CN113801127B - Oxa-thiaazulene derivatives and their use - Google Patents
Oxa-thiaazulene derivatives and their use Download PDFInfo
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Abstract
The invention relates to the technical field of organic electroluminescence, in particular to oxa-thia-azulene derivatives and application thereof. The structural general formula of the oxa-thiazulene derivative is shown as a formula I:
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to oxa-thia-azulene derivatives and application thereof.
Background
In recent years, organic electroluminescent display technologies have become mature, and some products have entered the market, but in the process of industrialization, many problems still need to be solved, especially, many problems still remain unsolved, such as carrier injection and transport properties, electroluminescent properties of materials, service life, color purity, matching between various materials and between various electrodes, and the like, of various organic materials used for manufacturing elements. Especially, the light emitting element has not yet achieved practical requirements in terms of luminous efficiency and service life, which greatly limits the development of OLED technology.
Organic electroluminescence is mainly divided into fluorescence and phosphorescence, but according to the spin quantum statistical theory, the probability of singlet excitons and triplet excitons is 1:3, the theoretical limit for fluorescence from radiative white singlet excitons is 25% and the theoretical limit for fluorescence from radiative triplet excitons is 75%. It is urgent to use 75% of the energy of triplet excitons. Forrest et al in 1997 discovered that the phosphorescence electroluminescence phenomenon breaks through the limitation of 25% efficiency of the quantum efficiency of the organic electroluminescence material, and arouses the wide attention of researchers to the metal complex phosphorescence material. Since then, researchers have conducted extensive research on phosphorescent materials.
Disclosure of Invention
The first purpose of the invention is to provide an oxa-thiaazulene derivative; the oxa-or thiaazulene derivatives are used as a raw material for an organic electroluminescent element, and thus, a material for an organic electroluminescent element and an organic electroluminescent element which are reduced in the starting voltage, improved in the luminous efficiency and improved in the luminance, and an electronic device using the organic electroluminescent element can be provided.
The structural general formula of the oxa-thiazulene derivative is shown as a formula I:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 Is selected, identically or differently on each occurrence, from hydrogen, deuterium, with C 1 ～C 40 Straight chain alkyl of (2) having C 1 ～C 40 Linear heteroalkyl group of (A) having C 3 ～C 40 A branched or cyclic alkyl group of (2), having C 3 ～C 40 A branched or cyclic heteroalkyl group of (2), having C 2 ～C 40 Alkenyl or alkynyl groups of (a), aromatic or heteroaromatic ring systems having 5 to 60 atoms, each of which may be substituted by one or more groups R;
x is selected from O or S;
w is selected from CR or N and two adjacent groups W represent a group of formula (a):
wherein G represents C (R) 2 NR, oxygen or sulfur; z represents CR or N; ^ represents a neighboring group W in the formula (a);
r is selected, identically or differently on each occurrence, from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a nitrile group, a nitro group, N (Ar) 1 ) 2 、N(R 8 ) 2 、C(＝O)Ar 1 、C(＝O)R 8 、P(＝O)(Ar 1 ) 2 Having a structure of C 1 ～C 40 Straight chain alkyl of (2) having C 1 ～C 40 Linear heteroalkyl group of (A) having C 3 ～C 40 A branched or cyclic alkyl group having C 3 ～C 40 A branched or cyclic heteroalkyl group of (A) having C 2 ～C 40 Alkenyl or alkynyl groups, aromatic or heteroaromatic ring systems having from 5 to 80, preferably from 5 to 60, atoms, aryloxy or heteroaryloxy groups having from 5 to 60 atoms, each of which may be substituted by one or more radicals R 8 Substituted, or combinations of these systems, wherein one or more non-adjacent-CH 2 The radicals may be substituted by R 8 C＝CR 8 、C≡C、Si(R 8 ) 2 、Ge(R 8 ) 2 、Sn(R 8 ) 2 、C＝O、C＝S、C＝Se、C＝NR 8 、P(＝O)(R 8 )、SO、SO 2 、NR 8 O, S or CONR 8 And in which one or more hydrogen atoms are replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, where two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R 8 Substitution;
R 8 selected, identically or differently on each occurrence, from hydrogen atoms, deuterium atoms, halogen atoms, nitrile groups, nitro groups, N (Ar) 1 ) 2 、N(R 9 ) 2 、C(＝O)Ar 1 、C(＝O)R 9 、P(＝O)(Ar 1 ) 2 Having a structure of C 1 ～C 40 Straight chain alkyl of (2) having C 1 ～C 40 Linear heteroalkyl group of (A) having C 3 ～C 40 A branched or cyclic alkyl group having C 3 ～C 40 A branched or cyclic heteroalkyl group of (A) having C 2 ～C 40 Alkenyl or alkynyl groups having 5 to 60 atoms, aromatic or heteroaromatic ring systems having 5 to 60 atoms, aryloxy or heteroaryloxy groups having 5 to 60 atoms, each of which may be interrupted by one or more radicals R 9 Substituted, or combinations of these systems, wherein one or more non-adjacent-CH 2 The radicals may be substituted by R 9 C＝CR 9 、C≡C、Si(R 9 ) 2 、Ge(R 9 ) 2 、Sn(R 9 ) 2 、C＝O、C＝S、C＝Se、C＝NR 9 、P(＝O)(R 9 )、SO、SO 2 、NR 9 O, S or CONR 9 And wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, wherein two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R 9 Substitution;
Ar 1 identical or different at each occurrence is an aromatic or heteroaromatic ring system having from 5 to 30 atoms which may be interrupted by one or more nonaromatic radicals R 9 Substitution; two groups Ar here bonded to the same nitrogen or phosphorus atom 1 Can also be selected from N (R) or through a single bond 9 )、C(R 9 ) 2 Oxygen or sulfur bridging groups;
R 9 selected from hydrogen atom, deuterium atom, fluorine atom, nitrile group, having C 1 ～C 20 An aromatic or heteroaromatic ring system having from 5 to 30 atoms in which one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms or nitrile groups, wherein two or more adjacent substituents R 9 They can form mono-or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.
Preferably, the oxa-thiaazulene derivative is selected from one of the compounds shown in the following formulas I-1 to I-6:
wherein the meaning of R, R, R, R, R, R, R, R, R, ar has the meaning given above;
R 10 、R 11 、R 12 、R 13 、R 14 each independently selected from a hydrogen atom, a deuterium atom, a fluorine atom, a nitrile group, having C 1 ～C 20 Wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups, wherein two or more adjacent substituents may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system with one another.
