CN106554320B - Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof - Google Patents
Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof Download PDFInfo
- Publication number
- CN106554320B CN106554320B CN201510641431.0A CN201510641431A CN106554320B CN 106554320 B CN106554320 B CN 106554320B CN 201510641431 A CN201510641431 A CN 201510641431A CN 106554320 B CN106554320 B CN 106554320B
- Authority
- CN
- China
- Prior art keywords
- aromatic hydrocarbon
- group
- formula
- changed
- bromo
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
-
- 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
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
-
- 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
- H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
-
- 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
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-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
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a condensed ring aromatic hydrocarbon derivative containing quinoxaline group, which has a structure shown as a formula (1). The quinoxaline group-containing polycyclic aromatic hydrocarbon derivative is suitable for being used as an ETL material in an electroluminescent display. The use of the material can effectively reduce the working voltage of the organic electroluminescent device and improve the luminous efficiency of the organic electroluminescent device.
Description
Technical Field
The invention belongs to the field of organic electroluminescence, and particularly relates to a condensed ring aromatic hydrocarbon derivative containing quinoxaline groups and application thereof in an electron transmission material.
Background
The electron transport material traditionally used in electroluminescent devices is Alq3However, Alq3Has a low electron mobility ratio (about 10-6 cm)2Vs). In order to improve the electron transport properties of electroluminescent devices, researchers have made a great deal of exploratory work.
LG chemistry in CN 101003508A reports a series of pyrene derivatives, used as electron transporting and injecting materials in electroluminescent devices, to improve the luminous efficiency of the devices. FFF-Blm4 (J.Am.chem.Soc.; (Communication); 2008; 130 (11); 3282-. Kodak in US patents (publication nos. US 2006/0204784 and US 2007/0048545) mentions a hybrid electron transport layer formed by doping one material with a low LUMO level with another electron transport material with a low ignition voltage and other materials such as metallic materials. Devices based on such hybrid electron transport layers provide improved device efficiency, but increase the complexity of the device fabrication process, which is detrimental to OLED cost reduction. The stable and efficient electron transport material and/or electron injection material are/is developed, so that the device lighting and working voltage is reduced, the device efficiency is improved, the device service life is prolonged, and the method has important practical application value.
Disclosure of Invention
The invention aims to provide a novel condensed ring aromatic hydrocarbon derivative containing quinoxaline groups, which can be used as an electron transport material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a condensed ring aromatic hydrocarbon derivative containing quinoxaline group has a structure shown in formula (1):
wherein: ar is selected from C10-C50The fused ring aromatic hydrocarbon group or the fused heterocyclic aromatic hydrocarbon group of (1);
l is selected from a single bond, a substituted or unsubstituted arylene group, and a substituted or unsubstituted heterocyclylene group.
R1And R2The same or different, are respectively and independently selected from H, aromatic hydrocarbon group, heterocyclic aromatic hydrocarbon group, condensed ring aromatic hydrocarbon group, or condensed heterocyclic aromatic hydrocarbon group, substituted or unsubstituted alkyl and cyano; r1And R2Or may be linked to each other to form a ring, which may be aromatic or aliphatic.
Preferably, Ar is a group represented by formula (2) to formula (6):
wherein Ar is1And Ar2The same or different, are respectively and independently selected from H and C4-C30An aromatic ring group, a heteroaromatic ring group, a condensed ring aromatic hydrocarbon group or a condensed heterocyclic aromatic hydrocarbon group;
R3to R10The same or different, are respectively and independently selected from H, aromatic hydrocarbon group, heterocyclic aromatic hydrocarbon group, condensed ring aromatic hydrocarbon group, or condensed heterocyclic aromatic hydrocarbon group, substituted or unsubstituted alkyl and cyano.
Further preferably, the compound has a structure represented by formula (7) to formula (11):
wherein Ar is1And Ar2Same or different, independently selected from H, substituted or unsubstituted C4-C30Aromatic ring group, heteroaromatic ring group, substituted or unsubstituted condensed ring aromatic hydrocarbon group or condensed heterocyclic aromatic hydrocarbon group;
l is a single bond, substituted or unsubstituted arylene, substituted or unsubstituted heterocyclylene;
R3to R10The same or different, are respectively and independently selected from H, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted heterocyclic aromatic hydrocarbon group, substituted or unsubstituted condensed ring aromatic hydrocarbon group or condensed heterocyclic aromatic hydrocarbon group, substituted or unsubstituted alkyl and cyano.
Preferably, the unsubstituted alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylethyl, pentyl or cyclohexyl;
the substituted alkyl is trifluoromethyl;
the substituted or unsubstituted aromatic hydrocarbon group is a phenyl group, an o-tolyl group, a p-tolyl group, a tert-butylphenyl group or the like. The substituted or unsubstituted heterocyclic aromatic hydrocarbon group is furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, carbazole, pyridine, pyrazine, 2.4-methyl-1.3.5 triazine, 4.6 diphenyl pyrimidine;
the substituted or unsubstituted condensed ring aromatic hydrocarbon group is naphthyl, phenanthryl, anthryl, pyrenyl and 9.9-dimethyl-2-fluorenyl. The substituted or unsubstituted fused heterocyclic aromatic hydrocarbon group is quinoline, isoquinoline or quinazoline.
The substitution is mono-substitution or multi-substitution.
The compound is preferably of the formula (12) to (54):
the application of the condensed ring aromatic hydrocarbon derivative containing quinoxaline group in an organic electroluminescent device.
The condensed ring aromatic hydrocarbon derivative containing the quinoxaline group can be used as an electron transport material.
An organic electroluminescent device comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate; the organic light-emitting functional layer comprises a hole transport layer, an organic light-emitting layer and an electron transport layer,
the electron transport material of the electron transport layer is the condensed ring aromatic hydrocarbon derivative containing quinoxaline group.
Compared with the prior art, the fused ring aromatic hydrocarbon derivative of the quinoxaline group has the advantages that:
the condensed ring aromatic hydrocarbon derivative of the quinoxaline group belongs to a typical electron-deficient system, and has suitable HOMO and LUMO energy levels, so that the condensed ring aromatic hydrocarbon derivative has good electron accepting capacity. The condensed ring aromatic hydrocarbon system which is coplanar in a space structure has good electron transfer capability. Therefore, the benzacridine compound is an excellent electron transport material.
Experiments show that when the condensed ring aromatic hydrocarbon derivative of the quinoxaline group is used as an electron transmission material, compared with Bphen which is used as the electron transmission material, the driving voltage of a device is reduced, the working voltage of the device is effectively reduced, the lumen efficiency is improved, the power consumption of the device is reduced, and the condensed ring aromatic hydrocarbon derivative is an electron transmission material with good performance.
Drawings
FIG. 1 shows a nuclear magnetic spectrum of a compound represented by the formula (14) ((1HNMR)；
FIG. 2 shows a nuclear magnetic spectrum of a compound represented by the formula (22) ((R))1HNMR)；
FIG. 3 is a nuclear magnetic spectrum of a compound represented by the formula (24) ((1HNMR)；
FIG. 4 is a nuclear magnetic spectrum of a compound represented by the formula (26) ((R))1HNMR)；
FIG. 5 is a nuclear magnetic spectrum of a compound represented by the formula (36) ((R))1HNMR)；
FIG. 6 is a nuclear magnetic spectrum of a compound represented by the formula (52) ((1HNMR)。
Detailed Description
Basic raw materials used in the present invention, for example, 4-bromoo-phenylenediamine, diphenylethanedione, 1, 2-cyclohexanedione, hexafluorobutanedione, butanedione, diaminomaleonitrile, various brominated derivatives of anthracene, brominated derivatives of diphenylbenzofluoranthene, brominated derivatives of diphenylfluoranthene, various brominated derivatives of triphenylene, various brominated derivatives of diphenylfluoranthene, and the like
The bromo-derivatives of (A) and (B) can be obtained from various pyrene bromo-derivatives, etc., or can be purchased from various chemical raw material markets at home, or can be synthesized by a common method in a laboratory.
The various bromides can be prepared into corresponding boric acid compounds by a common method.
The condensed ring aromatic hydrocarbon derivative containing quinoxaline group has a structure shown in a formula (1):
wherein: ar is selected from C10-C50The fused ring aromatic hydrocarbon group or the fused heterocyclic aromatic hydrocarbon group of (1);
l is selected from a single bond, a substituted or unsubstituted arylene group, and a substituted or unsubstituted heterocyclylene group.
R1And R2The same or different, are respectively and independently selected from H, aromatic hydrocarbon group, heterocyclic aromatic hydrocarbon group, condensed ring aromatic hydrocarbon group, or condensed heterocyclic aromatic hydrocarbon group, substituted or unsubstituted alkyl and cyano; r1And R2Or may be linked to each other to form a ring, which may be aromatic or aliphatic.
Preferably, Ar is a group represented by formula (2) to formula (6):
wherein Ar is1And Ar2The same or different, are respectively and independently selected from H and C4-C30An aromatic ring group, a heteroaromatic ring group, a condensed ring aromatic hydrocarbon group or a condensed heterocyclic aromatic hydrocarbon group;
R3to R10The same or different, are respectively and independently selected from H, aromatic hydrocarbon group, heterocyclic aromatic hydrocarbon group, condensed ring aromatic hydrocarbon group, or condensed heterocyclic aromatic hydrocarbon group, substituted or unsubstituted alkyl and cyano. The substitution may be mono-or polysubstituted.
Further preferably, the compound has a structure represented by formula (7) to formula (11):
wherein Ar is1And Ar2Same or different, independently selected from H, substituted or unsubstituted C4-C30Aromatic ring radical, hetero aromatic ring radical, substituted or unsubstituted condensed ring aromatic hydrocarbon radical or condensed heteroA cyclic aromatic hydrocarbon group;
l is a single bond, substituted or unsubstituted arylene, substituted or unsubstituted heterocyclylene;
R3to R10The same or different, are respectively and independently selected from H, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted heterocyclic aromatic hydrocarbon group, substituted or unsubstituted condensed ring aromatic hydrocarbon group or condensed heterocyclic aromatic hydrocarbon group, substituted or unsubstituted alkyl and cyano.
Preferably, the unsubstituted alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylethyl, pentyl or cyclohexyl;
the substituted alkyl is trifluoromethyl;
the substituted or unsubstituted aromatic hydrocarbon group is a phenyl group, an o-tolyl group, a p-tolyl group, a tert-butylphenyl group or the like. The substituted or unsubstituted heterocyclic aromatic hydrocarbon group is furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, carbazole, pyridine, pyrazine, 2.4-methyl-1.3.5 triazine, 4.6 diphenyl pyrimidine;
the substituted or unsubstituted condensed ring aromatic hydrocarbon group is naphthyl, phenanthryl, anthryl, pyrenyl and 9.9-dimethyl-2-fluorenyl. The substituted or unsubstituted fused heterocyclic aromatic hydrocarbon group is quinoline, isoquinoline or quinazoline.
The compound is preferably of the formula (12) to (54):
the application of the condensed ring aromatic hydrocarbon derivative containing quinoxaline group in an organic electroluminescent device.
The condensed ring aromatic hydrocarbon derivative containing the quinoxaline group can be used as an electron transport material.
An organic electroluminescent device comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate; the organic light-emitting functional layer comprises a hole transport layer, an organic light-emitting layer and an electron transport layer,
the electron transport material of the electron transport layer is the condensed ring aromatic hydrocarbon derivative containing quinoxaline groups according to any one of claims 1 to 4.
EXAMPLE 1 Synthesis of various quinoxaline boronic acid derivative intermediates
Synthesis of 1, 6-bromo-2, 3-diphenylquinoxaline
Adding 3.91 g (molecular weight 186, 0.021mol) of 4-bromo o-phenylenediamine, 4.41 g (molecular weight 210, 0.021mol) of diphenylethanedione and 40 ml of ethanol into a 250ml three-neck flask, dropwise adding 0.2 g of concentrated sulfuric acid within 3min under the stirring condition, reacting for 4 hours at 65 ℃, cooling to room temperature after the reaction is finished, filtering, and washing with 50ml of ethanol and 50ml of petroleum ether in sequence to obtain 6.66 g (molecular weight 360) of an intermediate compound 6-bromo-2, 3-diphenyl quinoxaline, wherein the yield is 88.1%.
Synthesis of 2, 7-bromo-1, 2,3, 4-tetrahydrophenazine
The reaction procedure was the same as for the synthesis of 6-bromo-2, 3-diphenylquinoxaline, except that diphenylethanedione was exchanged for 1, 2-cyclohexanedione to give the intermediate 7-bromo-1, 2,3, 4-tetrahydrophenazine.
Synthesis of 3, 6-bromo-2, 3-dimethylquinoxaline
The reaction procedure is the same as that for the synthesis of 6-bromo-2, 3-diphenylquinoxaline, except that diphenylethanedione is exchanged for butanedione, to obtain the intermediate 6-bromo-2, 3-dimethylquinoxaline.
Synthesis of 4, 6-bromoquinoxaline
The reaction procedure was the same as the synthesis of 6-bromo-2, 3-diphenylquinoxaline except that diphenylethanedione was changed to glyoxal to give the intermediate 6-bromoquinoxaline.
Synthesis of 5, 6-bromo-2, 3-bis (trifluoromethyl) quinoxaline
The reaction procedure was the same as for the synthesis of 6-bromo-2, 3-diphenylquinoxaline except that diphenylethanedione was exchanged for hexafluorobutanedione to give the intermediate 6-bromo-2, 3-bis (trifluoromethyl) quinoxaline.
Synthesis of 6, 6-bromo-2, 3-dicyanoquinoxaline
The reaction procedure was the same as for the synthesis of 6-bromo-2, 3-diphenylquinoxaline except that diphenylethanedione was converted to diaminomaleonitrile to give the intermediate 6-bromo-2, 3-dicyanoquinoxaline.
Example 2
Synthesis of Compound represented by the formula (12)
A1000 ml three-neck flask is equipped with magnetic stirring and nitrogen protection, 4.72g (molecular weight 236, 0.02mol) of 6-bromo-2, 3-dimethylquinoxaline, 11.0g (molecular weight 474, 0.022mol) of 9, 10-di (naphthalene-2-yl) anthracene-2-boronic acid, 1.16g (molecular weight 1154, 0.001mol) of tetrakis ((triphenylphosphine) palladium, 80ml of 2M aqueous sodium carbonate, 80ml of toluene, 80ml of ethanol, argon replacement, reflux, reaction monitoring by a Thin Layer Chromatography (TLC) method, TLC finds that the bromide of the raw material is completely reacted after 4 hours, only a product point is generated, the temperature is reduced to 25 ℃, an organic layer is separated, evaporated to dryness, column chromatography separation is carried out, ethyl acetate/petroleum ether are leached, and 11.7g of the compound shown as formula (12) is obtained, the molecular weight 586 is high, and the yield is 87.4%.
Product MS (m/e): 586 elemental analysis (C)44H30N2): theoretical value C: 90.07%, H: 5.15%, N: 4.77 percent; found value C: 90.04%, H: 5.13%, N: 4.83 percent.
Example 3
Synthesis of Compound represented by the formula (13)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline was changed to 7-bromo-1, 2,3, 4-tetrahydrophenazine, and the other reagents were not changed to obtain a compound represented by formula (13).
Product MS (m/e): 612, elemental analysis (C)46H32N2): theoretical value C: 90.16%, H: 5.26%, N: 4.57 percent; found value C: 90.12%, H: 5.22%, N: 4.66 percent.
Example 4
Synthesis of Compound represented by the formula (14)
The procedure was as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline was changed to 6-bromo-2, 3-diphenylquinoxaline and the other reagents were not changed to obtain a compound represented by the formula (14).
Product MS (m/e): 710 elemental analysis (C)54H34N2): theoretical value C: 91.24%, H: 4.82%, N: 3.94 percent; found value C: 91.27%, H: 4.84%, N: 3.89 percent; nuclear magnetic spectrum of (1HNMR) is shown in fig. 1.
Example 5
Synthesis of Compound represented by the formula (15)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline was changed to 6-bromo-2, 3-di (trifluoromethyl) quinoxaline and the other reagents were not changed to obtain a compound represented by formula (15).
Product MS (m/e): 710 elemental analysis (C)44H24F6N2): theoretical value C: 76.08%, H: 3.48%, F: 16.41%, N: 4.03 percent; found value C: 76.03%, H: 3.46 percent of the total weight of the steel,F:16.44％,N：4.07％。
example 6
Synthesis of Compound represented by the formula (16)
The procedure was as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline was changed to 6-bromo-2, 3-dicyanoquinoxaline and the other reagents were not changed to obtain a compound represented by the formula (16).
Product MS (m/e): 608, elemental analysis (C)44H24N4): theoretical value C: 86.82%, H: 3.97%, N: 9.20 percent; found value C: 86.83%, H: 3.94%, N: 9.23 percent.
Example 7
Synthesis of Compound represented by the formula (17)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline was changed to 6-bromoquinoxaline and the other reagents were not changed to obtain a compound represented by the formula (17).
Product MS (m/e): 558 elemental analysis (C)42H26N2): theoretical value C: 90.29%, H: 4.69%, N: 5.02 percent; found value C: 90.26%, H: 4.67%, N: 5.07 percent.
Example 8
Synthesis of Compound represented by the formula (18)
The procedure was the same as in example 2 except that one of the starting materials, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid, was changed to 9- (naphthalen-2-yl) -10- (p- (1-naphthyl) phenyl) anthracene-2-boronic acid, and the conditions for other drugs, reagents, reactions, separations, and the like were unchanged to give a compound represented by formula (18).
Product MS (m/e): 662, elemental analysis (C)50H34N2): theoretical value C: 90.60%, H: 5.17%, N: 4.23 percent; found value C: 90.63%, H: 5.16%, N: 4.21 percent.
Example 9
Synthesis of Compound represented by the formula (19)
The synthesis procedure was the same as in example 2 except that the starting material 6-bromo-2, 3-dimethylquinoxaline was changed to 7-bromo-1, 2,3, 4-tetrahydrophenazine, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 9- (naphthalen-2-yl) -10- (p- (1-naphthyl) phenyl) anthracene-2-boronic acid, and the conditions of other drugs, reagents, reactions, separations, and the like were not changed to obtain the compound represented by formula (19).
Product MS (m/e): 688 elemental analysis (C)52H36N2): theoretical value C: 90.67%, H: 5.27%, N: 4.07 percent; found value C: 90.66%, H: 5.30%, N: 4.04 percent.
Example 10
Synthesis of Compound represented by the formula (20)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromo-2, 3-diphenylquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 9- (naphthalen-2-yl) -10- (p- (1-naphthalenyl) phenyl) anthracene-2-boronic acid, and conditions such as other drugs, reagents, reactions, separations, etc. were not changed to obtain the compound represented by formula (20).
Product MS (m/e): 786 elemental analysis (C)60H38N2): theoretical value C: 91.57%, H: 4.87%, N: 3.56 percent; found value C: 91.55%, H: 4.86%, N: 3.59 percent.
Example 11
Synthesis of Compound represented by the formula (21)
The synthesis procedure was the same as in example 2 except that the starting material 6-bromo-2, 3-dimethylquinoxaline was changed to 6-bromo-2, 3-di (trifluoromethyl) quinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 9- (naphthalen-2-yl) -10- (p- (1-naphthyl) phenyl) anthracene-2-boronic acid, and the conditions of other drugs, reagents, reactions, separations, etc. were not changed to obtain the compound represented by formula (21).
Product MS (m/e): 770 elemental analysis (C)60H28F6N2): theoretical value C: 77.91%, H: 3.66%, F: 14.79%, N: 3.63 percent; found value C: 77.95%, H: 3.62%, F: 14.75%, N: 3.68 percent.
Example 12
Synthesis of Compound represented by the formula (22)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromo-2, 3-dicyanoquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 9- (naphthalen-2-yl) -10- (p- (1-naphthyl) phenyl) anthracene-2-boronic acid, and conditions such as other drugs, reagents, reactions, separations and the like were not changed to obtain the compound represented by formula (22).
Product MS (m/e): 684 elemental analysis (C)50H28N4): theoretical value C: 87.70%, H: 4.12%, N: 8.18 percent; found value C: 87.75%, H: 4.15%, N: 8.20 percent; nuclear magnetic spectrum of (1HNMR) is shown in fig. 2.
Example 13
Synthesis of Compound represented by the formula (23)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromoquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 9- (naphthalen-2-yl) -10- (p- (1-naphthyl) phenyl) anthracene-2-boronic acid, and conditions such as other chemicals, reagents, reaction, separation and the like were not changed to obtain a compound represented by formula (23).
Product MS (m/e): 634, elemental analysis (C)48H30N2): theoretical value C: 90.82%, H: 4.76%, N: 4.41 percent; found value C: 90.84%, H: 4.73%, N: 4.43 percent.
Example 14
Synthesis of Compound represented by the formula (24)
The synthesis procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromoquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7, 12-diphenylbenzo [ k ] fluoranthene-3-boronic acid, and conditions for other drugs, reagents, reactions, separations, and the like were unchanged to obtain the compound represented by formula (24).
Product MS (m/e): 532, elemental analysis (C)40H24N2): theoretical value C: 90.20%, H: 4.54%, N: 5.26 percent; found value C: 90.23%, H: 4.53%, N: 5.24 percent; nuclear magnetic spectrum of (1HNMR) is shown in fig. 3.
Example 15
Synthesis of Compound represented by the formula (25)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the raw material was changed to 6-bromo-2, 3-diphenylquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7, 12-diphenylbenzo [ k ] fluoranthene-3-boronic acid, and conditions for other drugs, reagents, reactions, separations and the like were unchanged to obtain the compound represented by formula (25).
Product MS (m/e): 684 elemental analysis (C)52H32N2): theoretical value C: 91.20%, H: 4.71%, N: 4.09%; found value C: 91.22%, H: 4.73%, N: 4.05 percent.
Example 16
Synthesis of Compound represented by the formula (26)
The procedure was the same as in example 2 except that the starting material, 6-bromo-2, 3-dimethylquinoxaline, was changed to 7-bromo-1, 2,3, 4-tetrahydrophenazine, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid, was changed to 7, 12-diphenylbenzo [ k ] fluoranthene-3-boronic acid, and the conditions for other drugs, reagents, reactions, separations, etc. were unchanged to give the compound represented by formula (26).
Product MS (m/e): 586 elemental analysis (C)44H30N2): theoretical value C: 90.07%, H: 5.15%, N: 4.77 percent; found value C: 90.08%, H: 5.13%, N: 4.79 percent; nuclear magnetic spectrum of (1HNMR) is shown in fig. 4.
Example 17
Synthesis of Compound represented by the formula (27)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as a raw material was changed to 6-bromo-2, 3-dicyanoquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7, 12-diphenylbenzo [ k ] fluoranthene-3-boronic acid, and conditions such as other drugs, reagents, reactions, separations and the like were not changed to obtain a compound represented by formula (27).
Product MS (m/e): 582, elemental analysis (C)42H22N4): theoretical value C: 86.58%, H: 3.81%, N: 9.62 percent; found value C: 86.54%, H: 3.86%, N: 9.60 percent.
Example 18
Synthesis of Compound represented by the formula (28)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as a raw material was changed to 6-bromo-2, 3-di (trifluoromethyl) quinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7, 12-diphenylbenzo [ k ] fluoranthene-3-boronic acid, and conditions of other drugs, reagents, reaction, separation and the like were not changed to obtain a compound represented by formula (28).
Product MS (m/e): 668 elemental analysis (C)42H22F6N2): theoretical value C: 75.45%, H: 3.32%, F: 17.05%, N: 4.19 percent; found value C: 75.47%, H: 3.34%, F: 17.02%, N: 4.17 percent.
Example 19
Synthesis of Compound represented by the formula (29)
The synthesis procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromo-2, 3-diphenylquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7, 10-diphenylfluoranthene-3-boronic acid, and conditions for other drugs, reagents, reactions, separations, and the like were unchanged to obtain the compound represented by formula (29).
Product MS (m/e): 634, elemental analysis (C)48H30N2): theoretical value C: 90.82%, H: 4.76%, N: 4.41 percent; found value C: 90.84%, H: 4.73%, N: 4.43 percent.
Example 20
Synthesis of Compound represented by the formula (30)
The procedure was the same as in example 2 except that the starting material 6-bromo-2, 3-dimethylquinoxaline was changed to 7-bromo-1, 2,3, 4-tetrahydrophenazine, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid to 7, 10-diphenylfluoranthene-3-boronic acid, and the conditions for other drugs, reagents, reactions, separations, etc. were unchanged to obtain the compound represented by formula (30).
Product MS (m/e): 536, elemental analysis (C)40H28N2): theoretical value C: 89.52%, H: 5.26%, N: 5.22 percent; found value C: 89.54%, H: 5.23%, N: 5.23 percent.
Example 21
Synthesis of Compound represented by the formula (31)
The synthesis procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromo-2, 3-dicyanoquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7, 10-diphenylfluoranthene-3-boronic acid, and conditions for other drugs, reagents, reactions, separations, and the like were unchanged to obtain the compound represented by formula (31).
Product MS (m/e):532, elemental analysis (C)38H20N4): theoretical value C: 85.70%, H: 3.79%, N: 10.52 percent; found value C: 85.72%, H: 3.75%, N: 10.53 percent.
Example 22
Synthesis of Compound represented by the formula (32)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as a raw material was changed to 6-bromo-2, 3-di (trifluoromethyl) quinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7, 10-diphenylfluoranthene-3-boronic acid, and conditions for other drugs, reagents, reactions, separations and the like were not changed to obtain a compound represented by formula (32).
Product MS (m/e): 618, elemental analysis (C)38H20F6N2): theoretical value C: 73.78%, H: 3.26%, F: 18.43%, N: 4.53 percent; found value C: 73.75%, H: 3.29%, F: 18.41%, N: 4.55 percent.
Example 23
Synthesis of Compound represented by the formula (33)
The procedure was the same as in example 2 except that the starting material 6-bromo-2, 3-dimethylquinoxaline was changed to 7-bromo-1, 2,3, 4-tetrahydrophenazine, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid to 7- (naphthalen-2-yl) triphenylene-2-boronic acid, and the conditions for other drugs, reagents, reactions, separations, etc. were changed to obtain the compound represented by formula (33).
Product MS (m/e): 536, elemental analysis (C)40H28N2): theoretical value C: 89.52%, H: 5.26%, N: 5.22 percent; found value C: 89.54%, H: 5.23%, N: 5.23 percent.
Example 24
Synthesis of Compound represented by the formula (34)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as a raw material was changed to 6-bromo-2, 3-di (trifluoromethyl) quinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7- (naphthalen-2-yl) triphenylene-2-boronic acid, and conditions such as other drugs, reagents, reaction, separation and the like were not changed to obtain a compound represented by the formula (34).
Product MS (m/e): 618, elemental analysis (C)38H20F6N2): theoretical value C: 73.78%, H: 3.26%, F: 18.43%, N: 4.53 percent; found value C: 73.74%, H: 3.28%, F: 18.42%, N: 4.56 percent.
Example 25
Synthesis of Compound represented by the formula (31)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromo-2, 3-dicyanoquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7- (naphthalen-2-yl) triphenylene-2-boronic acid, and conditions for other drugs, reagents, reactions, separations and the like were not changed to obtain the compound represented by formula (31).
Product MS (m/e): 532, elemental analysis (C)38H20N4): theoretical value C: 85.70%, H: 3.79%, N: 10.52 percent; found value C: 85.73%, H: 3.77%, N: 10.50 percent.
Example 26
Synthesis of Compound represented by the formula (36)
The synthesis procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromo-2, 3-diphenylquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7- (naphthalen-2-yl) triphenylene-2-boronic acid, and conditions for other drugs, reagents, reactions, separations, and the like were unchanged to obtain the compound represented by formula (36).
Product MS (m/e): 634, elemental analysis (C)48H30N2): theoretical value C: 90.82%, H: 4.76%, N: 4.41 percent; found value C: 90.85%, H: 4.72%, N: 4.43 percent; nuclear magnetic spectrum of (1HNMR) is shown in fig. 5.
Example 27
Synthesis of Compound represented by the formula (37)
The procedure of synthesis was the same as in example 2 except that 9, 10-bis (naphthalen-2-yl) anthracene-2-boronic acid as a starting material was changed to 7- (naphthalen-2-yl) triphenylene-2-boronic acid, and conditions for other drugs, reagents, reactions, separations and the like were not changed to obtain a compound represented by formula (37).
Product MS (m/e): 510, elemental analysis (C)38H26N2): theoretical value C: 89.38%, H: 5.13%, N: 5.49 percent; found value C: 89.36 percent，H：5.16％，N：5.48％。
Example 28
Synthesis of Compound represented by the formula (38)
The procedure was the same as in example 2 except that 9, 10-bis (naphthalen-2-yl) anthracene-2-boronic acid as a starting material was changed to 7- (p- (naphthalen-1-yl) phenyl) triphenylene-2-boronic acid, and conditions for other drugs, reagents, reactions, separations and the like were not changed to obtain a compound represented by formula (38).
Product MS (m/e): 586 elemental analysis (C)44H30N2): theoretical value C: 90.07%, H: 5.15%, N: 4.77 percent; found value C: 90.10%, H: 5.16%, N: 4.74 percent.
Example 29
Synthesis of Compound represented by the formula (39)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromo-2, 3-diphenylquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7- (p- (naphthalen-1-yl) phenyl) triphenylene-2-boronic acid, and conditions for other drugs, reagents, reactions, separations, etc. were changed to obtain the compound represented by formula (39).
Product MS (m/e): 710 elemental analysis (C)54H34N2): theoretical value C: 91.24%, H: 4.82%, N: 3.94 percent; found value C: 91.21%, H: 4.84%, N: 3.95 percent.
Example 30
Synthesis of Compound represented by the formula (40)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as a raw material was changed to 6-bromo-2, 3-dicyanoquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7- (p- (naphthalen-1-yl) phenyl) triphenylene-2-boronic acid, and conditions such as other chemicals, reagents, reaction, separation and the like were not changed to obtain a compound represented by formula (40).
Product MS (m/e): 608, elemental analysis (C)44H24N4): theoretical value C: 86.82%, H: 3.97%, N: 9.20 percent; found value C: 86.84%, H: 3.93%, N: 9.23 percent.
Example 31
Synthesis of Compound represented by the formula (41)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as a raw material was changed to 6-bromo-2, 3-di (trifluoromethyl) quinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7- (p- (naphthalen-1-yl) phenyl) triphenylene-2-boronic acid, and conditions of other drugs, reagents, reaction, separation and the like were changed to obtain a compound represented by formula (41).
Product MS (m/e): 694 elemental analysis (C)44H24F6N2): theoretical value C: 76.08%, H: 3.48%, F: 16.41%, N: 4.03 percent; found value C: 76.05%, H: 3.46%, F: 16.43%, N: 4.06 percent.
Example 32
Synthesis of Compound represented by the formula (42)
The synthesis procedure was the same as in example 2 except that the starting material, 6-bromo-2, 3-dimethylquinoxaline, was changed to 7-bromo-1, 2,3, 4-tetrahydrophenazine, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid, was changed to 7- (p- (naphthalen-1-yl) phenyl) triphenylene-2-boronic acid, and the conditions for other drugs, reagents, reactions, separations, etc. were unchanged to give the compound represented by formula (42).
Product MS (m/e): 612, elemental analysis (C)46H32N2): theoretical value C: 90.16%, H: 5.26%, N: 4.57 percent; found value C: 90.18%, H: 5.23%, N: 4.59 percent.
Example 33
Synthesis of Compound represented by the formula (43)
The synthesis procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromoquinoxaline, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 7- (p- (naphthalen-1-yl) phenyl) triphenylene-2-boronic acid, and the conditions of other drugs, reagents, reactions, separations, and the like were unchanged to obtain the compound represented by formula (43).
Product MS (m/e): 558 elemental analysis (C)42H26N2): theoretical value C: 90.29%, H: 4.69%, N: 5.01 percent; found value C: 90.32%, H: 4.65%, N: 5.03 percent.
Example 34
Synthesis of Compound represented by the formula (44)
Synthesis ofThe procedure was as in example 2, except that the starting material 6-bromo-2, 3-dimethylquinoxaline was changed to 6-bromo-2, 3-dicyanoquinoxaline and 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 12- (naphthalen-2-yl)
The 6-boric acid and other medicines, reagents, reaction, separation and other conditions are unchanged to obtain the compound shown in the formula (44).
Product MS (m/e): 532, elemental analysis (C)38H20N4): theoretical value C: 85.70%, H: 3.79%, N: 10.52 percent; found value C: 85.73%, H: 3.77%, N: 10.50 percent.
Example 35
Synthesis of Compound represented by the formula (45)
The procedure was the same as in example 2, except that the starting material 6-bromo-2, 3-dimethylquinoxaline was changed to 6-bromo-2, 3-di (trifluoromethyl) quinoxaline and 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 12- (naphthalen-2-yl)
-6-boric acid, and other medicines, reagents, reaction, separation and other conditions are unchanged to obtain the compound shown as the formula (45).
Product MS (m/e): 618, elemental analysis (C)38H20F6N2): theoretical value C: 73.78%, H: 3.26%, F: 18.43%, N: 4.53 percent; found value C: 73.74%, H: 3.28%, F: 18.41%, N: 4.57 percent.
Example 36
Synthesis of Compound represented by the formula (46)
The procedure was followed as in example 2 except that the starting material, 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid, was changed to 12- (naphthalen-2-yl)
The 6-boric acid and other medicines, reagents, reaction, separation and other conditions are unchanged to obtain the compound shown in the formula (46).
Product MS (m/e): 510, elemental analysis (C)38H26N2): theoretical value C: 89.38 percentH, H: 5.13%, N: 5.49 percent; found value C: 89.35%, H: 5.17%, N: 5.48 percent.
Example 37
Synthesis of Compound represented by the formula (47)
The procedure was the same as in example 2, except that the starting material 6-bromo-2, 3-dimethylquinoxaline was changed to 7-bromo-1, 2,3, 4-tetrahydrophenazine, and 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 12- (naphthalen-2-yl)
-6-boric acid, and other medicines, reagents, reaction, separation and other conditions are unchanged to obtain the compound shown as the formula (47).
Product MS (m/e): 536, elemental analysis (C)40H28N2): theoretical value C: 89.52%, H: 5.26%, N: 5.22 percent; found value C: 89.54%, H: 5.23%, N: 5.23 percent.
Example 38
Synthesis of Compound represented by the formula (48)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromo-2, 3-diphenylquinoxaline and 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 12- (naphthalen-2-yl)
The 6-boric acid and other medicines, reagents, reaction, separation and other conditions are unchanged to obtain the compound shown in the formula (48).
Product MS (m/e): 536, elemental analysis (C)40H28N2): theoretical value C: 89.52%, H: 5.26%, N: 5.22 percent; found value C: 89.54%, H: 5.23%, N: 5.23 percent.
Example 39
Synthesis of Compound represented by the formula (49)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromoquinoxaline and 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 12- (naphthalen-2-yl)
The 6-boric acid and other medicines, reagents, reaction, separation and other conditions are not changed to obtain the compound shown as the formula (49).
Product MS (m/e): 482 elemental analysis (C)36H22N2): theoretical value C: 89.60%, H: 4.60%, N: 5.81 percent; found value C: 89.57%, H: 4.56%, N: 5.87 percent.
Example 40
Synthesis of Compound represented by the formula (50)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as a starting material was changed to 6-bromo-2, 3-di (trifluoromethyl) quinoxaline and 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 12- (p- (naphthalen-1-yl) phenyl)
The 6-boric acid and other medicines, reagents, reaction, separation and other conditions are unchanged to obtain the compound shown in the formula (50).
Product MS (m/e): 694 elemental analysis (C)44H24F6N2): theoretical value C: 76.08%, H: 3.48%, F: 16.41%, N: 4.03 percent; found value C: 76.04%, H: 3.46%, F: 16.43%, N: 4.07 percent.
EXAMPLE 41
Synthesis of Compound represented by the formula (51)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as a starting material was changed to 6-bromo-2, 3-dicyanoquinoxaline and 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 12- (p- (naphthalen-1-yl) phenyl)
-6-boric acid, and other medicines, reagents, reaction, separation and other conditions are unchanged to obtain the compound shown as the formula (51).
Product MS (m/e): 608, elemental analysis (C)44H24N4): theoretical value C: 86.82%, H: 3.97%, N: 9.20 percent; found value C: 86.84%, H: 3.93%, N: 9.23 percent.
Example 42
Synthesis of Compound represented by the formula (52)
The procedure was the same as in example 2 except that 6-bromo-2, 3-dimethylquinoxaline as the starting material was changed to 6-bromo-2, 3-diphenylquinoxaline and 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 12- (p- (naphthalen-1-yl) phenyl)
The 6-boric acid and other medicines, reagents, reaction, separation and other conditions are unchanged to obtain the compound shown in the formula (52).
Product MS (m/e): 710 elemental analysis (C)54H34N2): theoretical value C: 91.24%, H: 4.82%, N: 3.94 percent; found value C: 91.22%, H: 4.85%, N: 3.93 percent; nuclear magnetic spectrum of (1HNMR) is shown in fig. 6.
Example 43
Synthesis of Compound represented by the formula (53)
The procedure was the same as in example 2, except that the starting material 6-bromo-2, 3-dimethylquinoxaline was changed to 7-bromo-1, 2,3, 4-tetrahydrophenazine, and 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid was changed to 12- (p- (naphthalen-1-yl) phenyl)
The compound shown as the formula (53) is obtained under the conditions of-6-boric acid, other medicines, reagents, reaction, separation and the like.
Product MS (m/e): 612, elemental analysis (C)46H32N2): theoretical value C: 90.16%, H: 5.26%, N: 4.57 percent; found value C: 90.18%, H: 5.24%, N: 4.58 percent.
Example 44
Synthesis of Compound represented by the formula (54)
The procedure was followed as in example 2 except that 9, 10-di (naphthalen-2-yl) anthracene-2-boronic acid, the starting material, was changed to 12- (p- (naphthalen-1-yl) phenyl)
-6-boric acid, and other medicines, reagents, reaction, separation and other conditions are unchanged to obtain the compound shown as the formula (54).
Product MS (m/e): 586 elemental analysis(C44H30N2): theoretical value C: 90.07%, H: 5.15%, N: 4.77 percent; found value C: 90.08%, H: 5.18%, N: 4.74 percent.
The following are examples of the use of the compounds of the invention:
example 45
To facilitate comparison of the transport properties of these electron transport materials, the present inventors designed a simple electroluminescent device using EM1 as the emissive material (EM1 is the host material and not the emissive material in order not to pursue high efficiency but to verify the possibility of these materials being practical) and using the high efficiency electron transport material Bphen as the comparative material. The structures of EM1 and Bphen are:
the structure of the organic electroluminescent device in the embodiment of the invention is as follows:
substrate/anode/Hole Transport Layer (HTL)/organic light Emitting Layer (EL)/Electron Transport Layer (ETL)/cathode.
The substrate may be a substrate used in a conventional organic light emitting device, for example: glass or plastic. In the invention, the glass substrate and the ITO are used as anode materials in the manufacture of the organic electroluminescent device.
Various triarylamine-based materials may be used for the hole transport layer. The hole transport material selected for use in the fabrication of the organic electroluminescent device of the present invention is NPB. The NPB structure is:
the cathode can adopt a metal and a mixture structure thereof, such as Mg: ag. Ca: ag, etc., or an electron injection layer/metal layer structure, such as LiF/Al, Li2O/Al and the like. The cathode material selected in the preparation of the organic electroluminescent device is LiF/Al.
The compound in this embodiment is used as an electron transport material in an organic electroluminescent device, and the EML is used as a light emitting layer material, so that a plurality of organic electroluminescent devices are prepared, and the structure of each organic electroluminescent device is as follows: ITO/NPB (40nm)/EM1(30nm)/ETL material (20nm)/LiF (0.5nm)/Al (150 nm);
in one comparative organic electroluminescent device, Bphen was used as the electron transport material, and the materials of the present invention were used for the remaining organic electroluminescent devices.
The preparation process of the organic electroluminescent device in the embodiment is as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to form NPB as a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 40 nm;
vacuum evaporating EM1 on the hole transport layer to serve as a light emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm;
vacuum evaporating a compound represented by a layer (13), a formula (14), a formula (16), a formula (25), a formula (27), a formula (33), a formula (35), a formula (36), a formula (44), a formula (46) or a formula (52) on the light-emitting layer to form an electron transport layer material of the device, using Bphen as a contrast material of the electron transport layer material of the device, wherein the evaporation rate is 0.1nm/s, and the total thickness of the evaporated film is 20 nm;
LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
The organic electroluminescent device properties are given in the following table:
| compound numbering | Required luminance cd/m2 | Voltage V | Current efficiency cd/A |
| Bphen | 1000.00 | 6.2 | 6.1 |
| Formula (13) | 1000.00 | 5.7 | 6.8 |
| Formula (14) | 1000.00 | 5.6 | 6.9 |
| Formula (16) | 1000.00 | 5.6 | 7.0 |
| Formula (25) | 1000.00 | 5.8 | 7.2 |
| Formula (27) | 1000.00 | 5.7 | 7.1 |
| Formula (33) | 1000.00 | 5.6 | 6.9 |
| Formula (35) | 1000.00 | 5.6 | 7.1 |
| Formula (36) | 1000.00 | 5.7 | 7.3 |
| Formula (44) | 1000.00 | 5.7 | 7.0 |
| Formula (46) | 1000.00 | 5.7 | 7.1 |
| Formula (52) | 1000.00 | 5.5 | 7.0 |
The results show that the novel organic material is used for the organic electroluminescent device, can effectively reduce the working voltage of the device and improve the current efficiency, and is an electron transport material with good performance.
Although the invention has been described in connection with the embodiments, the invention is not limited to the embodiments described above, and it should be understood that various modifications and improvements can be made by those skilled in the art within the spirit of the invention, and the scope of the invention is outlined by the appended claims.
Claims (5)
1. A fused ring aromatic hydrocarbon derivative containing a quinoxaline group, characterized by having a structure represented by formula (7):
wherein Ar is1And Ar2The same or different, are independently selected from unsubstituted fused ring aromatic hydrocarbon radicals;
l is a single bond;
R1and R2The same or different, are respectively and independently selected from H, aromatic hydrocarbon group, heterocyclic aromatic hydrocarbon group, condensed ring aromatic hydrocarbon group, or condensed heterocyclic aromatic hydrocarbon group, substituted or unsubstituted alkyl and cyano; r1And R2Or can be connected with each other to form a ring to form an aliphatic ring;
the unsubstituted alkyl group is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group or a cyclohexyl group;
the substituted alkyl is trifluoromethyl;
the aromatic hydrocarbon group is phenyl, o-tolyl, p-tolyl or tert-butylphenyl, and the heterocyclic aromatic hydrocarbon group is furyl, benzofuryl, dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, carbazolyl, pyridyl, pyrazinyl, 2, 4-methyl-1, 3, 5-triazinyl or 4, 6-diphenylpyrimidinyl;
the condensed ring aromatic hydrocarbon group is naphthyl, phenanthryl, anthryl, pyrenyl and 9.9-dimethyl-2-fluorenyl; the fused heterocyclic aromatic hydrocarbon group is quinolyl, isoquinolyl or quinazolinyl.
2. A fused ring aromatic hydrocarbon derivative containing a quinoxaline group, wherein the compound has a structure represented by formulae (12) to (23):
3. use of the quinoxaline group-containing polycyclic aromatic hydrocarbon derivative according to claim 1 in an organic electroluminescent device.
4. The use of the polycyclic aromatic hydrocarbon derivative according to claim 3 in an organic electroluminescent device, wherein the quinoxaline group-containing polycyclic aromatic hydrocarbon derivative is useful as an electron transport material.
5. An organic electroluminescent device comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate; the organic light-emitting functional layer comprises a hole transport layer, an organic light-emitting layer and an electron transport layer, and is characterized in that:
the electron transport material of the electron transport layer is the condensed ring aromatic hydrocarbon derivative containing quinoxaline group according to claim 1.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010042545.4A CN111187225B (en) | 2015-09-30 | 2015-09-30 | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof |
| CN201510641431.0A CN106554320B (en) | 2015-09-30 | 2015-09-30 | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof |
| CN202010042537.XA CN111205234A (en) | 2015-09-30 | 2015-09-30 | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510641431.0A CN106554320B (en) | 2015-09-30 | 2015-09-30 | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010042545.4A Division CN111187225B (en) | 2015-09-30 | 2015-09-30 | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof |
| CN202010042537.XA Division CN111205234A (en) | 2015-09-30 | 2015-09-30 | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106554320A CN106554320A (en) | 2017-04-05 |
| CN106554320B true CN106554320B (en) | 2020-07-07 |
Family
ID=58417879
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010042545.4A Active CN111187225B (en) | 2015-09-30 | 2015-09-30 | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof |
| CN201510641431.0A Active CN106554320B (en) | 2015-09-30 | 2015-09-30 | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof |
| CN202010042537.XA Pending CN111205234A (en) | 2015-09-30 | 2015-09-30 | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010042545.4A Active CN111187225B (en) | 2015-09-30 | 2015-09-30 | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010042537.XA Pending CN111205234A (en) | 2015-09-30 | 2015-09-30 | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN111187225B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107954942B (en) * | 2017-12-08 | 2019-04-09 | 北京鼎材科技有限公司 | Benzopyrazines replaces anthracene derivant and organic electroluminescence device |
| KR20210147884A (en) * | 2020-05-28 | 2021-12-07 | 주식회사 엘지화학 | Compound and organic light emitting device comprising the same |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325449C (en) * | 2001-04-19 | 2007-07-11 | Tdk株式会社 | Compound for organic el element and organic el element |
| US7074534B2 (en) * | 2002-07-10 | 2006-07-11 | E. I. Du Pont De Nemours And Company | Polymeric charge transport compositions and electronic devices made with such compositions |
| CN1751024A (en) * | 2003-01-10 | 2006-03-22 | 出光兴产株式会社 | Nitrogen-containing heterocyclic derivative and organic electroluminescent element using same |
| CN1777592B (en) * | 2003-04-18 | 2011-09-07 | 株式会社半导体能源研究所 | Quinoxaline derivatives, and organic semiconductor devices, electroluminescent devices and electronic appliances, made by using the derivatives |
| KR101362032B1 (en) * | 2006-11-15 | 2014-02-11 | 이데미쓰 고산 가부시키가이샤 | Fluoranthene compound, organic electroluminescent device using the fluoranthene compound, and organic electroluminescent material-containing solution |
| JP5064787B2 (en) * | 2006-12-26 | 2012-10-31 | キヤノン株式会社 | Benzofluoranthene compound and organic light-emitting device using the same |
| KR101625235B1 (en) * | 2007-09-20 | 2016-05-27 | 바스프 에스이 | Electroluminescent device |
| JP5575547B2 (en) * | 2010-05-28 | 2014-08-20 | 双葉電子工業株式会社 | Organic EL device |
| KR101288567B1 (en) * | 2010-06-01 | 2013-07-22 | 제일모직주식회사 | Compound for organic photoelectric device and organic photoelectric device including the same |
| JP5909179B2 (en) * | 2010-10-08 | 2016-04-26 | 出光興産株式会社 | Benzo [k] fluoranthene derivative and organic electroluminescence device comprising the same |
| KR101531612B1 (en) * | 2010-12-02 | 2015-06-25 | 제일모직 주식회사 | Compound for organic photoelectric device and organic photoelectric device including the same |
| KR101432600B1 (en) * | 2010-12-31 | 2014-08-21 | 제일모직주식회사 | Compound for organic photoelectric device and organic photoelectric device including the same |
| CN104039773B (en) * | 2011-11-11 | 2016-08-24 | 东曹株式会社 | There is the cyclic azine compound of nitrogenous contracting polycyclic aromatic group and manufacture method thereof and with this cyclic azine compound organic electroluminescent device as constituent |
| KR101918953B1 (en) * | 2012-03-06 | 2018-11-16 | 삼성디스플레이 주식회사 | Amine-based compound, organic light emitting diode comprising the same and organic light emitting apparatus comprising the same |
| KR101531615B1 (en) * | 2012-04-24 | 2015-07-02 | 제일모직 주식회사 | Compound for organic optoelectronic device, organic light emitting diode including the same and display including the organic light emitting diode |
| KR102268119B1 (en) * | 2013-08-30 | 2021-06-21 | 엘지디스플레이 주식회사 | Pyrene compound and organic light emitting diode device comprising the same |
| KR102164046B1 (en) * | 2013-12-03 | 2020-10-12 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
-
2015
- 2015-09-30 CN CN202010042545.4A patent/CN111187225B/en active Active
- 2015-09-30 CN CN201510641431.0A patent/CN106554320B/en active Active
- 2015-09-30 CN CN202010042537.XA patent/CN111205234A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN106554320A (en) | 2017-04-05 |
| CN111187225A (en) | 2020-05-22 |
| CN111205234A (en) | 2020-05-29 |
| CN111187225B (en) | 2021-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112079834B (en) | Organic electroluminescent compound and application thereof | |
| CN106554319B (en) | Quinazoline group-containing derivative and application thereof | |
| CN111662225A (en) | Organic compound containing pyrene and application thereof | |
| CN106554352B (en) | Polycyclic aromatic hydrocarbon derivative containing naphthyridine group and application thereof | |
| CN104513247A (en) | Benzo [c] benzo [3,4] carbazol derivatives and uses | |
| CN106554322B (en) | Phenazine derivative and application thereof in organic electroluminescent device | |
| CN104673276A (en) | Organic luminescent material and application thereof | |
| CN113402507A (en) | Triphenylene derivative, light-emitting device material, and light-emitting device | |
| CN106554323B (en) | Phenazine group-substituted polycyclic aromatic hydrocarbon derivative and application thereof | |
| CN107663169B (en) | 6H-naphtho [2,1,8,7-klmn ] acridine derivative and application thereof | |
| CN106554320B (en) | Condensed ring aromatic hydrocarbon derivative with quinoxaline group and application thereof | |
| CN112812104B (en) | Compound with nitrogen-containing heterocyclic structure, application thereof and organic electroluminescent device | |
| CN111233840A (en) | Quinoxaline derivative and application thereof in organic light-emitting device | |
| CN111675714A (en) | Organic electroluminescent compound with balanced carrier transmission performance and application thereof | |
| CN108164496B (en) | Compound and organic electronic device thereof | |
| CN111662306B (en) | OLED organic electroluminescent compound and main material of light-emitting layer | |
| CN109678799B (en) | Dihydrobenzandazole compound, organic electroluminescent device and display device | |
| CN116102395A (en) | Organic compound, application thereof and organic electroluminescent device | |
| CN115703784A (en) | Indolocarbazole compound with symmetrical structure, application thereof and organic electroluminescent device | |
| CN106558654B (en) | Benzophenazine derivative and application thereof in organic electroluminescent device | |
| CN115894484B (en) | Isoquinoline quinoline compound and preparation method and application thereof | |
| CN114057757B (en) | Organic compound containing heterocyclic structure, application thereof and organic electroluminescent device | |
| CN112745318B (en) | Compound and application thereof | |
| CN108922975B (en) | Organic electroluminescent element | |
| CN113512047B (en) | Compound and application 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |