CN112239452B - Electron transport type heteroanthracene derivative and organic electroluminescent device thereof - Google Patents

Electron transport type heteroanthracene derivative and organic electroluminescent device thereof Download PDF

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CN112239452B
CN112239452B CN202011095514.1A CN202011095514A CN112239452B CN 112239452 B CN112239452 B CN 112239452B CN 202011095514 A CN202011095514 A CN 202011095514A CN 112239452 B CN112239452 B CN 112239452B
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heteroanthracene
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CN112239452A (en
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穆广园
庄少卿
任春婷
徐鹏
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Wuhan Sunshine Optoelectronics Tech Co ltd
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Abstract

The invention discloses an electron-transport type heteroanthracene derivative, a preparation method and application thereof, and an organic electroluminescent device. The heteroanthracene derivative has a parent nucleus structure of heteroanthracene, and is modified by groups to form a D-A type compound. The material has remarkably excellent fluorescence electroluminescence property and electron transmission property, has higher quantum yield and electron mobility when being used as a luminescent object material, an electron transmission material or a hole blocking material of an organic electroluminescence device, can effectively solve the problem of unbalance of electrons and holes in the device, emits purer light color, and has more remarkable advantages than similar compounds and compounds in the prior art in starting voltage, current efficiency, service life and thermal stability.

Description

Electron transport type heteroanthracene derivative and organic electroluminescent device thereof
Technical Field
The invention relates to the field of photoelectric materials, in particular to an electron-transport type heteroanthracene derivative and an organic electroluminescent device thereof.
Background
OLEDs, i.e., organic light emitting diodes, are also known as organic electroluminescent displays. The OLED has a self-luminous characteristic, adopts a very thin organic material coating layer and a glass substrate, emits light when current passes through the organic material coating layer, has a large viewing angle of an OLED display screen, and can significantly save electric energy, so the OLED is regarded as one of the most promising products in the 21 st century. However, to date, OLED devices have not achieved widespread use, where device efficiency is an important reason that limits their popularity.
In OLED devices, the design and combination of the light-emitting layer plays a key role in the performance of the device, which directly determines the light-emitting efficiency and lifetime of the device. As a light emitting layer material of an OLED, it needs to have good electron and hole transport capabilities at the same time, so that carriers can be more balanced in recombination light emission in the light emitting layer. Most aromatic compounds have an electron-rich property due to a conjugated property, and the transport capacity of holes is higher than that of electrons, thereby causing transport imbalance of carriers in the device. Although the problem of unbalanced carrier transmission is solved by adding the hole blocking layer or the electron blocking layer in the device preparation process, the complexity and the cost of the device preparation are increased. In recent years, a light emitting material having a bipolar transport property and an electron transport material having high mobility have been receiving attention. At present, for a brand-new anthracene-hetero group in the field of photoelectric materials, because the anthracene-hetero group has a rigid structural framework of the anthracene group and nonmetal heavy atom sulfur, the electroluminescent characteristic of the anthracene-hetero group is preliminarily discovered, however, an electroluminescent device prepared from the anthracene-hetero compound is still at a lower level in the aspects of luminous efficiency, service life and the like, and cannot meet the requirements on the performance of the luminescent material in the prior art, so that the photoelectric property of the anthracene-hetero group is researched, a new compound which has better performance and takes the anthracene-hetero group as a core is designed, and the organic electroluminescent device with higher luminous efficiency and more stability is prepared, which is a technical problem to be solved in the field of photoelectric materials.
Disclosure of Invention
Based on the prior art, the invention aims at industrialization, aims at developing an OLED material taking a heteroanthracene group as a core, solves the problem of unmatched electron/hole migration in a material layer, and further obviously improves the comprehensive performance of a device in the aspects of luminous efficiency, service life, color coordinates and the like.
In a first aspect, the present invention provides an electron-transporting heteroanthracene derivative, which has a structure represented by formula (I) or formula (II):
Figure BDA0002723600110000011
wherein Z is independently selected from O, S, S ═ O, S (═ O)2、N-R1；R0Selected from: hydrogen, fluoro, nitro, cyano, sulfonyl, C1～20Alkyl of (C)1～20Alkoxy group of (C)1～20Silyl group of, substituted or unsubstituted by a substituent group C6～50Aryl of (a), substituted or unsubstituted C3～50Heteroaryl, substituted or unsubstituted C by a substituent6～50Aryloxy group of (1), substituted or unsubstituted by a substituent group C6～50Arylthio group of (a); r1Selected from: a phenyl group substituted or unsubstituted by a substituent, a biphenyl group substituted or unsubstituted by a substituent, a terphenyl group substituted or unsubstituted by a substituent, a naphthyl group substituted or unsubstituted by a substituent; l is0、L1、L2Each independently selected from: a single bond, phenylene substituted or unsubstituted with a substituent, biphenylene substituted or unsubstituted with a substituent, naphthylene substituted or unsubstituted with a substituent; ETG0、ETG1、ETG2Are electron transport groups, each independently selected from:
Figure BDA0002723600110000021
wherein:
each X is independently selected from: CR8Or N; each Y is independently selected from: c (R)9)(R10)、NR11O, S orS(＝O)2(ii) a Each Q is independently selected from: CH or N; r2-R3、R8-R11Each independently selected from: hydrogen, fluoro, nitro, cyano, sulfonyl, C1～20Alkyl of (C)1～20Alkoxy group of (C)1～20A silyl group, C substituted or unsubstituted by a substituent6～50Aryl group of (1), C substituted or unsubstituted by a substituent3～50Heteroaryl, C substituted or unsubstituted by a substituent6～50Aryloxy group of (1), C substituted or unsubstituted by a substituent6～50Arylthio group of (a); r4-R7Each independently selected from: c1～20Alkyl of (C)6～50Aryl of (C)3～50The heteroaryl group of (a); when ETG0、ETG1、ETG2Is selected from
Figure BDA0002723600110000022
At least one of X is selected from N.
Further, C1～20The alkyl group of (a) is selected from: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl; c1～20The alkoxy group of (a) is selected from: methoxy, ethoxy; c1～20The silane groups of (a) are selected from: trimethylsilyl, phenyldimethylsilyl, biphenyldimethylsilyl, methyldiphenylsilyl, tert-butyldiphenylsilyl; c substituted or unsubstituted by a substituent6～50Is selected from: a phenyl group substituted or unsubstituted by a substituent, a biphenyl group substituted or unsubstituted by a substituent, a terphenyl group substituted or unsubstituted by a substituent, a naphthyl group substituted or unsubstituted by a substituent, an anthracenyl group substituted or unsubstituted by a substituent, a phenanthrenyl group substituted or unsubstituted by a substituent, a pyrenyl group substituted or unsubstituted by a substituent, a benzophenanthrenyl group substituted or unsubstituted by a substituent, a fluorenyl group substituted or unsubstituted by a substituent, a spirobifluorenyl group substituted or unsubstituted by a substituent; c substituted or unsubstituted by a substituent3～50Is selected from: pyridyl substituted or unsubstituted with a substituent, pyrimidinyl substituted or unsubstituted with a substituent, pyranyl substituted or unsubstituted with a substituentAn oxazinyl group, a triazinyl group substituted or unsubstituted with a substituent, an indolyl group substituted or unsubstituted with a substituent, a benzofuranyl group substituted or unsubstituted with a substituent, a benzothienyl group substituted or unsubstituted with a substituent, a benzoxazolyl group substituted or unsubstituted with a substituent, a benzothiazolyl group substituted or unsubstituted with a substituent, a carbazolyl group substituted or unsubstituted with a substituent, a dibenzofuranyl group substituted or unsubstituted with a substituent, a dibenzothiophenyl group substituted or unsubstituted with a substituent, and C6～50The aryloxy group of (a) is selected from: an oxyphenyl group substituted or unsubstituted with a substituent; c substituted or unsubstituted by a substituent6～50Arylthio group of (a); a thiophenyl group substituted or unsubstituted with a substituent.