Aromatic or heteroaromatic ring systems in the sense of the present invention are intended to be taken to mean systems which do not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be linked by non-aromatic units, for example C, N, O or an S atom. Thus, as well as systems in which two or more aryl groups are linked by, for example, short alkyl groups, systems such as fluorene, 9,9' -spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered to refer to aromatic ring systems in the sense of the present invention.
Aryl in the sense of the present invention contains from 6 to 60 carbon atoms and heteroaryl in the sense of the present invention contains from 2 to 60 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O or S. Aryl or heteroaryl herein is considered to mean a simple aromatic ring, i.e. benzene, naphthalene, etc., or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, such as anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatic rings, such as biphenyl, which are connected to one another by single bonds, are, in contrast, not referred to as aryl or heteroaryl groups, but rather as aromatic ring systems.
Containing 1 to 40 carbon atoms and in which a single hydrogen atom or-CH 2 The aliphatic hydrocarbon or alkyl or alkenyl or alkynyl groups which the radicals may also be substituted by the abovementioned radicals are preferably to be understood as meaning the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. Alkoxy, preferably alkoxy having from 1 to 40 carbon atoms, is to be understood as meaning methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. Heteroalkyl is preferably alkyl having 1 to 40 carbon atoms, meaning that the individual hydrogen atoms or-CH 2 The radicals-which may be substituted by oxygen, sulfur or halogen atoms-are understood to mean alkoxy, alkylthio, fluorinated alkoxy, fluorinated alkylthio, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2,2,2-trifluoroethoxy, 2,2,2-trifluoroethylthio, vinyloxy, vinylthio, propenyloxy, propenylthio, butenylthio, butenyloxy, pentenyloxy, pentenylthio, cyclopentenyloxy, cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexenyloxy, cyclohexenylthio, ethynyloxyEthynylthio, propynyloxy, propynylthio, butynyloxy, butynylthio, pentynyloxy, pentynylthio, hexynyloxy, hexynylthio.
In general, the cycloalkyl, cycloalkenyl groups according to the invention may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, where one or more-CH may be present 2 The radicals may be replaced by the radicals mentioned above; furthermore, one or more hydrogen atoms may also be replaced by deuterium atoms, halogen atoms or nitrile groups.
The aromatic or heteroaromatic ring atoms according to the invention may in each case also be substituted by the abovementioned radicals R 8 Or R 9 Substituted aromatic or heteroaromatic ring systems, in particular radicals derived from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,
Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, cis-or trans-indenocarbazole, cis-or trans-indolocarbazole, triindene, isotridendene, spirotriindene, spiroisotridendene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo [5,6]Quinoline, benzo [6,7]Quinoline, benzo [7,8]Quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinimidazole, quinoxalimidazole, oxazole, benzoxazole, naphthooxazole, anthraoxazole, phenanthroixazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diaza anthracene, 2,7-diaza pyrene, 2,3-diaza pyrene, 1,6-diaza pyrene, 1,8-diaza pyrene, 4,5-diaza pyrene, 4,5,9,10-tetraazapyrylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorescein red ring, naphthyridine, azacarbazole,Benzocarbinoline, carboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, and benzothiadiazole, or groups derived from combinations of these systems.
Preferably, the oxa-thiaazulene derivative is selected from the group consisting of compounds represented by the following formulae P01 to P315:
wherein X is selected from O or S.
The second object of the present invention is to provide a material for an organic electroluminescent element comprising the above oxa-thiaazulene derivative.
In the present invention, the material for an organic electroluminescent element may be composed of the compound of the present invention alone or may contain other compounds.
The compound of the present invention contained in the material for an organic electroluminescent element of the present invention can be used as a host material; in this case, the material for an organic electroluminescent element may contain another compound as a dopant.
A third object of the present invention is to provide an organic electroluminescent element comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode;
at least one of the organic layers comprises the oxa-thiaazulene derivatives described above.
Further, the organic layer further comprises a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole barrier layer and an electron barrier layer.
Preferably, the oxa-or thiaazulene derivative is used as a host material, an electron transport material, a hole transport material, a dopant material or an encapsulation layer material in the organic electroluminescent element.
Specifically, the oxa-thiaazulene derivative is used as a red phosphorescent host material, a green phosphorescent host material, a blue phosphorescent host material, a fluorescent host material, a hole transport material, an electron blocking material, a hole blocking material or an encapsulation layer material in the organic electroluminescent element.
The organic electroluminescent element of the present invention may be either a top-emitting or a bottom-emitting element; the structure and the production method of the organic electroluminescent element are not limited. The organic electroluminescent element prepared by the compound can reduce the starting voltage and improve the luminous efficiency and brightness.
Typical configurations of the organic electroluminescent element of the present invention include, but are not limited to, the following structures:
(a) Anode/luminescent layer/cathode
(b) Anode/hole injection-transport layer/light-emitting layer/cathode
(c) Anode/light-emitting layer/electron injection-transport layer/cathode
(d) Anode/hole injection-transport layer/light-emitting layer/electron injection-transport layer/cathode
(e) Anode/hole injection-transport layer/first light-emitting layer/second light-emitting layer/electron injection-transport layer/cathode
(f) Anode/hole injection-transport layer/light-emitting layer/electron blocking layer/electron injection-transport layer/cathode
(g) Anode/hole injection-transport layer/hole blocking layer/light-emitting layer/electron injection-transport layer/cathode.
It is a fourth object of the present invention to provide use of the above-described organic electroluminescent element in an electronic device.
It is a fifth object of the present invention to provide an electronic device including the above-described organic electroluminescent element.
Preferably, the electronic device is a planar light emitting body, a copying machine, a printer, a light source, a display panel or a marker light;
preferably, the planar light-emitting body is a wall-mounted television, a flat panel display or a lighting device; the light source is a light source of a liquid crystal display or a light source of a measuring instrument.
The invention has the beneficial effects that:
the oxa-thiaazulene derivative shown in the formula I has high carrier mobility, and is suitable for being used as a material for an organic electroluminescent element. In addition, the novel compound of the present invention has excellent thermal stability and film-forming properties, and can be applied to materials for organic electroluminescent elements, and electronic devices to prolong the life of the organic electroluminescent elements, thereby reducing the manufacturing costs of the materials for organic electroluminescent elements, the organic electroluminescent elements, and the electronic devices.
