1, 2-bis (diarylamino) benzenes, and optical material, hole-transporting material, blue light-emitting material, organic EL element, and display using same

Abstract

The present invention provides a 1, 2-bis (diarylamino) benzene, and an optical material, a hole-transporting material, a blue light-emitting material, an organic EL element and a display using the 1, 2-bis (diarylamino) benzene. And the 1, 2-bis (diarylamino) benzene is one of the following formulae (1, 2-bis (diarylamino) benzene). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to an asymmetric 1,2-bis(diarylamino)benzene, a method for producing the same, and uses thereof as hole transport materials, blue light-emitting materials, etc. The asymmetric 1,2-bis(diarylamino)benzene is useful as an organic EL element material, particularly a hole transport material, a blue light-emitting material. Background Art

[0002] Organic EL (organic electro-luminescence: OEL) has attracted attention as the next generation of flat panel displays, and has high panel performance such as thin / lightweight, high viewing angle, high-speed response, high brightness and high energy efficiency. Therefore, domestic and foreign companies and research institutions are developing it for practical use and are beginning to use it in displays for mobile phones and thin TVs.

[0003] Generally, an organic EL element has a structure in which a hole transport material, a light emitting material (a host material and a dopant material), and an electron transport material are stacked between an anode and a cathode.

[0004] As technical issues of organic EL elements, it is required to search for materials suitable for the above-mentioned high panel performance, especially blue light emitting and hole transporting materials, and to develop materials suitable for industrial application thereof.

[0005] For materials suitable for blue light emission, the energy levels of HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) are considered to affect the wavelength of light emission, and HOMO and LUMO affect the injection barrier and efficiency of holes and electrons from the electrodes, so they are considered to be factors that should be considered in the compound design of hole transport materials. Therefore, materials with appropriate HOMO-LUMO energy levels are required.

[0006] As a representative hole transport material, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl shown below as NPB is generally known. However, the driving voltage of the device using NPB for the hole transport layer is insufficient, and the glass transition temperature (Tg) is low, so it has insufficient performance as a hole transport material.

[0007] In addition, compounds represented by TCTA and mCP in the following and compounds represented by L9 (N(2,3)DA-carbs in the following) in Patent Document 1 are proposed in Non-Patent Document 1. These materials cannot be said to have excellent property values ​​as hole transport materials and blue light-emitting materials from the viewpoint of ease of production, and development of new compounds is desired.

[0008]

[0009] Moreover, as an example of using 1,2-bis(diarylamino)benzenes as hole transport materials, for example, Patent Document 2 is reported. However, further improvement is needed for use as hole transport materials. In addition, the compounds recorded in the literature are only compounds with symmetrical structures, so it is estimated that they have a low glass transition temperature (Tg), and improvement is still needed as hole transport materials.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: Chinese Patent Application Publication No. 108299282

[0013] Patent Document 2: Japanese Patent No. 3171755

[0014] Non-patent literature

[0015] Non-patent literature 1: Nature Photonics, 2019, pp678-682 Summary of the invention

[0016] Problems to be solved by the invention

[0017] In view of the above background, the object of the present invention is to provide an asymmetric 1,2-bis(diarylamino)benzene and a method for producing the same, as well as the use of the asymmetric 1,2-bis(diarylamino)benzene as a hole transport material, a blue light emitting material, etc., wherein the asymmetric 1,2-bis(diarylamino)benzene is useful as an organic EL element material such as a hole transport material, a blue light emitting material, etc.

[0018] Furthermore, an object of the present invention is to provide o-phenylenediamines which are intermediates for producing asymmetric 1,2-bis(diarylamino)benzenes.

[0019] Solutions for solving problems

[0020] The present inventors have conducted intensive research on the above-mentioned problems and have found the following facts as a result, thereby completing the present invention: the specific asymmetric bis(1,2-diarylamino)benzenes shown below have appropriate HOMO-LUMO energy levels and particularly preferred Eg values ​​for use as hole transport materials, blue light-emitting materials and other organic EL device materials. In addition, by using diarylamines having various substituents as starting materials, an efficient method for producing asymmetric 1,2-bis(diarylamino)benzenes, which has been difficult to produce so far, has been established.

[0021] That is, the present invention relates to the following aspects.

[0022] [1] An asymmetric 1,2-bis(diarylamino)benzene represented by the following general formula (1).

[0023]

[0024] [In formula (1),

[0025] 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 carbazolyl group or a phenyl group,

[0026] 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,

[0027] 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 carbazolyl group or a phenyl group,

[0028] a, b, c, and d represent 0 or 1,

[0029] A represents an aryl group substituted with a substituted or unsubstituted fused polycyclic aromatic substituent or a substituent directly bonded to the nitrogen atom only at the meta position or at the para position, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted furanyl group or a substituted or unsubstituted phenylthio group, and A optionally forms a cyclic structure with the nitrogen atom directly bonded thereto and the phenyl group directly bonded thereto.]

[0030] It should be noted that, in the present specification, "asymmetric 1,2-bis(diarylamino)benzenes" also include structural analogs thereof, and as described above, also include structures in which A is a substituted or unsubstituted furyl group or a substituted or unsubstituted phenylthio group.

[0031] In the present specification, “asymmetric 1,2-bis(diarylamino)benzenes” may include compounds having a point-symmetrical structure.

[0032] [2] An asymmetric 1,2-bis(diarylamino)benzene, wherein A is an aryl group substituted with a substituent containing a nitrogen atom.

[0033] [3] The asymmetric 1,2-bis(diarylamino)benzenes according to [2] above, wherein the nitrogen atom contained in the substituent is directly bonded to an aryl group.

[0034] [4] The asymmetric 1,2-bis(diarylamino)benzenes according to [3] above, wherein the substituent is a carbazolyl group in which a nitrogen atom is directly bonded to an aryl group.

[0035] [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.

[0036] [6] The asymmetric 1,2-bis(diarylamino)benzene according to any one of [3] to [5] above, wherein the nitrogen atom is directly bonded to the para-position or meta-position of the aryl group.

[0037] [7] The asymmetric 1,2-bis(diarylamino)benzenes according to [2] above, wherein the substituent is a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group.

[0038] [8] The asymmetric 1,2-bis(diarylamino)benzene according to [1] above, which is any of the following formulas.

[0039]

[0040] [9] A hole transport material or a blue light emitting material, which is composed of the asymmetric 1,2-bis(diarylamino)benzene represented by the general formula (1) according to any one of [1] to [8].

[0041] It should be noted that, in this specification, the hole transport material includes a hole transport host material used in the light emitting layer and a hole transport material used in the hole transport layer.

[0042]

[10] An organic EL element comprising the above-mentioned hole transport material or blue light-emitting material.

[0043]

[11] A display comprising the above-mentioned organic EL element.

[0044] In the present invention, o-phenylenediamines represented by the following general formula (2) which are intermediates for producing the asymmetric 1,2-bis(diarylamino)benzenes of the present invention can be used.

[0045]

[0046] [In formula (2),

[0047] 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 carbazolyl group or a phenyl group,

[0048] 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,

[0049] 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 carbazolyl group or a phenyl group,

[0050] a, b, c, and d represent 0 or 1. ]

[0051] In the present invention, a method for producing an asymmetric 1,2-bis(diarylamino)benzene (1) can be used. The method is a method for producing the asymmetric 1,2-bis(diarylamino)benzene of the present invention, that is, a method for producing an asymmetric 1,2-bis(diarylamino)benzene represented by the following general formula (1), wherein a diarylamine represented by the following general formula (3) and a diarylamine represented by the following general formula (4) are reacted with a Grignard reagent to obtain a diaryl amide magnesium compound (5) represented by the following general formula (5) and a diaryl amide magnesium compound (6) represented by the following general formula (6), and then the diaryl amide magnesium compound (5) and the diaryl amide magnesium compound (6) are reacted with a transition metal catalyst and an oxidant to obtain an o-phenylenediamine (2) represented by the following general formula (2), and the o-phenylenediamine (2) is further reacted with a halogen compound represented by the following general formula (7) in the presence of a transition metal catalyst and a base.

[0052]

[0053] [In formula (1),

[0054] R 1represents 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 carbazolyl group or a phenyl group,

[0055] 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,

[0056] 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 carbazolyl group or a phenyl group,

[0057] a, b, c, and d represent 0 or 1,

[0058] A represents an aryl group substituted with a substituted or unsubstituted fused polycyclic aromatic substituent or a substituent directly bonded to the nitrogen atom only at the meta position or at the para position, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted furanyl group or a substituted or unsubstituted phenylthio group, and A optionally forms a ring structure with the nitrogen atom directly bonded thereto and the phenyl group directly bonded thereto.]

[0059]

[0060] [In formula (3), R 1 , R 2 , a and b are respectively the same as those in the above formula (1).]

[0061]

[0062] [In formula (4), R 3 , R 4 , c and d are respectively the same as those in the above formula (1).]

[0063]

[0064] [In formula (5), R 1 , R 2 , a and b are the same as those in the above formula (1), and X represents a halogen atom.]

[0065]

[0066] [In formula (6), R3 , R 4 , c and d are respectively the same as those in the above formula (1), and X represents a halogen atom.]