Further, the above substituents are selected from: cyano, fluoro, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, fluorenyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzofuranyl, benzothienyl, benzoxazolyl, benzothiazolyl, carbazolyl, dibenzofuranyl, dibenzothienyl.
Figure BDA0002723600110000031
Wherein: n is 0, 1, 2; m is 1 and 2; each X is independently selected from CH or N, and at least one X in each group is selected from N; r12-R23Each independently selected from: cyano, fluoro, nitro, methyl, ethyl, propyl, butyl, methoxy, ethoxy; each Ar0Each independently selected from: methyl, ethyl, propyl, butyl, phenyl unsubstituted or substituted by cyano, fluoro, nitro, methyl, ethyl, propyl, butyl, or biphenyl unsubstituted or substituted by cyano, fluoro, nitro, methyl, ethyl, propyl, butyl; ar (Ar)1-Ar26Each independently selected from: cyano, fluoro, nitro, methyl, ethyl, propyl, butyl, methoxy, ethoxyA radical or a phenyl radical.
Preferably, the first and second liquid crystal materials are,
Figure BDA0002723600110000041
may be further represented by one of the following groups:
Figure BDA0002723600110000042
preferably, the first and second liquid crystal materials are,
Figure BDA0002723600110000043
may be further represented by one of the following groups:
Figure BDA0002723600110000044
wherein R is24Each independently selected from: hydrogen, cyano, fluoro, nitro, methyl, methoxy or phenyl.
Preferably, the first and second liquid crystal materials are,
Figure BDA0002723600110000045
may be further represented by one of the following groups:
Figure BDA0002723600110000046
preferably, the first and second liquid crystal materials are,
Figure BDA0002723600110000051
may be further represented by one of the following groups:
Figure BDA0002723600110000052
Figure BDA0002723600110000053
preferably, the first and second liquid crystal materials are,
Figure BDA0002723600110000054
may be further represented by one of the following groups:
Figure BDA0002723600110000055
preferably, the first and second liquid crystal materials are,
Figure BDA0002723600110000056
may be further represented by one of the following groups:
Figure BDA0002723600110000057
in a preferred embodiment of the method of the invention,
Figure BDA0002723600110000058
may be further represented by one of the following groups:
Figure BDA0002723600110000059
wherein R is25Each independently selected from methyl, phenyl, or phenyl substituted by cyano, fluoro, nitro, methyl or methoxy; r26Each independently selected from hydrogen, cyano, fluoro, nitro, methyl, or, methoxy; r27Each independently selected from: hydrogen, methyl, phenyl, or phenyl substituted with cyano, fluoro, nitro, methyl or methoxy.
Preferably, the first and second liquid crystal materials are,
Figure BDA00027236001100000510
may be further represented by one of the following groups:
Figure BDA0002723600110000061
preferably, the first and second liquid crystal materials are,
Figure BDA0002723600110000062
may be further represented by one of the following groups:
Figure BDA0002723600110000063
preferably, the first and second liquid crystal materials are,
Figure BDA0002723600110000064
may be further represented by one of the following groups:
Figure BDA0002723600110000065
preferably, R0Selected from one of the following groups:
Figure BDA0002723600110000066
Figure BDA0002723600110000071
preferably, the compound represented by formula (I) or formula (II) is selected from the following compounds:
Figure BDA0002723600110000072
Figure BDA0002723600110000081
Figure BDA0002723600110000091
Figure BDA0002723600110000101
Figure BDA0002723600110000111
Figure BDA0002723600110000121
Figure BDA0002723600110000131
Figure BDA0002723600110000141
Figure BDA0002723600110000151
Figure BDA0002723600110000161
Figure BDA0002723600110000171
Figure BDA0002723600110000181
Figure BDA0002723600110000191
further, the electron transport type heteroanthracene derivative is used as an electron transport layer or a light emitting layer of an organic electroluminescent device.
Preferably, the electron-transporting heteroanthracene derivative is used as a light-emitting guest material of a light-emitting layer of an organic electroluminescent device.
In a second aspect, the present invention provides an organic electroluminescent device, comprising a cathode, an anode and an organic layer between the two electrodes, or comprising a light-emitting layer, a cathode, an anode and an organic layer between the two electrodes, wherein the organic layer between the two electrodes at least comprises an electron transport layer or a light-emitting layer, and the electron transport layer or the light-emitting layer contains the electron transport type heteroanthracene derivative.
The heteroanthracene derivative modifies the specific feeding/absorbing group provided by the application at 2 and 7 positions of heteroanthracene, a heteroanthracene core group has the rigid structure of anthracene and the strong electron-withdrawing property of heteroatoms such as oxygen, sulfur and the like, a D-A type compound is formed through modification of the specific group, the hole mobility of the material is kept, the micro regulation and control of molecules further improve the electron mobility of the material, and the problem of unmatched hole/electron mobility in the prior art is solved, compared with a disubstituted compound at other sites of the heteroanthracene, disubstituted of other types of groups of the heteroanthracene, a monosubstituted compound of the heteroanthracene or other compounds in the prior art, the material quantum yield is obviously improved, and the heteroanthracene is taken as the core, the groups with specific feeding and electron-withdrawing properties are modified at 2 and 7 positions of the heteroanthracene group, the pi conjugation degree of an acceptor segment is effectively reduced, thereby achieving the technical effect of blue shift of light color and improving the intrinsic color purity of the material. When the material is used as a luminescent layer material, an electron transport material or an electron blocking material, especially a luminescent guest material of a luminescent layer, and is applied to an organic electroluminescent device, the performance of the device in the aspects of starting voltage, current efficiency, service life and the like is obviously improved, the luminescent wavelength is blue-shifted, and purer deep blue light or deep green light is emitted, so that the material is an ideal luminescent layer material, an electron transport material and an electron blocking material.
The invention also provides a preparation method of the material, which comprises the following steps:
Figure BDA0002723600110000201
are each independently of R0And L is a halogen atom0-ETG0Boric acid ester or L0-ETG0Coupling of the boronic acid compound to giveA compound of formula (I);
alternatively, the first and second electrodes may be,
Figure BDA0002723600110000202
are respectively connected with L1-ETG1And L is a halogen atom of2-ETG2Boric acid ester or L2-ETG2To give a compound of formula (II);
or, L1、L2Same and ETG1And ETG2When the phase of the mixture is the same as the phase of the mixture,
Figure BDA0002723600110000203
and L1-ETG1、L2-ETG2Coupling the boronic acid ester or boronic acid compound to obtain the compound of formula (II).
Further, in the above step, the reaction is carried out in a mixed solvent of a palladium catalyst and a base, and a ligand may be added; the palladium catalyst may be at least one of [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium, tetratriphenylphosphine palladium, tris (dibenzylideneacetone) dipalladium and palladium acetate; the base can be at least one of potassium acetate, sodium hydroxide, potassium hydroxide, sodium tert-butoxide, potassium carbonate and sodium carbonate; the mixed solvent may be at least one of toluene, xylene, ethanol, N-dimethylformamide, N-dimethylacetamide, and water; the ligand may be tri-tert-butylphosphine tetrafluoroborate.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Synthesis example 1 preparation of Compound (6)
Figure BDA0002723600110000204
S1, putting 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol), sodium tert-butoxide (2.88g,30mmol), tri-tert-butylphosphine tetrafluoroborate (0.044g, 0.15mmol) and toluene (30mL-50mL) into a 100mL three-necked flask, adding tris (dibenzylideneacetone) dipalladium (0.091g,0.1mmol) under nitrogen atmosphere, heating to 100 ℃ and 115 ℃, slowly adding 5-10mL of a toluene solution of 7-bromodibenzodioxin-2-borate (5.83g,15mmol), reacting for 4-8h after adding, monitoring the reaction of a liquid phase to be basically completed, cooling to room temperature, washing with water, filtering, separating filtrate, concentrating an organic phase, pulping the organic phase together with a filter cake 1-3 times by using ethanol, ethyl acetate or a composition of the two, 6.93g of intermediate 1 can be obtained with a yield of 81%;
s2, putting the intermediate 1(5.70g,10mmol), 4-cyanobenzene boronic acid (1.47g,10mmol), sodium tert-butoxide (2g,20mmol), tri-tert-butylphosphine tetrafluoroborate (0.02g, 0.06mmol) and toluene (30mL-60mL) into a 100mL three-necked flask, adding tris (dibenzylideneacetone) dipalladium (0.02g,0.03mmol) under the nitrogen atmosphere, reacting at the temperature of 100 ℃ and 115 ℃ for 6-12h, monitoring the liquid phase to basically complete the reaction, cooling to room temperature, filtering, concentrating the filtrate, stirring the filtrate and the filter cake with silica gel, carrying out column chromatography by using 10:1 petroleum ether and dichloromethane, and concentrating the organic phase to obtain 4.39g of the target compound (6) with the yield of 74%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 592.6594, theoretical molecular weight: 592.6580, respectively; elemental analysis: theoretical value C40H24N4C81.07, H4.08 and N9.45 in percent; found C81.05, H4.08, N9.46.
Synthesis example 2 preparation of Compound (13)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol), replacing 7-bromodibenzodioxin-2-borate (5.83g,15mmol) with 7-bromothianthrene-2-borate (6.32g,15mmol), and performing the other synthesis steps similar to S1 in Synthesis example 1 to obtain 6.96g of intermediate 1 with a yield of 77%;
s2. by substituting intermediate 1(5.70g,10mmol) of S2 in Synthesis example 1 with intermediate 1(6.02g,10mmol) of this example, 4-cyanophenylboronic acid (1.47g,10mmol) with naphthalen-2-ylboronic acid (1.72g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 1, 4.68g of the objective compound (13) was obtained with a yield of 72%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 649.8306, theoretical molecular weight: 649.8300, respectively; elemental analysis: theoretical value C43H27N3C79.48, H4.19, N6.47; found C79.48, H4.20, N6.45.
Synthesis example 3 preparation of Compound (17)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in synthetic example 1 with 4-chloro-2, 6-diphenylpyrimidine (4.0g,15mmol), and performing the same synthetic procedures as S1 in synthetic example 1 to obtain 5.92g of intermediate 1 with a yield of 80%;
s2. by substituting intermediate 1(5.70g,10mmol) of S2 in Synthesis example 1 with intermediate 1(4.93g,10mmol) of this example, 4-cyanophenylboronic acid (1.47g,10mmol) with (10- (4-cyanophenyl) anthracen-9-yl) boronic acid (3.23g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 1, 4.77g of the objective compound (17) was obtained with a yield of 69%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 691.7894, theoretical molecular weight: 691.7900, respectively; elemental analysis: theoretical value C49H29N3C85.07, H4.23, N6.07; found C85.06, H4.25, N6.07.
Synthesis example 4 preparation of Compound (24)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol), and performing the other synthesis steps similar to S1 in Synthesis example 1 to obtain 6.67g of intermediate 1 with a yield of 78%;
s2. 4.60g of the objective compound (24) was obtained in a yield of 70% by replacing intermediate 1(5.70g,10mmol) of S2 in Synthesis example 1 with intermediate 1(5.70g,10mmol) of this example, 4-cyanobenzene boronic acid (1.47g,10mmol) with dibenzofuran-3-ylboronic acid (2.12g,10mmol), and the other synthesis steps were the same as those of S2 in Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 657.7282, theoretical molecular weight: 657.7290; elemental analysis: theoretical value C45H27N3C82.18, H4.14, N6.39; found C82.16, H4.15, N6.40.
Synthesis example 5 preparation of Compound (33)
S1, replacing 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol) of S1 in synthetic example 2 with 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol), and performing the other synthetic steps to the S1 in synthetic example 2 to obtain 6.32g of intermediate 1 with the yield of 80%;
s2. 5.20g of the objective compound (33) was obtained in a yield of 73% by substituting intermediate 1(6.02g,10mmol) in S2 in Synthesis example 2 for intermediate 1(5.26g,10mmol) in this example, substituting naphthalene-2-ylboronic acid (1.72g,10mmol) for 3- (9H-carbazol-9-yl) benzonitrile (3.12g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 2.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 713.8775, theoretical molecular weight: 713.8770; elemental analysis: theoretical value C46H27N5C77.40, H3.81 and N9.81; found C77.40, H3.79, N9.82.
Synthesis example 6 preparation of Compound (38)
S1. same as S1 in Synthesis example 1;
s2, 4.80g of the objective compound (38) was obtained in 68% yield by substituting 1.47g of 4-cyanobenzene boronic acid (10 mmol) in S2 in Synthesis example 1 with 3, 6-dinitrile-9H-carbazole (2.17g,10mmol) and carrying out the same synthetic procedures as in S2 in Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 706.7643, theoretical molecular weight: 706.7650, respectively; elemental analysis: theoretical value C47H26N6C79.87, H3.71 and N11.89; found C79.89, H3.70, N11.89.
Synthesis example 7 preparation of Compound (43)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (4.02g,15mmol), and performing the same synthesis steps as S1 in Synthesis example 1 to obtain 5.86g of intermediate 1 with a yield of 79%;
s2. by substituting intermediate 1(5.70g,10mmol) of S2 in Synthesis example 1 with intermediate 1(4.94g,10mmol) of this example, 4-cyanophenylboronic acid (1.47g,10mmol) with (4- (9H-carbazol-9-yl) -2-fluorophenyl) boronic acid (3.05g,10mmol), and the other synthesis procedures were the same as in S2 in Synthesis example 1, 4.38g of the objective compound (43) was obtained with a yield of 65%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 674.7359, theoretical molecular weight: 674.7354, respectively; elemental analysis: theoretical value C45H27N4C80.10, H4.03 and N8.30; found C80.13, H4.02, N8.29.
Synthesis example 8 preparation of Compound (48)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (4.02g,15mmol), and performing the same synthesis steps as S1 in Synthesis example 1 to obtain 5.86g of intermediate 1 with a yield of 79%;
s2. 5.07g of the objective compound (48) was obtained in 68% yield by substituting intermediate 1(5.70g,10mmol) of S2 in Synthesis example 1 with intermediate 1(4.94g,10mmol) of this example, 4-cyanophenylboronic acid (1.47g,10mmol) with spiro [ fluorene-9, 9' -xanthene ] -3-yl-boronic acid (3.76g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 745.8391, theoretical molecular weight: 745.8380, respectively; elemental analysis: theoretical value C52H31N3C83.74, H4.19, N5.63; found C83.74, H4.20, N5.62.
Synthesis example 9 preparation of Compound (59)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (4.02g,15mmol), and performing the same synthesis steps as S1 in Synthesis example 1 to obtain 5.86g of intermediate 1 with a yield of 79%;
s2. 5.14g of the objective compound (59) was obtained in 70% yield by substituting intermediate 1(5.70g,10mmol) in S2 in Synthesis example 1 with intermediate 1(4.94g,10mmol) in this example, 4-cyanophenylboronic acid (1.47g,10mmol) with bis ([1,1' -biphenyl ] -3-yl) amine (3.22g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 734.8598, theoretical molecular weight: 734.8590, respectively; elemental analysis: theoretical value C51H34N4C83.36, H4.66 and N7.62; found C83.35, H4.68, N7.62.
Synthesis example 10 preparation of Compound (64)
S1, replacing 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol) of S2 in synthetic example 2 with 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol), and performing the other synthetic steps to the S1 in synthetic example 2 to obtain 6.96g of intermediate 1 with a yield of 77%;
s2. 5.37g of the objective compound (64) was obtained in a yield of 70% by substituting intermediate 1(6.02g,10mmol) of S2 in Synthesis example 2 with intermediate 1(6.02g,10mmol) of this example, naphthalen-2-ylboronic acid (1.72g,10mmol) with (3- (diphenylamino) phenyl) boronic acid (2.89g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 2.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 766.9802, theoretical molecular weight: 766.9810, respectively; elemental analysis: theoretical value C51H34N4C79.87, H4.47, N7.31; found C79.85, H4.48, N7.30.
Synthesis example 11 preparation of Compound (79)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in synthetic example 1 with 4-bromo-1, 5-naphthyridine (3.14g,15mmol), and performing the same synthetic steps as S1 in synthetic example 1 to obtain 4.40g of intermediate 1 with a yield of 75%;
s2. by substituting intermediate 1(5.70g,10mmol) of S2 in Synthesis example 1 with intermediate 1(3.91g,10mmol) of this example, 4-cyanophenylboronic acid (1.47g,10mmol) with (10- (naphthalen-1-yl) anthracen-9-yl) boronic acid (3.48g,10mmol), and the other synthesis procedures were the same as in S2 in Synthesis example 1, 4.12g of the objective compound (79) was obtained with a yield of 67%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 614.7032, theoretical molecular weight: 614.7040, respectively; elemental analysis: theoretical value C44H26N2C85.97, H4.26 and N4.56; found C85.96, H4.26, N4.58.
Synthesis example 12 preparation of Compound (84)
S1. 4.52g of intermediate 1 was obtained in 77% yield by substituting 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2-bromoquinoline (3.14g,15mmol) and carrying out the same synthetic procedures as S1 in Synthesis example 1;
s2. 3.23g of the objective compound (84) was obtained in 65% yield by substituting intermediate 1(5.70g,10mmol) in S2 in Synthesis example 1 with intermediate 1(3.91g,10mmol) in this example, substituting 4-cyanobenzene boronic acid (1.47g,10mmol) with (7-fluorodibenzofuran-2-yl) boronic acid (2.30g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 496.4970, theoretical molecular weight: 496.4974, respectively; elemental analysis: theoretical value C32H17N2C77.41, H3.45, N5.64; found C77.42, H3.45, N5.65.
Synthesis example 13 preparation of Compound (92)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 7-bromo-4-methoxyquinoline (3.57g,15mmol), and the other synthesis steps were the same as in S1 in Synthesis example 1, whereby 5.04g of intermediate 1 was obtained in 80% yield;
s2, by replacing intermediate 1(5.70g,10mmol) of S2 in Synthesis example 1 with intermediate 1(4.20g,10mmol) of this example, 4-cyanophenylboronic acid (1.47g,10mmol) with (9- (3-cyanophenyl) -9H-carbazol-3-yl) boronic acid (3.12g,10mmol), and by following the same synthetic procedures as S2 in Synthesis example 1, 4.38g of the objective compound (92) was obtained in a yield of 72%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 607.6694, theoretical scoreAnd (2) sub-amount: 607.6690, respectively; elemental analysis: theoretical value C41H25N3C81.04, H4.15, N6.92; found C81.04, H4.17, N6.90.
Synthesis example 14 preparation of Compound (100)
S1, replacing 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol) of S1 in synthetic example 2 with 6-bromo-2-phenylquinoline (4.24g,15mmol), and performing the other synthetic steps to the S1 in synthetic example 2 to obtain 5.98g of intermediate 1 with the yield of 80%;
s2. by substituting intermediate 1(6.02g,10mmol) of S2 in Synthesis example 2 with intermediate 1(4.98g,10mmol) of this example, and substituting naphthalene-2-ylboronic acid (1.72g,10mmol) with (9, 9-dimethyl-9H-fluoro-3-yl) boronic acid (2.38g,10mmol), the other synthesis procedures were the same as those of S2 in Synthesis example 2, and 4.22g of the objective compound (100) was obtained with a yield of 69%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 611.8205, theoretical molecular weight: 611.8210, respectively; elemental analysis: theoretical value C42H29N (%): C82.45, H4.78, N2.29; found C82.44, H4.78, N2.30.
Synthesis example 15 preparation of Compound (114)
S1, replacing 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol) of S1 in synthetic example 2 with 2-bromoquinoxaline (3.14g,15mmol), and performing the other synthetic steps to the S1 in synthetic example 2 to obtain 4.83g of intermediate 1 with the yield of 76%;
s2. by substituting intermediate 1(6.02g,10mmol) of S2 in Synthesis example 2 with intermediate 1(4.23g,10mmol) of this example, naphthalen-2-ylboronic acid (1.72g,10mmol) with bis ([1,1' -biphenyl ] -3-yl) amine (3.21g,10mmol), and the other synthesis procedures were the same as in S2 of Synthesis example 2, 4.65g of the objective compound (114) was obtained with a yield of 70%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 663.8577, theoretical molecular weight: 663.8570, respectively; elemental analysis: theoretical value C44H29N 3C79.61, H4.40, N6.33; found C79.60, H4.40, N6.34.
Synthesis example 16 preparation of Compound (117)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2- (3-bromophenyl) -1-phenyl-1H-benzimidazole (5.24g,15mmol), and the other synthesis steps were the same as in S1 in Synthesis example 1, whereby 6.39g of intermediate 1 was obtained with a yield of 80%;
s2. by substituting intermediate 1(5.70g,10mmol) of S2 in Synthesis example 1 with intermediate 1(5.32g,10mmol) of this example, 4-cyanophenylboronic acid (1.47g,10mmol) with [1,1' -biphenyl ] -3-ylboronic acid (1.98g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 1, 4.47g of the objective compound (117) was obtained in a yield of 74%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 604.7086, theoretical molecular weight: 604.7090, respectively; elemental analysis: theoretical value C43H28N2C85.41, H4.67, N4.63; found C85.42, H4.65, N4.63.
Synthesis example 17 preparation of Compound (144)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in synthesis example 1 with 6-bromo-2-phenylbenzoxazole (4.11g,15mmol), and carrying out the other synthesis steps as in S1 in synthesis example 1 to obtain 5.34g of intermediate 1 with a yield of 78%;
s2. 3.68g of the objective compound (144) was obtained in 73% yield by substituting intermediate 1(5.70g,10mmol) in S2 in Synthesis example 1 with intermediate 1(4.56g,10mmol) in this example, substituting 4-cyanophenylboronic acid (1.47g,10mmol) with naphthalen-2-ylboronic acid (1.72g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 503.5576, theoretical molecular weight: 503.5570, respectively; elemental analysis: theoretical value C35H21N (%): C83.48, H4.20, N2.78; found C83.48, H4.22, N2.76.
Synthesis example 18 preparation of Compound (162)
S1, replacing 2- (4 bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol) of S1 in synthesis example 2 with 5-bromo-1-phenyl-1H-benzimidazole (4.10g,15mmol), and carrying out the other synthesis steps as in S1 in synthesis example 2 to obtain 5.63g of intermediate 1 with a yield of 77%;
s2. by substituting intermediate 1(6.02g,10mmol) of S2 in Synthesis example 2 with intermediate 1(4.87g,10mmol) of this example, and substituting naphthalene-2-ylboronic acid (1.72g,10mmol) with (10-phenylanthracen-9-yl) boronic acid (2.98g,10mmol), the other synthesis procedures were the same as those of S2 in Synthesis example 2, and 4.62g of the objective compound (162) was obtained with a yield of 70%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 660.8536, theoretical molecular weight: 660.8530, respectively; elemental analysis: theoretical value C45H28N2C81.79, H4.27, N4.24; found C81.80, H4.25, N4.24.
Synthesis example 19 preparation of Compound (165)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2-bromo- [1,2,4] thiazole [1,5-a ] pyridine (2.97g,15mmol), and performing the same synthetic procedures as S1 in Synthesis example 1 to obtain 4.28g of intermediate 1 with a yield of 75%;
s2. 3.82g of the objective compound (165) was obtained in 69% yield by substituting intermediate 1(5.70g,10mmol) in S2 in Synthesis example 1 with intermediate 1(3.80g,10mmol) in this example, substituting 4-cyanobenzene boronic acid (1.47g,10mmol) with (10-phenylanthracen-9-yl) boronic acid (2.98g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 553.6203, theoretical molecular weight: 553.6210, respectively; elemental analysis: theoretical value C38H23N3C82.44, H4.19, N7.59; found C82.44, H4.20, N7.80.
Synthesis example 20 preparation of Compound (173)
S1, replacing 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol) of S1 in synthetic example 2 with 2- (3-bromophenyl) benzothiazole (4.35g,15mmol), and carrying out the other synthetic steps in the same manner as S1 in synthetic example 2 to obtain 6.13g of intermediate 1 with the yield of 81%;
s2. by substituting intermediate 1(6.02g,10mmol) of S2 in Synthesis example 2 with intermediate 1(5.04g,10mmol) of this example, substituting naphthalene-2-ylboronic acid (1.72g,10mmol) with dibenzothiophen-3-ylboronic acid (2.28g,10mmol), and carrying out the same synthetic procedures as S2 in Synthesis example 2, 4.38g of the objective compound (173) was obtained with a yield of 72%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 607.8230, theoretical molecular weight: 607.8220, respectively; elemental analysis: theoretical value C37H21N (%): C73.11, H3.48, N2.30; found C73.10, H3.48, N2.30.
Synthesis example 21 preparation of Compound (193)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2-bromo- [1,2,4] thiazole [1,5-a ] pyridine (2.97g,15mmol), and performing the same synthetic procedures as S1 in Synthesis example 1 to obtain 4.28g of intermediate 1 with a yield of 75%;
s2. 4.00g of the title compound (193) was obtained in 65% yield by substituting intermediate 1(5.70g,10mmol) in S2 in Synthesis example 1 for intermediate 1(3.80g,10mmol) in this example, substituting 4-cyanobenzene boronic acid (1.47g,10mmol) for 9,9' -spirobifluoren-3-ylboronic acid (3.60g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 615.6914, theoretical molecular weight: 615.6920; elemental analysis: theoretical value C43H25N3C83.88, H4.09, N6.83; found C83.88, H4.09, N6.83.
Preparation of Compound (197) of Synthesis example 22
S1, replacing 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol) of S1 in synthetic example 2 with 2-bromobenzothiazole (3.21g,15mmol), and performing the other synthetic steps to the S1 in synthetic example 2 to obtain 4.95g of intermediate 1 with the yield of 77%;
s2. by substituting intermediate 1(6.02g,10mmol) of S2 in Synthesis example 2 with intermediate 1(4.28g,10mmol) of this example, and naphthalen-2-ylboronic acid (1.72g,10mmol) with spiro [ fluorene-9, 9' -thia-nthracene ] -3-ylboronic acid (3.92g,10mmol), 4.31g of the objective compound (197) was obtained in 62% yield by the same synthesis procedure as S2 in Synthesis example 2.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 695.9305, theoretical molecular weight: 695.9310, respectively; elemental analysis: theoretical value C44H25N (%): C75.94, H3.62, N2.01; found C75.95, H3.62, N2.00.
Synthesis example 23 preparation of Compound (213)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2- (3-bromophenyl) -1-phenyl-1H-benzimidazole (5.24g,15mmol), and the other synthesis steps were the same as in S1 in Synthesis example 1, whereby 6.54g of intermediate 1 was obtained with a yield of 82%;
s2. 5.20g of the title compound (213) was obtained in 75% yield by substituting intermediate 1(5.70g,10mmol) in S2 in Synthesis example 1 with intermediate 1(5.31g,10mmol) in this example, substituting 4-cyanophenylboronic acid (1.47g,10mmol) with (3- (9H-carbazol-9-yl) phenyl) boronic acid (2.87g,10mmol), and carrying out the same synthetic procedures as S2 in Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 693.8066, theoretical molecular weight: 693.8060, respectively; elemental analysis: theoretical value C49H31N3C84.83, H4.50, N6.06; found C84.83, H4.52, N6.05.
Synthesis example 24 preparation of Compound (216)
S1, replacing 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol) of S1 in synthetic example 2 with 2-bromobenzothiazole (3.21g,15mmol), and performing the other synthetic steps to the S1 in synthetic example 2 to obtain 4.95g of intermediate 1 with the yield of 77%;
s2. 3.96g of the objective compound (216) was obtained in 67% yield by substituting intermediate 1(6.02g,10mmol) of S2 in Synthesis example 2 with intermediate 1(4.28g,10mmol) of this example, substituting naphthalene-2-ylboronic acid (1.72g,10mmol) with 3-phenyl-9H-carbazole (2.43g,10mmol), and the other synthesis steps were the same as in Synthesis example 2, except that S2 was used.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 590.7765, theoretical molecular weight: 590.7770, respectively; elemental analysis: theoretical value C37H22N2C75.22, H3.75 and N4.74; found C75.20, H3.76, N4.74.
Synthesis example 25 preparation of Compound (237)
S1. 4.22g of intermediate 1 was obtained in 74% yield by substituting 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2-bromoimidazo [1,2-b ] pyridazine (2.97g,15mmol) and the other synthesis procedures were the same as in S1 in Synthesis example 1;
s2. by substituting intermediate 1(5.70g,10mmol) of S2 in Synthesis example 1 with intermediate 1(3.80g,10mmol) of this example, 4-cyanophenylboronic acid (1.47g,10mmol) with (9- (4-cyanophenyl) -9H-carbazol-3-yl) boronic acid (3.12g,10mmol), and by following the other synthesis procedures in Synthesis example 1, S2 was obtained, 3.97g of the objective compound (237) was obtained in a yield of 70%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 567.6077, theoretical molecular weight: 567.6080, respectively; elemental analysis: theoretical value C37H21N5C78.29, H3.73, N12.34; found C78.30, H3.73, N12.32.
Synthesis example 26 preparation of Compound (240)
S1. 4.45g of intermediate 1 was obtained in 78% yield by replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2-bromoimidazo [1,2-b ] pyridazine (2.97g,15mmol), and the other synthesis procedures were the same as in S1 in Synthesis example 1;
s2. 3.91g of the title compound (240) was obtained in 72% yield by substituting intermediate 1(5.70g,10mmol) in S2 in Synthesis example 1 with intermediate 1(3.80g,10mmol) in this example, substituting 4-cyanophenylboronic acid (1.47g,10mmol) with (9-phenyl-9H-carbazol-2-yl) boronic acid (2.87g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 542.5986, theoretical molecular weight: 542.5980, respectively; elemental analysis: theoretical value C36H22N4C79.69, H4.09 and N10.33; found C79.68, H4.10, N10.33.
Synthesis example 27 preparation of Compound (247)
S1, replacing 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol) of S2 in synthetic example 2 with 2-bromobenzothiazole (3.21g,15mmol), and performing the other synthetic steps to the S1 in synthetic example 2 to obtain 4.95g of intermediate 1 with the yield of 77%;
s2. by substituting intermediate 1(6.02g,10mmol) of S2 in Synthesis example 2 with intermediate 1(4.28g,10mmol) of this example, naphthalen-2-ylboronic acid (1.72g,10mmol) with (4- (diphenylamino) phenyl) boronic acid (2.89g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 2, 4.03g of the objective compound (247) was obtained with a yield of 68%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 592.7922, theoretical molecular weight: 592.7930, respectively; elemental analysis: theoretical value C37H24N2C74.97, H4.08, N4.73; found C74.98, H4.06, N4.74.
Preparation of Compound (258) of Synthesis example 28
S1, putting 2, 7-dibromo dibenzo-dioxin (3.41g,10mmol), 2, 4-diphenyl-6-pinacol ester-1, 3, 5-triazine (8.98g,25mmol), sodium tert-butoxide (2g,20mmol), tri-tert-butylphosphine tetrafluoroborate (0.02g, 0.06mmol) and toluene (30mL-60mL) into a 100mL three-necked flask, adding tris (dibenzylideneacetone) dipalladium (0.02g,0.03mmol) into the flask under nitrogen atmosphere, reacting at 115 ℃ for 6-12h, monitoring the reaction for a liquid phase to be basically completed, cooling the flask to room temperature, filtering, concentrating the filtrate, mixing the filtrate with a filter cake by silica gel, carrying out column chromatography by using petroleum ether with a ratio of 10:1 and dichloromethane, and concentrating the organic phase to obtain 3.36g of a target compound (258) with the yield of 52%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 646.7108, theoretical molecular weight: 646.7100, respectively; elemental analysis: theoretical value C42H26N6C78.00, H4.05 and N13.00 in percentage; found C78.02, H4.05, N12.99.
Synthesis example 29 preparation of Compound (261)
S1, replacing 2, 7-dibromo dibenzodioxin (3.41g,10mmol) of S1 in synthetic example 28 with 2, 7-dibromo dithiane (3.74g,10mmol), 2, 4-diphenyl-6-pinacol ester-1, 3, 5-triazine (8.98g,25mmol) with 2, 4-diphenyl-6- (4-borate) -1,3, 6-triazine (10.88g,25mmol), and the other synthetic steps were the same as S1 in synthetic example 28, whereby 4.74g of the objective compound (261) was obtained in a yield of 57%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 831.0277, theoretical molecular weight: 831.0280, respectively; elemental analysis: theoretical value C54H34N6C78.05, H4.12, N10.11; found C78.05, H4.14, N10.10.
Synthesis example 30 preparation of Compound (263)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2- (4-chloro-6-phenyl-1, 3, 5-triazin-2-yl) -9-phenyl-9H-carbazole (6.49g,15mmol), and the other synthesis steps were the same as S1 in Synthesis example 1, to obtain 7.32g of intermediate 1 with a yield of 74%;
s2. by substituting intermediate 1(5.70g,10mmol) of S2 in Synthesis example 1 with intermediate 1(6.60g,10mmol) of this example, and substituting (1.47g,10mmol) of 4-cyanophenylboronic acid with (7-carbonitrileisoquinolin-3-yl) boronic acid (1.98g,10mmol), the other synthesis procedures were the same as in S2 in Synthesis example 1, whereby 4.76g of the objective compound (263) was obtained in 65% yield.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 732.8022, theoretical molecular weight: 732.8030; elemental analysis: theoretical value C49H28N6C80.31, H3.85, N11.47; found C80.30, H3.85, N11.48.
Preparation of Compound (271) of Synthesis example 31
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in Synthesis example 1 with 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol), and performing the other synthesis steps similar to S1 in Synthesis example 1 to obtain 6.67g of intermediate 1 with a yield of 78%;
s2. 5.40g of the objective compound (271) was obtained in 71% yield by substituting intermediate 1(5.70g,10mmol) in S2 in Synthesis example 1 with intermediate 1(5.70g,10mmol) in this example, substituting 4-cyanobenzene boronic acid (1.47g,10mmol) with (3- (1-phenyl-1H-benzimidazol-2-yl) phenyl) boronic acid (3.14g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 759.8695, theoretical molecular weight: 759.8690, respectively; elemental analysis: theoretical value C52H33N5C82.19, H4.38, N9.22; found C82.17, H4.40, N9.22.
Synthesis example 32 preparation of Compound (282)
S1, replacing 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol) of S1 in synthetic example 2 with 2-chloro-4- (naphthalene-2-yl) -6-phenyl-1, 3, 5-triazine (4.77g,15mmol), and performing the same synthetic steps as S1 in synthetic example 2 to obtain 6.48g of intermediate 1 with a yield of 75%;
s2. by substituting intermediate 1(6.02g,10mmol) of S2 in Synthesis example 2 with intermediate 1(5.76g,10mmol) of this example, and naphthalen-2-ylboronic acid (1.72g,10mmol) with imidazo [1,2-a ] pyridin-3-ylboronic acid (1.62g,10mmol), the other synthesis procedures were the same as in S2 of Synthesis example 2, 4.11g of the objective compound (282) was obtained in 67% yield.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 613.7588, theoretical molecular weight: 613.7570, respectively; elemental analysis: theoretical value C38H23N5C74.36, H3.78, N11.41; found C74.35, H3.78, N11.42.
Synthesis example 33 preparation of Compound (286)
S1, replacing 2- ([1,1' -biphenyl ] -3-yl) -4-chloro-6-phenyl-1, 3, 5-triazine (5.16g,15mmol) of S1 in synthetic example 1 with 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (4.02g,15mmol), and performing the same synthetic procedures as S1 in synthetic example 1 to obtain 5.93g of intermediate 1 with a yield of 80%;
s2, by replacing intermediate 1(5.70g,10mmol) of S2 in Synthesis example 1 with intermediate 1(4.94g,10mmol) of this example, 4-cyanophenylboronic acid (1.47g,10mmol) with 3-azacarbazole (1.68g,10mmol), and the other synthetic steps were the same as in S2 of Synthesis example 1, 4.13g of the objective compound (286) was obtained with a yield of 71%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 581.6347, theoretical molecular weight: 581.6350, respectively; elemental analysis: theoretical value C38H23N5C78.47, H3.99, N12.04; found C78.47, H4.00, N12.05.
Synthesis example 34 preparation of Compound (312)
S1. 4.52g of the objective compound (312) was obtained with a yield of 60% by replacing 2, 7-dibromodibenzodioxin (3.41g,10mmol) in S1 in Synthesis example 28 with 2, 7-dibromodithiane (3.74g,10mmol), 2, 4-diphenyl-6-pinacol ester-1, 3, 5-triazine (8.98g,25mmol) with (4- (1-phenyl-1H-benzimidazol-2-yl) phenyl) boronic acid (7.85g,25mmol), and the other synthesis steps were the same as in S1 in Synthesis example 28.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 752.9530, theoretical molecular weight: 752.9540, respectively; elemental analysis: theoretical value C50H32N4C79.76, H4.28, N7.44; found C79.76, H4.30, N7.43.
Synthesis example 35 preparation of Compound (339)
S1. 4.21g of the objective compound (339) was obtained in 63% yield by substituting 8.98g,25mmol of 2, 4-diphenyl-6-pinacol ester-1, 3, 5-triazine (S1) in Synthesis example 28 with 7.20g,25mmol of (4- (2-azacarbazol-9-yl) phenyl) boronic acid and by following the same procedures as in Synthesis example 28 except for S1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 668.7554, theoretical molecular weight: 668.7560, respectively; elemental analysis: theoretical value C46H28N4C82.62, H4.22 and N8.38; found C82.62, H4.20, N8.39.
Synthesis example 36 preparation of Compound (345)
S1, replacing 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g,15mmol) of S1 in synthetic example 2 with 9- (3-bromophenyl) -2, 6-diazacarbazole (4.86g,15mmol), and performing other synthetic steps to the same as S1 in synthetic example 2 to obtain 6.38g of intermediate 1 with a yield of 79%;
s2. 5.00g of the title compound (345) was obtained in 68% yield by substituting intermediate 1(6.02g,10mmol) of S2 in Synthesis example 2 for intermediate 1(5.38g,10mmol) of this example, naphthalen-2-ylboronic acid (1.72g,10mmol) for (3-diphenylphosphino) phenylboronate (4.04g,10mmol), and the other synthesis steps were the same as in S2 in Synthesis example 2.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 735.8604, theoretical molecular weight: 735.8598, respectively; elemental analysis: theoretical value C46H30N3(％):C 75.08, H4.11, N5.71; found C75.10, H4.10, N5.71.
Compounds (1) to (346) were obtained according to substantially the same experimental procedures as in synthesis examples 1 to 36.
The embodiments of the present invention described in detail above are exemplary only for the purpose of illustrating the present invention and are not to be construed as limiting the present invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications.
Device example 1
The device preparation of the electron-transporting type heteroanthracene derivative provided by the invention as a guest material of a light-emitting layer can be prepared according to the method.
The evaporation was performed under high vacuum on an Indium Tin Oxide (ITO) glass substrate successively subjected to ultrasonic cleaning with a cleaning agent and deionized water. Firstly, a layer of molybdenum trioxide (MoO) with the thickness of 10nm is evaporated3) As a hole injection layer, a 70nm layer of 4,4 '-cyclohexylbis [ N, N-bis (4-methylphenyl) aniline (TAPC) was evaporated as a hole transport layer, 4' -tris (carbazol-9-yl) triphenylamine (TCTA) was evaporated in vacuum on the hole transport layer to form a 10nm electron blocking layer, and 30nm of an electron transporting type heteroanthracene derivative provided by the present invention and bis [2- ((oxo) diphenylphosphino) phenylphenyl group were mixed evaporated]Ether (DPEPO), as the luminescent layer material, the doping concentration of the electron-transporting type heteroanthracene derivative provided by the invention is 10 percent (calculated by mass fraction), and then 20nm of 3,3'- [5' - [3- (3-pyridyl) phenyl ] is evaporated][1,1':3', 1' -terphenyl]-3,3 "-diyl]Bipyridine (TmPyPB) is used as an electron transport layer, and finally a layer of lithium fluoride (LiF) with the thickness of 1nm and a layer of magnesium-silver alloy (Mg/Ag) with the thickness of 100nm are vacuum-evaporated on the electron transport layer to be used as an electron injection layer and a cathode respectively. The concrete structure is as follows: ITO/MoO3(10nm)/TAPC (70nm)/TCTA (10nm)/DPEPO: 10% wt of the electron transport type heteroanthracene derivative (30nm)/TmPyPB (20nm)/LiF (1nm)/Mg: Ag (100nm) provided by the invention.
The organic light-emitting devices 1 to 40 are prepared by respectively adopting the compounds 13, 17, 24, 26, 33, 38, 39, 43, 48, 59, 64, 79, 84, 90, 92, 96, 100, 106, 110, 114, 144, 162, 165, 173, 175, 193, 197, 201, 213, 216, 223, 230, 237, 240, 244, 247 and 253 in the electron-transporting heteroanthracene derivatives provided by the invention and the comparatives 1-2 and 4,4 '-bis (9-ethyl-3-carbazolevinyl) -1,1' -biphenyl (BCzVBi) with the following structural formulas as light-emitting object materials, and the prepared light-emitting devices 1 to 40 are subjected to performance detection.
Figure BDA0002723600110000301
Specific detection data are shown in table 1:
TABLE 1 characterization of organic electroluminescent device Properties
Figure BDA0002723600110000302
Figure BDA0002723600110000311
Figure BDA0002723600110000321
The detection result shows that the constructed heteroanthracene derivative shows excellent fluorescence electroluminescence property by utilizing the specific groups provided by the application at the 2 and 7 positions of the heteroanthracene group. Specifically, compared with a device which has the same device structure and is prepared by respectively taking a compound formed by mono-substitution of BCzVBi and a para-anthracene group commonly used in the prior art and a compound formed by double-substitution of other types of groups on the anthracene group as the light-emitting guest material, the organic electroluminescent device prepared by taking the anthracene derivative as the light-emitting guest material has remarkable advantages in the aspects of starting voltage, current efficiency, light color, service life and the like, and the increase amplitude is more than 1.19 times. The heteroanthracene derivative modifies the specific feeding/absorbing group provided by the application at 2,7 positions of heteroanthracene, a heteroanthracene core group has the rigid structure of anthracene and the strong electron-withdrawing characteristic of heteroatoms such as oxygen, sulfur and the like, a D-A type compound is formed through the modification of the specific group, the hole mobility of the material is kept, meanwhile, the electron mobility of the material is further improved through molecular microcosmic regulation, the pi conjugation degree of an acceptor fragment is effectively reduced, the problem of unmatched hole/electron mobility in the prior art is effectively solved, the quantum generation efficiency of the material is improved, the intrinsic color purity of the material is improved, and further when the heteroanthracene derivative is used as an object material of a light emitting layer to be applied to an organic electroluminescent device, the performances of the device in the aspects of starting voltage, current efficiency, service life and the like are remarkably improved, the light emitting wavelength is blue-shifted, and pure deep blue light is emitted, is an ideal light-emitting layer material, in particular a light-emitting guest material.
Device example 2
The electron transport type heteroanthracene derivative provided by the invention can be used as an electron transport material for preparing devices according to the method.
The evaporation was performed under high vacuum on an Indium Tin Oxide (ITO) glass substrate successively subjected to ultrasonic cleaning with a cleaning agent and deionized water. Firstly, a layer of molybdenum trioxide (MoO) with the thickness of 10nm is evaporated3) As a hole injection layer, next, 80nm of N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was deposited as a hole transport layer, and next, 15nm of tris (2-phenylpyridine) iridium (Ir (ppy) was deposited by mixing3) And 4,4' -bis (9-Carbazole) Biphenyl (CBP) as a light emitting layer material, Ir (ppy)3The doping concentration of the lithium ion battery is 6 percent (calculated by mass fraction), then a layer of 30nm electron transport type heteroanthracene derivative provided by the invention is evaporated to be used as an electron transport layer, and finally a layer of 1nm lithium fluoride (LiF) and 100nm magnesium-silver alloy (Mg/Ag) are evaporated to be used as an electron injection layer and a cathode in vacuum on the electron transport layer. The concrete structure is as follows: ITO/MoO3(10nm)/NPB(80nm)/CBP:6％wt Ir(ppy)3(15nm)/TmPyPB(30nm)/LiF(1nm)/Mg:Ag(100nm)。
The organic light-emitting devices 1 to 30 were produced using the compounds 6, 38, 92, 237, 258, 261, 263, 271, 280, 282, 286, 288, 312, 325, 332, 335, 339, 345 in the electron-transporting heteroanthracene derivatives provided by the present invention and the comparatives 1 to 3 and 1,3, 5-tris [ (3-pyridyl) -3-phenyl ] benzene (TmPyPB) of the following structural formulae as electron-transporting materials, respectively, and the produced light-emitting devices 1 to 31 were subjected to performance testing.
Figure BDA0002723600110000322
Figure BDA0002723600110000331
Specific detection data are shown in table 2:
TABLE 2 characterization of organic electroluminescent device Properties
Figure BDA0002723600110000332
The detection result shows that the constructed heteroanthracene derivative shows excellent electron transport property by utilizing the specific groups provided by the application at the 2 and 7 positions of the heteroanthracene group. Specifically, compared with a device which has the same device structure and is prepared by respectively using a compound formed by commonly used TmPyPB and p-heteroanthracene group monosubstitution in the prior art as an electron transport material, the organic electroluminescent device prepared by using the heteroanthracene derivative as the electron transport material has remarkable advantages in comprehensive performances in the aspects of starting voltage, current efficiency, light color, thermal stability, service life and the like, and the increase amplitude is more than 1.47 times. The heteroanthracene derivative modifies the specific electron-deficient group provided by the application at 2,7 positions of heteroanthracene, the heteroanthracene core group has the rigid structure of anthracene and the strong electron-withdrawing property of heteroatoms such as oxygen, sulfur and the like, and the double-substitution modification of the electron-deficient group greatly improves the intrinsic electron mobility of the material, ensures the thermal stability of the material, effectively solves the problem of unmatched hole/electron mobility in the prior art, and further remarkably improves the performances of the device in the aspects of starting voltage, current efficiency, thermal stability service life and the like when the heteroanthracene derivative is applied to an organic electroluminescent device as an electron transport material, so that the heteroanthracene derivative is an ideal electron transport material and also a better hole blocking material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.

Claims (6)

1. An electron-transporting heteroanthracene derivative having a structure represented by formula (I) or formula (II):
Figure FDA0003538240400000011
wherein each Z in each formula is independently selected from O, S;
R0selected from:
Figure FDA0003538240400000012
Figure FDA0003538240400000013
Figure FDA0003538240400000021
L0、L1、L2each independently selected from: a single bond, unsubstituted phenylene, unsubstituted biphenylene, unsubstituted naphthylene;
ETG0、ETG1are electron transport groups, each independently selected from:
Figure FDA0003538240400000022
Figure FDA0003538240400000023
ETG2are electron transport groups, each independently selected from:
Figure FDA0003538240400000024
wherein:
ETG2wherein each X is independently selected from: CR8Or N, R8Each independently selected from: hydrogen, unsubstituted C6～50And at least one X is selected from N;
unsubstituted C6～50Is selected from: unsubstituted phenyl, unsubstituted biphenyl, unsubstituted terphenyl, unsubstituted naphthyl.
2. The electron-transporting heteroanthracene derivative of claim 1, wherein:
Figure FDA0003538240400000025
may be further represented by one of the following groups
Figure FDA0003538240400000026
Figure FDA0003538240400000031
3. The electron transporting heteroanthracene derivative of claim 1, wherein the structure of formula (I) or formula (II) is selected from the following compounds:
Figure FDA0003538240400000032
Figure FDA0003538240400000041
Figure FDA0003538240400000051
Figure FDA0003538240400000061
4. a method for producing an electron transporting type heteroanthracene derivative according to any one of claims 1 to 3, comprising the steps of:
Figure FDA0003538240400000062
are each independently of R0And L is a halogen atom0-ETG0Boric acid ester or L0-ETG0To give a compound of formula (I);
alternatively, the first and second electrodes may be,
Figure FDA0003538240400000063
are respectively connected with L1-ETG1And L is a halogen atom of2-ETG2Boric acid ester or L2-ETG2To give a compound of formula (II);
or, L1、L2Same and ETG1And ETG2When the same phase is adopted, the two phases are the same,
Figure FDA0003538240400000064
and L1-ETG1、L2-ETG2Coupling the boronic acid ester or boronic acid compound to obtain the compound of formula (II).
5. Use of an electron-transporting heteroanthracene derivative according to any one of claims 1 to 3 as an electron-transporting layer and/or a light-emitting layer of an organic electroluminescent device.
6. An organic electroluminescent element comprising a cathode, an anode and an organic layer between the two electrodes, or comprising a light-emitting layer, a cathode, an anode and an organic layer between the two electrodes, the organic layer between the two electrodes comprising at least an electron transporting layer or a light-emitting layer, characterized in that the electron transporting layer or the light-emitting layer contains the electron transporting heteroanthracene derivative according to any one of claims 1 to 3.
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