Drawings
FIG. 1 is a schematic view showing an example of bottom emission of an organic electroluminescent element according to the present invention;
FIG. 2 is a schematic view showing an example of top emission of an organic electroluminescent element according to the present invention;
in fig. 1 and 2, the organic electroluminescent element includes a substrate 1, an anode 2, a cathode 8, and layers 3 to 7 disposed between the anode 2 and the cathode 8. A hole-blocking/electron-transporting layer 6 and an electron-injecting layer 7 are disposed between the cathode 8 and the light-emitting layer 5, and a hole-injecting layer 3 and a hole-transporting/electron-blocking layer 4 are disposed between the light-emitting layer 5 and the anode 2.
In the organic electroluminescent element of the present invention, the above-mentioned oxa-thiaazulene derivative of the present invention is preferably contained in the light-emitting layer 5.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
In addition, unless otherwise specified, all starting materials for use in the present invention are commercially available, and any range recited herein includes any value between the endpoints and any subrange between the endpoints and any value between the endpoints or any subrange between the endpoints.
In the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "upper", "lower", and the like, indicate orientations or positional relationships that are based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and to simplify the description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
In the present invention, the preparation method is a conventional method unless otherwise specified. The starting materials used are available from published commercial sources unless otherwise specified, and the percentages are by mass unless otherwise specified.
The following test instruments and methods for performance testing of OLED materials and devices were used in the examples as follows:
OLED element performance detection conditions:
luminance and chromaticity coordinates: testing with a photosresearch PR-715 spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: tested using NEWPORT 1931-C;
and (3) life test: LTS-1004AC life test equipment was used.
Example 1
A process for the preparation of compound P236 (X = O), comprising the steps of:
the first step is as follows: preparation of Compound Int-1
At room temperature, 0.10mol of 1,8-dibromonaphthalene was dissolved in 200mL of toluene, and 0.10mol of phenylboronic acid, 0.20mol of sodium carbonate, and 0.5mmol of Pd (PPh) were added 3 ) 4 Adding 100mL of ethanol and 20mL of water into the catalyst, heating to reflux, stirring, reacting for 6 hours, cooling to room temperature, adding 100mL of water for dilution, separating an organic phase, extracting a water phase with ethyl acetate, combining the organic phases, drying, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a white solid with the yield of 74%.
The second step is that: preparation of Compound Int-2
90.0mmol of 6-chloro-2-methoxyphenylboronic acid and 75.0mmol of the intermediate Int-1 prepared in the first step are dissolved in 150mL of toluene, and 0.36mol of sodium carbonate and 0.075mmol of Pd (PPh) are added at room temperature 3 ) 4 Adding 150mL of ethanol and 50mL of water into the catalyst, heating to reflux, stirring, reacting for 4 hours, cooling to room temperature, separating an organic phase, extracting a water phase by using ethyl acetate, combining the organic phases, drying, filtering, concentrating a filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a white solid with the yield of 87%.
The third step: preparation of Compound Int-3
82.6mmol of the intermediate Int-2 prepared in the second step, 24.8mmol of tricyclohexylphosphonium tetrafluoroborate and 16.5mmol of palladium acetate, 80.7g (247.8 mmol) of anhydrous cesium carbonate and 410mL of dimethylacetamide are added, the mixture is heated under reflux and stirred for reaction for 12 hours under the protection of nitrogen, the mixture is cooled to room temperature, 500mL of water is added for dilution, the extraction is carried out by dichloromethane, the organic phase is dried and filtered, the filtrate is concentrated under reduced pressure to dryness, and the dryness is separated and purified by a silica gel column to obtain the compound Int-3 with the yield of 72%.
The fourth step: preparation of Compound Int-4
70.0mmol of the intermediate Int-3 prepared in the third step is dissolved in 150mL of dry tetrahydrofuran, the temperature is reduced to-40 ℃ by liquid nitrogen under the protection of nitrogen, 33.6mL of 2.5M n-butyllithium n-hexane solution is added dropwise, the temperature is raised to 0 ℃, stirring reaction is carried out for 2 hours, 84.0mmol of bromine solution is added dropwise in 50mL of dry tetrahydrofuran, stirring reaction is carried out for 1 hour, 50mL of saturated sodium bisulfite aqueous solution is added, extraction is carried out by ethyl acetate, organic phase drying is carried out, filtration is carried out, reduced pressure concentration is carried out on filtrate, and separation and purification are carried out by a silica gel column, so that the compound Int-4 is obtained, and the yield is 65%.
The fifth step: preparation of Compound Int-5
65.0mmol of the intermediate Int-4 prepared in the fourth step is dissolved in 150mL of dry dichloromethane, cooled to 0 ℃ with ice water under the protection of nitrogen, 78.0mmol of boron tribromide is dropwise added, stirred and reacted for 2 hours, 20mL of saturated sodium thiosulfate aqueous solution is added, extraction is carried out with dichloromethane, an organic phase is dried and filtered, filtrate is concentrated under reduced pressure to be dry, and separation and purification are carried out by a silica gel column to obtain the compound Int-5 with the yield of 85%.
And a sixth step: preparation of Compound Int-6
60.0mmol of the intermediate Int-5 prepared in the fifth step is dissolved in 100mL of freshly distilled pyridine, 14.8g of copper oxide and 41.4g of anhydrous potassium carbonate are added under the protection of nitrogen, the mixture is heated under reflux and stirred for 12 hours, the reaction mixture is cooled to room temperature, 20mL of 3M dilute hydrochloric acid aqueous solution is added, dichloromethane is used for extraction, the organic phase is washed by 10% sodium hydroxide aqueous solution, the organic phase is dried and filtered, the filtrate is concentrated under reduced pressure to dryness, and the product is separated and purified by a silica gel column to obtain the compound Int-6 with the yield of 70%.
The seventh step: preparation of Compound Int-7
40.0mmol of intermediate Int-6 prepared in the sixth step is dissolved in 150mL of dry tetrahydrofuran, 40.0mmol of anhydrous lithium chloride is added under the protection of nitrogen, liquid nitrogen is used for cooling to-78 ℃, 19.2mL of 2.5M n-butyllithium n-hexane solution is dropwise added, stirring reaction is carried out for 1 hour, the temperature is increased to room temperature, stirring reaction is carried out for 2 hours, liquid nitrogen is used for cooling to-78 ℃, 48.0mmol of iodine solution is dropwise added into 50mL of dry tetrahydrofuran, stirring reaction is carried out for 1 hour, the temperature is increased to room temperature, stirring reaction is carried out for 1 hour, 50mL of saturated sodium bisulfite aqueous solution is added, ethyl acetate is used for extraction, organic phase drying is carried out, filtration is carried out, filtrate is subjected to reduced pressure concentration and drying, and is separated and purified by a silica gel column, and the compound Int-7 is obtained, and the yield is 62%.
Eighth step: preparation of Compound Int-8
50.0mmol of intermediate Int-7 prepared in the seventh step was dissolved in 150mL of dry toluene, and under nitrogen, 60.0mmol of o-bromoaniline and 75.0mmol of sodium tert-butoxide and 0.5mmol of Pd were added 2 (dba) 3 And 1.0mmol of 4,5-bis (diphenylphosphine) -9,9-dimethylxanthene, heating to 100 ℃, stirring for reaction for 4 hours, cooling to room temperature, adding 50mL of water for dilution, extracting with ethyl acetate, drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, and washing with ethanol to obtain a compound Int-8 as a white solid with a yield of 84%.
The ninth step: preparation of Compound Int-9
82.6mmol of the intermediate Int-8 prepared in the eighth step, 24.8mmol of tricyclohexylphosphonium tetrafluoroborate and 16.5mmol of palladium acetate, 80.7g (247.8 mmol) of anhydrous cesium carbonate and 350mL of dimethylacetamide are added, the mixture is heated under reflux and stirred for reaction for 12 hours under the protection of nitrogen, the mixture is cooled to room temperature, 500mL of water is added for dilution, the extraction is carried out by dichloromethane, the organic phase is dried and filtered, the filtrate is concentrated under reduced pressure to dryness, and the dryness is separated and purified by a silica gel column to obtain the compound Int-9 with the yield of 68%.
The tenth step: preparation of Compound P236
15.0mmol of the intermediate Int-9 prepared in the ninth step was dissolved in 80mL of N, N-dimethylformamide, cooled to 0 ℃ in an ice water bath, 18.0mmol of a 65% sodium hydride solid was added in portions, stirred for half an hour, 18.0mmol of 2-chloro-4- (2-naphthyl) -6-phenyl-1,3,5-triazine was added, stirred for 1 hour, warmed to room temperature, stirred for 2 hours, diluted with 200mL of water, filtered, the filter cake was washed with water, purified by silica gel column separation, and recrystallized with dichloromethane-ethanol to give the compound P236 as a yellow solid with a yield of 75%.
MS(MALDI-TOF)：m/z 663.2199[M+H] + ； 1 HNMR(δ、CDCl 3 )：9.24(1H,s)；8.92～8.87(2H,d)；8.58～8.56(4H,m)；8.42～8.40(1H,d)；8.32～8.28(1H,m)；8.08～7.94(7H,m)；7.65～7.44(6H,m)；7.18～7.07(2H,m)；6.96～6.89(2H,m)。
Example 2
A process for the preparation of compound P226 (X = O), comprising the steps of:
10.0mmol of the intermediate Int-9 prepared in the ninth step of example 1 was dissolved in 50mL of dry xylene, 12.0mmol of 9- (3-phenylphenyl) -3-bromo-9H-carbazole and 15.0mmol of sodium tert-butoxide were added under nitrogen protection, and 0.5mmol of Pd were added 2 (dba) 3 And 0.02mL of 10% tri-tert-Ding Lin toluene solution, heating to 110 ℃, stirring for reaction for 12 hours, cooling to room temperature, adding 50mL of water for dilution, extracting with ethyl acetate, drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by a silica gel column to obtain the compound P226 which is a yellow solid with the yield of 73%.
MS(MALDI-TOF)：m/z 699.2450[M+H] + ； 1 HNMR(δ、CDCl 3 )：8.78～8.76(1H,d)；8.44～8.38(2H,m)；8.32～8.28(2H,m)；8.22～8.20(1H,d)；8.08～7.99(3H,m)；8.08～7.94(7H,m)；7.65～7.53(6H,m)；7.51～7.42(3H,m)；7.38～7.29(2H,m)；7.23(1H,s)；7.16～7.14(1H,m)；7.10～7.08(1H,m)。
Example 3
A process for the preparation of compound P252 (X = S) comprising the steps of:
the first step is as follows: preparation of Compound Int-31
50.0mmol of intermediate Int-30 (prepared by the first to third steps of the preparation method in example 1) was dissolved in 200mL of dry tetrahydrofuran, 100mL of glacial acetic acid was added, 75mmol of 34.5% hydrogen peroxide was added, the mixture was stirred at room temperature for 24 hours, concentrated under reduced pressure and dried, dissolved in dichloromethane, washed with saturated aqueous sodium bicarbonate, the organic phase was dried, filtered, concentrated under reduced pressure and dried, dispersed in methanol, and filtered to obtain compound Int-31 with a yield of 100%.
The second step: preparation of Compound Int-32
And (3) cooling 40.8mL of concentrated sulfuric acid to 0 ℃ by using an ice salt bath, adding 40.0mmol of the intermediate Int-31 prepared in the previous step in batches, heating to room temperature, stirring for reacting for 2 hours, pouring the reaction liquid into 400g of crushed ice, adding potassium carbonate solid in batches to adjust the pH to 8, extracting by using dichloromethane, drying an organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain the compound Int-32 with the yield of 87%.
The third step: preparation of Compound Int-33
Referring to the seventh preparation step of example 1, compound Int-33 was prepared in 65% yield by replacing intermediate Int-6 with Int-32.
The fourth step: preparation of Compound Int-34
Referring to the eighth preparation process of example 1, compound Int-34 was prepared in 80% yield by replacing intermediate Int-7 with Int-33.
The fifth step: preparation of Compound Int-35
Referring to the ninth preparation process of example 1, compound Int-35 was prepared with 86% yield by replacing intermediate Int-8 with Int-34.
And a sixth step: preparation of compound P252 (X = S)
15.0mmol of the intermediate Int-35 prepared in the fifth step is dissolved in 80mL of N, N-dimethylformamide, the temperature is reduced to 0 ℃ by using an ice water bath, 18.0mmol of 65% sodium hydride solid is added in batches, the mixture is stirred and reacted for half an hour, 18.0mmol of 2-chloro-3-phenylquinoxaline is added, the mixture is stirred and reacted for 1 hour, the mixture is heated to room temperature, the mixture is stirred and reacted for 2 hours, 200mL of water is added for dilution, the filtration is carried out, a filter cake is washed by water, silica gel column is used for separation and purification, and the mixture is recrystallized by dichloromethane-ethanol to obtain a compound P252, a yellow solid and the yield is 48%.
MS(MALDI-TOF)：m/z 602.1707[M+H] + ； 1 HNMR(δ、CDCl 3 )：8.76～8.74(1H,d)；8.67～8.65(1H,d)；8.48～8.45(1H,m)；8.38～8.26(3H,m)；8.21～8.19(1H,d)；7.94～7.92(2H,m)；7.84～7.73(2H,m)；7.65～7.46(8H,m)；7.34～7.28(2H,m)；7.12～7.05(2H,m)。
Example 4
Preparation of compounds P211 to P225, P227 to P235 and P237 to P286 of formula I, wherein X = O, were prepared by substituting 2-chloro-4- (2-naphthyl) -6-phenyl-1,3,5-triazine in the tenth step of example 1 with a different halogen compound or substituting 9- (3-phenylphenyl) -3-bromo-9H-carbazole in example 2 with a different substituted halogen compound, with reference to the preparation methods of examples 1 and 2.
Referring to the preparation method of example 3, compounds P211 to P251, P253 to P286 of formula I, in which X = S, were prepared by substituting different halides for the 2-chloro-3-phenylquinoxaline of the sixth step in example 3.
Example 5
A process for the preparation of compound P14 (X = O) comprising the steps of:
the first step is as follows: preparation of Compound Int-50
At room temperature, 0.10mol of 1-iodo-2-bromo-4-anisole was dissolved in 200mL of toluene, and 0.10mol of 2-chlorobenzene was addedBoric acid and 0.20mol sodium carbonate, 0.5mmol Pd (PPh) 3 ) 4 Adding 100mL of ethanol and 20mL of water into the catalyst, heating to reflux, stirring, reacting for 4 hours, cooling to room temperature, adding 100mL of water for dilution, separating an organic phase, extracting a water phase by using ethyl acetate, combining the organic phases, drying, filtering, concentrating a filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a white solid with the yield of 66.5%.
The second step is that: preparation of Compound Int-51
50.0mmol of 2-methoxy-1-naphthaleneboronic acid and 41.6mmol of the intermediate Int-50 prepared in the first step were dissolved in 150mL of toluene, and 0.15mol of sodium carbonate, 0.05mmol of Pd (PPh) were added at room temperature 3 ) 4 Adding 100mL of ethanol and 50mL of water into the catalyst, heating to reflux, stirring, reacting for 4 hours, cooling to room temperature, separating an organic phase, extracting a water phase by using ethyl acetate, combining the organic phases, drying, filtering, concentrating a filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain a yellow solid with the yield of 86%.
The third step: preparation of Compound Int-52
45.0mmol of the intermediate Int-51 prepared in the second step, 13.5mmol of tricyclohexylphosphonium tetrafluoroborate and 9.0mmol of palladium acetate are added, 135.0mmol of anhydrous cesium carbonate and 220mL of dimethylacetamide are added, the mixture is heated, refluxed and stirred for reaction for 12 hours under the protection of nitrogen, cooled to room temperature, 300mL of water is added for dilution, dichloromethane is used for extraction, an organic phase is dried and filtered, and a filtrate is concentrated under reduced pressure and dried and is separated and purified by a silica gel column to obtain the compound Int-52 with the yield of 80%.
The fourth step: preparation of Compound Int-53
40.0mmol of the intermediate Int-52 prepared in the third step is dissolved in 150mL of dry tetrahydrofuran, the temperature is reduced to-40 ℃ by liquid nitrogen under the protection of nitrogen, 19.2mL of 2.5M n-butyllithium n-hexane solution is added dropwise, the temperature is raised to 0 ℃, stirring reaction is carried out for 2 hours, 48.0mmol of bromine solution is added dropwise and dissolved in 50mL of dry tetrahydrofuran, stirring reaction is carried out for 1 hour, 50mL of saturated sodium bisulfite aqueous solution is added, extraction is carried out by ethyl acetate, organic phase drying is carried out, filtration is carried out, reduced pressure concentration is carried out on filtrate, and separation and purification are carried out by a silica gel column, so that the compound Int-53 is obtained, and the yield is 78%.
The fifth step: preparation of Compound Int-54
65.0mmol of the intermediate Int-53 prepared in the fourth step is dissolved in 150mL of dry dichloromethane, cooled to 0 ℃ with ice water under the protection of nitrogen, 156.0mmol of boron tribromide is added dropwise, stirred for reaction for 2 hours, heated to room temperature, stirred for reaction for 2 hours, 50mL of saturated sodium thiosulfate aqueous solution is added, extraction is carried out with dichloromethane, an organic phase is dried and filtered, filtrate is concentrated under reduced pressure to be dried, and separation and purification are carried out by using a silica gel column, so that the compound Int-54 is obtained, wherein the yield is 80%.
And a sixth step: preparation of Compound Int-55
60.0mmol of intermediate Int-54 prepared in the fifth step is dissolved in 100mL of freshly distilled pyridine, 14.8g of copper oxide and 41.4g of anhydrous potassium carbonate are added under the protection of nitrogen, the mixture is heated under reflux and stirred for 12 hours, the reaction mixture is cooled to room temperature, 50mL of 3M dilute hydrochloric acid aqueous solution is added, dichloromethane is used for extraction, the organic phase is washed with 10% sodium carbonate aqueous solution, the organic phase is dried, filtered, the filtrate is concentrated under reduced pressure to dryness, and the filtrate is separated and purified by a silica gel column to obtain compound Int-55 with the yield of 46%.
The seventh step: preparation of Compound Int-56
40.0mmol of the intermediate Int-55 prepared in the sixth step is dissolved in 150mL of dichloromethane, the temperature is reduced to 10 ℃ in an ice-water bath, 80.0mmol of pyridine and 0.4mmol of DMAP are added, 48.0mmol of trifluoromethanesulfonic anhydride is added dropwise, the mixture is stirred at room temperature for reaction for 6 hours, 50mL of 1M dilute hydrochloric acid aqueous solution is added, dichloromethane is used for extraction, the organic phase is washed with brine, the organic phase is dried and filtered, the filtrate is concentrated under reduced pressure and dried, and is separated and purified by a silica gel column, so that the compound Int-56 is obtained, and the yield is 93%.
Eighth step: preparation of Compound Int-57
40.0mmol of intermediate Int-56 prepared in the seventh step is dissolved in 150mL of toluene, 48.0mmol of o-bromoaniline and 60.0mmol of sodium tert-butoxide are added, and 0.4mmol of Pd is added under nitrogen protection 2 (dba) 3 And 0.05mL of a 10% tri-tert-butylphosphine toluene solution, heating to reflux, stirring, reacting for 12 hours, cooling to room temperature, adding 100mL of water for dilution, filtering, and washing a filter cake with methanol to obtain a compound Int-57 with a yield of 74%.
The ninth step: preparation of Compound Int-58
Referring to the ninth step of the preparation of example 1, compound Int-58 was prepared in 82% yield by substituting intermediate Int-57 prepared in the previous step for intermediate Int-8 in the ninth step of example 1.
The tenth step: preparation of compound P14 (X = O)
Referring to the tenth preparation step of example 1, compound P14 was prepared as a yellow solid in 72% yield by replacing intermediate Int-9 of the tenth step of example 1 with intermediate Int-58 prepared in the previous step and replacing 2-chloro-4- (2-naphthyl) -6-phenyl-1,3,5-triazine therein with 2-chloro-4,6-diphenyl-1,3,5-triazine.
MS(MALDI-TOF)：m/z 613.2044[M+H] + ； 1 HNMR(δ、CDCl 3 )：9.13～9.11(1H,d)；8.65(1H,s)；8.59～8.56(5H,m)；8.44～8.41(2H,m)；8.28～8.17(3H,m)；7.56～7.49(8H,m)；7.28～7.21(2H,m)；7.16～7.14(1H,m)；7.07～7.05(1H,m)。
Example 6
Preparation of compounds P01 to P13, P15 to P81 referring to the preparation method of example 5, compounds P01 to P13, P15 to P81 of formula I, wherein X = O, were prepared by substituting different halides for 2-chloro-4,6-diphenyl-1,3,5-triazine in the tenth step of example 5;
referring to the preparation methods of example 3 and example 5, 2-methoxy-1-naphthalene boronic acid of the second step in example 5 was replaced with 2-mercaptomethyl-1-naphthalene boronic acid to prepare compounds P01 to P81 of formula I, wherein X = S.
Example 7
A process for the preparation of compound P84 (X = O) comprising the reaction steps of:
the first step is as follows: preparation of intermediate Int-70
5.0mmol of the intermediate Int-56 prepared in the seventh step of example 5 was dissolved in 60mL of tetrahydrofuran, and under nitrogen protection, 6.0mmol of o-nitrobenzeneboronic acid pinacol ester was added, followed by 20.0mmol of anhydrous potassium carbonate catalyst and 0.05mmol of Pd (PPh) 3 ) 4 Heating catalyst and 10mL of water, refluxing and stirring for reaction for 8 hours, cooling to room temperature, concentrating under reduced pressure to dryness, dissolving with dichloromethane, washing with water, collecting organic phase, concentrating under reduced pressureDried and purified by silica gel column separation to obtain intermediate Int-70 as yellow solid with yield of 82%.
The second step is that: preparation of Compound Int-71
10.0mmol of the intermediate Int-70 prepared in the second step and 50mL of triethyl phosphite are mixed, heated, refluxed and reacted for 10 hours, cooled to room temperature, concentrated under reduced pressure, dried, washed with water and dried to obtain the intermediate Int-71 as a yellow solid with a yield of 62%.
The third step: preparation of compound P84 (X = O)
5.0mmol of intermediate Int-71 prepared in the previous step was dissolved in 50mL dry xylene and 6.0mmol of 4- (3-bromophenyl) dibenzo [ b, d ] was added under nitrogen]Furan and 7.5mmol of sodium tert-butoxide, and 0.05mmol of Pd 2 (dba) 3 And 0.02mL of 10% tri-tert-Ding Lin toluene solution, heating to 110 ℃, stirring for reaction for 12 hours, cooling to room temperature, adding 50mL of water for dilution, extracting with toluene, drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by a silica gel column to obtain the compound P84, a yellow solid with the yield of 72%.
MS(MALDI-TOF)：m/z 624.1977[M+H] + ； 1 HNMR(δ、CDCl 3 )：8.53(1H,s)；8.48～8.46(1H,m)；8.37～8.35(1H,m)；8.22～8.13(3H,m)；8.07～7.98(3H,m)；7.85～7.78(2H,m)；7.69～7.61(2H,m)；7.52～7.34(6H,m)；7.23～7.11(4H,m)；7.15～7.13(1H,m)；7.10～7.08(1H,m)。
Example 8
Preparation of compounds P82, P83, P85 to P149, compounds P82, P83, P85 to P149 of formula I wherein X = O or S were prepared by substituting 4- (3-bromophenyl) dibenzo [ b, d ] furan of the third step in example 7 with a different halide with reference to the preparation method of example 7;
referring to the preparation methods of example 3, example 5 and example 7, 2-methoxy-1-naphthalene boronic acid of the second step in example 5 was replaced with 2-mercaptomethyl-1-naphthalene boronic acid to prepare compounds P82 to P149 of formula I, in which X = S.
Example 9
A process for the preparation of compound P183 (X = O), comprising the reaction steps of:
the first step is as follows: preparation of intermediate Int-90
Dissolving 10.0mmol of 1- (4-methylbenzenesulfonyl) 1H-indole-3-carboxylic acid methyl ester in 50mL of dry tetrahydrofuran, cooling to-78 ℃ with liquid nitrogen under the protection of nitrogen, dropwise adding 15.0mmol of LDA, stirring for reaction for 30 minutes, dropwise adding 12.0mmol of 2- (chloromethyl) naphtho [2,1-b ] furan, stirring for reaction for 1 hour, heating to room temperature, stirring for reaction for 1 hour, adding 50mL of saturated aqueous ammonium chloride solution, extracting with ethyl acetate, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying with a silica gel column to obtain an intermediate Int-90, a yellow solid with the yield of 52%.
The second step is that: preparation of intermediate Int-91
10.0mmol of the intermediate Int-90 prepared in the first step was dissolved in 20mL of tetrahydrofuran, 15.0mmol of lithium hydroxide monohydrate and 10mL of water were added, the mixture was stirred at room temperature for 12 hours, 2M aqueous diluted hydrochloric acid was added dropwise to adjust the pH to 3, the mixture was filtered, and the filter cake was washed with water to obtain intermediate Int-91 as a yellow solid with a yield of 84%.
The third step: preparation of intermediate Int-92
Mixing 50mL of concentrated sulfuric acid and 0.5g of boric acid, cooling to 0 ℃ by using an ice salt bath, adding 15.0mmol of the intermediate Int-91 prepared in the second step in batches, stirring for reaction for 2 hours, heating to room temperature, stirring for reaction for 10 hours, pouring the reaction solution into 500g of crushed ice, filtering, washing a filter cake with water and ethanol to obtain an intermediate Int-92, a brown solid with the yield of 76%.
The fourth step: preparation of intermediate Int-93
Dissolving 12.0mmol of o-dibromobenzene in 80mL of dry tetrahydrofuran, cooling to-78 ℃ by liquid nitrogen, dropwise adding 4.8mL of 2.5M butyl lithium hexane solution, stirring for reaction for 30 minutes, dropwise adding 10.0mmol of a solution of an intermediate Int-92 prepared in the third step in 10mL of tetrahydrofuran, stirring for reaction for 2 hours at room temperature, adding 50mL of saturated aqueous ammonium chloride solution, extracting with ethyl acetate, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure to dryness, adding 50mL of toluene for dispersion, adding 0.5g of p-toluenesulfonic acid, heating for reflux reaction for 2 hours, cooling to room temperature, filtering, washing a filter cake with water and ethanol to obtain an intermediate Int-93, a yellow solid with a yield of 86%.
The fifth step: preparation of intermediate Int-94
45.0mmol of the intermediate Int-93 prepared in the fourth step, 13.5mmol of tricyclohexylphosphonium tetrafluoroborate and 9.0mmol of palladium acetate, and then 135.0mmol of anhydrous cesium carbonate and 220mL of dimethylacetamide are added, the mixture is heated under reflux and stirred for reaction for 12 hours under the protection of nitrogen, the mixture is cooled to room temperature, 300mL of water is added for dilution, dichloromethane is used for extraction, the organic phase is dried and filtered, and the filtrate is concentrated under reduced pressure and dried, and is separated and purified by a silica gel column, so that the compound Int-94 is obtained, wherein the yield is 66%.
And a sixth step: preparation of intermediate Int-95
30.0mmol of the intermediate Int-94 prepared in the fifth step and 60.0mmol of potassium hydroxide are mixed, 200mL of ethanol is added, the mixture is heated, refluxed and stirred for reaction for 5 hours, cooled to room temperature, decompressed, concentrated and dried, 200mL of 2M dilute hydrochloric acid aqueous solution is added for dilution, the mixture is stirred for 1 hour, the filter cake is filtered, the filter cake is washed by water and is separated and purified by a silica gel column, and the compound Int-95 is obtained, yellow solid is obtained, and the yield is 96%.
The seventh step: preparation of Compound P183
15.0mmol of the intermediate Int-95 prepared in the sixth step is dissolved in 80mL of dimethyl sulfoxide, the temperature is reduced to 5 ℃ by using an ice water bath, 18.0mmol of 85% potassium hydroxide solid is added in batches, stirring reaction is carried out for half an hour, 18.0mmol of 2-chloro-3- (2-naphthyl) quinoxaline is added, the temperature is increased to 55 ℃, stirring reaction is carried out for 12 hours, the temperature is cooled to room temperature, 200mL of water is added for dilution, filtration is carried out, a filter cake is washed by water, silica gel column is used for separation and purification, and then dichloromethane-methanol is used for recrystallization, so that the compound P183, yellow solid and the yield of 82% are obtained.
MS(MALDI-TOF)：m/z 636.2092[M+H] + ； 1 HNMR(δ、CDCl 3 )：8.96(1H,s)；8.90(1H,s)；8.65～8.57(3H,m)；8.38～8.32(3H,m)；8.19～7.88(11H,m)；7.77～7.64(4H,m)；7.45～7.42(1H,m)；7.07～7.04(1H,m)。
Example 10
Preparation of compounds P150 to P182 and P184 to P210 referring to the preparation method of example 9, compounds P150 to P182 and P184 to P210 of compound formula I, wherein X = O, were prepared by substituting 2-chloro-3- (2-naphthyl) quinoxaline of the seventh step in example 9 with a different halide;
with reference to the preparation method of example 9, 2- (chloromethyl) naphtho [2,1-b ] furan of the first step in example 9 was replaced with 2- (chloromethyl) naphtho [2,1-b ] thiophene, and compounds P150 to P210 of X = S in formula I were prepared.
Example 11
A process for the preparation of compound P293 (X = O), comprising the reaction steps of:
the first step is as follows: preparation of Compound Int-110
20.0mmol of the intermediate Int-7 prepared in the seventh step of example 1 was dissolved in 100mL of toluene, and 24.0mmol of pinacol o-nitrobenzoate and 80.0mmol of anhydrous sodium carbonate were added under nitrogen protection, followed by 0.2mmol of Pd (PPh) 3 ) 4 Heating, refluxing and stirring the mixture with 50mL of ethanol and 50mL of water for reaction for 4 hours, cooling to room temperature, adding 50mL of water for dilution, extracting with ethyl acetate, drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying by using a silica gel column to obtain the compound Int-110 as a yellow solid with the yield of 87%.
The second step is that: preparation of Compound Int-111
15.0mmol of the intermediate Int-110 prepared in the first step is dissolved in 150mL of chlorobenzene, 45.0mmol of triphenyl phosphine is added under the protection of nitrogen, the mixture is heated and refluxed and stirred for reaction for 10 hours, the reaction product is cooled to room temperature, reduced pressure is concentrated to dryness, 50mL of dichloromethane is added for dilution, the filtration is carried out, and a filter cake is washed by dichloromethane, so that the compound Int-111 is obtained as a white solid with the yield of 54%.
The third step: preparation of compound P293 (X = O)
10.0mmol of the intermediate Int-111 prepared in the second step was dissolved in 50mL of xylene, and 12.0mmol of 2- (3-bromobenzene was added under nitrogen protectionYl) -4,6-diphenyl-1,3,5-triazine, 15.0mmol of sodium tert-butoxide, 0.01mmol of Pd 2 (dba) 3 CHCl 3 The catalyst and 0.02mL of 10% tri-tert-butylphosphine toluene solution are heated to 110 ℃ and stirred to react for 10 hours, the reaction solution is cooled to room temperature, 50mL of water is added for dilution, dichloromethane is used for extraction, an organic phase is collected, the drying and the filtration are carried out, the filtrate is concentrated under reduced pressure and dried, and the compound P293 is obtained by separation and purification through a silica gel column, yellow solid is obtained, and the yield is 64%.
MS(MALDI-TOF)：m/z 689.2359[M+H] + ； 1 HNMR(δ、CDCl 3 )：8.46～8.43(2H,m)；8.34～8.31(4H,m)；8.22～8.17(3H,m)；8.03～7.92(4H,m)；7.69～7.66(2H,d)；7.47～7.28(9H,m)；7.16～7.12(2H,m)；7.05～7.02(2H,m)。
Example 12
Preparation of compounds P287 to P292 and P294 to P315 referring to the preparation method of example 11, compounds P287 to P292 and P294 to P315 of formula I, in which X = O, were prepared by replacing 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine in the third step of example 11 with a different halide;
compounds P287 to P315 of formula I, wherein X = S, were prepared by substituting intermediate Int-7 of the first step in example 11 with intermediate Int-33 prepared in the third step in example 3, with reference to the preparation process of example 11.
Comparative example of organic electroluminescent element
An organic electroluminescent element was prepared as follows using a compound represented by the following formula a as a green host material, a compound represented by the following formula B as a green dopant material, a compound represented by the following formula C as a hole injection material, a compound represented by the following formula D as a hole transport material, a compound represented by the following formula E as a red host material, a compound represented by the following formula F as a red dopant material, a compound represented by the following formula G as an electron transport dopant material, and LiQ as an electron transport host material.
Will be of the chemical formula
An organic electroluminescent element as a green comparative example was prepared by depositing an EL evaporator manufactured by DOV on ITO glass in this order.
Will be of the chemical formula
An organic electroluminescent element as a red comparative example was prepared by depositing an EL deposition machine manufactured by DOV on ITO glass in this order.
Examples of organic electroluminescent elements
Compound in the green comparative example of organic electroluminescent element, an organic electroluminescent element was produced in the same manner as in the above example except that Compound A was replaced with Compounds P01 to P315 of the present invention
[ Compound of the present invention
An example of bottom emission of the organic electroluminescent element is shown in fig. 1, and an example of top emission is shown in fig. 2;
the results of the performance test of the obtained element are shown in Table 1.
Table 1: green light element performance test result
As is clear from Table 1, the green light element produced from the organic material of the present invention has a low driving voltage, a high current efficiency, and a good color purity, and the element using the compound of the present invention as a green light host material has a much longer life under the condition that the initial emission luminance of the element is 1000 nits.
In the red comparative example of the organic electroluminescent element, an organic electroluminescent element was produced in the same manner except that the compound E was replaced with the compounds P01 to P315 of the present invention:
/[ Compound of the invention
The results of the performance test of the obtained element are shown in Table 2.
TABLE 2 Performance test results of red light elements
As can be seen from the results of the performance test of the red light element shown in Table 2, the element prepared from the organic material of the present invention has significantly reduced driving voltage, high current efficiency, and good purity of luminescent color, and the life of the element LT90% using the compound of the present invention as a red light host material is much slower in decay under the condition that the initial luminance of the element at the time of light emission is 1000 nits.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.
Claims (10)
1. An oxa-thiaazulene derivative is characterized in that the structural general formula is as follows:
wherein X is selected from O or S;
R 1 ～R 14 is a hydrogen atom, ar 1 Is an aromatic or heteroaromatic ring system having from 5 to 30 carbon atoms.
2. An oxa, thiaazulene derivative according to claim 1, characterized in that it is selected from the group consisting of the compounds represented by the following formulae P01 to P315:
wherein X is selected from O or S.
3. A material for organic electroluminescent elements, comprising the oxa-thiaazulene derivative according to claim 1 or 2.
4. An organic electroluminescent element comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode;
the light-emitting layer of the organic layer comprises the oxa, thiaazulene derivative according to claim 1 or 2.
5. The organic electroluminescent element according to claim 4, wherein the organic layer further comprises a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole barrier layer, and an electron barrier layer.
6. The organic electroluminescent element according to claim 4 or 5, characterized in that the oxa, thiaazulene derivative is used as a host material in the organic electroluminescent element.
7. Use of the organic electroluminescent element according to any one of claims 4 to 6 in an electronic device.
8. An electronic device comprising the organic electroluminescent element according to any one of claims 4 to 6.
9. The electronic device of claim 8, wherein the electronic device is a flat light, a copier, a printer, a light source, a display panel, or a marker light.
10. The electronic device of claim 9, wherein the planar light emitter is a wall-mounted television, a flat-panel display, or a lighting device; the light source is a light source of a liquid crystal display or a light source of a measuring instrument.
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| WO2019177407A1 (en) * | 2018-03-16 | 2019-09-19 | Rohm And Haas Electronic Materials Korea Ltd. | Composition material for organic electroluminescent device, plurality of host materials, and organic electroluminescent device comprising the same |
| KR20190109261A (en) * | 2018-03-16 | 2019-09-25 | 롬엔드하스전자재료코리아유한회사 | Composition material for organic electroluminescent device, plurality of host materials, and organic electroluminescent device comprising the same |
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| KR20150121337A (en) * | 2014-04-18 | 2015-10-29 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| WO2019177407A1 (en) * | 2018-03-16 | 2019-09-19 | Rohm And Haas Electronic Materials Korea Ltd. | Composition material for organic electroluminescent device, plurality of host materials, and organic electroluminescent device comprising the same |
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