[0067]

[0068] [In formula (2), R 1 , R 2 , R 3 , R 4 , a, b, c and d are respectively the same as those in the above formula (1).]

[0069] AX n (7)

[0070] [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.]

[0071] In the asymmetric bis(1,2-diarylamino)benzenes represented by the above general formula (1), in the 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 carbazolyl group or a phenyl group, and 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, and 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 carbazolyl group or a phenyl group, a, b, c and d represent 0 or 1, A represents an aryl group substituted with a substituted or unsubstituted fused polycyclic aromatic substituent or a substituent directly bonded to the nitrogen atom only at the meta position or at the para position, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted furanyl group, or a substituted or unsubstituted phenylthio group, and A optionally forms a ring structure with the nitrogen atom to which it is directly bonded and the phenyl group directly bonded to the nitrogen atom.

[0072] It is suitable as a hole transport material or a blue light emitting material containing an asymmetric 1,2-bis(diarylamino)benzene represented by the above general formula (1).

[0073] Examples of the linear, branched or cyclic alkyl group having 3 to 6 carbon atoms include n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0074] Examples of the alkoxy group having 3 to 6 carbon atoms include n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy.

[0075] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0076] In addition, 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 not contain heteroatoms such as nitrogen atoms, oxygen atoms, and sulfur atoms, or may contain heteroatoms such as nitrogen atoms, oxygen atoms, and sulfur atoms.

[0077] Examples of the aromatic fused polycyclic group include carbon fused polycyclic groups such as naphthyl and fluorenyl; and fused heterocyclic groups such as quinolyl, indolyl, benzimidazolyl, phenoxazinyl, phenothiazinyl, 9-dimethylacridinyl, iminobistilbene, 1,12-iminoperyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, and oxanthrenyl.

[0078] In addition, R 1 ~R 4 All of them may be the same substituent or hydrogen atom, or may be different substituents.

[0079] If some specific examples of the asymmetric bis(1,2-diarylamino)benzenes represented by the above general formula (1) are shown, the following compounds can be listed: (1-1) to (1-16), (2-1) to (2-18), (3-1) to (3-16), (3-1) to (3-16), (4-1) to (4-7), (5-1) to (5-2), (6-1) to (6-6), (7-1) to (7-4), (8-1) to (8-4), (9-1) to (9-3), (10-1) to (10-2), etc.

[0080] (1-1)~(1-16)

[0081]

[0082] (2-1)~(2-18)

[0083]

[0084] (3-1)~(3-16

[0085]

[0086] (4-1)~(4-7)

[0087]

[0088] (5-1)~(5-2)

[0089]

[0090] (6-1)~(6-6)

[0091] (7-1)~(7-4)

[0092]

[0093] (8-1)~(8-4)

[0094]

[0095] (9-1)~(9-3)

[0096]

[0097] (10-1)~(10-2)

[0098]

[0099] 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))

[0100]

[0101] F-1~F-18

[0102] Regarding the following general formula (F), compounds F-1 to F-18 of compound Nos. are also exemplified. These compounds define the substituent R of the following general formula (F): 1 ~R 3 .

[0103] (F-1 is the same as (3-1), F-2 is the same as (3-2), F-17 is the same as OPDA-7,)

[0104]

[0105]

[0106]

[0107]

[0108] Among the above compounds, 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 below. In addition, materials having the structures of OPDA-1 to OPDA-11 as skeletons are also preferably used as hole transport materials, blue light emitting materials, and materials for organic EL.

[0109] In addition, regarding the above compounds (1-1) to (10-2), HOMO-LUMO energy levels, namely, EHOMO, ELUMO, Eg, ET, ETO, λ-, λ+, IP, and EA were calculated and the results are shown in Tables 1 to 5 below.

[0110] The calculation method is as follows.

[0111] All calculations were performed using the Gaussian 16 program (Revision C01) using the B3LYP density functional method in combination with the 6-31G* basis function. The triplet energy is calculated as the difference (ET) between the electron energies of the optimized geometry (geometry) of the triplet state and the singlet state. It is known that the triplet energy (ET0) calculated including the zero-point energy correction is in better agreement with the experimental value, so they are also calculated and compared. The reorganization energy is the difference in the change in the electron energy associated with the change in the geometry of the molecular structure between the charge transfer state and the neutral state. The internal reorganization energy (l) is the energy required to change the geometry of the two molecules in order to promote the movement of electrons / holes between the two molecules. The calculation is performed using the adiabatic potential energy surface using the following formula.

[0112] λ=λ1+λ2=(Echarged state in neutral geometry-Echarged state incharged geometry)+(Eneutral state in charged geometry-Eneutral state inneutral geometry)

[0113] (Wherein, Echarged state in neutral geometry represents the electron energy in the charged state obtained for the neutral molecular structure, Echarged state in charged geometry represents the electron energy in the charged state obtained for the molecular structure in the charged state, Eneutral state in charged geometry represents the electron energy in the neutral state obtained for the molecular structure in the charged state, and Eneutral state in neutral geometry represents the electron energy in the charged state obtained for the molecular structure in the neutral state.)

[0114] In the case of the internal reorganization energy of hole transport (λ+) and electron transport (λ-), the charged states are cations and anions, respectively. The energy required for the structural changes of the surrounding molecules to surround the two molecules involved in the charge transfer is called the external reorganization energy, which is considered to be small and is not considered in the current calculation. Furthermore, the adiabatic ionization potential (IP) and electron affinity (EA) are also calculated. In this calculation, the energy of the optimized charged state is used and the calculation is performed using the following formula.

[0115] IP=Ecationic state geometry-Eneutral state geometry

[0116] EA=Eanionic state geometry-Eneutral state geometry

[0117] (Wherein, IP represents ionization potential (adiabatic), EA represents electron affinity (adiabatic), Ecationic state geometry represents cationic state molecular structure, Eneutral state geometry represents neutral state molecular structure, Eanionic state geometry represents anionic state molecular structure, and Eneutral state geometry represents neutral state molecular structure.)

[0118] In addition, citations are given below.

[0119] (Revision C01)Gaussian 16,Revision C.01,Frisch,MJTrucks,GWSchlegel,HBScuseria,GERobb,MACheeseman,JRScalmani,GBarone,VPetersson,GA Nakatsuji,H.Li,X.Caricato,M.Marenich,AVBloino,J.Janesko,BGGomperts,R.Mennucci,B.Hratchian,HP / Or tiz,JVIzmaylov,AFSonnenberg,JLWilliams-Young,DDing,FLipparini,FEgidi,FGoings,JPeng,BPetro ne,A.Henderson,T.Ranasinghe,D.Zakrzewski,VGGao,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. and Throssell, K. Montgom ery,JA,Jr.Peralta,JEOgliaro,F.Bearpark,MJHeyd,JJBrothers,ENKudin,KNStaroverov,VNKeith,TA,Kobayas hi,R.Normand,J.Raghavachari,K.Rendell,APBurant,JC.Iyengar,SS.Tomasi,J.Cossi,M.Millam,JM.Klene,M.A damo,C.Cammi,R.Ochterski,JWMartin,RLMorokuma,K.Farkas,O.Foresman,JBFox,DJGaussian,Inc.,Wallingford CT,2016.

[0120] (B3LYP functional)Becke,ADJChem.Phys.1993,98,5648-5652.

[0121] (6-31G*basis sets) (a) Ditchfie, R.; Hehre, WJ; Pople, JAJChem.Phys.1971, 54, 724-728. (b) Hehre, WJ; Ditchfie, R.; Pople, JAJChem.Phys.1972, 56, 2257-2261. (c) Hariharan, PC; 1973, 28, 213-222. (d) Francl, MM; Pietro, WJ; Hehre, WJ; Binkley, JS; Gordon, MS; Defrees, DJ; Pople, JAJChem. Phys. 1982, 77, 3654-3665.

[0122] (formula: l) (a) Yamada, T.; Sato, T.; Tanaka, K.; Kaji, H.Organic Electronics2010,11,255-265.(b)Sakanoue,K.;Motoda,M.;Sugimoto,M.;Sakaki,SJPhys.Chem.A1999,103,5551-5556.(c)Malagoli,M.;Bredas,JLChem.Phys.Lett.2000,327,13-17.

[0123] In the above calculations, the following defined parameters are calculated and summarized in Tables 1 to 5.

[0124] Procedure for calculation of different photophysical properties

[0125] Eg=ELUMO-EHOMO

[0126] ET=ETriplet-Esinglet

[0127] ET0=ETriplet(with ZPE)-ESinglet(with ZPE)

[0128] λ=(Echarged state in neutral geometry-Eneutral state geometry)+(Eneutral state in charged geometry-Echarged state geometry)

[0129] (In the formula, λ (Internal Reorganisation energy) is the internal reorganization energy, and the definitions of other energies are the same as the above calculation method.)

[0130] Or, in the case of λ=λ1+λ2,

[0131] λ1=Echarged state in neutral geometry-Echarged state in charged geometry

[0132] λ2=Eneutral state in charged geometry-Eneutral state in neutral geometry

[0133] (Where l1(e) and l1(h) are the l1 values ​​for electron transport and hole transport, respectively.)

