CN113121584A - Heterocyclic compound and organic electroluminescent device comprising same - Google Patents

Heterocyclic compound and organic electroluminescent device comprising same Download PDF

Info

Publication number
CN113121584A
CN113121584A CN202110338709.2A CN202110338709A CN113121584A CN 113121584 A CN113121584 A CN 113121584A CN 202110338709 A CN202110338709 A CN 202110338709A CN 113121584 A CN113121584 A CN 113121584A
Authority
CN
China
Prior art keywords
group
unsubstituted
substituent
substituted
group substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110338709.2A
Other languages
Chinese (zh)
Inventor
穆广园
庄少卿
方祥
刘迪雅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Shangsai Optoelectronics Technology Co ltd
Original Assignee
Wuhan Shangsai Optoelectronics Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Shangsai Optoelectronics Technology Co ltd filed Critical Wuhan Shangsai Optoelectronics Technology Co ltd
Priority to CN202110338709.2A priority Critical patent/CN113121584A/en
Publication of CN113121584A publication Critical patent/CN113121584A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms

Abstract

The invention relates to the technical field of photoelectric material application, and discloses a heterocyclic compound and an organic electroluminescent device comprising the same. According to the invention, a series of abundant silicon-containing luminescent materials with excellent comprehensive performance are obtained by changing the types of electron-transport groups or hole-transport groups bonded with the core structure of the silafluorene, and the defects of the existing blue light luminescent material in the aspects of efficiency, luminescent color, stability 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 a significant application value as a luminescent material in a blue light device.

