CN113321659B - Organic electroluminescent material and device thereof - Google Patents

Organic electroluminescent material and device thereof Download PDF

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Publication number
CN113321659B
CN113321659B CN202110606615.9A CN202110606615A CN113321659B CN 113321659 B CN113321659 B CN 113321659B CN 202110606615 A CN202110606615 A CN 202110606615A CN 113321659 B CN113321659 B CN 113321659B
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synthesis example
synthesis
yield
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organic electroluminescent
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CN113321659A (en
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穆广园
庄少卿
王林
刘迪雅
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Wuhan Sunshine Optoelectronics Tech Co ltd
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Wuhan Sunshine Optoelectronics Tech Co ltd
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  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to the technical field of photoelectric material application, and discloses an organic electroluminescent material and a device thereof. The compound core structure of the invention contains electron-deficient pyrazine, electron-donating aromatic rings are incorporated at two sides of the parapyrazine, the electron cloud density of the compound core structure is increased, the conjugation is enlarged, the compound can obtain higher fluorescence quantum efficiency and stronger rigidity, the compound can realize better exciton dispersion and energy transmission by bonding an electron transmission type group or a hole transmission type group to the side edge of the core structure, and the defects of the current blue light luminescent material in the aspects of luminescent efficiency, luminescent color, service life and the like are effectively overcome, so that the OLED device has excellent comprehensive performance in the aspects of driving voltage, current efficiency, service life and the like, and has obvious application value as a luminescent material in a blue light device.

Description

Organic electroluminescent material and device thereof
Technical Field
The invention belongs to the technical field of photoelectric material application, and particularly relates to an organic electroluminescent material and a device thereof.
Background
With the development of the information age, organic electroluminescent flat panel displays (OLEDs) and large-area white light illumination, which have excellent characteristics such as high efficiency, energy saving, light weight, and thinness, have drawn more and more attention.
According to the principle of light emission, the OLED light-emitting materials are mainly classified into fluorescent materials and phosphorescent materials. The efficiency of the traditional fluorescent material cannot meet the requirement of high-efficiency device performance because the traditional fluorescent material cannot utilize triplet excitons. Phosphorescent materials containing noble metals such as iridium and platinum and novel fluorescent materials can fully utilize triplet exciton energy to realize high-efficiency luminescence with 100% internal quantum efficiency, however, the luminescent devices of the existing phosphorescent materials and the novel fluorescent materials often have one or more defects such as large efficiency roll-off, short service life, complex device structures and the like, and especially for blue materials. The blue light material with wide band gap has higher energy, and can transfer to organic luminescent materials such as green light, yellow light, red light and the like with low energy through the energy, so that a full-luminescent organic electroluminescent device is prepared.
The pyrazine structure has strong electron deficiency, the HOMO energy level of a compound material can be effectively reduced, so that a wider energy level band gap is given to the luminescent material, the aromatic ring can enhance the molecular rigidity while carrying out conjugation expansion on the core structure of the compound containing pyrazine, the material is more favorable for pore-free high-quality film formation, in addition, some cavities or electron transmission type groups are properly accessed to the side edge of the core structure, the energy transmission is more favorable, and the charge transmission efficiency and the charge transmission balance of the luminescent material are improved.
Disclosure of Invention
The invention aims to provide an organic electroluminescent material and a device thereof, which solve the defects of the existing blue light luminescent material in the aspects of luminous efficiency, luminous color, service life and the like, so that the OLED device has excellent comprehensive performance in the aspects of driving voltage, current efficiency, service life and the like.
In a first aspect, the present invention provides an organic electroluminescent material represented by the following general structural formula (1) or (2):
Figure BDA0003087611430000011
wherein the content of the first and second substances,
x is selected from O, S, N (R) 9 )、C(R 10 )(R 11 )；
Y is selected from O, S, N (R) 12 )、C(R 13 )(R 14 )；
Z 1 And Z 2 Each independently selected from C or N, and at least one is N,
R 1 to R 8 Are the same or different from each other and are each independently selected from hydrogen, fluoro, nitro, cyano, C 1～20 Alkyl of (C) 1～20 Alkoxy group of (C) 1～20 Alkylthio of, C 1～20 Silane radical of (C) 6～50 Aryl of, C 3～50 Heteroaryl of (A), C 6～50 Arylamine group of (1), C 6～50 Aryloxy group of (A), C 6～50 The arylthio group (b) of (a),
R 9 to R 11 Each independently selected from C 1～20 Alkyl of (C) 6～50 Aryl of (C) 3～50 Heteroaryl of (A), C 6～50 Arylamino group of R 10 And R 11 Independently of one another or by a single bond;
R 12 to R 14 Each independently selected from C 1～20 Alkyl of (C) 6～50 Aryl of (C) 3～50 Heteroaryl of (1), C 6～50 Of arylamine group, R 13 And R 14 Independently of one another, or by single bonds.
Further, the formula (1) is further represented by the following compounds represented by the formulae (1-1) to (1-10):
Figure BDA0003087611430000021
the formula (2) is further represented by the following compounds represented by the formulae (2-1) to (2-10):
Figure BDA0003087611430000022
further, Z is 1 And Z 2 Are all N.
Further, said R 1 To R 8 One of them is selected from C 1～20 Alkyl of (C) 1～20 Alkoxy group of (C) 1～20 Alkylthio of, C 1～20 Silane group of (C) 6～50 Aryl of, C 3～50 Heteroaryl of (A), C 6～50 Arylamine group of (1), C 6～50 Aryloxy group of (1), C 6～50 The arylthio group(s) of (a),
the R is 1 To R 8 Wherein the remaining groups are all hydrogen.
Further, said C 1～20 The alkyl group of (a) is selected from: one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
said C is 1～20 The alkoxy group of (a) is selected from: one of methoxy and ethoxy;
said C is 1～20 The alkylthio group of (a) is selected from: one of methylthio and ethylthio;
said C is 1～20 The silane groups of (a) are selected from: one of trimethylsilyl, phenyldimethylsilyl, biphenyldimethylsilyl and methyldiphenylsilyl;
said C is 6～50 The aryl group of (a) is selected from: at least one of 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, and a spirobifluorenyl group substituted or unsubstituted by a substituent;
said C is 3～50 Is selected from: at least one of a pyridyl group substituted or unsubstituted by a substituent, a pyrimidyl group substituted or unsubstituted by a substituent, a pyrazinyl group substituted or unsubstituted by a substituent, a triazinyl group substituted or unsubstituted by a substituent, an indolyl group substituted or unsubstituted by a substituent, a benzofuranyl group substituted or unsubstituted by a substituent, a benzothiophenyl group substituted or unsubstituted by a substituent, a benzoxazolyl group substituted or unsubstituted by a substituent, a benzothiazolyl group substituted or unsubstituted by a substituent, a carbazolyl group substituted or unsubstituted by a substituent, a phenylcarbazolyl group substituted or unsubstituted by a substituent, a carbazolylphenyl group substituted or unsubstituted by a substituent, a dibenzofuranyl group substituted or unsubstituted by a substituent, a dibenzothiophenyl group substituted or unsubstituted by a substituent;
said C is 6～50 The arylamine group of (a) is selected from: at least one of a diphenylamine group substituted or unsubstituted with a substituent, an N-phenylbenzidine group substituted or unsubstituted with a substituent, a diphenylene amine group substituted or unsubstituted with a substituent, an N-phenylnaphthylamine group substituted or unsubstituted with a substituent, a dinaphthylamine group substituted or unsubstituted with a substituent, and a triphenylamine group substituted or unsubstituted with a substituent;
wherein: the substituents are selected from: cyano, fluoro, nitro, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, phenyl, or combinations thereof.
Further, said R 1 To R 8 One of which is selected from the following structural formulas:
Figure BDA0003087611430000031
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Figure BDA0003087611430000041
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Figure BDA0003087611430000051
preferably, the organic electroluminescent material is selected from compounds represented by any one of the following structural formulas:
Figure BDA0003087611430000061
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Figure BDA0003087611430000071
/>
Figure BDA0003087611430000081
/>
Figure BDA0003087611430000091
/>
Figure BDA0003087611430000101
/>
Figure BDA0003087611430000111
/>
Figure BDA0003087611430000121
in a second aspect, the present invention provides an organic electroluminescent device, which mainly comprises a cathode, an anode and an organic layer between the two electrodes, or mainly comprises a light emitting layer, a cathode, an anode and an organic layer between the two electrodes, wherein the organic layer between the two electrodes contains the organic electroluminescent material.
Further, the organic layer between the two electrodes comprises a light-emitting layer, and the light-emitting layer contains the organic electroluminescent material.
Further, the light-emitting layer is composed of a light-emitting host and a light-emitting guest, and the light-emitting host contains the organic electroluminescent material.
The core structure of the organic electroluminescent material compound provided by the invention comprises pyrazine, and a strong electron-withdrawing group or a strong electron-donating group is bonded on the side edge of the pyrazine. Pyrazine structure has the electron deficiency nature, can effectively reduce the HOMO energy level of compound material to satisfy the wide energy band gap demand of dark blue light material, through the aromatic ring of incorporating into electron supply nature to pyrazine's both sides, core structure electron cloud density increases, and the conjugation enlarges, therefore compound molecule can obtain higher fluorescence quantum efficiency, and in addition, the molecular rigidity of compound also can strengthen, and thermal stability improves. In addition, the introduction of the strong electron-withdrawing or strong electron-donating side group can not only increase the molecular weight of the compound and further improve the glass transition temperature of the compound, but also effectively reduce the interaction among molecules of the compound and reduce the tight stacking among the molecules, and the compound can obtain better exciton dispersion capacity and better energy transmission, so that the invention realizes high-efficiency deep blue light emission and makes remarkable progress on the comprehensive properties of driving voltage, current efficiency, service life and the like of the device.
Detailed Description
It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Synthesis example 1: synthesis of Compound (A-5)
Figure BDA0003087611430000131
S1, adding 2-bromo-4-chlorophenol (33.19g, 160mmol), 2, 6-difluoropyrazine (19.15g, 165mmol) and potassium carbonate (33.12g, 240mmol) into a 1L reaction bottle, adding 10-15 times of N, N-dimethylformamide according to the weight of 2-bromo-4-chlorophenol, introducing nitrogen to exhaust air, heating to 145 ℃, stirring for reacting for 2-4h, cooling to room temperature, adding water into the reaction liquid, filtering, and purifying the filter cake with ethanol and/or tetrahydrofuran to obtain 31.57g of an intermediate a1 with a yield of 65%;
s2, adding the intermediate a1 (24.28g, 80mmol), 2-bromophenol (13.84g, 80mmol) and potassium carbonate (16.59g, 120mmol) into a 500mL reaction bottle, adding 10-15 times of N, N-dimethylformamide according to the weight of the intermediate a1, introducing nitrogen to exhaust air, heating to 145 ℃, stirring for reaction for 2-4h, cooling to room temperature, adding water into the reaction liquid, filtering, and purifying a filter cake with ethanol and/or tetrahydrofuran to obtain 24.47g of the intermediate b1, wherein the yield is 68%;
s3, adding the intermediate b1 (18.26g, 40mmol) into a 500mL reaction bottle, adding dimethylacetamide with the volume 10 times of that of the intermediate b1 according to the weight of the intermediate b1, introducing nitrogen to exhaust air, adding palladium acetate (0.27g, 1.2mmol) and tricyclohexylphosphine (0.34g, 1.2mmol), heating to 160 ℃, stirring for reaction for 2-4h, monitoring that no raw material remains in a liquid phase, stopping heating, cooling to room temperature, adding water, filtering, and purifying a filter cake with ethanol and/or tetrahydrofuran to obtain 6.13g of the intermediate c1 with the yield of 52%;
s4, adding magnesium (0.55g, 23mmol) and the intermediate c1 (5.89g, 20mmol) into a 250mL reaction bottle, adding 10-15 times of tetrahydrofuran by weight of the intermediate c1, introducing nitrogen, heating to 65 ℃, reacting for 2-4 hours, cooling to 0 ℃ -5 ℃, slowly dropwise adding 2-bromo-4, 6-diphenyl-1, 3, 5-triazine tetrahydrofuran solution (6.24g, 20mmol), stirring, reacting for 8-16 hours, then returning to room temperature, adding dilute hydrochloric acid into the reaction solution, quenching, separating, extracting an aqueous phase with tetrahydrofuran, combining with an organic phase, concentrating, leaching with a filter cake in a silica gel column by using 10 1 petroleum ether and dichloromethane, and concentrating to obtain 6.19g of the compound (A-5) with a yield of 63%.
Mass spectrometer MALDI-TOF-MS (m/z) =491.5063, theoretical molecular weight: 491.5100, elemental analysis: theoretical value: c 31 H 17 N 5 (%): c75.75; h3.49; n14.25; measured value: c75.76; h3.48; and (3) N14.26.
Synthetic example 2: synthesis of Compound (A-6)
Figure BDA0003087611430000132
S1, obtaining 30.11g of an intermediate a2 with a yield of 62% according to the step S1 of the synthesis example 1 in the synthesis process;
s2, replacing the intermediate a1 in the step S2 of the synthesis example 1 with the intermediate a2 (24.28g, 80mmol), and performing other synthesis processes according to the step S2 of the synthesis example 1 to obtain 24.10g of the intermediate b2 with the yield of 66%;
s3, replacing the intermediate b1 in the step S3 of the synthesis example 1 with the intermediate b2 (18.26g, 40mmol), and performing other synthesis processes according to the step S3 of the synthesis example 1 to obtain 6.72g of the intermediate c2 with the yield of 57%;
s4. The intermediate c1 in step S4 of Synthesis example 1 was replaced with the intermediate c2 (5.89g, 20mmol), and 2-bromo-4, 6-diphenyl-1, 3, 5-triazine was replaced with 2-bromo-4, 6-diphenylpyrimidine (6.22g, 20mmol), and the other synthesis procedures were followed in step S4 of Synthesis example 3, whereby 5.89g of the compound (A-6) was obtained in a yield of 60%.
Mass spectrometer MALDI-TOF-MS (m/z) =490.5248, theoretical molecular weight: 490.5220, elemental analysis: theoretical value: c 32 H 18 N 4 (%): c78.36; h3.70; n11.42; measured value: c78.35; h3.68; n11.44.
Synthetic example 3: synthesis of Compound (A-11)
Figure BDA0003087611430000141
S1, adding 5-chloro-2- (methylsulfinyl) phenylboronic acid (34.95g, 160mmol), 2, 6-dibromopyrazine (39.25g, 165mmol), potassium carbonate (44.16g, 320mmol), a 400mL toluene/ethanol/water mixed solvent with a volume ratio of 2;
s2, adding the intermediate a3 (27.19g, 82mmol), 2- (methylsulfinyl) phenylboronic acid (14.729g, 80mmol), potassium carbonate (22.08g, 160mmol) and 250mL of a toluene/ethanol/water mixed solvent with the volume ratio of 2;
s3, adding the intermediate b3 (19.55g, 50mmol) into a 250mL reaction bottle, stirring at room temperature for 24h, adding 150mL of a water/pyridine mixed solvent with a volume ratio of 8:1, stirring at 110 ℃ for 30min, cooling to room temperature, extracting with dichloromethane, drying the obtained substance with magnesium sulfate, distilling under reduced pressure, and then, carrying out column separation on the residue obtained to obtain 6.54g of an intermediate c3 with the yield of 40%;
s4, adding the intermediate c3 (3.27g, 10mmol), (10-phenylanthracen-9-yl) boric acid (2.98g, 10mmo), potassium carbonate (2.76g, 20mmol) and a 50mL toluene/ethanol/water mixed solvent with the volume ratio of 2.
Mass spectrometer MALDI-TOF-MS (m/z) =544.6957, theoretical molecular weight: 544.6900, elemental analysis: theoretical value: c 36 H 20 N 2 (%): c79.38; h3.70; n5.14; measured value: c78.36; h3.69; and (5) N5.16.
