affinity (adiabatic), and E anionic geometry - E neutral state geometry It is calculated by [this method].

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

[0048] [[ID=S20]]Table 1 [Table 1]

[0049] [[ID=S30]]Table 2 [Table 2]

[0050] [[ID=S40]]Table 3 [Table 3]

[0051] [[ID=S50]]Table 4 [Table 4]

[0052] [[ID=S60]]Table 5 [Table 5] [[ID=S66]]

[0053] In addition, in an organic EL device, for example, other factors such as compatibility with other layers may have a great influence. Therefore, it cannot be generally determined which of the above-exemplified compounds is suitable as a hole-transporting material or a blue light-emitting material. However, generally, in the case of a hole-transporting host material, the compound preferably satisfies one or more of the conditions that the HOMO is small, the Eg is large, the E T0 is large, and the λ + is small.

[0054] From the viewpoint of being likely to satisfy the above conditions, generally, in the case of a hole-transporting host material, in the general formula (1), A is preferably 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 aromatic group, and more preferably an aryl group substituted by a substituent containing a substituted or unsubstituted nitrogen-containing condensed polycyclic aromatic group or a substituted or unsubstituted nitrogen-containing condensed polycyclic aromatic group. Further, it is more preferable that the nitrogen atom of the substituted or unsubstituted nitrogen-containing condensed 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. Also, generally, 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-position or m-position.

[0055] Also, from the viewpoint of being likely to satisfy the above conditions, generally, in the case of a hole-transporting host material, in the general formula (1), R 1 ~R 4 are preferably electron-withdrawing groups. Also, R 1 , R 3 , R 4 are preferably substituted at the p-position. Note that the types of R 1 ~R 4 , and / or R 1 ~R 4By appropriately changing the number of groups other than hydrogen atoms that are substituted, asymmetric bis(1,2-diarylamino)benzenes that easily satisfy the above conditions can be obtained, similar to changing A.

[0056] The bis(1,2-diarylamino)benzenes represented by the above general formula (1) have an asymmetric structure, resulting in low molecular crystallinity and high amorphousness. Therefore, they are thought to have a high glass transition temperature (Tg). In particular, (1-1)~(1-15), (2-1)~(2-16), (2-18), (3-1)~(3-16), (3-1)~(3-16), (4-1)~(4-7), (5-1)~(5-2), (6-1)~(6-6), (7-1)~(7-4), (8-1)~(8-4), and (9-1)~(9-3), OPDA-1~OPDA-11, and F-1~F-18 have particularly high amorphousness and are thought to have a particularly high glass transition temperature (Tg).

[0057] Orthophenylenediamines are intermediate compounds for producing asymmetric bis(1,2-diarylamino)benzenes represented by the above general formula (1), and in the present invention, they are represented by general formula (2). [ka] Some specific examples of asymmetric bis(1,2-diarylamino)benzenes represented by the general formula (2) above are 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 These are some examples.

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

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

change

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

change

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

change

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

change

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

change

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

change

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

change

[0066] OPDA-1a~OPDA-11a

change

[0067] The diarylamines represented by the above general formula (3) may be the same as or different from the diarylamines represented by the above general formula (4). In the magnesium diarylamides represented by the above general formulas (5) and (6), X represents a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, or iodine.

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

[0069] [ka]

[0070] Some specific examples of halogen compounds represented by the general formula (7) above are 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 These are some examples.

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

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

change

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

[0082] <Asymmetric 1,2-bis(diarylamino)benzenes> The asymmetric 1,2-bis(diarylamino)benzenes represented by general formula (1) can be produced by the following processes, although this is not particularly limited.

[0083] [ka]

[0084] In other words, 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 substances such as hole transporting materials and blue light emitting materials).

[0085] (Step 1: OPDA synthesis) Magnesium diarylamides represented by general formulas (5) and (6) can be produced by reacting diarylamines represented by general formulas (3) and (4) with a Grignard reagent.

[0086] The Grignard reagent can be an aliphatic or 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 used is preferably 1.0 to 100 molar equivalents, and more preferably 1.1 to 10.0 molar equivalents, relative to diarylamines (3) or diarylamines (4). Grignard reagents may also be prepared from alkyllithium and magnesium salts.

[0087] Examples of organic solvents used in the reaction include ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and dioxane. The solvent may be used alone or in a mixture of two or more. The amount of solvent used is usually 1 to 1000 parts by weight relative to diarylamines (3) or diarylamines (4).

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

[0089] Orthophenylenediamines 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, and more preferably 1.0 to 2.0 molar equivalents, relative to the magnesium diarylamide (6) represented by general formula (6).

[0091] Suitable transition metal catalysts include iron compounds, palladium compounds, nickel compounds, cobalt compounds, or copper compounds. Examples include iron(II) chloride, iron(III) chloride, iron(II) bromide, iron(III) bromide, iron(II) acetate, iron(II) fluoride, 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(II) chloride, cobalt(II) chloride, copper acetylacetonate, copper(II) chloride, and iron acetylacetonate. Of these, iron(II) chloride, iron(III) chloride, iron(II) acetate, and iron(II) fluoride are more desirable for further improving the reaction yield. The amount of 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). More preferably, it is in the range of 0.05 mol% to 5.0 mol%.

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

[0093] The organic solvent used in the reaction may be either a polar or nonpolar solvent. Examples include aromatic hydrocarbons such as benzene, toluene, and xylene, and ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and dioxane. The solvent may be used alone or as a mixture of two or more. The amount of solvent used is usually 1 to 1000 parts by weight relative to the magnesium diarylamide (5) or magnesium diarylamide (6).

[0094] The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and can also be carried out under atmospheric pressure or pressurized pressure. The reaction temperature is preferably in the range of 0°C to 300°C, but more preferably in the range of 50°C to 150°C. The reaction time varies depending on the type of substrate and reaction temperature, and is not particularly limited, but the reaction can usually be completed within a range of 1 to 48 hours.

[0095] After the reaction is complete, generally known purification methods can be used. For example, the organic layer can be separated by liquid-liquid extraction, washed with water, saline solution, or an alkaline aqueous solution, and then isolated and purified by general methods such as column chromatography or crystallization.

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

[0097] The transition metal compounds constituting the transition metal catalyst can be palladium compounds, nickel compounds, copper compounds, or iron compounds. Examples 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. Furthermore, this transition metal compound may be used in combination with various ligands. The ligands may be added either by reacting the transition metal compound and ligands outside the system beforehand and then adding them, or by adding the transition metal compound and ligands to the reaction system and preparing the mixture in situ. The amount of transition metal compound added is preferably in the range of 0.01 mol% to 100 mol% per mole of orthophenylenediamine represented by general formula (2). To further improve the reaction selectivity, a range of 0.1 mol% to 5 mol% is more desirable.

[0098] Any ligand that coordinates to a transition metal compound can be used, including phosphine compounds, nitrogen compounds, and olefin 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)zanthene [XANTphos], as well as 1,5-cyclooctadiene [COD] and 2,2'-bipyridyl. Of these, tricyclohexylphosphine or tri(tert-butyl)phosphine are preferable to improve reaction selectivity. The amount of ligand added is preferably in the range of 0.1 to 100 times the molar amount relative to the transition metal compound. To further improve reaction selectivity, a range of 1 to 10 times the molar amount is more desirable.

[0099] The organic solvent used in the reaction may be either a polar or nonpolar solvent. Examples 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 a mixture of two or more. The amount of solvent used is usually 1 to 10,000 parts by weight per 100 parts by weight of orthophenylenediamine represented by general formula (2).

[0100] Examples of 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 bicarbonate, potassium bicarbonate, tripotassium phosphate, sodium sulfate, sodium bisulfate, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, etc. Of these, potassium hydroxide, potassium carbonate, tripotassium phosphate, and sodium tert-butoxide are preferred. The amount used is preferably in the range of 1 to 50 moles per mole of the halogen compound represented by general formula (7). To further improve reaction selectivity, a range of 1.5 to 5 times the mole is more desirable. The base may be used alone or in combination of two or more types.

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

[0102] The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and can also be carried out under atmospheric pressure or pressurized pressure. The reaction temperature is preferably in the range of 0°C to 300°C, but more preferably in the range of 50°C to 150°C. The reaction time varies depending on the type of substrate and reaction temperature, and is not particularly limited, but the reaction can usually be completed within a range of 1 to 48 hours.

[0103] After the reaction is complete, generally known purification methods can be used. For example, the organic layer can be separated by liquid-liquid extraction, washed with water, saline solution, or an alkaline aqueous solution, and then isolated and purified by general methods such as column chromatography or crystallization. [Effects of the Invention]

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

[0105] [Figure 1] This figure shows 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, where the horizontal axis (X axis) represents the material used to calculate the energy levels, and the vertical axis (Y axis) represents the energy levels (in units of eV). [Figure 2] This figure shows the stacked structure for evaluating the device. The OPDA layer was evaluated using m-CBP as a control, as well as OPDA-3 and OPDA-4 according to the present invention. For reference, the data was also compared with the data presented in the paper. [Figure 3] This figure shows the voltage-current characteristics of the device, with the horizontal axis (X-axis) representing voltage (V in volts) and the vertical axis (Y-axis) representing current density (mA / cm²). 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, with the horizontal axis (X-axis) representing wavelength (in nm) and the vertical axis (Y-axis) representing EL intensity (normalized). The materials used in the figure are m-CBP as a control and OPDA-3 and OPDA-4 according to the present invention. [Examples]

[0106] The present invention will be described in more detail below with reference to examples, but these examples are intended to illustrate the outline of the present invention and are not limited to these examples.

[0107] The identification of the target compound is 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 1F nuclear magnetic resonance (F) spectroscopy, mass spectrometry (MS), IR analysis, HRMS analysis, melting point analysis, and 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. Recycled preparative GPC was used for the purification of the target product as needed. The equipment used is as follows: Nuclear magnetic resonance spectra: JEOL ECS-400NR, Bruker AVANCE III 800US Plus IR device: PerkinElmer Spectrum One FT-IR Spectrometer HR-MS instrument: JEOL JMS-700 massspectrometer Melting point measuring device: Yanaco MP-500D GC device: Shimadzu GC-2010(FID) Column: ZB-1MS (10m x 0.10mm I.D. df: 0.1μm) (manufactured by Phenomenex) Detector: Flame ionization detector Recycling Separation 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 Et2O (108 mL) were added to 500 mL of coruben. Under ice cooling, EtMgBr (39.0 mL, 3.0 M in Et2O, 121 mmol) was added, and the mixture was heated and stirred at 40°C for 2 hours. Subsequently, Et2O was removed under reduced pressure, and FeCl2 (0.67 g, 5.5 mmol), dibromoethane (18.0 mL, 220 mmol), and Bu2O 108 mL were added. The mixture was heated and stirred at 80°C for 24 hours, then at room temperature, 108 mL of 1N HCl was added, followed by extraction with 108 mL x 3 of AcOEt, and washing with 108 mL of brine.

[0110] MgSO4 was added to the obtained organic layer, filtered using 90 g of Florisil, and then concentrated using an evaporator. 22 g of the obtained Crude was mixed with 53 mL of EtOH, heated and dissolved, stirred at room temperature for 1 hour, and the precipitate was filtered to obtain a beige powder. Since the 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 white powdered OPDA in 83% yield.

[0111] The analysis results were as follows: 1 H NMR (DMSO-d6392 MHz) δ 6.76-6.79 (m, 1H), 6.91-6.97 (m, 9H), 7.08-7.29 (m, 10H)

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

[0113] Under an argon atmosphere, diarylamine (14.0 g, 70.8 mmol) and Bu2O (94 mL) were added to a 500 mL corvette. At room temperature (25 °C), BuMgBr (100 mL, 0.779 M in Bu2O, 77.9 mmol) was added, and the mixture was heated and stirred at 100 °C for 1 hour.

[0114] Subsequently, at room temperature (25 °C), FeCl2 (0.45 g, 3.54 mmol) and dibromoethane (26.6 g, 142 mmol) were added, and the mixture was heated and stirred at 80 °C for 24 hours. After adding 1N HCl (200 mL) to the reaction solution, it was filtered through celite and extracted with 100 mL x 3 of AcOEt. The obtained organic layer was filtered through filter paper and then concentrated using an evaporator to obtain 15.6 g of Crude. Using 500 g of silica gel and hexane as the developing solvent, silica gel column purification was performed to obtain 8.97 g of OPDA with a GC purity >99% in a 64% yield and 4.80 g of OPDA with a GC purity of 92% in a 34% yield, respectively.