Description

Heterocyclic compound and organic electroluminescent device comprising same
Technical Field
The invention belongs to the technical field of photoelectric material application, and particularly relates to a heterocyclic compound and an organic electroluminescent device containing the same.
Background
The organic semiconductor material has the advantages of diversified structures, relatively low manufacturing cost, excellent photoelectric performance and the like, so the organic semiconductor material has great application potential in the field of photoelectric devices such as Organic Light Emitting Diodes (OLEDs) and the like.
At present, phosphorescent light-emitting materials are the mainstream light-emitting materials in the field of OLEDs, particularly red and green light. The phosphorescent light emitting material can emit light by using singlet excitons and triplet excitons at the same time, and can achieve almost 100% of internal electroluminescence emission quantum efficiency. Compared with red light and green light materials, the blue light material has higher energy, can be transferred to organic luminescent materials with low energy such as green light, yellow light, red light and the like through energy, and is very suitable for preparing a full-luminescent organic electroluminescent device. However, the efficiency roll-off of blue phosphorescent materials at high current density is serious, the stability of devices is poor, and the technical progress is greatly restricted.
The luminescent material containing the silicon heterofluorene structural unit has higher glass transition temperature and better thermal stability, which can improve the stability and the service life of a device.
Disclosure of Invention
The invention aims to provide a heterocyclic compound and an organic electroluminescent device containing the same, which overcome the defects of the existing blue light emitting material in the aspects of efficiency, light emitting color, stability 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.
The first aspect of the present invention provides a heterocyclic compound represented by the following chemical formula 1:
chemical formula 1
Figure BDA0002998611610000011
Wherein R is1And R2Or R2And R3Or R3And R4Is a group bound to any of the following chemical formula 2;
R1to R4Wherein R is a group not bonded to R in the following chemical formula 25To R8Are the same or different from each other and are each independently selected from hydrogen, fluoro, nitro, cyano, C1～20Alkyl of (C)1～20Alkoxy group of (C)1～20Alkylthio of, C1～20Silane group of (C)6～50Aryl of (C)3～50Heteroaryl of (A), C6～50Arylamine group of (1), C6～50Aryloxy group of (A), C6～50Arylthio group of (a);
chemical formula 2
Figure BDA0002998611610000012
Wherein is R of the chemical formula 11And R2Or R2And R3Or R3And R4The position of the combination is the position of the combination,
z is independently selected from O, S, N (R)13)、C(R14)(R15)，
R9To R12Are the same or different from each other and are each independently selected from hydrogen, fluoro, nitro, cyano, C1～20Alkyl of (C)1～20Alkoxy group of (C)1～20Alkylthio of, C1～20Silane group of (C)6～50Aryl of (C)3～50Heteroaryl of (A), C6～50Arylamine group of (1), C6～50Aryloxy group of (A), C6～50The arylthio group(s) of (a),
R13-R15are respectively selected from C1～20Alkyl of (a), phenyl unsubstituted or substituted by alkyl, alkoxy, nitrile, nitro, fluoro, biphenyl unsubstituted or substituted by alkyl, alkoxy, nitrile, nitro, fluoro, terphenyl unsubstituted or substituted by alkyl, alkoxy, nitrile, nitro, fluoro, naphthyl unsubstituted or substituted by alkyl, alkoxy, nitrile, nitro, fluoro;
R14and R15Independently of one another, or by single bonds.
Further, R of chemical formula 11To R4Wherein the group not bonded to x in chemical formula 2 is hydrogen;
chemical formula 1 is further represented by any one of chemical formulae (1-1) or (1-2):
Figure BDA0002998611610000021
wherein R is5To R8Is the same as in chemical formula 1,
z and R9To R12Is the same as chemical formula 2.
Further, the chemical formula (1-1) is further represented by chemical formulas (1-3) to (1-5):
Figure BDA0002998611610000022
the chemical formula (1-2) is further represented by chemical formulas (1-6) to (1-8):
Figure BDA0002998611610000023
wherein R is5To R8Is the same as in chemical formula 1,
z and R9To R12Is the same as chemical formula 2.
Further, R5To R12One of them is selected from C1～20Alkyl of (C)1～20Alkoxy group of (C)1～20Alkylthio of, C1～20Silane group of (C)6～50Aryl of (C)3～50Heteroaryl of (A), C6～50Arylamine group of (1), C6～50Aryloxy group of (A), C6～50Arylthio of, R5To R12Wherein the remaining groups are all hydrogen.
Preferably, R5To R8One of them is selected from C1～20Alkyl of (C)1～20Alkoxy group of (C)1～20Alkylthio of, C1～20Silane group of (C)6～50Aryl of (C)3～50Heteroaryl of (A), C6～50Arylamine group of (1), C6～50Aryloxy group of (A), C6～50Arylthio of, R5To R8Of the remaining radical, R9To R12Are both hydrogen.
Further, R5-R12The method comprises the following steps:
each of said C1～20The alkyl group of (a) is selected from: one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
each of said C1～20The alkoxy group of (a) is selected from: one of methoxy and ethoxy;
each of said C1～20The alkylthio group of (a) is selected from: one of methylthio and ethylthio;
each of said C1～20The silane groups of (a) are selected from: one of trimethylsilyl, phenyldimethylsilyl, biphenyldimethylsilyl and methyldiphenylsilyl;
each of said C6～50Is 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;
each of said C3～50Is selected from: a pyridyl group substituted or unsubstituted with a substituent, a pyrimidyl group substituted or unsubstituted with a substituent, a pyrazinyl group substituted or unsubstituted with a substituent, 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 phenylcarbazolyl group substituted or unsubstituted with a substituent, a carbazolylphenyl group substituted or unsubstituted with a substituent, a dibenzofuranyl group substituted or unsubstituted with a substituent, a dibenzothiophenyl group substituted or unsubstituted with a substituentOne kind of the material is selected;
each of said C6～50The 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 above substituents are selected from: one or the combination of cyano, fluoro, nitro, methyl, ethyl, isopropyl, tertiary butyl, methoxy, ethoxy and phenyl, and each substitution is single substitution or multiple substitution.
Further, R5To R12One of which is selected from the following structural formulas:
Figure BDA0002998611610000031
Figure BDA0002998611610000041
Figure BDA0002998611610000051
further, chemical formula 1 is selected from the following compounds:
Figure BDA0002998611610000061
Figure BDA0002998611610000071
Figure BDA0002998611610000081
Figure BDA0002998611610000091
Figure BDA0002998611610000101
Figure BDA0002998611610000111
Figure BDA0002998611610000121
Figure BDA0002998611610000131
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, the organic layer between the two electrodes comprising the heterocyclic compound.
Further, the organic layer between the two electrodes includes a light-emitting layer composed of a light-emitting host and a light-emitting guest, and the light-emitting host or the light-emitting guest contains the heterocyclic compound.
The organic electroluminescent material compound provided by the invention takes silafluorene as a core structure and is bonded with a strong electron-withdrawing group or a strong hole-transporting group. The invention obtains a series of compounds containing silicon structures by changing the side groups in the molecular structure, the silicon-containing core structure of the compounds can endow the luminescent material with higher glass transition temperature and better thermal stability, in addition, the larger space volume of the core structure and the methyl on the silafluorene can effectively reduce the interaction among the molecules of the compounds and reduce the compact stacking among the molecules, and meanwhile, the compounds can have better exciton dispersion capability and realize better energy transmission by properly matching the electron transmission type or hole transmission side groups, thereby obviously improving the luminescent performance of the organic electroluminescent device prepared by the compounds compared with the device in the prior art.
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 (1-13)
Figure BDA0002998611610000141
S1, in a 500mL reaction bottle, adding 10-15 times of N, N-dimethylformamide by volume based on the weight of 3-hydroxy-8-chloro-5, 5-dimethylsilafluoroalkane (20.86g,80mmol), 1-bromo-2-fluorobenzene (14g,80mmol) and potassium carbonate (16.59g,120mmol), introducing nitrogen to exhaust air, heating to 145 ℃, stirring for reaction for 2-4h, cooling to room temperature, adding water into a reaction solution, filtering, purifying a filter cake by using a mixture of ethanol and petroleum ether to obtain 22.29g of an intermediate a1, wherein the yield is 67%;
s2, adding the intermediate a1(16.63g,40mmol) into a 250mL reaction bottle, adding dimethylacetamide with the volume 10 times of that of the intermediate a1 according to the weight of the intermediate a1, introducing nitrogen to exhaust air, adding palladium acetate (0.18g,0.8mmol) and tricyclohexylphosphine (0.22g,0.8mmol), heating to 160 ℃, stirring for reaction for 2-4 hours, 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 or ethyl acetate to obtain 7.50g of intermediate b1 with the yield of 56%.