[0134] λ+ is the internal reorganization energy for hole transport, and the charged state is a cation.

[0135] λ- is the internal reorganization energy for electron transport, and the charged state is anion.

[0136] IP is the ionization potential (adiabatic), which is calculated based on Ecationic geometry-Eneutral state geometry.

[0137] EA is the electron affinity (adiabatic), which is calculated according to Eanionic geometry-Eneutral state geometry.

[0138] According to the calculation results, it can be judged that the asymmetric 1,2-bis(diarylamino)benzenes of the general formula (1) of the present invention have appropriate HOMO-LUMO energy levels, that is, have appropriate EHOMO, ELUMO, Eg, ET, ET0, λ-, λ+, IP, EA, and can be used as hole transport materials (hole transport host materials and / or hole transport materials) and blue light-emitting materials.

[0139] [Table 1]

[0140]

[0141] [Table 2]

[0142]

[0143] [Table 3]

[0144]

[0145] [Table 4]

[0146]

[0147] [Table 5]

[0148]

[0149] It should be noted that, for example, in an organic EL element, other factors such as compatibility with other layers may sometimes have a significant impact. Therefore, it is not possible to determine which of the above-mentioned compounds is suitable for hole transport materials or blue light-emitting materials. However, in the case of hole transport host materials, the compound is preferably a compound that satisfies one or more of the conditions of a small HOMO, a large Eg, a large ET0, and a small λ+.

[0150] From the viewpoint of easily satisfying the above conditions, usually, in the case of a hole transporting host material, in the above general formula (1), A is preferably an aryl group substituted by a substituent comprising 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 by a substituent comprising a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group or a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group. In addition, it is further preferred that the nitrogen atom of the substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group is directly bonded to the aryl group, and the substituent is further preferably a carbazolyl group in which the nitrogen atom is directly bonded to the aryl group. In addition, usually, in the case of a hole transporting host material, A in the above general formula (1) is preferably an aryl group directly bonded to a nitrogen atom at the para or meta position.

[0151] In addition, from the viewpoint of easily satisfying the above conditions, in general, in the case of a hole transporting host material, in the above general formula (1), R 1 ~R 4 Preferably, it is an electron withdrawing group. 1 , R 3 , R 4 It should be noted that by appropriately changing the R 1 ~R 4 Type and / or R 1 ~R 4 By changing the number of substitutions with groups other than hydrogen atoms in , it is possible to obtain an asymmetric bis(1,2-diarylamino)benzene that easily satisfies the above conditions in the same manner as changing A.

[0152] The bis(1,2-diarylamino)benzenes represented by the general formula (1) have an asymmetric structure, so the crystallinity of the molecule decreases and the amorphous property increases. Therefore, it is considered that they 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), (9-1) to (9-3), OPDA-1 to OPDA-11, and F-1 to F-18 are considered to have particularly high amorphous properties and particularly high glass transition temperatures (Tg).

[0153] As an intermediate compound for producing the asymmetric bis(1,2-diarylamino)benzenes represented by the above general formula (1), there are o-phenylenediamines, which are represented by the general formula (2) in the present invention.

[0154]

[0155] If some specific examples of the asymmetric bis(1,2-diarylamino)benzenes represented by the above general formula (2) are shown, the following compounds can be listed: (1-1a) to (1-16a), (2-1a) to (2-18a), (3-1a) to (3-16a), (3-1a) to (3-16a), (4-1a) to (4-7a), (5-1a) to (5-2a), (6-1a) to (6-6a), (7-1a) to (7-4a), (8-1a) to (8-4a), (9-1a) to (9-3a), (10-1a) to (10-2a), OPDA-1a to OPDA-11a, etc. 〔1-1a) to (1-16a)

[0156]

[0157] (2-1a)~(2-18a)

[0158] (3-1a)~(3-16a)

[0159]

[0160] (4-1a)~(4-7a)

[0161]

[0162] (5-1a)~(5-2a)

[0163]

[0164] (6-1a)~(6-6a)

[0165]

[0166] (7-1a)~(7-4a)

[0167]

[0168] (8-1a)~(8-4a)

[0169]

[0170] OPDA-1a~OPDA-11a

[0171]

[0172] The diarylamines represented by the general formula (3) may be the same as or different from the diarylamines represented by the general formula (4).

[0173] In the diaryl magnesium amides represented by the general formula (5) and the general formula (6), X represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0174] In the halogen compound represented by the above general formula (7), in the formula (7), X represents a halogen atom. Examples of the halogen atom include: a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In addition, if a part of the specific examples is shown, the following structures can be listed. In the following formula, X represents a halogen atom. Examples of the halogen atom include: a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. As shown in the following formula, in the above general formula (7), n (the number substituted by X) represents an integer of 1 to 3.

[0175]

[0176] If some specific examples of the halogen compound represented by the above general formula (7) are shown, the following compounds can be listed: (1-1b) to (1-16b), (2-1b) to (2-18b), (3-1b) to (3-16b), (3-1b) to (3-16b), (4-1b) to (4-7b), (5-1b) to (5-2b), (6-1b) to (6-6b), (7-1b) to (7-4b), (8-1b) to (8-4b), (9-1b) to (9-3b), (10-1b) to (10-2b), OPDA-1b to OPDA-11b.

[0177] (1-1b)~(1-16b)

[0178]

[0179] (2-1b)~(2-18b)

[0180]

[0181] (3-1b)~(3-16b)

[0182]

[0183] (4-1b)~(4-7b)

[0184]

[0185] (5-1b)~(5-2b)

[0186]

[0187] (6-1b)~(6-6b)

[0188]

[0189] (7-1b)~(7-4b)

[0190]

[0191] (8-1b)~(8-4b)

[0192]

[0193] OPDA-1b~OPDA-11b

[0194]

[0195] As in the case of the general formula (1), in the above formula (7), A is preferably an aryl group substituted with a substituent comprising 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 comprising a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group or a substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group. In addition, the nitrogen atom of the substituted or unsubstituted nitrogen-containing fused polycyclic aromatic group is further preferably directly bonded to the aryl group, and the substituent is further preferably a carbazolyl group in which the nitrogen atom is directly bonded to the aryl group. In addition, A in the above general formula (7) is preferably an aryl group to which a nitrogen atom is directly bonded at the para or meta position relative to X (halogen).

[0196] <Asymmetric 1,2-bis(diarylamino)benzenes>

[0197] The asymmetric 1,2-bis(diarylamino)benzenes represented by the general formula (1) are not particularly limited and can be produced according to the steps shown below.

[0198]

[0199] That is, the asymmetric 1,2-bis(diarylamino)benzenes of the present invention can be produced through step 1 (OPDA synthesis step) and step 2 (synthesis step of target products such as hole transport materials and blue light emitting materials).

[0200] (Step 1: OPDA synthesis)

[0201] The diaryl magnesium amides represented by the general formula (5) and the general formula (6) can be produced by reacting diarylamines represented by the general formula (3) and the general formula (4) with a Grignard reagent.

[0202] The Grignard reagent may be an aliphatic Grignard reagent or an aromatic Grignard reagent, for example, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, isopropylmagnesium bromide, isopropylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium chloride, etc., and the amount used is preferably 1.0 to 100 molar equivalents, more preferably 1.1 to 10.0 molar equivalents, relative to the diarylamines (3) or the diarylamines (4).

[0203] In addition, Grignard reagents can also be prepared from alkyl lithium and magnesium salts.

[0204] Examples of the organic solvent used in the reaction include ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and dioxane. The solvent may be used alone or in combination of two or more.

[0205] The amount of the solvent used is preferably 1 to 1000 parts by weight based on the diarylamines (3) or (4).

[0206] The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon, and may be carried out at normal pressure or under pressure. The reaction temperature is preferably in the range of -50°C to 300°C, more preferably in the range of 0°C to 150°C.

[0207] The reaction time varies depending on the type of substrate and the reaction temperature and is not particularly limited, but the reaction can usually be completed within a range of 1 hour to 48 hours.

[0208] After the reaction is completed, the solvent can be removed under vacuum or normal pressure, or the product can be directly used in the next step 2.

[0209] The o-phenylenediamines represented by the general formula (2) can be produced by reacting a transition metal catalyst and an oxidizing agent with a diaryl magnesium amide (5) represented by the general formula (5) and a diaryl magnesium amide (6) represented by the general formula (6).

[0210] The amount of the diaryl magnesium amide (5) represented by the general formula (5) used is preferably 1.0 to 10 molar equivalents, more preferably 1.0 to 2.0 molar equivalents, based on the diaryl magnesium amide (6) represented by the general formula (6).

[0211] As the transition metal catalyst, any iron compound, palladium compound, nickel compound, cobalt compound or copper compound may be used, and examples thereof 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, trichlorobis(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, iron acetylacetonate, etc. Among them, iron (II) chloride, iron (III) chloride, iron (II) acetate and iron (II) fluoride are more preferred in order to further improve the reaction yield.

[0212] The amount of the transition metal catalyst added is preferably in the range of 0.01 mol% to 100 mol% relative to the diaryl magnesium amide (5) or the diaryl magnesium amide (6), and more preferably in the range of 0.05 mol% to 5.0 mol%.

[0213] Examples of the oxidizing agent include 1,2-diiodoethane, 1,2-dibromoethane, 1,2-dichloroethane, 1-chloro-2-iodoethane, 1-bromo-2-chloroethane, and 1-iodo-2-bromoethane. Among these, 1,2-dichloroethane and 1,2-dibromoethane are preferred, and more preferred.

[0214] The amount of the oxidant added is preferably in the range of 0.5 to 10 molar equivalents, more preferably in the range of 1 to 5 molar equivalents, based on the diaryl magnesium amide (5) or the diaryl magnesium amide (6).

[0215] The organic solvent used in the reaction may be any of polar solvents and non-polar solvents, for example, aromatic hydrocarbons such as benzene, toluene, and xylene; ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and dioxane. In addition, the solvent may be used alone or in combination of two or more.

[0216] The amount of the solvent used is preferably 1 to 1000 parts by weight based on the diaryl magnesium amide (5) or the diaryl magnesium amide (6).

[0217] The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon, and may be carried out at 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.

[0218] The reaction time varies depending on the type of substrate and the reaction temperature and is not particularly limited, but the reaction can usually be completed within a range of 1 hour to 48 hours.

[0219] After 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 or alkaline aqueous solution, and then separated and purified by a general method such as column chromatography and crystallization.

[0220] Step 2 (step for synthesizing the target product)

[0221] The bis(1,2-diarylamino)benzenes represented by the general formula (1) can be produced by reacting o-phenylenediamines represented by the general formula (2) with a halogen compound represented by the general formula (7) in the presence of a transition metal catalyst.

[0222] As the transition metal compound constituting the transition metal catalyst, any palladium compound, nickel compound, copper compound or iron compound may be used, 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, tetraaminodichloropalladium, dichloro(cycloocta-1,5-diene)palladium, trifluoroacetylpalladium, tris(dibenzylideneacetone)dipalladium, tris(dibenzylideneacetone)dipalladium chloroform complex, tetrakis(triphenylphosphine)palladium, nickel acetylacetonate, nickel chloride, copper acetylacetonate, copper chloride, iron acetylacetonate, iron chloride, etc. In addition, the transition metal compound may be used in combination with various ligands, and the method of adding the ligand may be a method of reacting the transition metal compound and the ligand in advance outside the system and then adding the ligand, or a method of adding the transition metal compound and the ligand to the reaction system and preparing the ligand in the system.

[0223] The amount of the transition metal compound added is preferably in the range of 0.01 to 100 mol % based on 1 mol of o-phenylenediamine represented by the general formula (2), and more preferably in the range of 0.1 to 5 mol % in order to further increase the reaction selectivity.

[0224] As the ligand, any ligand that coordinates with the transition metal compound may be used, and examples thereof include phosphine compounds, nitrogen compounds, olefin compounds, and the like. Examples thereof include alkyl phosphines such as triethylphosphine, tricyclohexylphosphine, and tri(tert-butyl)phosphine, aryl phosphines such as triphenylphosphine, 1,1'-bis(diphenylphosphino)ferrocene [dppf], and 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene [XANTphos], and 1,5-cyclooctadiene [COD], 2,2'-bipyridine, and the like. Among them, tricyclohexylphosphine or tri(tert-butyl)phosphine is preferred in order to increase the reaction selectivity.

[0225] The amount of the ligand added is preferably in the range of 0.1-100 times the mole of the transition metal compound, and more preferably in the range of 1-10 times the mole in order to further increase the reaction selectivity.

[0226] The organic solvent used in the reaction may be any polar solvent or non-polar solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, etc.; ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, dioxane, etc.; hydrocarbon solvents such as hexane, heptane, pentane, octane, nonane, decane, etc.; acetonitrile, N,N-dimethylformamide (DMF), 1-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), hexamethylphosphoric acid triamide (HMPA), triethyl phosphate (TEP), trimethyl phosphate (TMP), acetic acid, etc. In addition, the solvent may be used alone or in combination of two or more.

[0227] The amount of the solvent used is preferably 1 part by weight to 10,000 parts by weight based on 100 parts by weight of the o-phenylenediamine represented by the general formula (2).

[0228] The base used in the reaction can be listed as: metal hydroxides, metal carbonates, metal phosphates, metal sulfates, metal alkoxides. For example, it can be listed as: 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. Among them, potassium hydroxide, potassium carbonate, tripotassium phosphate, sodium tert-butoxide are preferred. Their usage is preferably in the range of 1 to 50 moles relative to 1 mole of the halogen compound represented by the general formula (7). In order to further improve the reaction selectivity, the range of 1.5 to 5 times the mole is more preferred, and the base can be used alone or in combination of two or more.

[0229] The amount of the halogen compound (7) used is preferably in the range of 0.1 to 10 times the mole of 1 mole of o-phenylenediamine represented by the general formula (2), and more preferably in the range of 0.3 to 5 times the mole in order to further improve the reaction selectivity.

[0230] The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon, and may be carried out at 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.

[0231] The reaction time varies depending on the type of substrate and the reaction temperature and is not particularly limited, but the reaction can usually be completed within a range of 1 hour to 48 hours.

[0232] After 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 or alkaline aqueous solution, and then separated and purified by a general method such as column chromatography and crystallization.

[0233] Effects of the Invention

[0234] According to the present invention, the asymmetric bis(1,2-diarylamino)benzenes represented by the general formula (1) have an appropriate HOMO-LUMO energy level and can be used as organic EL device materials such as hole transport materials and blue light emitting materials.

[0235] According to the present invention, asymmetric bis(1,2-diarylamino)benzenes, which have been difficult to produce so far, can be efficiently produced. Furthermore, through this production method, various substituents can be easily introduced position-selectively, and molecules with energy levels suitable for organic EL element materials such as hole transport materials and blue light-emitting materials can be designed. BRIEF DESCRIPTION OF THE DRAWINGS

[0236] Figure 1 This is a diagram showing the HOMO-LUMO energy levels calculated from the absorption edge and oxidation potential of the solution for the material used in the present invention and the conventional material. The horizontal axis (X axis) is the material used for energy level calculation, and the vertical axis (Y axis) is the energy level (unit: eV).

[0237] Figure 2 This is a diagram showing the stacked structure used for evaluating the device. In the OPDA layer, m-CBP as a control and OPDA-3 and OPDA-4 of the present invention were evaluated. For reference, the data shown in the paper were also compared.

[0238] Figure 3 The data obtained by evaluating the device is a graph showing the voltage-current characteristics. The horizontal axis (X-axis) is voltage (Voltage, unit: V (volts)) and the vertical axis (Y-axis) is current density (Current Density, unit: mA / cm 2 ) In the figure, the materials used are m-CBP as a control and OPDA-3 and OPDA-4 of the present invention.

[0239] Figure 4 This is data obtained from evaluating the element, and is a graph showing the EL (electroluminescence) spectrum, with the horizontal axis (X axis) being the wavelength (wavelength, in nm) and the vertical axis (Y axis) being the EL intensity (normalized). In the graph, the materials used are m-CBP as a control and OPDA-3 and OPDA-4 of the present invention. DETAILED DESCRIPTION

[0240] Example

[0241] Hereinafter, the present invention will be described in further detail using Examples. However, these Examples are intended to illustrate the outline of the present invention, and the present invention is not limited to these Examples.

[0242] The target compound was identified by 1 H NMR ( 1 H NMR spectroscopy), 13 C NMR ( 13 C NMR spectroscopy), 19 F NMR ( 19 F nuclear magnetic resonance spectrum), MS (mass spectrometry), IR analysis, HRMS analysis, melting point analysis and elemental analysis. Purity and isomer ratio were determined by GC analysis, and yield was determined by NMR analysis using dibromoethane as an internal standard. In addition, for the purification of the target product, a recovery preparation GPC was used as required. The apparatus used is as follows.

[0243] Nuclear magnetic resonance spectrum: JEOL ECS-400NR, Bruker AVANCE III 800US Plus.

[0244] IR device: PerkinElmer Spectrum One FT-IR Spectrometer.

[0245] HR-MS device: JEOL JMS-700 mass spectrometer.

[0246] Melting point determination apparatus: Yanaco MP-500D.

[0247] GC device: Shimadzu GC-2010 (FID).

[0248] Column: ZB-1MS (10 m×0.10 mm I.D. df: 0.1 μm) (manufactured by Phenomenex).

[0249] Detector: Hydrogen flame ionization detector.

[0250] Recycling preparation GPC: Japan Analytical Industry LC-9204 instrument.

[0251] Column: JAIGEL-1H-40 / JAIGEL-2H-40.

[0252] Example 1 Synthesis of OPDA (1-1a)

[0253]

[0254] Under argon atmosphere, diphenylamine (18.0 g, 110 mmol) and Et 2 O (108 mL) was added to a 500 mL flask, and EtMgBr (39.0 mL, 3.0 M in Et 2 O, 121 mmol), and heated with stirring at 40°C for 2 hours.