[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] Synthesis of Example 3 OPDA - biphenyl [Chemical formula] [Chemical formula]

[0117] Under an argon atmosphere, diarylamine (5.00 g, 15.6 mmol) and Et2O (50 mL) were added to 300 mL of coruben. At room temperature, EtMgBr (5.73 mL, 3.0 M in Et2O, 17.2 mmol) was added, and the mixture was heated and stirred at 40°C for 2 hours. Then, under reduced pressure, the Et2O was removed, and FeCl2 (98.8 mg, 0.78 mmol), dibromoethane (5.8 g, 31.2 mmol), and Bu2O (50 mL) were added. The mixture was heated and stirred at 80°C for 12 hours, and then heated and stirred at 140°C for 24 hours. At room temperature, 1N HCl (50 mL) was added, and the mixture was extracted with AcOEt (30 mL x 3). MgSO4 was added to the resulting organic layer, filtered through filter paper, and concentrated using an evaporator. 0.78 g of OPDA-biphenyl was obtained from 4.21 g of the obtained Crude by silica gel column purification in <16% yield.

[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 4-Br-N,N-dimethylaniline substituted derivatives [ka]

[0120] Under an argon atmosphere, OPDA (4.68 g, 13.9 mmol) obtained in Example 1, along with 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 300 mL of coruben. The mixture was dissolved at room temperature (25°C), and then heated and stirred at 120°C for 4 hours. After adding 1N HCl (50 mL) to the reaction solution at room temperature (25°C), it was extracted with AcOEt (20 mL x 3) and concentrated using an evaporator. The target product was obtained in 5.63 g, <89% yield, by reprecipitation using a toluene / hexane solvent system.

[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 4-Br-N,N-dimethylaniline substituted derivatives [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 corvette, dissolved at room temperature (25 °C), and then heated and stirred at 120 °C for 6 hours. After adding 1N HCl (50 mL) to the reaction solution at room temperature (25 °C), extraction was performed with AcOEt (50 mL x 3). The obtained organic layer was dried over MgSO4, filtered through florisil, and concentrated using an evaporator to obtain 6.71 g of Crude. An attempt was made to purify 3.00 g of Crude by GPC (toluene), but it was considered that the peak was tailing and oxidation occurred. The remaining 3.71 g of Crude was reprecipitated using a toluene / hexane solvent system to obtain 2.88 g of the target product with a GC purity >99% in a 49% yield.

[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] [[ID=​​​​​​​​​​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 100 mL of coruben and dissolved at room temperature (25°C). The mixture was then heated and stirred at 120°C for 4 hours. After adding 1N HCl (30 mL) to the reaction solution at room temperature (25°C), it was extracted with CHCl3 (20 mL x 3), dried over MgSO4, filtered through filter paper, and concentrated using an evaporator. Crude 885 mg was obtained in <95% yield by reprecipitation using a toluene / hexane solvent system.

[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 3-Br-9-phenyl-9H-carbazole-substituted derivatives [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)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 100 mL of coruben, dissolved at room temperature (25°C), and then heated and stirred at 130°C for 14 hours. Furthermore, Pd(OAc)2 (141 mg, 0.63 mmol) and tBu3P (141 mg, 0.70 mmol) were added at room temperature (25°C), and the mixture was heated and stirred at 130°C for 5 hours. At room temperature (25°C), 1N HCl (50 mL) was added to the reaction solution, followed by extraction with AcOEt (30 mL x 3) and concentration using an evaporator. Reprecipitation using a toluene / hexane solvent system yielded 3.67 g in <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 length 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)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 and extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSO4, and filtered through a Florisil pad. The solvent was removed under reduced pressure to obtain the crude product. The crude product was recrystallized from EtOH and toluene to obtain the target product OPDA-1 (0.43 g, 74% yield) as a white solid.

[0133] The target object 1 Analysis using 1H-NMR yielded the following results. 1 H NMR (DMSO-d6392MHz) 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.

[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 hours. 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 fluorisil pad. The solvent (hexane:ethyl acetate = 30:1) was removed under reduced pressure to obtain the crude product. The crude product was recrystallized from EtOH and toluene to obtain the target product OPDA-2 (0.50772 g, 88% yield) as a white solid.

[0136] The target object 1 Analysis using 1H-NMR yielded the following results. 1 H 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.

[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)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 hours. The reaction was quenched at room temperature with 1.5 ml of 1 M HCl and extracted with 10 ml of ethyl acetate. The mixture was filtered through a 1.5 g fluorisil pad. The solvent was removed under reduced pressure to obtain the crude product. The crude product was recrystallized from EtOH and toluene to obtain the target product OPDA-3 (0.51068 g, 88% yield) as a white solid.

[0139] The target object 1 Analysis using 1H-NMR yielded 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)2 (4.5 mg, 0.02 mmol), tBu3P (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. After adding 1N HCl (1.5 mL) to the reaction solution at room temperature (25°C), it was extracted with AcOEt (2 mL x 2), passed through 1.34 g of Florisil (60-100 mesh), washed with AcOEt (2 mL), and evaporated. The solution was a brown, oily substance. This was purified by silica gel column chromatography and filtered. 0.48 g of the target product (Me-OPDA-4) was obtained. The target product was a white powder.

[0142] The target object 1 Analysis using 1H-NMR yielded 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 compound) [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)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). The mixture was then heated and stirred 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 yielded 467 mg of the target product (F-OPDA-4). The yield was 57.3%. The target product was a light brown solid.

[0145] The target object 1 Analysis using 1H-NMR yielded the following results. 1 H 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.

[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 stopped by adding 1N-HCl at room temperature (25°C), the solution was passed through 1.5 g of Florisil, and purified using 20 g of silica gel (solvent:hexane:AcOEt=30:1) to obtain 507.72 mg of the target product (OPDA-5). The yield was 88%. The target product was a white solid.

[0148] The target object 1 Analysis using 1H-NMR yielded the following results. 1 H 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.

[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). After heating and stirring at 150°C for 7 hours, the mixture was stopped by adding 1N-HCl at room temperature (25°C), extracted with AcOEt (20 mL x 3), and dried over MgSO4. The solution was passed through 1.5 g of Florisil, and after solvent extraction, recrystallization was performed to obtain 566.91 mg of the target product (OPDA-6). The yield was 90.3%. The target substance was a white solid.

[0151] The target object 1 Analysis using 1H-NMR yielded 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). After 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 (salt water), and then passing the solution through 3.5 g of silica gel and evaporating it. The result was a brown, amber-like substance. This was solidified, filtered, and dried to obtain 0.65 g of the target product (OPDA-7). The target product was a light beige powder.

[0154] The target object 1 Analysis using 1H-NMR yielded 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)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 hours. After adding 1N HCl (3 mL) to the reaction solution at room temperature (25°C), it was extracted with AcOEt (5 mL, 3 mL) and washed with Brine (salt water) to obtain a crude gray powder (0.8 g). This was dissolved in CHCl3, passed through 7.5 g of silica gel, and evaporated. The resulting solution was a green, foamy substance. This was dissolved, filtered, and dried to obtain 0.69 g of the target substance (OPDA-8). The target substance was a pale grayish-white powder.

[0157] The target object 1 Analysis using 1H-NMR yielded the following results. 1 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 hours. The reaction was stopped by adding 1N-HCl at room temperature (25°C), extracted with AcOEt (20 mL x 3), and dried over MgSO4. The solution was passed through 25 g of silica gel, extracted with solvent (hexane:siRNA = 25:1), and recrystallized to obtain 782.62 mg of the target product (OPDA-9). The yield was 85.8%. The target substance was a white solid.

[0160] The target object 1 Analysis using 1H-NMR yielded 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 hours. After adding 1N HCl (1.5 mL) to the reaction solution at room temperature (25°C), it was extracted with AcOEt (5 mL, 3 mL) and washed with Brine (salt water) to obtain a crude beige powder (0.83 g). This was purified by column chromatography, dissolved in CHCl3, and then passed through 8 g of silica gel and evaporated. 0.93 g of a reddish-purple, foamy crude substance was obtained. This was dissolved in a solvent, filtered, and dried to obtain 0.67 g of the target substance (OPDA-10). The target substance was a white powder.

[0163] The target object 1 Analysis using 1H-NMR yielded the following results. 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.

[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 hours. After adding 1N HCl (1.5 mL) to the reaction solution at room temperature (25°C), it was extracted with AcOEt (5 mL, 3 mL) and washed with Brine (salt water) to obtain a brown, foamy crude product (0.97 g). This was purified by column chromatography using silica gel (9 g), and when CHCl3 was added, it became a purple foam. When 10 ml of IpA was added to this, it became clay-like and powdered. Filtration yielded a light brownish-white powder (0.76 g). Further purification by column chromatography using silica gel (11 g) and extraction with solvent (hexane:SiO = 10:1 → 4:1) yielded a yellowish-orange foamy substance (0.72 g). 5 ml of ethanol was added to this, and filtration and drying yielded 0.64 g of the target product (OPDA-11) from the light brownish-white powder.