S3, adding the intermediate b1(6.70g,20mmol), (4- (4, 6-diphenyl-1, 3, 5-triazine-2-yl) phenyl) boric acid (7.06g,20mmol), potassium carbonate (5.52g,40mmol) and 90mL of toluene/ethanol/water mixed solvent with the volume ratio of 2:1:1 into a 250mL reaction bottle, introducing nitrogen to exhaust air, then adding tetrakis (triphenylphosphine) palladium (0.12g,0.1mmol), heating to 85 ℃, stirring and reacting for 6-12h, then cooling to room temperature, filtering, separating the filtrate, concentrating the organic phase, leaching the organic phase and the filter cake together with petroleum ether and dichloromethane with the ratio of 10:1 in a silica gel column, and concentrating to obtain 9.00g of the compound (1-13) with the yield of 74%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 607.7865, theoretical molecular weight: 607.7880, elemental analysis: theoretical value: c41H29N3(%): c81.02; h4.81; n6.91; measured value: c81.01; h4.80; and N6.92.
Synthesis example 2: synthesis of Compound (1-17)
Figure BDA0002998611610000142
S1, replacing 3-hydroxy-8-chloro-5, 5-dimethylsilylfluorethane in the step S1 of the synthesis example 1 with 3-hydroxy-7-chloro-5, 5-dimethylsilylfluorethane (20.86g,80mmol), and performing the other synthesis processes according to the step S1 of the synthesis example 1 to obtain 21.28g of an intermediate a2 with the yield of 64%.
S2, replacing the intermediate a1 in the step S2 of the synthetic example 1 with the intermediate a2(16.63g,40mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 1 to obtain 6.70g of the intermediate b2 with the yield of 50%.
S3. by substituting intermediate b1 in step S3 of Synthesis example 1 with intermediate b2(6.70g,20mmol) and substituting (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid with (3- (1-phenyl-1H-benzimidazol-2-yl) phenyl) boronic acid (6.28g,20mmol), 8.08g of compound (1-17) was obtained in 71% yield by following the procedure of step S3 of Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 568.7612, theoretical molecular weight: 568.7510, elemental analysis: theoretical value: c39H28N2(%): c82.36; h4.96; n4.93; measured value: c82.37; h4.95; and N4.94.
Synthetic example 3: synthesis of Compound (1-21)
Figure BDA0002998611610000151
S1, replacing 3-hydroxy-8-chloro-5, 5-dimethylsilylfluorethane in the step S1 of the synthesis example 1 with 2-hydroxy-7-chloro-5, 5-dimethylsilylfluorethane (20.86g,80mmol), and carrying out other synthesis processes according to the step S1 of the synthesis example 1 to obtain 20.62g of an intermediate a3 with the yield of 62%.
S2, replacing the intermediate a1 in the step S2 of the synthetic example 1 with the intermediate a3(16.63g,40mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 1 to obtain 7.10g of the intermediate b3 with the yield of 53%.
S3. in a 250mL reaction flask, intermediate b3(6.70g,20mmol) above, 3-phenyl-9-hydro-carbazole (6.08g,25mmol), potassium carbonate 5.52g (40mmol), and 100mL of N, N-dimethylacetamide were added. Introducing nitrogen, adding 0.38g (2mmol) of cuprous iodide and 0.72g (4mmol) of phenanthroline, heating, refluxing and stirring for 8 hours, cooling to room temperature, adding water, separating liquid, performing organic phase vacuum distillation, and purifying with ethanol to obtain 8.67g of a compound (1-21) with the yield of 80%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 541.7217, theoretical molecular weight: 541.7250, elemental analysis: theoretical value: c38H27N (%): c84.25; h5.02; n2.59; measured value: c84.25; h5.01; and (5) N2.60.
Synthetic example 4: synthesis of Compound (1-33)
Figure BDA0002998611610000152
S1, adding 7-bromo-2-chloro-5, 5-dimethylsilylfluorenane (28.48g,88mmol), (2- (methylsulfinyl) phenyl) boric acid (14.72g,80mmol), potassium carbonate (22.08g,160mmol) and 200mL of a toluene/ethanol/water mixed solvent with a volume ratio of 2:1:1 in a 500mL reaction bottle, introducing nitrogen to discharge air, adding tetrakis (triphenylphosphine) palladium (0.46g,0.4mmol), heating to 85 ℃, stirring to react for 6-12h, cooling to room temperature, filtering, separating filtrate, concentrating organic phase, leaching the organic phase together with filter cake in silica gel column with 10:1 petroleum ether and dichloromethane, and concentrating to obtain 20.83g of intermediate a4 with the yield of 68%.
S2. in a 250mL reaction flask, the above intermediate a4(19.15g,50mmol) was added, stirred at room temperature for 24h, then 150mL of a water/pyridine mixed solvent with a volume ratio of 8:1 was added, stirred at 110 ℃ for 30min, then cooled to room temperature, extracted with dichloromethane, the resulting material was dried over magnesium sulfate and distilled under reduced pressure, and then the residue thus obtained was subjected to column separation to obtain 7.72g of intermediate b4 with a yield of 44%.
S3, adding the intermediate b4(3.51g,10mmol), (9, 9-dimethyl-9H-fluoren-3-yl) boric acid (2.38g,10mmol), potassium carbonate (2.76g,20mmol) and 50mL of toluene/ethanol/water mixed solvent with the volume ratio of 2:1:1 into a 100mL reaction bottle, introducing nitrogen to exhaust air, then adding tetrakis (triphenylphosphine) palladium (0.06g,0.05mmol), heating to 85 ℃, stirring for reaction for 6-12h, cooling to room temperature, filtering, separating filtrate, concentrating an organic phase, rinsing the organic phase together with a filter cake in a silica gel column by using 10:1 petroleum ether and dichloromethane, and concentrating to obtain 3.66g of the compound (1-33) with the yield of 72%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 508.7483, theoretical molecular weight: 508.7540, elemental analysis: theoretical value: c35H28(%): c82.63; h5.55; measured value: c82.62; H5.54.
synthesis example 5: synthesis of Compound (1-34)
Figure BDA0002998611610000161
S1, the raw materials and the synthetic process are carried out according to the step S1 of the synthetic example 4, and 19.92g of the intermediate a5 can be obtained with the yield of 65%.
S2, replacing the intermediate a4 in the step S2 of the synthetic example 4 with the intermediate a5(19.15g,50mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 4 to obtain 7.03g of the intermediate b5 with the yield of 40%.
S3, adding magnesium (0.28g,11.5mmol), the intermediate b5(3.51g,10mmol) into a 100mL reaction bottle, adding 10-15 times of tetrahydrofuran according to the weight of the intermediate b5, introducing nitrogen, heating to 65 ℃, reacting for 2-4h, cooling to 0 ℃ -5 ℃, slowly dropwise adding 2-bromo-4, 6-diphenyl-1, 3, 5-triazine tetrahydrofuran solution (3.12g,10mmol), stirring, reacting for 8-16h, then returning to room temperature, adding dilute hydrochloric acid into the reaction liquid to quench the reaction, separating, extracting the aqueous phase with tetrahydrofuran, combining with the organic phase, concentrating, purifying with ethanol and/or tetrahydrofuran to obtain 3.40g of the compound (1-34), wherein the yield is 62%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 547.7409, theoretical molecular weight: 547.7510, elemental analysis: theoretical value: c35H25N3(%): c76.75; h4.60; n7.67; measured value: c76.74; h4.59; and N7.68.
Synthetic example 6: synthesis of Compound (1-35)
Figure BDA0002998611610000162
S1, replacing 7-bromo-2-chloro-5, 5-dimethylsilylfluorethane in step S1 of Synthesis example 4 with 6-bromo-2-chloro-5, 5-dimethylsilylfluorethane (28.48g,88mmol), and performing other synthesis processes according to step S1 of Synthesis example 4 to obtain 19.00g of intermediate a6 with a yield of 62%.
S2, replacing the intermediate a4 in the step S2 of the synthetic example 4 with the intermediate a6(19.15g,50mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 4 to obtain 6.66g of the intermediate b6 with the yield of 38%.
S3. 3.56g of the compound (1-35) was obtained with a yield of 65% by substituting intermediate b5 in step S3 of Synthesis example 5 with intermediate b6(3.51g,10mmol) and by following the procedure of step S3 of Synthesis example 5.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 547.7474, theoretical molecular weight: 547.7510, elemental analysis: theoretical value: c35H25N3(%): c76.75; h4.60; n7.67; measured value: c76.76; h4.59; and N7.66.
Synthetic example 7: synthesis of Compound (1-55)
Figure BDA0002998611610000163
S1, adding 7-bromo-2-chloro-5, 5-dimethyl silafluorene (28.48g,88mmol), (2- (methoxycarbonyl) phenyl) boric acid (14.40g,80mmol), potassium carbonate (22.08g,160mmol) and 200mL of toluene/ethanol/water mixed solvent with the volume ratio of 2:1:1 into a 500mL reaction bottle, introducing nitrogen to discharge air, then adding tetrakis (triphenylphosphine) palladium (0.46g,0.4mmol), heating to 85 ℃, stirring to react for 6-12h, then cooling to room temperature, filtering, separating filtrate, concentrating organic phase, leaching the organic phase together with filter cake in silica gel column with 10:1 petroleum ether and dichloromethane, and concentrating to obtain 19.71g of intermediate a7 with the yield of 65%.
S2, adding the intermediate a7(15.16g,40mmol) and 3mol/L methylmagnesium bromide (55mL,160mmol) into a 250mL reaction flask, adding 10 times of tetrahydrofuran by weight of the intermediate a7, 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 an aqueous phase with tetrahydrofuran, concentrating the aqueous phase together with an organic phase, and purifying a mixture of ethanol and petroleum ether to obtain 10.91g of the intermediate b7 with the yield of 72%.
S3, adding the intermediate b7(7.58g,20mmol) and 220mL of acetic acid/concentrated hydrochloric acid solvent with the volume ratio of 10:1 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 toluene and/or ethanol to obtain 4.76g of intermediate c7 with the yield of 66%.
S4, replacing the intermediate b5 in the step S3 of the synthesis example 5 with the intermediate c7(3.61g,10mmol), replacing 2-bromo-4, 6-diphenyl-1, 3, 5-triazine with 2-bromo-4, 6-diphenylpyridine (3.10g,10mmol), and performing other synthesis processes according to the step S3 of the synthesis example 5 to obtain 3.50g of the compound (1-55) with a yield of 63%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 555.7862, theoretical molecular weight: 555.7960, elemental analysis: theoretical value: c40H33N (%): c86.44; h5.98; n2.52; measured value: c86.45; h5.97; and (5) N2.51.
Synthesis example 8: synthesis of Compound (1-65)
Figure BDA0002998611610000171
S1, the procedure for synthesizing the starting material followed step S1 of Synthesis example 7, 19.10g of intermediate a8 was obtained with a yield of 63%.
S2, replacing the intermediate a7 in the step S2 of the synthetic example 7 with the intermediate a8(15.16g,40mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 7 to obtain 11.22g of the intermediate b8 with the yield of 74%.
S3, replacing intermediate b7 in step S3 of synthetic example 7 with intermediate b8(7.58g,20mmol), and performing other synthetic processes according to step S3 of synthetic example 7 to obtain 4.48g of intermediate c8 with the yield of 62%.
S4, adding the intermediate c8(3.61g,10mmol), (4- (9-hydrogen-carbazole-9-yl) phenyl) boric acid (2.87g,10mmol), potassium carbonate (2.76g,20mmol) and 50mL of toluene/ethanol/water mixed solvent with the volume ratio of 2:1:1 into a 100mL reaction bottle, introducing nitrogen to exhaust air, then adding tetrakis (triphenylphosphine) palladium (0.06g,0.05mmol), heating to 85 ℃, stirring for reaction for 6-12h, cooling to room temperature, filtering, separating filtrate, concentrating organic phase, eluting with filter cake in a silica gel column by using petroleum ether with the weight ratio of 10:1 and dichloromethane, and concentrating to obtain 3.98g of the compound (1-65) with the yield of 70%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 567.8127, theoretical molecular weight: 567.8070, elemental analysis: theoretical value: c41H33N (%): c86.73; h5.86; n2.47; measured value: c86.72; h5.86; and (6) N2.48.
Synthetic example 9: synthesis of Compound (1-68)
Figure BDA0002998611610000172
S1, 20.01g of intermediate a9 was obtained in 66% yield by substituting 7-bromo-2-chloro-5, 5-dimethylsilylheterofluorene in step S1 of Synthesis example 7 with 2-bromo-7-chloro-5, 5-dimethylsilylheterofluorene (28.48g,88mmol), and the other synthesis procedures in accordance with step S1 of Synthesis example 7.
S2, replacing the intermediate a7 in the step S2 of the synthetic example 7 with the intermediate a9(15.16g,40mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 7 to obtain 10.60g of the intermediate b9 with the yield of 70%.
S3. the intermediate b7 in step S3 of Synthesis example 7 was replaced with intermediate b9(7.58g,20mmol), and the other syntheses were carried out in accordance with step S3 of Synthesis example 7, whereby 4.61g of intermediate c8 was obtained in a yield of 64%.
S4. in a 100mL reaction flask, the above intermediate c9(3.61g,10mmol), diphenylamine (1.69g,10mmol), potassium carbonate (2.76g,20mmol), and 50mL of N, N-dimethylacetamide were added. Introducing nitrogen, adding 0.19g (1mmol) of cuprous iodide and 0.36g (2mmol) of phenanthroline, heating, refluxing and stirring for 8 hours, cooling to room temperature, adding water, separating liquid, performing organic phase vacuum distillation, and purifying with ethanol to obtain 3.800g of a compound (1-68), wherein the yield is 77%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 493.7149, theoretical molecular weight: 493.7250, elemental analysis: theoretical value: c35H31N (%): c85.15; h6.33; n2.84; measured value: c85.16; h6.32; and (4) N2.84.
Synthetic example 10: synthesis of Compound (1-69)
Figure BDA0002998611610000181
S1, adding 7-bromo-2-chloro-5, 5-dimethyl silafluorene (28.48g,88mmol), (2-nitrophenyl) boric acid (13.35g,80mmol), potassium carbonate (22.08g,160mmol) and 200mL of a toluene/ethanol/water mixed solvent with a volume ratio of 2:1:1 in a 500mL reaction bottle, introducing nitrogen to discharge air, then adding tetrakis (triphenylphosphine) palladium (0.46g,0.4mmol), heating to 85 ℃, stirring to react for 6-12h, cooling to room temperature, filtering, separating liquid, concentrating an organic phase, leaching the organic phase and a filter cake with petroleum ether and dichloromethane of 10:1 in a silica gel column, and concentrating to obtain 23.42g of an intermediate a10 with the yield of 70%.
S2, adding the intermediate a10(14.64g,40mmol), triethyl phosphite (33.24g,200mmol) and chlorobenzene (22.51g,200mmol) into a 100mL 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 to obtain 7.08g of intermediate b10 with the yield of 53%.
S3. in a 250mL reaction flask, intermediate b10(6.68g,20mmol) above, 4-bromo-1, 1' -biphenyl (5.82g,25mmol), potassium carbonate 5.52g (40mmol), and 100mL of N, N-dimethylacetamide were added. Introducing nitrogen, adding 0.38g (2mmol) of cuprous iodide and 0.72g (4mmol) of phenanthroline, heating, refluxing and stirring for 8 hours, cooling to room temperature, adding water, separating liquid, performing organic phase vacuum distillation, and purifying with ethanol to obtain 7.48g of an intermediate c10, wherein the yield is 77%.
S4, adding the intermediate c10(4.86g,10mmol), phenylboronic acid (1.57g,10mmol), potassium carbonate (2.76g,20mmol) and 50mL of a toluene/ethanol/water mixed solvent with the volume ratio of 2:1:1 in a 100mL reaction bottle, introducing nitrogen to exhaust air, adding tetrakis (triphenylphosphine) palladium (0.06g,0.05mmol), heating to 85 ℃, stirring for reaction for 6-12h, cooling to room temperature, filtering, separating, concentrating an organic phase, leaching the organic phase together with a filter cake in a silica gel column by using 10:1 petroleum ether and dichloromethane, and concentrating to obtain 3.96g of the compound (1-69) with the yield of 75%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 527.7522, theoretical molecular weight: 527.7420, elemental analysis: theoretical value: c38H29N (%): c86.49; h5.54; n2.65; measured value: c86.48; h5.53; and (6) N2.66.
Synthetic example 11: synthesis of Compound (1-71)
Figure BDA0002998611610000182
S1, 19.31g of intermediate a11 was obtained in 66% yield by substituting 7-bromo-2-chloro-5, 5-dimethylsilylheterofluorene in step S1 of Synthesis example 10 with 8-bromo-1-chloro-5, 5-dimethylsilylheterofluorene (28.48g,88mmol), and the other synthetic procedures in accordance with step S1 of Synthesis example 10.
S2, replacing the intermediate a10 in the step S2 of the synthetic example 10 with the intermediate a11(14.64g,40mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 10 to obtain 7.22g of the intermediate b11 with the yield of 54%.
S3, replacing intermediate b10 in step S3 of synthetic example 10 with intermediate b11(6.68g,20mmol), replacing 4-bromo-1, 1' -biphenyl with bromobenzene (3.93g,25mmol), and performing other synthetic processes according to step S3 of synthetic example 10 to obtain 6.72g of intermediate c11 with the yield of 82%.
S4. substitution of intermediate c10 for intermediate c11(4.10g,10mmol), substitution of phenylboronic acid for [1,1' -biphenyl ] -4-ylboronic acid (1.98g,10mmol) in step S4 of Synthesis example 10, and the other synthetic procedures were followed in accordance with step S4 of Synthesis example 10 to give 3.71g of compound (1-71) in a yield of 70%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 527.7367, theoretical molecular weight: 527.7420, elemental analysis: theoretical value: c38H29N (%): c86.49; h5.54; n2.65; measured value: c86.49; h5.55; and (4) N2.64.
Synthetic example 12: synthesis of Compound (1-83)
Figure BDA0002998611610000191
S1, replacing 7-bromo-2-chloro-5, 5-dimethyl silafluorene in step S1 of Synthesis example 10 with 8-bromo-1-chloro-5, 5-dimethyl silafluorene (28.48g,88mmol), and the other synthesis processes follow step S1 of Synthesis example 10 to obtain 19.91g of intermediate a12 with a yield of 68%.
S2, the intermediate a10 in the step S2 of the synthetic example 10 is replaced by the intermediate a12(14.64g,40mmol), and other synthetic processes follow the step S2 of the synthetic example 10, so that 6.95g of the intermediate b12 can be obtained, and the yield is 52%.
S3, replacing the intermediate b10 in the step S3 of the synthetic example 10 with the intermediate b12(6.68g,20mmol), replacing 4-bromo-1, 1' -biphenyl with bromobenzene (3.93g,25mmol), and carrying out other synthetic processes according to the step S3 of the synthetic example 10 to obtain 6.48g of the intermediate c12 with the yield of 79%.
S4. replacement of intermediate c10 in step S4 of Synthesis example 10 with intermediate c12(4.10g,10mmol), replacement of phenylboronic acid with imidazo [1,2-a ] pyridin-2-ylboronic acid (1.62g,10mmol), and the other synthetic procedures in step S4 of Synthesis example 10 gave 3.59g of compound (1-83) in 73% yield.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 491.6775, theoretical molecular weight: 491.6690, elemental analysis: theoretical value: c33H25N3(%): c80.62; h5.13; n8.55; measured value: c80.61; h5.12; and N8.56.
Synthetic example 13: synthesis of Compound (2-5)