[0255] Afterwards, Et was removed under reduced pressure. 2 O, add FeCl 2 (0.67 g, 5.5 mmol) and dibromoethane (18.0 mL, 220 mmol), Bu 2 O 108 mL, heated and stirred at 80°C for 24 hours, and then 108 mL of 1N HCl was added at room temperature, extracted with AcOEt 108 mL x 3, and washed with brine 108 mL.

[0256] MgSO 4 The obtained organic layer was added, filtered using 90 g of Florisil, and concentrated using an evaporator. 53 mL of EtOH was added to 22 g of the obtained crude product, heated and dissolved, and stirred at room temperature for 1 hour, and the precipitate was filtered to obtain a beige powder.

[0257] Since this powder contained a small amount of impurities, 48 ​​mL of EtOH was added again to dissolve it by heating. 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 with a yield of 83%.

[0258] The analysis results are as follows.

[0259] 1 H NMR (DMSO-d 6 392MHz) δ6.76-6.79 (m, 1H), 6.91-6.97 (m, 9H), 7.08-7.29 (m, 10H)

[0260] Example 2 Synthesis of OPDA (2-8a)

[0261]

[0262] Under argon atmosphere, diarylamine (14.0 g, 70.8 mmol) and Bu 2 O (94 mL) was added to a 500 mL flask, and BuMgBr (100 mL, 0.779 M in Bu2 O, 77.9 mmol), and heated with stirring at 100°C for 1 hour.

[0263] Then, FeCl was added at room temperature (25°C). 2 (0.45 g, 3.54 mmol) and dibromoethane (26.6 g, 142 mmol) were heated and stirred at 80° C. for 24 hours. 1N HCl (200 mL) was added to the reaction solution, followed by celite filtration and extraction with AcOEt 100 mL×3.

[0264] The obtained organic layer was filtered with filter paper and concentrated with an evaporator to obtain 15.6 g of crude product. 500 g of silica gel and hexane were used as developing solvents and silica gel column purification was performed to obtain 8.97 g of OPDA with a GC purity of >99% with a yield of 64%, and 4.80 g of OPDA with a GC purity of 92% with a yield of 34%.

[0265] The analysis results are as follows.

[0266] 1 H NMR (CDCl 3 , 392MHz) δ2.20 (s, 3H), 2.24 (s, 3H), 2.26 (s, 6H), 5.66 (s, 1H), 6.78 (d, 2 H, J=8.2Hz), 6.89-6.94 (m, 6H), 6.97-7.06 (m, 6H), 7.16 (d, 1H, J=8.6Hz)

[0267] Example 3 Synthesis of OPDA-biphenyl

[0268]

[0269] Under argon atmosphere, diarylamine (5.00 g, 15.6 mmol) and Et 2 O (50 mL) was added to a 300 mL flask, and EtMgBr (5.73 mL, 3.0 M in Et 2 O, 17.2 mmol), and heated and stirred at 40°C for 2 hours. Then, Et 2 O, add FeCl 2 (98.8 mg, 0.78 mmol), dibromoethane (5.8 g, 31.2 mmol), Bu 2 O (50 mL), heated and stirred at 80°C for 12 hours, and then heated and stirred at 140°C for 24 hours. 1N HCl (50 mL) was added at room temperature, and extracted with AcOEt (30 mL x 3). MgSO was added to the obtained organic layer.4 The residue was filtered through filter paper and concentrated by an evaporator. 4.21 g of the crude product was purified by silica gel column to obtain 0.78 g of OPDA-biphenyl at a yield of <16%.

[0270] The analysis results are as follows.

[0271] 1 HNMR (CDCl 3 , 392MHz) δ5.99 (s, 1H), 7.01-7.03 (m, 2H), 7.21-7.31 (m, 7H), 7.36-7.56 (m, 26H)

[0272] Example 4 Synthesis of 4-Br-N,N-dimethylaniline substituted compounds

[0273]

[0274] 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) 2 (62.9 mg, 0.28 mmol), tBu 3 P (228 mg, 1.12 mmol), NaOtBu (2.67 g, 27.8 mmol), and toluene (70 mL) were added to a 300 mL flask, dissolved at room temperature (25°C), and heated and stirred at 120°C for 4 hours. 1N HCl (50 mL) was added to the reaction solution at room temperature (25°C), extracted with AcOEt (20 mL x 3), and concentrated with an evaporator. 5.63 g of the target product was obtained with a yield of <89% by reprecipitation using a toluene / hexane solvent system.

[0275] The analysis results are as follows.

[0276] 1 H NMR (CDCl 3 , 392MHz) δ3.02 (s, 6H), 6.70 (d, 4H, J = 7.8Hz), 6.76 (t, 4H, J = 9.6Hz), 6.86 (t, 2H, J = 7 .4Hz), 6.94-7.01(m, 1H), 7.08(t, 4H, J=7.8Hz), 7.14-7.15(m, 6H), 7.32-7.44(m, 2H)

[0277] GC purity 100.0%

[0278] Example 5 Synthesis of 4-Br-N,N-dimethylaniline substituted compounds

[0279]

[0280] 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), tBu 3 P (186 mg, 0.92 mmol), NaOtBu (2.23 g, 23.2 mmol), and toluene (58 mL) were added to a 300 mL flask, dissolved at room temperature (25°C), and then heated and stirred at 120°C for 6 hours. 1N HCl (50 mL) was added to the reaction solution at room temperature (25°C), and then extracted with AcOEt (50 mL x 3). MgSO 4 The obtained organic layer was dried, filtered with Florisil, and concentrated with an evaporator to obtain 6.71 g of crude product. 3.00 g of crude product was tried to be purified by GPC (toluene), but it is believed that the peak tailing caused oxidation. The remaining 3.71 g of crude product was reprecipitated using a toluene / hexane solvent system to obtain 2.88 g of the target product with a GC purity of >99% at a yield of 49%.

[0281] The analysis results are as follows.

[0282] 1 H NMR (CDCl 3 , 392MHz) δ2.22 (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 = 8.8Hz), 6.73 (d, 2H, J = 9.0Hz), 6.87-6.98 (m, 9H), 7.32 (d, 2H, J = 8.6Hz)

[0283] GC purity 100.0%

[0284] Example 6 Synthesis of 4-Br-N,N-dimethylaniline Substituted Compounds

[0285]

[0286] 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), tBu 3P (19.6 mg, 0.096 mmol), NaOtBu (177 mg, 1.83 mmol), and toluene (12 mL) were added to a 100 mL flask, dissolved at room temperature (25°C), and then heated and stirred at 120°C for 4 hours. 1N HCl (30 mL) was added to the reaction solution at room temperature (25°C), and then CHCl 3 (20mL x 3) extraction, using MgSO 4 The residue was dried, filtered through filter paper, and concentrated using an evaporator. Reprecipitation using a toluene / hexane solvent system gave 885 mg of a crude product at a yield of <95%.

[0287] The analysis results are as follows.

[0288] 1 H NMR (CDCl 3 , 392MHz) δ3.00 (s, 6H), 6.91-6.96 (m, 4H), 7.16-7.46 (m, 18H), 7.48-7.55 (m, 8H)

[0289] Example 7 Synthesis of 3-Br-9-phenyl-9H-carbazole substituted compounds

[0290]

[0291] 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), tBu 3 P (140 mg, 0.692 mmol), NaOtBu (1.25 g, 12.99 mmol), and xylene (43 mL) were added to a 100 mL flask, dissolved at room temperature (25°C), and then heated and stirred at 130°C for 14 hours. Pd(OAc) was further added at room temperature (25°C). 2 (141 mg, 0.63 mmol) and tBu 3 P (141 mg, 0.70 mmol) was heated and stirred at 130°C for 5 hours. 1N HCl (50 mL) was added to the reaction solution at room temperature (25°C), extracted with AcOEt (30 mL x 3), and concentrated by an evaporator. 3.67 g was obtained by reprecipitation using a toluene / hexane solvent system with a yield of <73%.

[0292] The analysis results are as follows.

[0293] 1H NMR (CDCl 3 , 392MHz) δ6.77-6.90 (m, 5H), 7.07-7.61 (m, 25H), 7.91 (d, 1H, J=7.6Hz)

[0294] GC purity 94.3%

[0295] Example 8 Synthesis of OPDA-1

[0296]

[0297] OPDA (336 mg, 1 mmol), 2-bromo-9-phenylcarbazole (322 mg, 1 mmol), Pd(OAc) (30 mg, 1 mmol) (40 mg, 2 mmol) (50 mg, 1 mmol) (60 mg, 2 mmol) (70 mg, 2 ...1 mmol) (70 mg 2 (4.5 mg, 0.02 mmol), tBu 3 P (16.2 mg, 0.08 mmol) and NaOtBu (144 mg, 1.5 mmol) in mesitylene (2.7 mL) were stirred for 4 hours. The reaction was quenched with 1 M HCl at room temperature (stop the reaction) and extracted with ethyl acetate. The organic layer was washed with brine and MgSO 4 The mixture was dried and filtered through a pad of Florisil. The solvent was removed under reduced pressure to obtain a crude product. The crude product was recrystallized from EtOH and toluene to obtain the target product OPDA-1 (0.43 g, 74% yield) as a white solid.