[0166] The target object 1 Analysis using 1H-NMR yielded 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 Similarly to the above, OPDA-7-X, OPDA-7-cbz, and OPDA-8-X were synthesized under the following reaction equation and used for evaluation. [ka] [ka] [ka]

[0168] 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, fluorescence maximum wavelength, fluorescence quantum yield, and oxidation potential vsAg / Ag+ were measured, and the results are shown in Table 6.

[0169] Each measurement was performed under the following conditions. glass transition temperature Differential scanning calorimetry (instrument: Hitachi High-Tech Science DSC / TG-DTA 6200) was used. The measurement conditions were: sample amount ~5 mg, heating temperature 10°C / min, cooling rate between 1st and 2nd run 20°C / min, and the glass transition temperature value from the 2nd run was adopted. Absorption maximum wavelength The measurement was performed using a spectrometer SEC2020 (manufactured by BAS Corporation). The measurement conditions were as follows: the material was dissolved in tetrahydrofuran for 10 minutes. -5 A solution of approximately mol / L was prepared, and the wavelength of the maximum point in the longest wavelength absorption band in the absorption spectrum observed with the above measuring device was determined as the absorption maximum wavelength. logε is the logarithm of the molar extinction coefficient at the longest absorption wavelength. The absorption edge is the wavelength at which the curve, when approximated as a straight line, intersects the x-axis (absorbance of 0) at the long-wavelength end of the absorption spectrum. Fluorescence maximum wavelength Fluorescence spectroscopy was performed using a JASCO F8200 instrument. The measurement conditions were: excitation wavelength 310 nm, excitation light band 2.5 nm, and fluorescence band 2.5 nm. Fluorescence quantum yield The determination was made by a relative method using 9,10-diphenylanthracene in a cyclohexane solution. Oxidation potential vs Ag / Ag+ The measurement was performed by cyclic voltammetry. The measurement conditions were as follows: 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 Basic Physical Properties Part 1 [Table 6]

[0171] 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 levels were calculated, and the results are shown in Table 7.

[0172] Table 7 Basic Physical Properties Part 2 [Table 7]

[0173] In Table 7 above, The HOMO level was obtained by cyclic voltammetry. The measurement conditions were NPD oxidation potential of 477 mV vs. Ag / Ag+, with a HOMO reference 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 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 Figure 1. The NPD and TPD values ​​for conventional materials were calculated and added to Figure 1. 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 indicate that the OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, OPDA-6, OPDA-7, and OPDA-9 materials related to the present invention have an appropriate intensity in their energy levels as a difference between 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 Basic Physical Properties Part 3 (Calculated Values) [Table 8]

[0177] In Table 8 above, the S1 level was calculated from the short-wavelength edge of the fluorescence spectrum, and the T1 level was calculated from the short-wavelength edge of the phosphorescence spectrum.

[0178] Table 8 shows that the T1 levels of OPDA-3 and OPDA-9 are higher in energy than NPD and CBP, and the ΔE of OPDA-3 and OPDA-9 is also higher.ST It was found that this is smaller than NPD, CBP, and m-CBP. From this, it is thought that OPDA-3 and OPDA-9 possess energy levels favorable for use as hosts or exciton diffusion stopping layers for triplet Blue. In this specification, 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 products by sublimation. We investigated sublimation purification methods 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. Investigation of purification methods for products by sublimation, Part 1. [Table 9]

[0181] Example 26: Investigation of a method for purifying the product by sublimation. We investigated sublimation purification methods for OPDA-3, OPDA-4, OPDA-7, OPDA-9, OPDA-10, and OPDA-11, and the results are shown in Table 10. Table 10 Investigation of product purification methods by sublimation, part 2 [Table 10] OPDA-10: Purity after sublimation: 99.1% OPDA-11: Purity after sublimation: 97.1%

[0182] From Tables 9 and 10 above, it was found that the material according to the present invention can be purified to a high degree by sublimation, and that this method is useful for purification.

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

[0184] In Table 11, measurements were performed using ellipsometry. The measurement is performed as usual, observing the change in the polarization state of the emitted light relative to the polarization state of the incident light, and Ψ(tanΨ=│r p │ / │r s │) and Δ(=δ rp -δ rs The refractive index was obtained from measurements. Then, an optical model was created, and the model was fitted to the measured values ​​to determine the refractive index.