Figure BDA0002998611610000192
S1, replacing 3-hydroxy-8-chloro-5, 5-dimethylsilylfluorethane in the step S1 of the synthetic example 1 with 2-hydroxy-5, 5-dimethylsilylfluorethane (18.11g,80mmol), replacing 1-bromo-2-fluorobenzene with 1-bromo-3-chloro-2-fluorobenzene (16.76g,80mmol), and performing other synthetic processes according to the step S1 of the synthetic example 1 to obtain 20.29g of an intermediate a13 with the yield of 61%.
S2, replacing the intermediate a1 in the step S2 of the synthetic example 1 with the intermediate a13(16.63g,40mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 1 to obtain 7.09g of the intermediate b13 with the yield of 53%.
S3. 6.06g of the compound (2-5) was obtained in 71% yield by substituting intermediate b1 in step S3 of Synthesis example 1 with intermediate b13(6.70g,20mmol) and substituting (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid with naphthalen-1-ylboronic acid (3.44g,20mmol), and the other synthesis procedures were followed in step S3 of Synthesis example 1.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 426.5862, theoretical molecular weight: 426.5900, elemental analysis: theoretical value: c30H22(%): c84.47; h5.20; measured value: c84.48; H5.19.
synthesis example 14: synthesis of Compound (2-20)
Figure BDA0002998611610000193
S1, replacing 3-hydroxy-8-chloro-5, 5-dimethylsilylfluorethane in the step S1 of the synthetic example 1 with 2-hydroxy-5, 5-dimethylsilylfluorethane (18.11g,80mmol), replacing 1-bromo-2-fluorobenzene with 1-bromo-4-chloro-2-fluorobenzene (16.76g,80mmol), and performing other synthetic processes according to the step S1 of the synthetic example 1 to obtain 20.96g of an intermediate a14 with the yield of 63%.
S2, replacing the intermediate a1 in the step S2 of the synthetic example 1 with the intermediate a14(16.63g,40mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 1 to obtain 6.96g of the intermediate b14 with the yield of 52%.
S3. the intermediate b3 in step S3 of Synthesis example 3 was replaced with intermediate b14(6.70g,20mmol), and the other synthesis procedures were followed in step S3 of Synthesis example 3 to obtain 8.24g of the compound (2-20) with a yield of 76%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 541.7326, theoretical molecular weight: 541.7250, elemental analysis: theoretical value: c38H27N (%): c84.25; h5.02; n2.59; measured value: c84.24; h5.02; and (5) N2.60.
Synthetic example 15: synthesis of Compound (2-21)
Figure BDA0002998611610000201
S1, replacing 3-hydroxy-8-chloro-5, 5-dimethylsilylfluorethane in the step S1 of the synthetic example 1 with 1-hydroxy-5, 5-dimethylsilylfluorethane (18.11g,80mmol), replacing 1-bromo-2-fluorobenzene with 2-bromo-4-chloro-1-fluorobenzene (16.76g,80mmol), and performing other synthetic processes according to the step S1 of the synthetic example 1 to obtain 19.95g of an intermediate a15 with the yield of 60%.
S2, the intermediate a1 in step S2 of Synthesis example 1 was replaced with the intermediate a15(16.63g,40mmol), and the other synthesis procedures were followed in step S2 of Synthesis example 1 to obtain 6.83g of intermediate b15 with a yield of 51%.
S3. by substituting intermediate b3 in step S3 of Synthesis example 3 with intermediate b15(6.70g,20mmol), and by following the procedure of step S3 of Synthesis example 3, 8.45g of compound (2-21) was obtained with a yield of 78%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 541.7189, theoretical molecular weight: 541.7250, elemental analysis: theoretical value: c38H27N (%): c84.25; h5.02; n2.59; measured value: c84.26; h5.01; and (5) N2.60.
Synthetic example 16: synthesis of Compound (2-30)
Figure BDA0002998611610000202
S1. 18.69g of intermediate a16 was obtained in 61% yield from step S1 of Synthesis example 4 by substituting 7-bromo-2-chloro-5, 5-dimethylsilylfluorenan in step S1 with (5, 5-dimethylsilylfluorenan-4-yl) boronic acid (20.33g,80mmol) and (2- (methylsulfinyl) phenyl) boronic acid with 2-bromo-4-chloro-1- (methylsulfinyl) benzene (22.31g,88 mmol).
S2, replacing the intermediate a4 in the step S2 of the synthetic example 4 with the intermediate a16(19.15g,50mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 4 to obtain 6.49g of the intermediate b16 with the yield of 37%.
S3. replacement of intermediate b4 to intermediate b16 in step S3 of Synthesis example 4 and replacement of (9, 9-dimethyl-9H-fluoren-3-yl) boronic acid to (10-phenylanthracen-9-yl) boronic acid (2.98g,10mmol) and the other synthetic procedures were followed in step S3 of Synthesis example 4 to give 4.10g of compound (2-30) with a yield of 72%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 568.8153, theoretical molecular weight: 568.8090, elemental analysis: theoretical value: c40H28(%): c84.46; h4.96; measured value: c84.46; h4.95.
Synthetic example 17: synthesis of Compound (2-35)
Figure BDA0002998611610000211
S1. 19.30g of intermediate a17 was obtained in 63% yield from 7-bromo-2-chloro-5, 5-dimethylsilylfluorenane in step S1 of Synthesis example 4 by replacing (5, 5-dimethylsilylfluorenan-4-yl) boronic acid (20.33g,80mmol) and (2- (methylsulfinyl) phenyl) boronic acid by 1-bromo-4-chloro-2- (methylsulfinyl) benzene (22.31g,88mmol), and the other syntheses were carried out in accordance with step S1 of Synthesis example 4.
S2, replacing the intermediate a4 in the step S2 of the synthetic example 4 with the intermediate a17(19.15g,50mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 4 to obtain 6.84g of the intermediate b17 with the yield of 39%.
S3, replacing the intermediate b5 in the step S3 of the synthetic example 5 with the intermediate b17, and carrying out other synthetic processes according to the step S3 of the synthetic example 5 to obtain 3.45g of the compound (2-35) with the yield of 63%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 547.7602, theoretical molecular weight: 547.7510, elemental analysis: theoretical value: c35H25N3(%): c76.75; h4.60; n7.67; measured value: c76.75; h4.59; and N7.68.
Synthetic example 18: synthesis of Compound (2-45)
Figure BDA0002998611610000212
S1. 19.92g of intermediate a16 was obtained in 65% yield from step S1 of Synthesis example 4 by substituting 7-bromo-2-chloro-5, 5-dimethylsilylfluorenan in step S1 of Synthesis example 4 with (5, 5-dimethylsilylfluorenan-3-yl) boronic acid (20.33g,80mmol) and (2- (methylsulfinyl) phenyl) boronic acid with 1-bromo-4-chloro-2- (methylsulfinyl) benzene (22.31g,88 mmol).
S2, replacing the intermediate a4 in the step S2 of the synthetic example 4 with the intermediate a18(19.15g,50mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 4 to obtain 7.20g of the intermediate b18 with the yield of 41%.
S3, replacing the intermediate b4 in the step S3 of the synthesis example 4 with the intermediate b18, replacing the (9, 9-dimethyl-9H-fluoren-3-yl) boronic acid with (9- (4-cyanophenyl) -9H-carbazol-2-yl) boronic acid (3.12g,10mmol), and performing the other synthesis processes according to the step S3 of the synthesis example 4 to obtain 4.32g of the compound (2-45) with the yield of 74%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 582.7881, theoretical molecular weight: 582.7960, elemental analysis: theoretical value: c39H26N2(%): c80.38; h4.50; n4.81; measured value: c80.38; h4.49; and N4.82.
Synthetic example 19: synthesis of Compound (2-62)
Figure BDA0002998611610000213
S1. replacement of 7-bromo-2-chloro-5, 5-dimethylsilylheterofluorene by (5, 5-dimethylsilylheterofluoren-2-yl) boronic acid (20.33g,80mmol) and of (2- (methoxycarbonyl) phenyl) boronic acid by methyl 2-bromo-4-chlorobenzoate (21.96g,88mmol) in step S1 of Synthesis example 7 were carried out in the same procedure as in step S1 of Synthesis example 7 to give 20.01g of intermediate a19 in 66% yield.
S2, replacing the intermediate a7 in the step S2 of the synthetic example 7 with the intermediate a19(15.16g,40mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 7 to obtain 10.46g of the intermediate b19 with the yield of 69%.
S3, replacing intermediate b7 in step S3 of synthetic example 7 with intermediate b19(7.58g,20mmol), and performing other synthetic processes according to step S3 of synthetic example 7 to obtain 4.62g of intermediate c19 with the yield of 64%.
S4, replacing the intermediate c8 in the step S4 of the synthesis example 8 with the intermediate c19(3.61g,10mmol), replacing the (4- (9-hydro-carbazol-9-yl) phenyl) boronic acid with (1.63g,10mmol), and performing the other synthesis processes according to the step S4 of the synthesis example 8 to obtain 3.67g of the compound (2-62) with the yield of 76%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 443.6175, theoretical molecular weight: 443.6210, elemental analysis: theoretical value: c30H25N (%): c81.22; h5.68; n3.16; measured value: c81.22; h5.67; and (3) N3.17.
Synthesis example 20: synthesis of Compound (2-70)
Figure BDA0002998611610000221
S1. replacement of 7-bromo-2-chloro-5, 5-dimethylsilylheterofluorene by (5, 5-dimethylsilylfluoren-2-yl) boronic acid (20.33g,80mmol) and 2- (methoxycarbonyl) phenyl) boronic acid by methyl 2-bromo-5-chlorobenzoate (21.96g,88mmol) in step S1 of Synthesis example 7 were carried out in accordance with step S1 of Synthesis example 7 to give 19.10g of intermediate a20 with a yield of 63%.
S2, replacing the intermediate a7 in the step S2 of the synthetic example 7 with the intermediate a20(15.16g,40mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 7 to obtain 10.76g of the intermediate b20 with the yield of 71%.