Synthetic example 4: synthesis of Compound (A-24)
Figure BDA0003087611430000142
S1, replacing 5-chloro-2- (methylsulfinyl) phenylboronic acid in the step S1 of the synthesis example 3 with (4-chloro-2- (carbomethoxy) phenyl) boronic acid (34.31g, 160mmol), and performing the other synthesis processes according to the step S1 of the synthesis example 1 to obtain 31.45g of an intermediate a4 with the yield of 60%;
s2, replacing the intermediate a3 in the step S2 of the synthesis example 3 with an intermediate a4 (26.20g, 82mmol), replacing 2- (methylsulfinyl) phenylboronic acid with (2- (carbomethoxy) phenyl) boronic acid (14.40g, 80mmol), and performing the other synthesis processes according to the step S2 of the synthesis example 3 to obtain 19.60g of an intermediate b4 with the yield of 64%;
s3, adding the intermediate b4 (15.31g, 40mmol) and 3mol/L methylmagnesium bromide (107mL, 320mmol) into a 500mL reaction bottle, adding 10 times of tetrahydrofuran according to the weight of the intermediate b4, introducing nitrogen to exhaust air, heating to 65 ℃, stirring for reaction for 2-4h, cooling to room temperature, adding saturated ammonium chloride to quench the reaction, separating liquid, extracting a water phase with tetrahydrofuran, concentrating the water phase together with an organic phase, and purifying with ethanol and/or tetrahydrofuran to obtain 10.41g of intermediate c4 with the yield of 68%;
s4, adding the intermediate c4 (7.66g, 20mmol) and 220mL of acetic acid/concentrated hydrochloric acid solvent with the volume ratio of 10;
s5, adding the intermediate d4 (3.47g, 10mmol), benzoxazol-2-yl boric acid (1.63g, 10mmol), potassium carbonate (2.76g, 20mmol) and a 50mL toluene/ethanol/water mixed solvent with the volume ratio of 2.
Mass spectrometer MALDI-TOF-MS (m/z) =429.5175, theoretical molecular weight: 429.5230, elemental analysis: theoretical value: c 29 H 23 N 3 (%): c81.09; h5.40; n9.78; measured value: c81.10; h5.38; and (9) N9.77.
Synthesis example 5: synthesis of Compound (A-28)
Figure BDA0003087611430000151
S1, replacing 5-chloro-2- (methylsulfinyl) phenylboronic acid in the step S1 of the synthesis example 3 with (5-chloro-2-nitrophenyl) boronic acid (32.22g, 160mmol), and performing the other synthesis processes according to the step S1 of the synthesis example 3 to obtain 31.70g of an intermediate a5 with a yield of 63%;
s2, replacing the intermediate a3 in the step S2 of the synthesis example 3 with an intermediate a5 (25.16g, 82mmol), replacing 2- (methylsulfinyl) phenylboronic acid with (2-nitrophenyl) boronic acid (13.35g, 80mmol), and performing other synthesis processes according to the step S1 of the synthesis example 3 to obtain 19.69g of an intermediate b5 with a yield of 69%;
s3, adding the intermediate b5 (14.27g, 40mmol), triethyl phosphite (66.46g, 400mmol) and chlorobenzene (49.02g, 400mmol) into a 250mL reaction bottle, heating and refluxing for 12h, cooling to room temperature, adding water, extracting with dichloromethane, separating liquid, concentrating an organic phase, and purifying with ethanol and/or tetrahydrofuran to obtain 6.09g of an intermediate c5 with the yield of 52%;
s4. In a 250mL reaction flask, the above intermediate c5 (5.85g, 20mmol), bromobenzene (7.07g, 45mmol), potassium carbonate 5.52g (40 mmol) and 100mL of N, N-dimethylacetamide were added. Introducing nitrogen, adding 0.76g (4 mmol) of cuprous iodide and 1.44g (8 mmol) of phenanthroline, heating, refluxing and stirring for 8 hours, cooling to room temperature, adding water into the reaction solution, filtering, and purifying the filter cake with ethanol and/or tetrahydrofuran to obtain 6.32g of an intermediate d5, wherein the yield is 71%;
s5. Into a 100mL reaction flask, the above intermediate d5 (4.45g, 10mmol), di-p-tolylamine (2.37g, 12mmol), potassium carbonate 2.76g (20 mmol) and 50mL of N, N-dimethylacetamide were added. Introducing nitrogen, adding 0.19g (1 mmol) of cuprous iodide and 0.36g (2 mmol) of phenanthroline, heating, refluxing and stirring for 8 hours, then cooling to room temperature, adding water into the reaction solution, filtering, leaching a filter cake with petroleum ether and dichloromethane of 10.
Mass spectrometer MALDI-TOF-MS (m/z) =605.7536, theoretical molecular weight: 605.7450, elemental analysis: theoretical value: c 42 H 31 N 5 (%): c83.28; h5.16; n11.56; measured value: c83.27; h5.15; n11.57.
Synthetic example 6: synthesis of Compound (A-37)
Figure BDA0003087611430000152
S1, replacing 2-bromo-4-chlorophenol with 2-bromo-5-chlorophenol (33.19g, 160mmol) and 2, 6-difluoropyrazine with 2-bromo-5-fluoropyrazine (28.32g, 160mmol) in step S1 of synthetic example 1, and performing other synthetic processes according to step S1 of synthetic example 1 to obtain 43.15g of intermediate a6 with a yield of 74%;
s2, adding the intermediate a6 (29.15g, 80mmol) into a 500mL reaction bottle, adding dimethylacetamide with the volume 10 times of that of the intermediate a6 according to the weight of the intermediate a6, introducing nitrogen to exhaust air, adding palladium acetate (0.36g, 1.6 mmol) and tricyclohexylphosphine (0.45g, 1.6 mmol), heating to 160 ℃, stirring for reaction for 2-4h, monitoring that no raw material remains in a liquid phase, stopping heating, cooling to room temperature, adding water, filtering, and purifying a filter cake with ethanol and/or tetrahydrofuran to obtain 12.47g of the intermediate b6 with the yield of 55%;
s3, adding the intermediate b6 (11.62g, 41mmol), 2- (methylsulfinyl) phenylboronic acid (7.36g, 40mmol), potassium carbonate (11.04g, 80mmol) and 100mL of a toluene/ethanol/water mixed solvent with a volume ratio of 2;
s4, adding the intermediate c6 (6.86g, 20mmol) into a 250mL reaction bottle, stirring at room temperature for 24 hours, then adding 150mL of a water/pyridine mixed solvent with the volume ratio of 8:1, stirring at 110 ℃ for 30 minutes, then cooling to room temperature, extracting by using dichloromethane, drying the obtained substance by using magnesium sulfate, distilling under reduced pressure, and then carrying out column separation on the residue obtained by the step to obtain 2.8g of the intermediate d6, wherein the yield is 45%;
s5. Into a 50mL reaction flask, the above intermediate d6 (1.56g, 5 mmol), 5-hydro-pyrido [4,3-b ] indole (1.01g, 6 mmol), potassium carbonate 1.38g (10 mmol) and 20mL of N, N-dimethylacetamide were charged. Introducing nitrogen, adding 0.1g (0.5 mmol) of cuprous iodide and 0.18g (1 mmol) of phenanthroline, heating, refluxing and stirring for 8 hours, then cooling to room temperature, adding water into the reaction solution, filtering, leaching a filter cake in a silica gel column by using petroleum ether and dichloromethane of 10.
Mass spectrometer MALDI-TOF-MS (m/z) =442.4861, theoretical molecular weight: 442.4960, elemental analysis: theoretical value: c 27 H 14 N 4 (%): c73.29; h3.19; n12.66; measured value: c73.28; h3.20; and N12.64.
Synthetic example 7: synthesis of Compound (A-45)
Figure BDA0003087611430000161
S1, replacing 2-bromo-4-chlorophenol with 2-bromo-5-chlorophenol (33.19g, 160mmol) and 2, 6-difluoropyrazine with 2-bromo-5-fluoropyrazine (28.32g, 160mmol) in step S1 of synthetic example 1, and performing other synthetic processes according to step S1 of synthetic example 1 to obtain 41.39g of intermediate a7 with a yield of 71%;
s2, replacing a6 in the step S2 of the synthetic example 6 with a7 (29.15g, 80mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 6 to obtain 11.95g of an intermediate b7 with the yield of 53%;
s3, replacing b6 of S3 in the synthesis example 6 with b7 (11.62g, 41mmol), replacing 2- (methylsulfinyl) phenylboronic acid with (2- (carbomethoxy) phenyl) boronic acid (7.20 g, 40mmol), and performing the other synthesis processes according to the step S3 in the synthesis example 6 to obtain 8.40g of an intermediate c7 with the yield of 62%;
s4, adding the intermediate c7 (6.78g, 20mmol), 3mol/L methylmagnesium bromide (26.67mL, 80mmol) and 10 times of tetrahydrofuran according to the weight of the intermediate c7 into a 250mL reaction bottle, introducing nitrogen to exhaust air, heating to 65 ℃, stirring for reaction for 2-4 hours, cooling to room temperature, adding saturated ammonium chloride to quench the reaction, separating liquid, extracting an aqueous phase with tetrahydrofuran, concentrating the aqueous phase together with an organic phase, and purifying with ethanol and/or tetrahydrofuran to obtain 5.01g of intermediate d7, wherein the yield is 74%;
s5, adding the intermediate d7 (3.39g, 10mmol) and 100mL of acetic acid/concentrated hydrochloric acid solvent with the volume ratio of 10 in a 250mL reaction bottle, heating to 85 ℃, stirring and reacting for 2-4 hours, monitoring that no raw material is remained in a liquid phase, stopping heating, adding water to quench the reaction, filtering, and purifying a filter cake by using ethanol and/or tetrahydrofuran to obtain 2.25g of the intermediate e7, wherein the yield is 70%;
s6, adding the intermediate e7 (1.6 g,5 mmol), [1,1' -biphenyl ] -4-yl boronic acid (0.99g, 5 mmol), potassium carbonate (1.38g, 10 mmol) and 20mL of a toluene/ethanol/water mixed solvent with the volume ratio of 2.
Mass spectrometer MALDI-TOF-MS (m/z) =438.5356, theoretical molecular weight: 438.5300, elemental analysis: theoretical value: c 31 H 22 N 2 (%): c84.91; h5.06; n6.39; measured value: c84.91; h5.07; and 6.38 of N.
Synthesis example 8: synthesis of Compound (A-68)
Figure BDA0003087611430000171
S1, replacing 2-bromo-4-chlorophenol in S1 of synthetic example 1 with 2-bromophenol (27.68g, 160mmol), replacing 2, 6-difluoropyrazine with 2-bromo-5-fluoropyrazine (28.32g, 160mmol), and performing other synthetic processes according to S1 of synthetic example 1 to obtain 40.12g of intermediate a8 with a yield of 76%;
s2, replacing a6 in the step S2 of the synthetic example 6 with a8 (26.40g, 80mmol), and performing other synthetic processes according to the step S2 of the synthetic example 6 to obtain 11.16g of an intermediate b8 with the yield of 56%;
s3. Substitution of b6 in S3 of Synthesis example 6 with b8 (10.21g, 41mmol), substitution of 2- (methylsulfinyl) phenylboronic acid with (4-chloro-2-nitrophenyl) boronic acid (8.05g, 40mmol), and other syntheses were carried out in S3 of Synthesis example 6 to give 8.73g of intermediate c8 in 67% yield;
s4, adding the intermediate c8 (6.51g, 20mmol), triethyl phosphite (16.62g, 100mmol) and chlorobenzene (12.26g, 100mmol) into a 50mL reaction bottle, heating and refluxing for 12 hours, cooling to room temperature, adding water, extracting with dichloromethane, separating liquid, concentrating an organic phase, and purifying with ethanol and/or tetrahydrofuran to obtain 3.41g of intermediate d8, wherein the yield is 58%;
s5, into a 100mL reaction flask, the above intermediate d8 (2.94g, 10mmol), bromobenzene (1.73g, 111mmol), potassium carbonate 2.76g (20 mmol) and 50mL of N, N-dimethylacetamide were added. Introducing nitrogen, adding 0.19g (1 mmol) of cuprous iodide and 0.36g (2 mmol) of phenanthroline, heating, refluxing and stirring for 8 hours, cooling to room temperature, adding water into the reaction solution, filtering, and purifying the filter cake with ethanol and/or tetrahydrofuran to obtain 2.74g of an intermediate e8, wherein the yield is 74%;
s6. replacement of intermediate e7 in step S6 of Synthesis example 7 by e8 (1.85g, 5 mmol), [1,1' -biphenyl ] -4-ylboronic acid by imidazo [1,2-b ] pyridazin-2-ylboronic acid (0.81g, 5 mmol) and the other synthetic procedures in step S6 of Synthesis example 7 gave 1.77g of Compound A-68 in 78% yield.
Mass spectrometer MALDI-TOF-MS (m/z) =452.4697, theoretical molecular weight: 452.4770, elemental analysis: theoretical values are as follows: c 28 H 16 N 6 (%): c74.33; h3.56; n18.57; measured value: c74.31; h3.54; n18.58.
Synthetic example 9: synthesis of Compound (A-73)
Figure BDA0003087611430000172
S1. Replacement of 5-chloro-2- (methylsulfinyl) phenylboronic acid in step S1 of Synthesis example 3 by (4-chloro-2- (methylsulfinyl) phenyl) boronic acid (34.95g, 160mmol) and further Synthesis procedure in step S1 of Synthesis example 3 gave 32.89g of intermediate a9 in 62% yield;
s2, adding the intermediate a9 (33.16g, 100mmol) into a 500mL reaction bottle, stirring at room temperature for 24h, adding 300mL of a water/pyridine mixed solvent with a volume ratio of 8:1, stirring at 110 ℃ for 30min, cooling to room temperature, extracting with dichloromethane, drying the obtained substance with magnesium sulfate and distilling under reduced pressure, and then, carrying out column separation on the residue obtained to obtain 12.88g of the intermediate b9 with the yield of 43%;
s3, replacing b6 of S3 in the synthesis example 6 with b9 (12.28g, 41mmol), replacing 2- (methylsulfinyl) phenylboronic acid with (2- (carbomethoxy) phenyl) boronic acid (7.20 g, 40mmol), and performing the other synthesis processes according to the step S3 in the synthesis example 6 to obtain 9.51g of an intermediate c9 with the yield of 67%;
s4, replacing c7 in the step S4 of the synthesis example 7 with c9 (7.10 g, 20mmol), and performing the other synthesis processes according to the step S4 of the synthesis example 7 to obtain 5.39g of an intermediate d9 with the yield of 76%;
s5, replacing d7 in the step S5 of the synthesis example 7 with d9 (3.55g, 10mmol), and performing other synthesis processes according to the step S5 of the synthesis example 7 to obtain 2.46g of an intermediate e9 with the yield of 73%;
s6. Substitution of e7 in step S6 of Synthesis example 7 with e9 (1.68g, 5mmol) and [1,1' -biphenyl ] -4-ylboronic acid with (4- (benzothiazol-2-yl) phenyl) boronic acid (1.28g, 5mmol) and the other synthetic procedures in step S6 of Synthesis example 7 gave 1.82g of Compound A-73 in 71% yield.
Mass spectrometer MALDI-TOF-MS (m/z) =511.6559, theoretical molecular weight: 511.6610, elemental analysis: theoretical value: c 32 H 21 N 3 (%): c75.12; h4.14; n8.21; measured value: c75.13; h4.13; and N8.22.
Synthetic example 10: synthesis of Compound (A-88)
Figure BDA0003087611430000181
S1, replacing 5-chloro-2- (methylsulfinyl) phenylboronic acid in the step S1 of the synthesis example 3 with (2- (methylsulfinyl) phenyl) boronic acid (29.44g, 160mmol), and performing the other synthesis processes according to the step S1 of the synthesis example 3 to obtain 30.91g of an intermediate a10 with a yield of 65%;
s2, replacing the intermediate a9 in the step S2 of the synthesis example 9 with a10 (29.72g, 100mmol), and performing other synthesis processes according to the step S2 of the synthesis example 9 to obtain 12.20g of the intermediate b10 with the yield of 46 percent;
s3. Substitution of intermediate b6 in step S3 of Synthesis example 6 with b10 (10.87g, 41mmol), substitution of 2- (methylsulfinyl) phenylboronic acid with (4-chloro-2-nitrophenyl) boronic acid (8.05g, 40mmol), and other syntheses were carried out in step S3 of Synthesis example 6 to give 9.43g of intermediate c10 in 69% yield;
s4, replacing the intermediate c8 in the step S4 of the synthesis example 8 with c10 (6.84g, 20mmol), and performing other synthesis processes according to the step S4 of the synthesis example 8 to obtain 3.41g of the intermediate d10 with the yield of 55%;
s5, replacing the intermediate d8 in the step S5 of the synthesis example 8 with d10 (3.10 g,10 mmol), and performing other synthesis processes according to the step S5 of the synthesis example 8 to obtain 2.97g of the intermediate e10 with the yield of 77 percent;
s6. In a 50mL reaction flask, the above intermediate e10 (1.93g, 5 mmol), 9-hydrogen-carbazole (1.00g, 6 mmol), potassium carbonate 1.38g (10 mmol), and 20mL of N, N-dimethylacetamide were added. Introducing nitrogen, adding 0.1g (0.5 mmol) of cuprous iodide and 0.18g (1 mmol) of phenanthroline, heating, refluxing and stirring for 8 hours, then cooling to room temperature, adding water into the reaction solution, filtering, leaching a filter cake in a silica gel column by using petroleum ether and dichloromethane of 10.
Mass spectrometer MALDI-TOF-MS (m/z) =516.6274, theoretical molecular weight: 516.6220, elemental analysis: theoretical value: c 34 H 20 N 4 (%): c79.05; h3.90; n10.85; measured value: c79.05; h3.91; n10.84.
Synthetic example 11: synthesis of Compound (A-104)
Figure BDA0003087611430000182
S1, adding (2- (carbomethoxy) phenyl) boric acid (57.59g, 320mmol), 2, 6-dibromopyrazine (78.50g, 330mmol), potassium carbonate (88.32g, 640 mmol), 600mL of a toluene/ethanol/water mixed solvent with the volume ratio of 2;
s2, adding the intermediate a11 (46.89g, 160mmol), 3mol/L methylmagnesium bromide (213.33mL, 640mmol) and 10 times of tetrahydrofuran by weight of the intermediate a11 into a 1L reaction bottle, introducing nitrogen to exhaust air, heating to 65 ℃, stirring for reaction for 2-4 hours, cooling to room temperature, adding saturated ammonium chloride to quench the reaction, separating liquid, extracting an aqueous phase with tetrahydrofuran, concentrating the aqueous phase together with an organic phase, and purifying with ethanol and/or tetrahydrofuran to obtain 33.77g of the intermediate b11 with the yield of 72%;
s3, adding the intermediate b11 (23.45g, 80mmol) and 220mL of acetic acid/concentrated hydrochloric acid solvent with the volume ratio of 10 to the intermediate b11 into a 500mL reaction bottle, heating to 85 ℃, stirring for reacting for 2-4h, monitoring that no raw material is left in a liquid phase, stopping heating, adding water for quenching reaction, filtering, and purifying a filter cake by using ethanol and/or tetrahydrofuran to obtain 14.97g of the intermediate c11 with the yield of 68%;
s4, adding the intermediate c11 (11.28g, 41mmol), (4-chloro-2-nitrophenyl) boric acid (8.05g, 40mmol), potassium carbonate (11.04g, 80mmol) and 100mL of a toluene/ethanol/water mixed solvent with the volume ratio of 2;
s5, adding the intermediate d11 (7.04g, 20mmol), triethyl phosphite (16.62g, 100mmol) and chlorobenzene (12.26g, 100mmol) into a 50mL reaction bottle, heating and refluxing for 12 hours, cooling to room temperature, adding water, extracting with dichloromethane, separating liquid, concentrating an organic phase, and purifying with ethanol and/or tetrahydrofuran to obtain 3.58g of intermediate e11, wherein the yield is 56%;
s6, in a 100mL reaction flask, the above intermediate e11 (3.20g, 10mmol), bromobenzene (1.73g, 111mmol), potassium carbonate 2.76g (20 mmol) and 50mL of N, N-dimethylacetamide were added. Introducing nitrogen, adding 0.19g (1 mmol) of cuprous iodide and 0.36g (2 mmol) of phenanthroline, heating, refluxing and stirring for 8 hours, cooling to room temperature, adding water into the reaction solution, filtering, and purifying the filter cake with ethanol and/or tetrahydrofuran to obtain 2.89g of an intermediate f11 with the yield of 73%;
s7, adding the intermediate f11 (1.98g, 5 mmol), (4- (2-phenyl-1 hydrogen-benzimidazol-1-yl) phenyl) boric acid (1.57g, 5 mmol), potassium carbonate (1.38g, 10mmol) and 30mL of a toluene/ethanol/water mixed solvent with the volume ratio of 2.
Mass spectrometer MALDI-TOF-MS (m/z) =629.7583, theoretical molecular weight: 629.7670, elemental analysis: theoretical value: c 44 H 31 N 5 (%): c83.92; h4.96; n11.12; measured value: c83.94; h4.95; and (3) N11.12.
Synthetic example 12: synthesis of Compound (B-5)
Figure BDA0003087611430000191
S1, replacing 2, 6-difluoropyrazine in S1 of Synthesis example 1 with 2, 5-difluoropyrazine (19.15g, 165mmol), and performing the other synthesis procedures according to S1 of Synthesis example 1 to obtain 30.59g of intermediate a12 with a yield of 63%;
s2, replacing the intermediate a1 in the step S2 of the synthesis embodiment 1 with an intermediate a12 (24.28g, 80mmol), and performing other synthesis processes according to the step S2 of the synthesis embodiment 1 to obtain 23.74g of the intermediate b12 with the yield of 65%;
s3, replacing the intermediate b1 in the step S3 of the synthesis example 1 with an intermediate b12 (18.26g, 40mmol), and performing other synthesis processes according to the step S3 of the synthesis example 1 to obtain 5.90g of the intermediate c12 with the yield of 50%;
s4. Substitution of intermediate c3 for intermediate c12 (2.95g, 10 mmol) and (10-phenylanthren-9-yl) boronic acid for (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid (3.53g, 10 mmol) in step S4 of Synthesis example 4, and other Synthesis procedures in accordance with step S4 of Synthesis example 4 gave 4.20g of Compound B-5 in a yield of 74%.
Mass spectrometer MALDI-TOF-MS (m/z) =567.6123, theoretical molecular weight: 567.6080, elemental analysis: theoretical value: c 37 H 21 N 5 (%): c78.29; h3.73; n12.34; measured value: c78.27; h3.74; and (6) N12.34.
Synthetic example 13: synthesis of Compound (B-6)
Figure BDA0003087611430000201
S1, replacing 2, 6-difluoropyrazine in S1 of Synthesis example 1 with 2, 5-difluoropyrazine (19.15g, 165mmol), and performing the other synthesis procedures according to S1 of Synthesis example 1 to obtain 29.62g of intermediate a13 with a yield of 61%;
s2, replacing the intermediate a1 in the step S2 of the synthesis embodiment 1 with an intermediate a13 (24.28g, 80mmol), and performing other synthesis processes according to the step S2 of the synthesis embodiment 1 to obtain 24.47g of the intermediate b13 with the yield of 67%;
s3, replacing the intermediate b1 in the step S3 of the synthesis example 1 with an intermediate b13 (18.26g, 40mmol), and performing other synthesis processes according to the step S3 of the synthesis example 1 to obtain 6.25g of the intermediate c13 with the yield of 53 percent;
s4, replacing the intermediate c1 in the step S4 of the synthesis example 1 with the intermediate c13 (5.89g, 20mmol), and performing the other synthesis processes according to the step S4 of the synthesis example 1 to obtain 6.40g of the compound B-6 with the yield of 65%.
Mass spectrometer MALDI-TOF-MS (m/z) =491.5046, theoretical molecular weight: 491.5100, elemental analysis: theoretical value: c 31 H 17 N 5 (%): c75.75; h3.49; n14.25; measured value: c75.76; h3.48; and N14.24.
Synthesis example 14: synthesis of Compound (B-10)
Figure BDA0003087611430000202
S1, replacing 2, 6-dibromopyrazine in the step S1 of the synthesis example 3 with 2, 5-dibromopyrazine (39.25g, 165mmol), and performing the other synthesis processes according to the step S1 of the synthesis example 1 to obtain 35.56g of an intermediate a14 with a yield of 65%;
s2, replacing the intermediate a3 in the step S2 of the synthesis example 3 with the intermediate a14 (27.19g, 82mmol), and performing other synthesis processes according to the step S2 of the synthesis example 3 to obtain 21.89g of the intermediate b14 with the yield of 70%;
s3, replacing the intermediate b3 in the step S3 of the synthesis example 3 with an intermediate b14 (19.55g, 50mmol), and performing other synthesis processes according to the step S3 of the synthesis example 3 to obtain 6.21g of an intermediate c14 with the yield of 38%;
s4, replacing the intermediate c3 in the step S4 of the synthesis example 3 with the intermediate c14 (3.27g, 10mmol), and performing other synthesis processes according to the step S4 of the synthesis example 3 to obtain 3.70g of the compound B-10 with the yield of 68%.
Mass spectrometer MALDI-TOF-MS (m/z) =544.6958, theoretical molecular weight: 544.6900, elemental analysis: theoretical value: c 36 H 20 N 2 (%): c79.38; h3.70; n5.14; measured value: c79.36; h3.72; and (5) N5.15.
Synthetic example 15: synthesis of Compound (B-20)
Figure BDA0003087611430000203
S1, replacing 5-chloro-2- (methylsulfinyl) phenylboronic acid in the step S1 of the synthesis example 3 with (4-chloro-2- (carbomethoxy) phenyl) boronic acid (34.31g, 160mmol) and 2, 6-dibromopyrazine with 2, 5-dibromopyrazine (39.25g, 165mmol), and performing the other synthesis processes according to the step S1 of the synthesis example 1 to obtain 32.50g of an intermediate a15 with the yield of 62%;
s2, replacing the intermediate a3 in the step S2 of the synthesis example 3 with the intermediate a15 (26.20g, 82mmol), replacing 2- (methylsulfinyl) phenylboronic acid with (2- (carbomethoxy) phenyl) boronic acid (14.40g, 80mmol), and performing other synthesis processes according to the step S2 of the synthesis example 3 to obtain 19.89g of the intermediate b15 with the yield of 65%;
s3, replacing the intermediate b4 in the step S3 of the synthesis example 4 with an intermediate b15 (15.31g, 40mmol), and performing other synthesis processes according to the step S3 of the synthesis example 4 to obtain 10.11g of an intermediate c15 with the yield of 66%;
s4, replacing the intermediate c4 in the step S4 of the synthesis example 4 with the intermediate c15 (7.66g, 20mmol), and performing other synthesis processes according to the step S4 of the synthesis example 4 to obtain 4.37g of the intermediate d15 with the yield of 63%;
s5. Replacement of intermediate d4 in step S5 of Synthesis example 4 by intermediate d15 (3.47g, 10mmol), replacement of benzoxazol-2-ylboronic acid by (4- (diphenylamino) phenyl) boronic acid (2.89g, 10mmol), and other procedures in step S5 of Synthesis example 4 gave 4.01g of compound B-20 in a yield of 72%.
Mass spectrometer MALDI-TOF-MS (m/z) =555.7327, theoretical molecular weight: 555.7250, elemental analysis: theoretical values are as follows: c 40 H 33 N 3 (%): c86.45; h5.99; n7.56; measured value: c86.45; h5.97; and N7.58.
Synthetic example 16: synthesis of Compound (B-30)
Figure BDA0003087611430000211
S1. Substitution of 5-chloro-2- (methylsulfinyl) phenylboronic acid for (5-chloro-2-nitrophenyl) boronic acid (32.22g, 160mmol) and 2, 6-dibromopyrazine for 2, 5-dibromopyrazine (39.25g, 165mmol) in step S1 of Synthesis example 3, and the other synthesis procedures were in accordance with step S1 of Synthesis example 3, 32.20g of intermediate a16 was obtained with a yield of 64%;
s2, replacing a3 in the step S2 of the synthetic example 3 with a16 (25.16g, 82mmol), replacing 2- (methylsulfinyl) phenylboronic acid with (2-nitrophenyl) boronic acid (13.35g, 80mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 3 to obtain 19.41g of an intermediate b16 with the yield of 68%;
s3, replacing the intermediate b5 in the step S3 of the synthesis example 5 with an intermediate b16 (14.27g, 40mmol), and performing other synthesis processes according to the step S3 of the synthesis example 5 to obtain 6.3g of an intermediate c16 with the yield of 54%;
s4, replacing the intermediate c5 in the step S4 of the synthesis example 5 with an intermediate c16 (5.85g, 20mmol), and performing other synthesis processes according to the step S4 of the synthesis example 5 to obtain 5.78g of an intermediate d16 with the yield of 65%;
s5. Replacement of intermediate d5 in step S5 of Synthesis example 5 by intermediate d16 (4.45g, 10mmol), replacement of di-p-toluidine by 9H-pyrrolo [2,3-B:4,5-c' ] bipyridine (1.69g, 10mmol), and other Synthesis procedures in accordance with step S5 of Synthesis example 5, 4.34g of Compound B-30 was obtained in a yield of 75%.
Mass spectrometer MALDI-TOF-MS (m/z) =577.6472, theoretical molecular weight: 577.6510, elemental analysis: theoretical value: c 38 H 23 N 7 (%): c79.01; h4.01; n16.97; measured value: c79.00; h4.02; and N16.96.
Synthetic example 17: synthesis of Compound (B-43)
Figure BDA0003087611430000212
S1, replacing 2-bromo-4-chlorophenol in S1 in the step of synthetic example 1 with 2-bromophenol (27.68g, 160mmol), and replacing 2, 6-difluoropyrazine with 2-bromo-6-fluoropyrazine (28.32g, 160mmol), and performing other synthetic processes according to the step S1 of synthetic example 1 to obtain 39.06g of intermediate a17 with a yield of 74%;
s2, replacing the intermediate a6 in the step S2 of the synthesis example 6 with the intermediate a17 (26.40g, 80mmol), and carrying out other synthesis processes according to the step S2 of the synthesis example 6 to obtain 11.36g of the intermediate b17 with the yield of 57%;
s3. Replacement of intermediate b6 in step S3 of Synthesis example 6 with intermediate b17 (10.21g, 41mmol), replacement of 2- (methylsulfinyl) phenylboronic acid with (5-chloro-2- (methylsulfinyl) phenyl) boronic acid (8.74g, 40mmol), and the other syntheses were carried out in step S3 of Synthesis example 6 to give 9.86g of intermediate c17 in a yield of 65%;
s4, replacing the intermediate c6 in the step S4 of the synthesis example 6 with the intermediate c17 (6.86g, 20mmol), and performing other synthesis processes according to the step S3 of the synthesis example 6 to obtain 9.27g of the intermediate d17 with the yield of 48%;
s5, replacing the intermediate e7 in the step S6 of the synthesis example 7 with the intermediate d17 (1.55g, 5 mmol) and replacing the [1,1' -biphenyl ] -4-yl boronic acid with the (3- (benzoxazol-2-yl) phenyl) boronic acid (1.20g, 5 mmol), and performing the other synthesis processes according to the step S6 of the synthesis example 7 to obtain 1.71g of the compound B-43 with the yield of 73%.
Mass spectrometer MALDI-TOF-MS (m/z) =469.5096, theoretical molecular weight: 469.5180, elemental analysis: theoretical value: c 29 H 15 N 3 (%): c74.19; h3.22; n8.95; measured value: c74.20; h3.20; and N8.96.