[0298] pass 1 The target product was analyzed by H-NMR and the following results were obtained.

[0299] 1 H NMR (DMSO-d 6 392MHz) 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), Anal.Calcd for C 42 H 31 N3 C, 87.32; H, 5.41; N, 7.27. Found C, 87.42; H, 5.52; N, 7.16.

[0300] Example 9 Synthesis of OPDA-2

[0301]

[0302] OPDA (336 mg, 1 mmol), 3-bromo-9-phenylcarbazole (322 mg, 1 mmol), Pd(OAc) (30 mg, 1 mmol) (40 mg, 2 mmol) (50 mg, 1 mmol) (60 mg, 2 mmol) (7 ... 2 (4.5 mg, 0.02 mmol), tBu 3 P (16.2 mg, 0.08 mmol) and NaOtBu (144 mg, 1.5 mmol) in mesitylene (5 mL) were stirred for 4 hours. The reaction was quenched with 1M HCl at room temperature (to stop the reaction) and extracted with 4 ml of ethyl acetate. Filtered through a pad of 1.5 g of fluorisil. The solvent was removed under reduced pressure (hexane: ethyl acetate = 30: 1) to obtain a 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.

[0303] pass 1 The target product was analyzed by H-NMR and the following results were obtained.

[0304] 1 H NMR (CDCl 3 , 392MHz) 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, 1.3Hz), 8.1 (d, 2H, J=7.6Hz); Anal.Calcd for C 42 H 31 N 3 C, 87.32; H, 5.41; N, 7.27. Found C, 87.09; H, 5.57; N, 7.09.

[0305] Example 10 Synthesis of OPDA-3

[0306]

[0307] OPDA (336 mg, 1 mmol), 2-bromo-9-phenylcarbazole (322 mg, 1 mmol), Pd(OAc) (30 mg, 1 mmol) (40 mg, 2 mmol) (50 mg, 1 mmol) (60 mg, 2 mmol) (70 mg, 2 ...1 mmol) (70 mg 2 (4.5 mg, 0.02 mmol), tBu 3 P (16.2 mg, 0.08 mmol) and NaOtBu (144 mg, 1.5 mmol) in mesitylene (2.5 mL) were stirred for 5.5 hours. The reaction was quenched with 1.5 ml of 1M HCl at room temperature (to stop the reaction) and extracted with 10 ml of ethyl acetate. Filtered through a pad of 1.5 g of fluorisil. The solvent was removed under reduced pressure to obtain a 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.

[0308] pass 1 The target product was analyzed by H-NMR and the following results were obtained.

[0309] 1 H NMR (DMSO-d 6 , 392MHz) δ6.59 (s, 1H), 6.63 (d, 4H, J=8.0Hz), 6.82 (m, 5H), 6.92 (dd, 1H, J=7.6, 7.6Hz), 6 .99-7.09(m, 6H), 7.16-7.26(m, 9H), 7.35-7.43(m, 3H), 8.19(d, 2H, J=7.6Hz); Anal.Calcd for C 42 H 31 N 3 C, 87.32; H, 5.41; N, 7.27. Found C, 87.53; H, 5.48; N, 7.48.

[0310] Example 11 Synthesis of Me-OPDA-4 (methyl substituted compound)

[0311]

[0312] 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), tBu 3P (16.2 mg) and NaOtBu (144 mg) were added to the reaction vessel, dissolved at room temperature (25°C), and 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 mLx2), passed into 1.34 g of Florisil (60-100 mesh), washed with AcOEt (2 mL) and evaporated. It was a brown oil. It 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.

[0313] pass 1 The target product was analyzed by H-NMR and the following results were obtained.

[0314] 1 H NMR (DMSO-d 6 , 392MHz) δ2.02 (s, 6H), 2.14 (s, 3H), 2.19 (s, 3H), 6.46 (d, J = 8.5Hz, 4H), 6.64 (d, J = 8.1Hz, 4H), 6.74-6.77 (m, 3H) , 6.95-7.02 (m, 3H), 7.1 (d, J=8.5Hz, 2H), 7.27-7.31 (m, 6H), 7.39-7.47 (m, 8H), 8.23 ​​(d, J=8.1Hz, 4H); Anal.Calcd for C 58 H 46 N 4 C, 87.19; H, 5.80; N, 7.01. Found C, 87.25; H, 5.88; N, 6.75.

[0315] Example 12 Synthesis of F-OPDA-4 (fluorine-substituted compound)

[0316]

[0317] Under 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), tBu 3P (144.2 mg, 1.50 mmol), NaOtBu (144 mg, 1.5 mmol), and mesitylene (5.0 ml) were added to the reaction vessel and dissolved at room temperature (25°C), and 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 MgSO 4 After drying, the product was purified by column chromatography to obtain 467 mg of the target product (F-OPDA-4). The yield was 57.3%. The target product was a light brown solid.

[0318] pass 1 The target product was analyzed by H-NMR and the following results were obtained.

[0319] 1 H NMR (DMSO-d 6 , 392MHz) δ6.64-6.68 (m, 3H), 6.71-6.78 (m, 5H), 7.09 (td, 1H, J=8.2, 2.7Hz), 7.11 (d , 3H, J=2.7Hz), 7.15-7.30 (m, 7H), 7.40-7.56 (m, 10H), 8.21-8.26 (m, 5H); Anal.Calcd for C 54 H 34 F 4 N 4 C, 79.59; H, 4.21; N, 6.88. Found C, 80.97; H, 4.39; N, 6.63.

[0320] Example 13 Synthesis of OPDA-5

[0321]

[0322] Under an argon atmosphere, OPDA (OPDA-5a) (336.44 mg, 1.00 mmol) and OPDA-5b (Br derivative) (322.21 mg, 1.00 mmol), Pd(OAc) 2 (4.5 mg, 0.02 mmol), tBu 3P (16.2 mg, 0.08 mmol), NaOtBu (144 mg, 1.5 mmol), mesitylene (5.0 ml) were added to a reaction vessel, dissolved at room temperature (25°C), and heated and stirred at 150°C for 8 hours. 1N-HCl was added at room temperature (25°C) to stop the reaction, and 1.5 g of Florisil was passed through, 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.

[0323] pass 1 The target product was analyzed by H-NMR and the following results were obtained.

[0324] 1 H NMR (DMSO-d 6 , 392MHz) 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 .3Hz), 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 C 48 H 35 N 3 C, 88.18; H, 5.39; N, 6.43. Found C, 88.33; H, 5.44; N, 6.23.

[0325] Example 14 Synthesis of OPDA-6

[0326]

[0327] Under an argon atmosphere, OPDA (OPDA-6a) (336.44 mg, 1.00 mmol) and OPDA-6b (Br derivative) (372.27 mg, 1.00 mmol), Pd(OAc) 2 (4.5 mg, 0.02 mmol), tBu 3 P (16.2 mg, 0.08 mmol), NaOtBu (144 mg, 1.5 mmol), and mesitylene (5.0 ml) were added to the reaction vessel, dissolved at room temperature (25°C), and then heated and stirred at 150°C for 7 hours. 1N-HCl was added at room temperature (25°C) to stop the reaction, and the mixture was extracted with AcOEt (20 mL x 3). The mixture was then precipitated with MgSO 4The mixture was dried and passed into 1.5 g of Florisil, and then recrystallized after solvent extraction to obtain 566.91 mg of the target product (OPDA-6). The yield was 90.3%. The target product was a white solid.

[0328] pass 1 H-NMR analysis of the target product gave the following results.

[0329] 1 H NMR (DMSO-d 6 , 392MHz) δ6.66 (d, 6H, J=7.6Hz), 6.76 (s, 3H), 6.84-6.88 (m, 4H), 7.08 (dd, 7H, J=14.7, 7.6Hz), 7.18-7.24 (m, 4H), 7.31 (dd, 2H, J=14.1 , 7.4Hz), 7.44 (s, 1H), 7.59 (dd, 1H, J=7.6, 7.6Hz), 7,70-7.79 (m, 2H), 8.07 (d, 1H, J=7.6Hz), 8.16 (dd, 2H, J=18.1, 8.2Hz); Anal.Calcd for C 46 H 33 N 3 C, 88.01; H, 5.30; N, 6.69. Found C, 87.77; H, 5.36; N, 6.55.

[0330] Example 15 Synthesis of OPDA-7

[0331]

[0332] 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), tBu 3 P (32.4 mg) and NaOtBu (290 mg) were added to the reaction vessel, dissolved at room temperature (25°C), and 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), washed with brine (Brine), and passed into 3.5 g of silica gel to evaporate it. It was a brown viscous state. It was solidified, filtered and dried to obtain 0.65 g of the target product (OPDA-7). The target product was a light beige powder.

[0333] pass 1The target product was analyzed by H-NMR and the following results were obtained.

[0334] 1 H NMR (DMSO-d 6 , 392MHz) δ6.23 (dd, J=8.1, 2.2Hz, 2H), 6.27-6.28 (m, 1H), 6.43 (d, J=7.6Hz, 4 H), 6.57-6.59(m, 8H), 6.76-6.89(m, 8H), 6.93-7.17(m, 19H); Anal.Calcdfor C 54 H 42 N 4 C, 86.83; H, 5.67; N, 7.50. Found C, 86.62; H, 5.67; N, 7.39.

[0335] Example 16 Synthesis of OPDA-8

[0336]

[0337] 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), tBu 3 P (32.4 mg) and NaOtBu (290 mg) were added to the reaction container, dissolved at room temperature (25°C), and then heated and stirred at 150°C for 6 hours. 1N HCl (3 mL) was added to the reaction solution at room temperature (25°C), extracted with AcOEt (5 mL, 3 mL), and washed with brine to obtain a crude product (0.8 g) of gray powder. The product was dissolved in CHCl 3 Then, 7.5 g of silica gel was passed to evaporate. It was green foamy. It was dissolved, filtered and dried to obtain 0.69 g of the target product (OPDA-8). The target product was light gray white powder.

[0338] pass 1 The target product was analyzed by H-NMR and the following results were obtained.

[0339] 1 H NMR (DMSO-d 6, 392MHz) 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 C 54 H 42 N 4 C, 86.83; H, 5.67; N, 7.50. Found C, 86.64; H, 5.72; N, 7.46.

[0340] Example 17 Synthesis of OPDA-9

[0341]

[0342] Under an argon atmosphere, OPDA (OPDA-9a) (472.88 mg, 1.50 mmol) and OPDA-9b (Br derivative) (401.1 mg, 1.00 mmol), Pd(OAc) 2 (9 mg, 0.04 mmol), tBu 3 P (32.4 mg, 0.16 mmol), NaOtBu (288.3 mg, 3 mmol), and mesitylene (5.0 ml) were added to the reaction vessel, dissolved at room temperature (25°C), and then heated and stirred at 150°C for 6 hours. 1N-HCl was added at room temperature (25°C) to stop the reaction, and the mixture was extracted with AcOEt (20 mL x 3). The mixture was then precipitated with MgSO 4 The mixture was dried and passed through 25 g of silica gel, extracted with a solvent (hexane: EtOAc = 25:1) and recrystallized to obtain 782.62 mg of the target product (OPDA-9). The yield was 85.8%. The target product was a white solid.

[0343] pass 1 The target product was analyzed by H-NMR and the following results were obtained.

[0344] 1 H NMR (DMSO-d 6 , 392MHz) δ5.92 (s, 2H), 6.56-6.63 (m, 13H), 6.74 (dd, 3H, J=7.4, 7.4Hz), 6.83 -7.20 (m, 27H), 7.31 (dd, 2H, J=7.4, 7.4Hz), 8.12 (d, 2H, J=7.6Hz); Anal.Calcd for C 66 H 49 N 5C, 86.91; H, 5.41; N, 7.68. Found C, 86.91; H, 5.56; N, 7.72.

[0345] Example 18 Synthesis of OPDA-10

[0346]

[0347] 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), tBu 3 P (16.2 mg, 0.08 mmol) and NaOtBu (144 mg, 1.5 mmol) were added to the reaction vessel, dissolved at room temperature (25°C), and 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), extracted with AcOEt (5 mL, 3 mL), and washed with brine (Brine) to obtain a crude product (0.83 g) of beige powder. It was purified by column chromatography and dissolved in CHCl 3 Then, it was passed into 8g of silica gel and evaporated. 0.93g of the crude target product in the form of reddish purple foam was obtained. It was dissolved in a solvent, filtered and dried to obtain 0.67g of the target product (OPDA-10). The target product was a white powder.

[0348] pass 1 The target product was analyzed by H-NMR and the following results were obtained.

[0349] 1 H NMR (CDCl 3 , 392MHz) 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 C 60 H 44 N 2 C, 90.87; H, 5.59; N, 3.53. Found C, 91.06; H, 5.69; N, 3.25.

[0350] Example 19 Synthesis of OPDA-11

[0351]

[0352] 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), tBu 3 P (16.2 mg, 0.08 mmol) and NaOtBu (144 mg, 1.5 mmol) were added to the reaction vessel, dissolved at room temperature (25°C), and 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), extracted with AcOEt (5 mL, 3 mL), and washed with brine to obtain a brown foamy crude product (0.97 g). It was purified by column chromatography using silica gel (9 g), and CHCl was added. 3 When 10 ml of IpA was added, it became clay-like and powdered. After filtration, a light brown white powder (0.76 g) was obtained. It was further purified by column chromatography using silica gel (11 g) and extracted with a solvent (hexane: EtOAc = 10: 1 → 4: 1) to obtain an orange-yellow foam (0.72 g). 5 mL of ethanol was added, filtered and dried to obtain 0.64 g of the target product (OPDA-11) as a light brown white powder.

[0353] pass 1 The target product was analyzed by H-NMR and the following results were obtained.

[0354] 1 H NMR (DMSO-d 6 , 392MHz) δ6.72 (t, J=2.0Hz, 1H), 6.90 (d, J=8.5Hz, 4H), 7.04 (d, J=9.0Hz, 3H), 7.70-7.45(m, 29H), 7.49-7.63(m, 8H), 8.22(d, J=7.2, 1.3Hz, 2H); Anal.Calcd for C 66 H 47 N 3 C, 89.87; H, 5.37; N, 4.76. Found C, 89.66; H, 5.48; N, 4.61.

[0355] Example 20 Synthesis of OPDA-7-X, OPDA-7-cbz and OPDA-8-X

[0356] OPDA-7-X, OPDA-7-cbz and OPDA-8-X were synthesized in the same manner as above according to the following reaction formula and used for evaluation.

[0357]

[0358]

[0359] Example 21 Determination of basic physical properties

[0360] Regarding 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, maximum absorption wavelength, logε, absorption edge, maximum fluorescence wavelength, fluorescence quantum yield and oxidation potential vsAg / Ag+ were measured. The results are shown in Table 6.

[0361] Each measurement was performed under the following conditions.

[0362] Glass transition temperature

[0363] The measurement was performed by differential scanning calorimetry (device: Hitachi High-Tech Science DSC / TG-DTA 6200) with a sample weight of 5 mg, a heating temperature of 10°C / min, a cooling rate of 20°C / min between the first and second runs, and the glass transition temperature was the value of the second run.

[0364] Maximum absorption wavelength

[0365] The measurement was performed using a spectrometer SEC2020 (manufactured by BAS Co., Ltd.) as a measuring device. The measuring conditions were to adjust the material to be dissolved in a solution of about 10-5 mol / l of tetrahydrofuran, and in the absorption spectrum observed by the above measuring device, the wavelength of the maximum point of the absorption band on the longest wavelength side was determined as the absorption maximum wavelength.

[0366] logε is the logarithm of the molar absorptivity at the wavelength of maximum absorption.

[0367] The absorption edge is the wavelength of a point on the long-wavelength edge side of the absorption spectrum where a straight line approximates the curve and intersects the x-axis (absorbance 0).

[0368] Fluorescence maximum wavelength

[0369] The fluorescence spectrum was measured (device: JASCO F8200) under the following conditions: an excitation wavelength of 310 nm, an excitation light band of 2.5 nm, and a fluorescence band of 2.5 nm.

[0370] Fluorescence quantum yield

[0371] Determined by the relative method of 9,10-diphenylanthracene to cyclohexane solution.

[0372] Oxidation Potential vs Ag / Ag+

[0373] The measurement conditions were as follows: solvent: dichloromethane, compound concentration: 10-3 mol / l, supporting electrolyte: TBAP 0.1 M, working electrode: platinum disc, counter electrode: platinum wire, reference electrode: Ag / AgNO 3 0.01M CH 3 CN solution, scanning speed: 50mV / sec.

[0374] [Table 6]

[0375] Basic physical properties

[0376]

[0377] Example 22 Determination of basic physical properties

[0378] Regarding OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, Me-OPDA-4, F-OPDA-4, OPDA-7, and OPDA-9, the optical band gap, and the energy levels of HOMO and LUMO were calculated. The results are shown in Table 7.

[0379] [Table 7]

[0380] Basic physical properties 2

[0381]

[0382] In the above Table 7, the HOMO energy level was obtained from cyclic voltammetry. The measurement conditions were NPD oxidation potential 477 mV vs Ag / Ag+, HOMO 5.43 eV.

[0383] The optical band gap is calculated from the long wavelength edge of the absorption spectrum.

[0384] The LUMO energy level is calculated from the difference between the optical energy gap and the HOMO energy level.

[0385] Example 23 HOMO-LUMO diagram calculated based on the absorption edge and oxidation potential of the solution

[0386] Energy levels were calculated for OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, OPDA-6, OPDA-7, and OPDA-9, and the results are shown in FIG. Figure 1 .

[0387] The NPD and TPD of existing materials are calculated and added to Figure 1 It should be noted that NPD used in this specification is the abbreviation of N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-diphenyl)-4,4'-diamine (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine), and TPD is the abbreviation of N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-diphenyl)-4,4'-diamine.