[0185] Table 11 shows that the material according to the present invention exhibits less total internal reflection compared to conventional NPD materials, and that this is particularly low at low wavelengths such as 400 nm, similar to that at high wavelengths.

[0186] Example 28: Element Evaluation For OPDA-3 and OPDA-4, and for m-CBP as a comparison, the device configuration (a stacked structure consisting of organic layers) for evaluation was created as shown in Figure 2, and the driving voltage, brightness, luminous efficiency, and chromaticity CIE1931 were measured, and the results are shown in Table 12. The layered structure is configured as follows: The organic borane used as the luminescent material is the material shown below and can be prepared by referring 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 composition: ITO / HAT-CN(5nm) / NPD(40nm) / TCTA(15nm) / m-CBP(15nm) / m-CBP+1wt%Organoborane(20nm) / NBPhen(40nm) / Al OPDA-3 configuration: ITO / HAT-CN(5nm) / NPD(50nm) / TCTA(20nm) / OPDA-3+1wt%Organoborane(20nm) / NBPhen(40nm) / Al OPDA-4 configuration: ITO / HAT-CN(5nm) / NPD(50nm) / TCTA(20nm) / OPDA-4+1wt%Organoborane(20nm) / NBPhen(40nm) / Al

[0187] Table 12 Element Evaluation [Table 12]

[0188] In Table 12, the drive voltage was measured by IV measurement, and the luminance was measured by a colorimeter. The luminous efficiency is the luminance current efficiency.

[0189] Table 12 shows that 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 that it is comparable in terms of brightness, luminous efficiency, and chromaticity, indicating that it is suitable as a light-emitting material.

[0190] Example 29 Voltage-Current Characteristics Figure 3 shows the voltage-current characteristics measured for stacked structures using OPDA-3, OPDA-4, and m-CBP as a control. The configuration of the stacked structures was the same as that shown in Figure 2. Figure 3 shows that OPDA devices having a stacked structure using OPDA-3 and a stacked structure using OPDA-4 according to the present invention can reduce the driving voltage compared to m-CBP devices having a stacked structure using m-CBP.

[0191] Example 30 EL spectrum Figure 4 shows the EL spectra measured for the stacked structure using OPDA-3, the stacked structure using OPDA-4, and, as a control, the stacked structure using m-CBP. The configuration of the stacked structure was the same as that of the stacked structure in Figure 2. Figure 4 shows that the OPDA devices having a stacked structure using OPDA-3 and a stacked structure using OPDA-4 according to the present invention have spectra with nearly 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, Working electrode: Platinum disk, Counter electrode: Platinum wire, Reference electrode: Ag / AgNO30.01M CH3CN solution, Sweep speed: 50mV / sec However, NPD oxidation potential 477mV vs Ag / Ag+, HOMO 5.43eV standard, It was done at [location].

[0193] Table 13 Cyclic voltammetry of dichloromethane solution [Table 13]

[0194] Table 14 Cyclic voltammetry of dichloromethane solution [Table 14] OPDA-10: Oxidation-reduction potential 590mV, HOMO 5.52eV OPDA-11: Oxidation-reduction potential 650mV, HOMO 5.58eV [Industrial applicability]

[0195] These materials are industrially useful as organic EL element materials, such as hole transport materials and blue light-emitting materials.

Claims

1. The following general formula (1) 【Chemistry 75】 [In formula (1), R １ This 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 This 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 of these 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, a substituted or unsubstituted fused polycyclic aromatic group, or a substituent to which a nitrogen atom is directly attached to only one of the m positions or to 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 with a directly bonded nitrogen atom and a phenyl group directly bonded to that nitrogen atom. However, excluding any of the asymmetric 1,2-bis(diarylamino)benzenes of the following formulas, 【Transformation 76】 Asymmetric 1,2-bis(diarylamino)benzenes.

2. One of the following asymmetric 1,2-bis(diarylamino)benzene compounds. 【Chemical 77】

3. One of the following asymmetric 1,2-bis(diarylamino)benzene compounds. 【Transformation 78】

4. An optical material which is a 1,2-bis(diarylamino)benzene as described in any one of claims 1 to 3.

5. A hole-transporting material or a blue light-emitting material comprising 1,2-bis(diarylamino)benzenes according to any one of claims 1 to 4.

6. An organic EL element comprising the hole transport material or blue light-emitting material described in claim 5.

7. A display comprising the organic EL element described in claim 6.

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