Synthetic example 18: synthesis of Compound (B-48)
Figure BDA0003087611430000221
S1, replacing 2, 6-difluoropyrazine in S1 of synthetic example 1 with 2-bromo-6-fluoropyrazine (28.32g, 160mmol), and carrying out other synthetic processes according to S1 of synthetic example 1 to obtain 41.98g of intermediate a18 with a yield of 72%;
s2, replacing a6 in the step S2 of the synthesis example 6 with a18 (29.15g, 80mmol), and performing other synthesis processes according to the step S2 of the synthesis example 6 to obtain 12.25g of the intermediate b18 with the yield of 54 percent;
s3, replacing b6 of S3 in the synthesis example 6 with b18 (11.62g, 41mmol), replacing 2- (methylsulfinyl) phenylboronic acid with (2- (carbomethoxy) phenyl) boronic acid (7.20 g, 40mmol), and performing the other synthesis processes according to the step S3 in the synthesis example 6 to obtain 8.54g of an intermediate c18 with a yield of 63%;
s4, replacing c7 in the step S4 of the synthesis example 7 with c18 (6.78g, 20mmol), and performing other synthesis processes according to the step S4 of the synthesis example 7 to obtain 5.15g of an intermediate d18 with the yield of 76%;
s5, replacing d7 in the step S5 of the synthesis example 7 with d18 (3.39g, 10mmol), and performing other synthesis processes according to the step S5 of the synthesis example 7 to obtain 2.28g of an intermediate e18 with the yield of 71%;
s6, adding magnesium (0.14g, 5.75mmol), the intermediate e18 (1.6g, 5 mmol) and 10-15 times of tetrahydrofuran by weight of the intermediate e18 into a 50mL reaction bottle, introducing nitrogen, heating to 65 ℃ for reaction for 2-4h, cooling to 0-5 ℃, slowly dropwise adding a tetrahydrofuran solution (1.55g, 5 mmol) of 2-bromo-4, 6-diphenylpyridine into the reaction bottle, stirring for reaction for 8-16h, then returning to room temperature, adding dilute hydrochloric acid into the reaction solution for quenching reaction, separating, extracting a water phase with tetrahydrofuran, combining with an organic phase, concentrating, leaching the water phase with a filter cake in a silica gel column by using 10.
Mass spectrometer MALDI-TOF-MS (m/z) =515.6235, theoretical molecular weight: 515.6160, elemental analysis: theoretical value: c 36 H 25 N 3 (%): c83.86; h4.89; n8.15; measured value: c83.84; h4.90; and (8) N8.14.
Synthetic example 19: synthesis of Compound (B-63)
Figure BDA0003087611430000222
S1, replacing 2-bromo-4-chlorophenol in S1 of synthetic example 1 with 2-bromophenol (27.68g, 160mmol), replacing 2, 6-difluoropyrazine with 2-bromo-6-fluoropyrazine (28.32g, 160mmol), and carrying out other synthetic processes according to S1 of synthetic example 1 to obtain 37.49g of intermediate a19 with a yield of 71%;
s2, replacing a6 in the step S2 of the synthetic example 6 with a19 (26.40g, 80mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 6 to obtain 11.36g of an intermediate b19 with the yield of 57%;
s3. The substitution of b6 for b19 (10.21g, 41mmol), the substitution of 2- (methylsulfinyl) phenylboronic acid for (4-chloro-2-nitrophenyl) boronic acid (8.05g, 40mmol) and the other synthetic procedures, as per step S3 of Synthesis example 6, gave 8.69g of intermediate c19, 69% yield;
s4, replacing c8 in the step S4 of the synthesis example 8 with c19 (6.51g, 20mmol), and performing other synthesis processes according to the step S4 of the synthesis example 8 to obtain 3.23g of an intermediate d19 with the yield of 55%;
s5. Replacing d8 in step S5 of Synthesis example 8 as d19 (2.94g, 10mmol), and performing the other synthesis procedures in step S5 of Synthesis example 8 to obtain 2.81g of intermediate e19 with a yield of 76%;
s6. replacement of e7 in step S6 of Synthesis example 7 with e19 (1.85g, 5 mmol) and [1,1 '-biphenyl ] -4-ylboronic acid with [1,1':3',1 "-terphenyl ] -5' -ylboronic acid (1.37g, 5 mmol) and the other syntheses proceed according to step S6 of Synthesis example 7 to give 1.94g of Compound B-63 in 69% yield.
Mass spectrometer MALDI-TOF-MS (m/z) =563.6564, theoretical molecular weight: 563.6600, elemental analysis: theoretical value: c 40 H 25 N 3 (%): c85.24; h4.47; n7.46; measured value: c85.25; h4.47; and (7) N7.45.
Synthesis example 20: synthesis of Compound (B-79)
Figure BDA0003087611430000231
S1. Substitution of 5-chloro-2- (methylsulfinyl) phenylboronic acid for (2- (methylsulfinyl) phenyl) boronic acid (29.44g, 160mmol) and 2, 6-dibromopyrazine for 2, 5-dibromopyrazine (39.25g, 165mmol) in step S1 of Synthesis example 3, and the other synthesis procedures were in accordance with step S1 of Synthesis example 3, whereby 31.38g of intermediate a20 was obtained in a yield of 66%;
s2, replacing the intermediate a9 in the step S2 of the synthesis example 9 with an intermediate a20 (29.72g, 100mmol), and performing other synthesis processes according to the step S2 of the synthesis example 9 to obtain 12.46g of the intermediate b20 with the yield of 47%;
s3. Replacement of b6 by b20 (10.87g, 41mmol), 2- (methylsulfinyl) phenylboronic acid by (4-chloro-2- (carbomethoxy) phenyl) boronic acid (8.58g, 40mmol) in step S3 of Synthesis example 6, and the other syntheses follow step S3 of Synthesis example 6 to afford 8.80g of intermediate c20, 62% yield;
s4, replacing c7 in the step S4 of the synthesis example 7 with c20 (7.10 g, 20mmol), and performing other synthesis processes according to the step S4 of the synthesis example 7 to obtain 5.18g of an intermediate d20 with the yield of 73%;
s5, replacing d7 in the step S5 of the synthesis example 7 with d20 (3.55g, 10mmol), and performing other synthesis processes according to the step S5 of the synthesis example 7 to obtain 2.39g of an intermediate e20 with the yield of 71%;
s6. replacement of e7 in step S6 of Synthesis example 7 by e20 (1.68g, 5 mmol) and [1,1' -biphenyl ] -4-ylboronic acid by (1-phenyl-1H-benzimidazol-2-yl) boronic acid (1.19g, 5 mmol) and the other synthetic procedures were in accordance with step S6 of Synthesis example 7, whereby 1.71g of Compound B-79 was obtained in a yield of 69%.
Mass spectrometer MALDI-TOF-MS (m/z) =494.6248, theoretical molecular weight: 494.6160, element analysis: theoretical value: c 32 H 22 N 4 (%): c77.71; h4.48; n11.33; measured value: c77.69; h4.49; n11.33.
Synthetic example 21: synthesis of Compound (B-92)
Figure BDA0003087611430000232
S1, replacing 5-chloro-2- (methylsulfinyl) phenylboronic acid in the step S1 of the synthesis example 3 with (2- (methylsulfinyl) phenyl) boronic acid (29.44g, 160mmol) and 2, 6-dibromopyrazine with 2, 5-dibromopyrazine (39.25g, 165mmol), and performing the other synthesis processes according to the step S1 of the synthesis example 3 to obtain 32.34g of an intermediate a21 with a yield of 68%;
s2, replacing the intermediate a9 in the step S2 of the synthesis example 9 with a21 (29.72g, 100mmol), and performing other synthesis processes according to the step S2 of the synthesis example 9 to obtain 12.20g of the intermediate b21 with the yield of 46 percent;
s3. Substitution of intermediate b6 in step S3 of Synthesis example 6 with b21 (10.87g, 41mmol), substitution of 2- (methylsulfinyl) phenylboronic acid with (4-chloro-2-nitrophenyl) boronic acid (8.05g, 40mmol), and other syntheses were carried out in step S3 of Synthesis example 6 to give 9.57g of intermediate c21 in a yield of 70%;
s4, replacing the intermediate c8 in the step S4 of the synthesis example 8 with c21 (6.84g, 20mmol), and performing the other synthesis processes according to the step S4 of the synthesis example 8 to obtain 3.35g of the intermediate d21 with the yield of 54%;
s5, replacing the intermediate d8 in the step S5 of the synthesis example 8 with d21 (3.10 g,10 mmol), and performing other synthesis processes according to the step S5 of the synthesis example 8 to obtain 2.77g of the intermediate e21 with the yield of 72 percent;
s6. Replacement of intermediate e7 in step S6 of Synthesis example 7 by e21 (1.93g, 5 mmol) and [1,1' -biphenyl ] -4-ylboronic acid by imidazo [1,2-a ] pyridin-3-ylboronic acid (0.81g, 5 mmol) gave, according to step S6 of Synthesis example 8, 1.74g of Compound B-92 in 74% yield.
Mass spectrometer MALDI-TOF-MS (m/z) =467.5461, theoretical molecular weight: 467.5500, elemental analysis: theoretical value: c 29 H 17 N 5 (%): c74.50; h3.67; n14.98; measured value: c74.51; h3.65; and N14.99.