S3. the intermediate b7 in step S3 of Synthesis example 7 was replaced with intermediate b20(7.58g,20mmol), and the other syntheses were carried out in accordance with step S3 of Synthesis example 7, whereby 4.83g of intermediate c20 was obtained in 67% yield.
S4. replacement of intermediate c9 in step S4 of Synthesis example 9 by intermediate c20(3.61g,10mmol) and other synthetic procedures in accordance with step S4 of Synthesis example 9 gave 3.85g of compound (2-70) in 78% yield.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 493.7321, theoretical molecular weight: 493.7250, elemental analysis: theoretical value: c35H31N (%): c85.15; h6.33; n2.84; measured value: c85.14; h6.34; and (4) N2.84.
Synthetic example 21: synthesis of Compound (2-71)
Figure BDA0002998611610000222
S1, 20.61g of intermediate a21 was obtained in 68% yield from step S1 of Synthesis example 7 by replacing 7-bromo-2-chloro-5, 5-dimethylsilylheterofluorene in step S1 of Synthesis example 7 with (5, 5-dimethylsilylfluoren-3-yl) boronic acid (20.33g,80mmol) and (2- (methoxycarbonyl) phenyl) boronic acid with methyl 2-bromo-4-chlorobenzoate (21.96g,88 mmol).
S2, replacing the intermediate a7 in the step S2 of the synthetic example 7 with the intermediate a21(15.16g,40mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 7 to obtain 10.01g of the intermediate b21 with the yield of 66%.
S3. the intermediate b7 in step S3 of Synthesis example 7 was replaced with intermediate b21(7.58g,20mmol), and the other syntheses were carried out in accordance with step S3 of Synthesis example 7, whereby 4.55g of intermediate c21 was obtained in 63% yield.
S4. replacement of intermediate c9 in step S4 of Synthesis example 9 by intermediate c21(3.61g,10mmol), and the other synthetic procedures were followed in step S4 of Synthesis example 9 to give 4.05g of compound (2-71) in 82% yield.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 493.7317, theoretical molecular weight: 493.7250, elemental analysis: theoretical value: c35H31N (%): c85.15; h6.33; n2.84; measured value: c85.16; h6.32; and (3) N2.83.
Synthetic example 22: synthesis of Compound (2-84)
Figure BDA0002998611610000223
S1. 18.15g of intermediate a22 was obtained in 62% yield from the other synthetic procedures in accordance with step S1 of synthetic example 10, substituting 7-bromo-2-chloro-5, 5-dimethylsilafluorene in step S1 of synthetic example 10 with (5, 5-dimethylsilafluoren-4-yl) boronic acid (20.33g,80mmol) and (2-nitrophenyl) boronic acid with 1-bromo-4-chloro-2-nitrobenzene (20.81g,88 mmol).
S2, the intermediate a10 in step S2 of Synthesis example 10 was replaced with the intermediate a22(14.64g,40mmol), and other synthetic procedures were followed in step S2 of Synthesis example 10 to obtain 6.80g of intermediate b22 with a yield of 51%.
S3, replacing the intermediate b10 in the step S3 of the synthetic example 10 with the intermediate b22(6.68g,20mmol), replacing 4-bromo-1, 1' -biphenyl with 2-bromoanthracene (5.18g,25mmol), and carrying out other synthetic processes according to the step S3 of the synthetic example 10 to obtain 7.09g of the intermediate c22 with the yield of 77%.
S4. substitution of intermediate c10 for intermediate c22(4.60g,10mmol), substitution of phenylboronic acid for benzothiazol-2-ylboronic acid (1.79g,10mmol) in step S4 of Synthesis example 10, and the other synthetic procedures were followed in step S4 of Synthesis example 10 to give 4.19g of compound (2-84) with a yield of 75%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 558.7618, theoretical molecular weight: 558.7740, elemental analysis: theoretical value: c37H26N2(%): c79.53; h4.69; n5.01; fruit of Chinese wolfberryMeasuring: c79.54; h4.70; and N5.00.
Synthetic example 23: synthesis of Compound (2-85)
Figure BDA0002998611610000231
S1. the procedure of step S1 of Synthesis example 10 was followed except that 7-bromo-2-chloro-5, 5-dimethylsilylheterofluorene in step S1 of Synthesis example 10 was replaced with (5, 5-dimethylsilylheterofluoren-1-yl) boronic acid (20.33g,80mmol) and (2-nitrophenyl) boronic acid was replaced with 1-bromo-4-chloro-2-nitrobenzene (20.81g,88mmol), to obtain 17.56g of intermediate a23 with a yield of 60%.
S2, replacing the intermediate a10 in the step S2 of the synthetic example 10 with the intermediate a23(14.64g,40mmol), and carrying out other synthetic processes according to the step S2 of the synthetic example 10 to obtain 7.08g of the intermediate b23 with the yield of 53%.
S3, replacing the intermediate b10 in the step S3 of the synthetic example 10 with the intermediate b23(6.68g,20mmol), replacing 4-bromo-1, 1' -biphenyl with bromobenzene (3.93g,25mmol), and carrying out other synthetic processes according to the step S3 of the synthetic example 10 to obtain 6.48g of the intermediate c23 with the yield of 79%.
S4. substitution of intermediate c10 for intermediate c23(4.60g,10mmol), substitution of phenylboronic acid for benzothiazol-2-ylboronic acid (1.79g,10mmol) in step S4 of Synthesis example 10, and the other synthetic procedures were followed in step S4 of Synthesis example 10 to give 4.19g of compound (2-84) with a yield of 75%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 558.7792, theoretical molecular weight: 558.7740, elemental analysis: theoretical value: c37H26N2(%): c79.53; h4.69; n5.01; measured value: c79.54; h4.70; and N5.00.
Synthetic example 24: synthesis of Compound (2-86)
Figure BDA0002998611610000232
S1. the procedure of step S1 of Synthesis example 10 was followed except that 7-bromo-2-chloro-5, 5-dimethylsilylheterofluorene in step S1 of Synthesis example 10 was replaced with (5, 5-dimethylsilylfluoren-2-yl) boronic acid (20.33g,80mmol) and (2-nitrophenyl) boronic acid was replaced with 2-bromo-4-chloro-1-nitrobenzene (20.81g,88mmol), to obtain 19.62g of intermediate a24 with a yield of 67%.
S2, the intermediate a10 in step S2 of Synthesis example 10 was replaced with the intermediate a24(14.64g,40mmol), and other synthetic procedures were followed in step S2 of Synthesis example 10 to obtain 6.81g of intermediate b24 with a yield of 51%.
S3, replacing intermediate b10 in step S3 of synthetic example 10 with intermediate b24(6.68g,20mmol), replacing 4-bromo-1, 1' -biphenyl with bromobenzene (3.93g,25mmol), and performing other synthetic processes according to step S3 of synthetic example 10 to obtain 6.32g of intermediate c23 with a yield of 77%.
S4. replacement of intermediate c10 in step S4 of Synthesis example 10 with intermediate c24(4.60g,10mmol), replacement of phenylboronic acid with imidazo [1,2-a ] pyridin-2-ylboronic acid (1.62g,10mmol), and the other synthetic procedures in step S4 of Synthesis example 10 gave 3.59g of compound (2-86) in 73% yield.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 491.6626, theoretical molecular weight: 491.6690, elemental analysis: theoretical value: c33H25N3(%): c80.62; h5.13; n8.55; measured value: c80.62; h5.13; and N8.56.
Device example 1
And (3) sequentially ultrasonically cleaning the glass substrate with the 120nm ITO transparent film for 10min by using acetone, isopropanol and deionized water, drying for 2h in vacuum at 105 ℃, then washing for 15min by using UV ozone, and conveying the ITO glass substrate to a vacuum evaporation machine.
Vacuum evaporating molybdenum trioxide (MoO) on the surface of the ITO film3) 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, 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA) was vacuum-evaporated to form an electron blocking layer of 10 nm;
next, on the above electron blocking layer, compounds 1 to 13 (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, 3'- [5' - [3- (3-pyridyl) phenyl ] [1,1':3',1 '-terphenyl ] -3, 3' -diyl ] bipyridine (TmPyPB) was vacuum-evaporated on the above light-emitting layer 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 24
Organic electroluminescent devices were prepared in the same manner as in device example 1, except that the compounds synthesized in the above synthesis examples 2 to 24 were respectively used instead of the compounds 1 to 13 prepared in the above synthesis example 1.
Comparative device example 25 to comparative device example 28
An organic electroluminescent device was produced in the same manner as in device example 1, except that the following compounds a-1, a-2, a-3 and a-4 were used in place of the compounds 1 to 13 produced in synthesis example 1, respectively;
Figure BDA0002998611610000241
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:
TABLE 1
Figure BDA0002998611610000242
Figure BDA0002998611610000251
As can be seen from the data in the above Table 1, the organic electroluminescent material provided by the invention, which uses silafluorene as a core structure and is bonded with a strong electron-withdrawing or electron-donating side group, because of the higher fluorescence quantum efficiency and the higher glass transition temperature of the silicon-containing core structure, the invention realizes the high-efficiency deep blue light emission and the excellent thermal stability of the compound, the core structure is modified by the specific electron transport group or hole transport group, and the compound can obtain better exciton dispersion capacity and realize better energy transmission, compared with the compound A-1 with the core structure being disubstituted, or other compounds A-2, A-3 and A-4 outside the technical scheme of the invention, the device has remarkable progress in comprehensive performance of driving voltage, current efficiency, service life, color coordinates and the like.
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 (10)