[0388] Based on these results, it can be seen that the OPDA-1, OPDA-2, OPDA-3, OPDA-4, OPDA-5, OPDA-6, OPDA-7 and OPDA-9 materials of the present invention have appropriate intensity as the difference in HOMO-LUMO energy levels and are suitable as light-emitting materials.

[0389] Example 24 Determination of basic physical properties

[0390] Table 8 shows the results of calculating the energy levels of OPDA-3 and OPDA-9, and NPD, CBP, and m-CBP as comparison objects.

[0391] [Table 8]

[0392] Basic physical properties (calculated values)

[0393] OPDA-3 Comparison 1) NPD Comparison 2) CBP OPDA-9 Comparison) m-CBP S1 energy level (eV) 3.63 3.14 3.59 3.52 3.69 T1 energy level (eV) 3.01 2.33 2.82 3.00 3.05 <![CDATA[△E ST (eV)]]> 0.62 0.70 0.78 0.52 0.64

[0394] In the above Table 8, the S1 level is calculated based on the short-wavelength edge of the fluorescence spectrum, and the T1 level is calculated based on the short-wavelength edge of the phosphorescence spectrum.

[0395] As shown in Table 8, the T1 levels of OPDA-3 and OPDA-9 are higher in energy than those of NPD and CBP. In addition, the ΔEST of OPDA-3 and OPDA-9 is smaller than that of NPD, CBP, and m-CBP. e Favorable energy levels of the host and exciton diffusion prevention layer.

[0396] It should be noted that m-CBP used in the present specification is an abbreviation for 3,3'-bis(9H-carbazol-9-yl)-1,1'-diphenyl (3,3'-bis(9H-carbazol-9-yl)-1,1'-biphenyl).

[0397] Example 25 Study on the method of purifying the product by sublimation

[0398] About OPDA-1, OPDA-2, OPDA-5, OPDA-6, M e For the OPDA-4 and F-OPDA-4, purification by sublimation was investigated, and the results are shown in Table 9.

[0399] [Table 9]

[0400] Study on the method of purifying the product by sublimation (Part 1)

[0401]

[0402] Example 26 Study on the method of purifying the product by sublimation

[0403] Regarding OPDA-3, OPDA-4, OPDA-7, OPDA-9, OPDA-10, and OPDA-11, a purification method by a sublimation method was studied. The results are shown in Table 10.

[0404] [Table 10]

[0405] Study on the purification method of products by sublimation (Part 2)

[0406]

[0407] OPDA-10: Purity after sublimation: 99.1%

[0408] OPDA-11: Temperature after sublimation: 97.1%

[0409] As can be seen from Tables 9 and 10 above, the material of the present invention can be highly purified by the sublimation method, which is useful as a purification method.

[0410] Example 27 Evaluation of refractive index (total reflection difficulty)

[0411] The refractive indexes of F-OPDA-4, OPDA-4, and NPD as a comparative object were measured. The results are shown in Table 11.

[0412] [Table 11]

[0413] Evaluation of refractive index (total reflection difficulty)

[0414] 400nm 450nm 500nm 600nm 700nm F-OPDA-4 1.79 1.74 1.72 1.69 1.67 OPDA-4 1.84 1.78 1.75 1.72 1.70 NPD 2.12 1.89 1.83 1.78 1.76

[0415] In Table 11, the measurements were performed by ellipsometry.

[0416] The measurement is carried out in a general manner, observing the change in the polarization state of the outgoing light relative to the polarization state of the incident light, and obtaining Ψ (tanΨ = |rp| / |rs|) and Δ (=δrp-δrs) based on the measurement. On this basis, an optical model is made, and the model and the measured values ​​are combined through fitting to obtain the refractive index.

[0417] As can be seen from Table 11, the NPD of the material of the present invention is less likely to be totally reflected than that of the conventional material, and is particularly low at a low wavelength of 400 nm, as much as at a high wavelength.

[0418] Example 28 Component Evaluation

[0419] Regarding OPDA-3 and OPDA-4, m-CBP as a control was prepared. Figure 2 The structure of the element used for evaluation (laminated structure composed of organic layers) was measured, and the driving voltage, brightness, luminous efficiency and chromaticity CIE1931 were measured. The results are shown in Table 12.

[0420] The configuration of the stacked structure is as follows.

[0421] It should be noted that the organoborane used as the light-emitting material is the material shown below, and can be prepared with reference to Nat. Photon. 8, 326-332 (2014).

[0422] 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.

[0423] Composition of m-CBP:

[0424] ITO / HAT-CN (5nm) / NPD (40nm) / TCTA (15nm) / m-CBP (15nm) / m-CBP+1wt%organoborane (20nm) / NBPhen (40nm) / Al.

[0425] Composition of OPDA-3:

[0426] ITO / HAT-CN (5nm) / NPD (50nm) / TCTA (20nm) / OPDA-3+1wt%organoborane (20nm) / NBPhen (40nm) / Al.

[0427] Composition of OPDA-4:

[0428] ITO / HAT-CN (5nm) / NPD (50nm) / TCTA (20nm) / OPDA-4+1wt%organoborane (20nm) / NBPhen (40nm) / Al.

[0429] [Table 12]

[0430] Component Evaluation

[0431] Driving voltage brightness Luminous efficiency Chromaticity CIE 1931 m-CBP 8.2V 258cd / m2 2.6cd / A (0.136，0.107) OPDA-3 5.7V 196cd / m2 2.0cd / A (0.138，0.115) OPDA-4 6.1V 128cd / m2 1.3cd / A (0.138，0.085)

[0432] In Table 12, the driving voltage was measured by IV measurement, and the brightness was measured by a colorimeter. In addition, the luminous efficiency is the brightness current efficiency.

[0433] As can be seen from Table 12, the driving voltage of the stacked structure using OPDA-3 of the present invention and the stacked structure using OPDA-4 are lower than that of the stacked structure using the existing material m-CBP, and they are not inferior in terms of brightness, luminous efficiency and chromaticity, and are suitable as light-emitting materials.

[0434] Example 29 Voltage-Current Characteristics

[0435] Regarding the stacked structures of m-CBP using OPDA-3 and OPDA-4 as comparative controls, Figure 3 The voltage-current characteristics are measured and the results are shown. Figure 2 The stacking structure is the same.

[0436] Depend on Figure 3 It was confirmed that the OPDA device having the stacked structure using OPDA-3 and OPDA-4 of the present invention can reduce the driving voltage compared to the m-CBP device having the stacked structure using m-CBP.

[0437] Example 30 EL spectrum

[0438] Regarding the stacked structure using OPDA-3, the stacked structure using OPDA-4, and the stacked structure using m-CBP as a comparative control, Figure 4 The EL spectrum is measured and the results are shown. Figure 2 The stacking structure is the same.

[0439] Depend on Figure 4 It is found that the OPDA devices having the stacked structure using OPDA-3 of the present invention and the stacked structure using OPDA-4 have spectra with almost the same maximum value as the m-CBP device, and the OPDA device having the stacked structure using OPDA-4 has a shoulder on the low wavelength side.

[0440] Example 31 Cyclic Voltammetry of Dichloromethane Solution

[0441] Cyclic voltammetry in a dichloromethane solution was measured for OPDA-1, OPDA-2, OPDA-5, OPDA-6, Me-OPDA-4, F-OPDA-4, OPDA-7, OPDA-9, OPDA-10, and OPDA-11. The results are shown in Tables 13 and 14.

[0442] The measurement conditions are as follows: solvent: dichloromethane, compound concentration: 10-3 mol / l, supporting electrolyte: TBAP 0.1 M, working electrode: platinum disc, counter electrode: platinum wire, reference electrode: Ag / AgNO 3 0.01M CH 3 CN solution, scan rate: 50mV / sec, NPD oxidation potential 477mV vs Ag / Ag+, HOMO 5.43eV.

[0443] [Table 13]

[0444] Cyclic Voltammetry in Dichloromethane Solution

[0445] OPDA-1 OPDA-2 OPDA-5 OPDA-6 Me-OPDA-4 F-OPDA Oxidation Potential vs Ag / Ag+ 519mV 605mV 500mV 392mV 521mV 821mV HOMO level ※ 5.47eV 5.56eV 5.45eV 5.35eV 5.47eV 5.77eV

[0446] [Table 14]

[0447] Cyclic Voltammetry in Dichloromethane Solution

[0448] OPDA-7 OPDA-9 Oxidation Potential vs Ag / Ag+ 597mV (irreversible) 651mV HOMO level ※ 5.51eV 5.60eV

[0449] OPDA-10: Redox potential 590mV, HOMO 5.52eV

[0450] OPDA-11: Redox potential 650mV, HOMO 5.58eV

[0451] Industrial Applicability

[0452] Industrially, it is useful as an organic EL device material such as a hole transport material and a blue light emitting material.

Claims

1. A 1,2-bis(diarylamino)benzene, which is any one of the following formulas, 2. An optical material, which is a 1,2-bis(diarylamino)benzene of any one of the following formulas, 3 . A hole transport material or a blue light emitting material, which is composed of the 1,2-bis(diarylamino)benzene according to claim 1 . 4 . An organic EL element comprising the hole transport material or the blue light emitting material according to claim 3 .

5. A display comprising the organic EL element according to claim 4.

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