Synthesis example 22: synthesis of Compound (B-95)
Figure BDA0003087611430000241
S1, replacing (2- (carbomethoxy) phenyl) boric acid in the step S1 of the synthesis example 11 with (4-chloro-2- (carbomethoxy) phenyl) boric acid (68.61g, 320mmol) and 2, 6-dibromopyrazine with 2, 5-dibromopyrazine (78.50g, 330mmol), and performing the other synthesis processes according to the step S1 of the synthesis example 11 to obtain 64.99g of an intermediate a22 with the yield of 62 percent;
s2, replacing the intermediate a11 in the step S2 of the synthesis example 11 with the intermediate a22 (52.41g, 160mmol), and carrying out other synthesis processes according to the step S2 of the synthesis example 11 to obtain 35.12g of the intermediate b22 with the yield of 67%;
s3, replacing the intermediate b11 in the step S3 of the synthesis example 11 with the intermediate b22 (26.21g, 80mmol), and performing other synthesis processes according to the step S3 of the synthesis example 11 to obtain 17.09g of the intermediate c22 with the yield of 69%;
s4, replacing the intermediate c11 in the step S4 of the synthesis example 11 with the intermediate c22 (12.69g, 41mmol), and replacing the (4-chloro-2-nitrophenyl) boric acid with the (2-nitrophenyl) boric acid (6.67g, 40mmol), and performing the other synthesis processes according to the step S4 of the synthesis example 11 to obtain 9.15g of the intermediate d22 with the yield of 65%;
s5, replacing the intermediate d11 in the step S5 of the synthesis example 11 with the intermediate d22 (7.04g, 20mmol), and performing the other synthesis processes according to the step S5 of the synthesis example 11 to obtain 3.71g of the intermediate e22 with the yield of 58%;
s6. replacement of intermediate e11 in step S6 of Synthesis example 11 by intermediate e22 (3.19g, 10mmol), and other Synthesis procedures in accordance with step S6 of Synthesis example 11, 3.01g of intermediate f22 was obtained in a yield of 76%;
s7, 2.17g of Compound B-95 was obtained in 72% yield in accordance with S7 of Synthesis example 11, except that intermediate f11 in S7 of Synthesis example 11 was replaced with f22 (1.98g, 5 mmol) and (4- (2-phenyl-1H-benzimidazol-1-yl) phenyl) boronic acid was replaced with (9-phenyl-9H-carbazol-2-yl) boronic acid (1.44g, 5 mmol).
Mass spectrometer MALDI-TOF-MS (m/z) =602.7506, theoretical molecular weight: 602.7410, elemental analysis: theoretical value: c 43 H 30 N 4 (%): c85.69; h5.02; n9.30; measured value: c85.67; h5.03; and (9) N9.30.
Device example 1
The glass substrate with the 120nm ITO transparent film is sequentially and respectively ultrasonically cleaned for 10min by acetone, isopropanol and deionized water, vacuum drying is carried out for 2h at 105 ℃, then UV ozone washing is carried out for 15min, and the ITO glass substrate is conveyed to a vacuum evaporation machine.
Vacuum evaporating molybdenum trioxide (MoO) on the surface of the ITO film 3 ) To form a10 nm thick hole injection layer;
next, on the above hole injection layer, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC) was vacuum-evaporated to form a hole transport layer having a thickness of 70 nm;
next, on the above hole transport layer, compound a-5 (as a light emitting host material, 90 wt%) prepared in the above synthesis example 1 and 4,4 '-bis (9-ethyl-3-carbazolevinyl) -1,1' -biphenyl (BCzVBi, as a light emitting guest material, 10 wt%) were co-vacuum evaporated to form a light emitting layer with a thickness of 30 nm;
next, on the above light emitting layer, 3'- [5' - [3- (3-pyridyl) phenyl ] [1,1':3',1 "-terphenyl ] -3,3" -diyl ] bipyridine (TmPyPB) was vacuum-evaporated to form an electron transporting layer having a thickness of 40 nm;
next, on the electron transport layer, lithium fluoride (LiF) was vacuum evaporated to form an electron injection layer with a thickness of 1 nm;
finally, on the above electron injection layer, aluminum (Al) was vacuum-evaporated to form a cathode of 100 nm.
Device example 2 to device example 22
An organic electroluminescent device was prepared in the same manner as in device example 1, except that the compounds synthesized in the above synthesis examples 2 to 22 were respectively used instead of the compounds a-5 prepared in the above synthesis example 1.
Comparative device example 23 to comparative device example 26
An organic electroluminescent device was produced in the same manner as in device example 1, except that the compound A-5 produced in Synthesis example 1 was replaced with the following compounds C-1, C-2, C-3 and C-4, respectively;
Figure BDA0003087611430000251
the organic electroluminescent devices prepared in the device examples and the device comparative examples were subjected to performance tests, and the results are shown in table 1:
Figure BDA0003087611430000252
as can be seen from the data in table 1 above, the core structure provided by the present invention includes pyrazine and organic electroluminescent material bonded with a strong electron-withdrawing or strong electron-donating side group, and due to the electron-deficiency property of the pyrazine structure and the conjugated expansion of the aromatic ring to the pyrazine-containing core structure, the compound molecule can obtain higher fluorescence quantum efficiency and stronger rigidity, so that the present invention realizes high-efficiency deep blue light emission and excellent compound thermal stability, and the compound is good in film formation by vacuum evaporation.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. An organic electroluminescent material, characterized in that: the general structural formula of the compound of the organic electroluminescent material is shown as formula (1) or formula (2):
Figure FDA0004034917050000011
wherein the content of the first and second substances,
x is selected from O, S, N (R) 9 )、C(R 10 )(R 11 )；
Y is selected from O, S, N (R) 12 )、C(R 13 )(R 14 )；
Z 1 And Z 2 Are all N, and are all N,
the R is 1 To R 8 One of which is selected from the following structural formulas:
Figure FDA0004034917050000012
/>
Figure FDA0004034917050000021
/>
Figure FDA0004034917050000031
Figure FDA0004034917050000032
wherein each Z is 3 Each independently selected from CH, N, and at least one Z in each group 3 Is selected from N;
the R is 1 To R 8 Wherein the remaining groups are all hydrogen;
R 9 to R 11 Each independently selected from C 1～20 Alkyl of (C) 6～50 Aryl of (A), R 10 And R 11 Independently of one another, or connected by a single bond;
R 12 to R 14 Each independently selected from C 1～20 Alkyl of (C) 6～50 Aryl of (A), R 13 And R 14 Independently of one another, or connected by a single bond;
said C is 1～20 The alkyl group of (a) is selected from: one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
said C is 6～50 Is selected from: phenyl substituted or unsubstituted with a substituent;
wherein: the substituent is selected from: cyano, fluoro, nitro, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, phenyl, or combinations thereof.
2. An organic electroluminescent material according to claim 1, wherein:
the formula (1) is further represented by the following compounds represented by the formulae (1-1) to (1-10):
Figure FDA0004034917050000033
the formula (2) is further represented by the following compounds represented by the formulae (2-1) to (2-10):
Figure FDA0004034917050000041
/>
3. an organic electroluminescent material according to claim 1, wherein: the organic electroluminescent material is selected from a compound shown in any one of the following structural formulas:
Figure FDA0004034917050000051
/>
Figure FDA0004034917050000061
/>
Figure FDA0004034917050000071
/>
Figure FDA0004034917050000081
/>
Figure FDA0004034917050000091
/>
Figure FDA0004034917050000101
/>
Figure FDA0004034917050000111
4. an organic electroluminescent device mainly comprises a cathode, an anode and an organic layer between the two electrodes, or mainly comprises a light emitting layer, the cathode, the anode and the organic layer between the two electrodes, and is characterized in that: the organic layer between the two electrodes comprises the organic electroluminescent material according to any one of claims 1 to 3.
5. The organic electroluminescent device according to claim 4, wherein: the organic layer between the two electrodes comprises a light-emitting layer comprising the organic electroluminescent material according to any one of claims 1 to 3.
6. The organic electroluminescent device according to claim 4, wherein: the light-emitting layer is composed of a light-emitting host and a light-emitting guest, and the light-emitting host comprises the organic electroluminescent material according to any one of claims 1 to 3.
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