1. A heterocyclic compound represented by the following chemical formula 1: the method is characterized in that:
chemical formula 1
Figure FDA0002998611600000011
In the chemical formula 1, the metal oxide is represented by,
R1and R2Or R2And R3Or R3And R4Is a group bound to any of the following chemical formula 2;
R1to R4Wherein R is a group not bonded to R in the following chemical formula 25To R8Are the same or different from each other and are each independently selected from hydrogen, fluoro, nitroRadical, cyano radical, C1～20Alkyl of (C)1～20Alkoxy group of (C)1～20Alkylthio of, C1～20Silane group of (C)6～50Aryl of (C)3～50Heteroaryl of (A), C6～50Arylamine group of (1), C6～50Aryloxy group of (A), C6～50Arylthio group of (a);
chemical formula 2
Figure FDA0002998611600000012
In the chemical formula 2, the first and second organic solvents,
is a group of formula 11And R2Or R2And R3Or R3And R4The position of the combination is the position of the combination,
z is independently selected from O, S, N (R)13)、C(R14)(R15)，
R9To R12Are the same or different from each other and are each independently selected from hydrogen, fluoro, nitro, cyano, C1～20Alkyl of (C)1～20Alkoxy group of (C)1～20Alkylthio of, C1～20Silane group of (C)6～50Aryl of (C)3～50Heteroaryl of (A), C6～50Arylamine group of (1), C6～50Aryloxy group of (A), C6～50The arylthio group(s) of (a),
R13-R15are respectively selected from C1～20Alkyl of (a), phenyl unsubstituted or substituted by alkyl, alkoxy, nitrile, nitro, fluoro, biphenyl unsubstituted or substituted by alkyl, alkoxy, nitrile, nitro, fluoro, terphenyl unsubstituted or substituted by alkyl, alkoxy, nitrile, nitro, fluoro, naphthyl unsubstituted or substituted by alkyl, alkoxy, nitrile, nitro, fluoro;
R14and R15Independently of one another, or by single bonds.
2. A heterocyclic compound according to claim 1, characterized in that:
r of chemical formula 11To R4Wherein the group not bonded to x in chemical formula 2 is hydrogen;
the chemical formula 1 is represented by any one of the following chemical formulas (1-1) or (1-2):
Figure FDA0002998611600000021
in the chemical formulae (1-1) and (1-2):
R5to R8Is the same as that of said chemical formula 1,
z and R9To R12Is the same as the definition of said chemical formula 2.
3. A heterocyclic compound according to claim 2, characterized in that:
the chemical formula (1-1) is further represented by chemical formulas (1-3) to (1-5):
Figure FDA0002998611600000022
the chemical formula (1-2) is further represented by chemical formulas (1-6) to (1-8):
Figure FDA0002998611600000023
the chemical formulae (1-3) to (1-8):
R5to R8Is the same as that of said chemical formula 1,
z and R9To R12Is the same as the definition of said chemical formula 2.
4. A heterocyclic compound according to claim 3, characterized in that:
the R is5To R12One of them is selected from C1～20Alkyl group of (A) or (B),C1～20Alkoxy group of (C)1～20Alkylthio of, C1～20Silane group of (C)6～50Aryl of (C)3～50Heteroaryl of (A), C6～50Arylamine group of (1), C6～50Aryloxy group of (A), C6～50Arylthio of (A), said R5To R12Wherein the remaining groups are all hydrogen.
5. A heterocyclic compound according to claim 4, characterized in that:
the R is5To R8One of them is selected from C1～20Alkyl of (C)1～20Alkoxy group of (C)1～20Alkylthio of, C1～20Silane group of (C)6～50Aryl of (C)3～50Heteroaryl of (A), C6～50Arylamine group of (1), C6～50Aryloxy group of (A), C6～50Arylthio of (A), said R5To R8Of the remaining radical, R9To R12Are both hydrogen.
6. A heterocyclic compound according to claim 4, characterized in that R is5-R12The method comprises the following steps:
each of said C1～20The alkyl group of (a) is selected from: one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
each of said C1～20The alkoxy group of (a) is selected from: one of methoxy and ethoxy;
each of said C1～20The alkylthio group of (a) is selected from: one of methylthio and ethylthio;
each of said C1～20The silane groups of (a) are selected from: one of trimethylsilyl, phenyldimethylsilyl, biphenyldimethylsilyl and methyldiphenylsilyl;
each of said C6～50Is selected from: phenyl substituted or unsubstituted by a substituent, biphenyl substituted or unsubstituted by a substituent, terphenyl substituted or unsubstituted by a substituent, naphthyl substituted or unsubstituted by a substituentAt least one of an anthracenyl group, a phenanthryl group substituted or unsubstituted by a substituent, a pyrenyl group substituted or unsubstituted by a substituent, a benzophenanthryl 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;
each of said C3～50Is 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;
each of said C6～50The 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.
7. The heterocyclic compound according to claim 6, characterized in that:
the R is5To R12One of which is selected from the following structural formulas:
Figure FDA0002998611600000041
Figure FDA0002998611600000051
Figure FDA0002998611600000061
8. a heterocyclic compound according to claim 7, characterized in that: the chemical formula 1 is selected from the following compounds:
Figure FDA0002998611600000071
Figure FDA0002998611600000081
Figure FDA0002998611600000091
Figure FDA0002998611600000101
Figure FDA0002998611600000111
Figure FDA0002998611600000121
Figure FDA0002998611600000131
Figure FDA0002998611600000141
9. 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, characterized in that: the organic layer between the two electrodes comprises the heterocyclic compound according to any of claims 1 to 8.
10. The organic electroluminescent device according to claim 9, wherein the organic layer between the two electrodes comprises a light-emitting layer composed of a light-emitting host and a light-emitting guest, and the light-emitting host or the light-emitting guest contains the heterocyclic compound.
CN202110338709.2A 2021-03-30 2021-03-30 Heterocyclic compound and organic electroluminescent device comprising same Pending CN113121584A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110338709.2A CN113121584A (en) 2021-03-30 2021-03-30 Heterocyclic compound and organic electroluminescent device comprising same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110338709.2A CN113121584A (en) 2021-03-30 2021-03-30 Heterocyclic compound and organic electroluminescent device comprising same

Publications (1)

Publication Number Publication Date
CN113121584A true CN113121584A (en) 2021-07-16

Family

ID=76775377

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110338709.2A Pending CN113121584A (en) 2021-03-30 2021-03-30 Heterocyclic compound and organic electroluminescent device comprising same

Country Status (1)

Country Link
CN (1) CN113121584A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114213376A (en) * 2021-12-31 2022-03-22 上海钥熠电子科技有限公司 Compound containing fused fluorene derivative fragment and application thereof in organic electroluminescent device
CN114907394A (en) * 2022-06-21 2022-08-16 上海八亿时空先进材料有限公司 Silafluorene derivative and organic electroluminescent element containing same
CN117756860A (en) * 2024-02-22 2024-03-26 吉林奥来德光电材料股份有限公司 Organic metal compound, organic electroluminescent device containing organic metal compound and application of organic electroluminescent device

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102625819A (en) * 2009-07-23 2012-08-01 罗门哈斯电子材料韩国有限公司 Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN103313979A (en) * 2010-11-16 2013-09-18 罗门哈斯电子材料韩国有限公司 Novel compound for organic electronic material and organic electroluminescent device using the same
CN104066739A (en) * 2011-12-01 2014-09-24 罗门哈斯电子材料韩国有限公司 Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN104271700A (en) * 2012-04-03 2015-01-07 罗门哈斯电子材料韩国有限公司 Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
CN105164120A (en) * 2013-05-16 2015-12-16 罗门哈斯电子材料韩国有限公司 Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN105793246A (en) * 2013-12-06 2016-07-20 默克专利有限公司 Substituted oxepines
KR20170056425A (en) * 2015-11-13 2017-05-23 에스에프씨 주식회사 Heterocyclic compound comprising aromatic amine group and organic light-emitting diode including the same
KR20170086243A (en) * 2016-01-18 2017-07-26 에스에프씨 주식회사 Organic light-emitting compounds and Organic light-emitting device comprising the same
CN107428773A (en) * 2015-03-03 2017-12-01 德山新勒克斯有限公司 Organic electric element compound, organic electric element and its electronic installation using it
CN115443281A (en) * 2020-04-21 2022-12-06 三星Sdi株式会社 Organic photoelectric element compound, organic photoelectric element composition, organic photoelectric element, and display device

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102625819A (en) * 2009-07-23 2012-08-01 罗门哈斯电子材料韩国有限公司 Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN103313979A (en) * 2010-11-16 2013-09-18 罗门哈斯电子材料韩国有限公司 Novel compound for organic electronic material and organic electroluminescent device using the same
CN104066739A (en) * 2011-12-01 2014-09-24 罗门哈斯电子材料韩国有限公司 Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN104271700A (en) * 2012-04-03 2015-01-07 罗门哈斯电子材料韩国有限公司 Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
CN105164120A (en) * 2013-05-16 2015-12-16 罗门哈斯电子材料韩国有限公司 Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN105793246A (en) * 2013-12-06 2016-07-20 默克专利有限公司 Substituted oxepines
CN107428773A (en) * 2015-03-03 2017-12-01 德山新勒克斯有限公司 Organic electric element compound, organic electric element and its electronic installation using it
KR20170056425A (en) * 2015-11-13 2017-05-23 에스에프씨 주식회사 Heterocyclic compound comprising aromatic amine group and organic light-emitting diode including the same
KR20170086243A (en) * 2016-01-18 2017-07-26 에스에프씨 주식회사 Organic light-emitting compounds and Organic light-emitting device comprising the same
CN115443281A (en) * 2020-04-21 2022-12-06 三星Sdi株式会社 Organic photoelectric element compound, organic photoelectric element composition, organic photoelectric element, and display device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114213376A (en) * 2021-12-31 2022-03-22 上海钥熠电子科技有限公司 Compound containing fused fluorene derivative fragment and application thereof in organic electroluminescent device
CN114907394A (en) * 2022-06-21 2022-08-16 上海八亿时空先进材料有限公司 Silafluorene derivative and organic electroluminescent element containing same
CN117756860A (en) * 2024-02-22 2024-03-26 吉林奥来德光电材料股份有限公司 Organic metal compound, organic electroluminescent device containing organic metal compound and application of organic electroluminescent device

Similar Documents

Publication Publication Date Title
EP3750875A2 (en) Nitrogen-containing compound, organic electroluminescent device and photoelectric conversion device
CN110862381B (en) Organic electroluminescent compound and preparation method and application thereof
EP3792259B1 (en) Heterocyclic compound and organic electroluminescent device comprising the same
CN113121584A (en) Heterocyclic compound and organic electroluminescent device comprising same
CN112500397B (en) Organic electroluminescent material with dibenzofuran-connected anthracene core structure and preparation method and device thereof
CN110981899B (en) Polycyclic organoboron derivatives and electronic devices
CN113105420A (en) Fused ring arylamine compound, application thereof and organic electroluminescent device containing compound
CN112239452B (en) Electron transport type heteroanthracene derivative and organic electroluminescent device thereof
CN112679534A (en) Heterocyclic organic electroluminescent material, preparation method, application and device thereof
KR20110137897A (en) Fluoranthene derivatives and organic electroluminescent device using the same
WO2022242521A1 (en) Condensed azacyclic compound, use thereof, and organic electroluminescent device comprising condensed azacyclic compound
CN109942541B (en) Fluorenocarbazole derivative and preparation method and application thereof
KR20110057008A (en) New diamine derivatives, preparation method thereof and organic electronic device using the same
KR102615340B1 (en) Organic electroluminescent material, method for producing the same, and organic electroluminescent device
CN110655486A (en) Compound with dibenzosuberene as core and application thereof
TWI397516B (en) Triphenylene based aromatic compounds and oleds utilizing the same
CN113816909B (en) Organic electroluminescent material containing phenanthrene structure and device thereof
CN110551132A (en) ketone-containing compound and application thereof in organic electroluminescent device
CN112300152B (en) Novel bipolar green phosphorescent host material and OLED (organic light emitting diode) light emitting device containing same
CN112939788A (en) Amantadine compound, application thereof and organic electroluminescent device containing amantadine compound
CN115873025A (en) Condensed heterocyclic compound, application thereof and organic electroluminescent device containing compound
CN115160342A (en) Compound, application thereof and organic electroluminescent device comprising compound
CN111393458A (en) Heterocyclic compound and organic electroluminescent device thereof
TWI579283B (en) Organic electroluminescent materials containing n-phenylcarboline and organic electroluminescent device by using the same
CN113321659B (en) Organic electroluminescent material and device thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination