CN104725369A - Binary phenothiazine imidazole derivative, preparation method and organic light emitting device - Google Patents

Binary phenothiazine imidazole derivative, preparation method and organic light emitting device Download PDF

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CN104725369A
CN104725369A CN201510130631.XA CN201510130631A CN104725369A CN 104725369 A CN104725369 A CN 104725369A CN 201510130631 A CN201510130631 A CN 201510130631A CN 104725369 A CN104725369 A CN 104725369A
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binary
thiodiphenylamine
compound
imidazole derivative
solvent
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CN104725369B (en
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汪康
王贺
孙毅
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Olide (Shanghai) Photoelectric Material Technology Co., Ltd.
Shanghai Sheng Xi Photoelectric Technology Co. Ltd.
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Jilin Optical and Electronic Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur

Abstract

The invention aims to provide a binary phenothiazine imidazole derivative. The derivative comprises a green-light host material with excellent light emitting performance, a hole injection material or a hole transmission material, and phenothiazine is a heteroaromatic compound containing electron-enriched nitrogen and sulfur atoms, is combined with the characteristics of nitrogen-heterocyclic substances, and is a potential light emitting and transmitting material element, so that the efficiency of an organic electroluminescence device is expected to be improved. According to the preparation method of the binary phenothiazine imidazole derivative, group A-containing chloride reacts with binary phenothiazine imidazole intermediate to prepare the binary phenothiazine imidazole derivative.

Description

Containing binary thiodiphenylamine and imidazole derivative, preparation method and organic luminescent device
Technical field
The present invention relates to organic photoelectrical material field, particularly relate to a class and contain binary thiodiphenylamine and imidazole derivative, preparation method and organic luminescent device.
Background technology
Organic electroluminescent (EL) device (hereinafter, simply referred to as " organic EL device ").Generally be made up of two opposed electrodes and at least one deck organic luminescent compounds be inserted between these two electrodes.Electric charge is injected in the organic layer formed between the anode and cathode, to form electronics and hole pair, makes the organic compound with fluorescence or phosphorescent characteristics create light emission.
Organic electroluminescence device (OLED) is a kind of novel flat panel display device, has the features such as energy-conservation, fast response time, colour stable, environmental compatibility are strong, radiationless, the life-span is long, quality is light, thickness is thin.Due to developing rapidly of photoelectric communication in recent years and MultiMedia Field, organic optoelectronic material has become the core of modern society's information and electronic industry.
Research for organic EL Material is from nineteen fifty Bernose applies the observation of high current/voltage to the macromolecule membrane containing organic pigment.Nineteen sixty-five, people's Late Cambrian such as Pope Electroluminescence Properties of anthracene single crystal, this is the first electro optical phenomenon of organic compound.1987, the people such as the Tang of Kodak found, even if the organic luminescent device with separation function lamination formed by organic materials also can provide 1000cd/cm under the low voltage of 10V or less 2or higher high brightness.
At present, the material of main part in electroluminescent device mainly contains small molecule host material and polymer host material two class.Small molecule host material doping phosphorescent complexes is utilized to prepare many efficient electroluminescent devices as luminescent layer.But prepare small molecule electroluminescent device and need to adopt the complicated technology such as vacuum evaporation, substantially increase preparation cost.Meanwhile, small molecules itself is easy to the stability that the character such as crystallization also significantly limit device.In recent years, the polymer host material various phosphorescent complexes object that adulterates is utilized to prepare electroluminescent device as luminescent layer and receive more concern.But the solubility property of the polymer host material reported at present is relative with film forming properties poor, thus affects it as luminescent layer.
Thiodiphenylamine is that a class contains the nitrogen of electron rich and the heteroaromatic compound of sulphur atom, due to thiodiphenylamine height electron rich degree, conjugated polymer material containing thiodiphenylamine primitive especially binary thiodiphenylamine is beneficial to injection and the transmission in hole very much, and therefore thiodiphenylamine is considered to a kind of extraordinary structural motif that can reduce luminescent material ionization potential.And the most noticeable feature is that thiodiphenylamine molecule has nonplanar structure, and the carbazole of this point and flush type is very different.Nonplanarity due to thiodiphenylamine molecule can stop the formation of π key gathering and the intermolecular exciplex causing device quantum efficiencies to reduce, and in conjunction with the feature of nitrogen heterocycles material, the injection of current carrier can be to some extent solved, be very potential class luminescence and the transport material primitive of a class, be thus expected to the efficiency improving organic electroluminescence device.
Summary of the invention
The object of this invention is to provide one and contain binary thiodiphenylamine and imidazole derivative, there is green glow material of main part, hole-injecting material or the hole mobile material of superior luminescence performance.
General formula of molecular structure provided by the invention is:
（1）
In general formula (1), A is selected from the alkyl that R is 1 ~ 40 carbon atom, has the aryl of carbonatoms 1 ~ 40, the heterocyclic radical of carbon atom numerical digit 1 ~ 40, or A substituting group is general formula (2).
（2）
Wherein, X, Y, Z, W represent carbon atom or nitrogen-atoms.R represents hydrogen atom, D atom, replacement and unsubstituted C 1-C 30alkyl, replacement and unsubstituted C 3-C 30cycloalkyl, replacement and unsubstituted C 1-C 30alkoxyl group, replacement and unsubstituted C 5-C 30aryloxy, replacement and unsubstituted C 5-C 30arylthio, replacement and unsubstituted C 5-C 30aryl, by C 5-C 30the amino that aryl replaces, replacement and unsubstituted C 4-C 40heteroaryl, replacement and unsubstituted C 6-C 40condensation polycyclic base, halogen atom, cyano group, nitro, hydroxyl and carboxyl.
Preferred A substituting group is phenyl, 1-naphthyl, phenanthryl, anthryl, 9,9-dimethyl fluorenyls, N-phenyl carbazole base, or in general formula 2, when , , , ,
R substituent is phenyl, 1-naphthyl, 2-naphthyl, 4-xenyl, 3-xenyl, 9-phenanthryl.
Above-mentioned preferred electroluminescent organic material of the present invention, concrete structural formula corresponds to as following table 1 chemical structural formula respectively:
Table 1
1 2
3 4
5 6
7 8
9 10
11 12
13 14
15 16
17 18
19 20
21 22
23 24
25 26
27 28
29 30
The preparation method that present invention also offers, is characterized in that, comprises the steps:
Step S1: add binary thiodiphenylamine and the muriate of the intermediate of imidazole derivative, described A group, catalyzer, alkali and solvent in the reaction vessel after degassed;
Step S2: raise temperature of reaction and reflux, fully reacting;
Step S3: filter, washing, recrystallization obtains described binary thiodiphenylamine and imidazole derivative.
The muriate of the quinoline A group in described step S1 is that the boric acid coupling replaced by 2-chlorine-4-iodine base quinoline derivatives and R is prepared from.
The muriatic preparation method of the quinoline A group in described step S1, comprises the steps:
Step N1: add 2-chlorine-4-iodine base quinoline derivatives in the reaction vessel after degassed, boric acid, salt of wormwood and solvent that described R group replaces;
Step N2: backflow, fully reacts;
Step N3: through extraction, washing, dry, column chromatography purification obtains can for step S1 quinoline A group muriate directly.
Binary thiodiphenylamine in described step S1 the synthesis of imidazole derivative, comprise the steps:
Step M1: add thiodiphenylamine, p-methyl benzene sulfonic chloride in the reactor, alkali lye, normal temperature refluxes, and extracts, filters, washs, revolves steaming, crystallization, and drying obtains the phenothiazine compound of p-toluenesulfonyl protection;
Step M2: be dissolved in solvent by the phenothiazine compound that described p-toluenesulfonyl is protected, stirs the solution adding N-bromo-succinimide at 0 DEG C, after reaction terminates, and washing, the phenothiazines bromo-derivative that dry, purification obtains p-toluenesulfonyl protection;
Step M3: the phenothiazines bromo-derivative that above-mentioned p-toluenesulfonyl is protected, with 3-boronate thiodiphenylamine, palladium, tri-butyl phosphine, cesium carbonate, be dissolved in solvent, at 120 DEG C stirring reaction fully after, washing, dry, purifying obtains the binary phenothiazine compound of p-toluenesulfonyl protection;
Step M4: the binary phenothiazine compound that p-toluenesulfonyl is protected, and four triphenyl phosphorus palladiums, salt of wormwood, the benzoglyoxaline of boronation, be dissolved in solvent, after 110 DEG C of sufficient reactings, washing, dry, purify the binary thiodiphenylamine glyoxaline compound that obtain p-toluenesulfonyl protection;
Step M5: the binary thiodiphenylamine protect p-toluenesulfonyl glyoxaline compound and potassium hydroxide, is dissolved in Isosorbide-5-Nitrae-dioxane, 50 DEG C of backflows fully after reaction suction filtration, dryings obtain required binary thiodiphenylamine and the intermediate of imidazole derivative.
A kind of described containing binary thiodiphenylamine and the organic luminescent device made of imidazole derivative, it comprises the first electrode, the second electrode and is placed in the one or more organic compound layers between described first electrode, described second electrode, it is characterized in that, described in organic compound layer described at least one comprises, contain binary thiodiphenylamine and imidazole derivative compound.
Described binary thiodiphenylamine an application for imidazole derivative, is characterized in that, described binary thiodiphenylamine imidazole derivative is used as phosphorescence green material of main part, hole-injecting material or hole mobile material in described organic electroluminescence device.
Beneficial effect:
A class binary thiodiphenylamine provided by the invention imidazole derivative compound, preparation method and the application in organic electroluminescence device thereof.This binary thiodiphenylamine imidazole derivative compound has high luminous efficiency, high luminous efficiency shows that this compound can be used as luminescent material or light emitting host material, especially can as the green material of main part of phosphorescence, for showing high-level efficiency, high brightness, long lifetime in organic electroluminescence device, there is the advantage that manufacturing cost is lower, reduce the manufacturing cost of organic electroluminescence device.
embodiment:
Particularly, some binary thiodiphenylamine provided by the invention imidazole derivative are prepared by following methods: the acid reaction that 2-chlorine-4-iodine quinazoline and R group are replaced, generates the muriate (1-1) of the quinazoline containing R substituent; Should quinazoline containing R substituent muriate (1-2) or containing the substituent muriate of A (1-3) and binary thiodiphenylamine and imidazoles intermediate reaction obtain containing binary thiodiphenylamine and imidazole derivative.Concrete synthetic route is as follows:
binary thiodiphenylamine the synthetic method of imidazole derivative is as follows:
In the 1L there-necked flask that reflux is housed, drop into the compound of 0.100mol formula III, 0.120mol thiodiphenylamine, three (dibenzalacetone) two palladium 0.005mol, sodium tert-butoxide 0.400mol, tri-butyl phosphine 0.020mol, 500ml toluene dissolves, 110 DEG C of back flow reaction 24h, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, sherwood oil recrystallization, suction filtration, the compound 0.091mol of formula (IV) is obtained after drying, it is the binary phenothiazine compound of a kind of p-toluenesulfonyl protection, yield 91.0%.
The compound 0.050mol of formula (IV) is dissolved in 200ml DMF(N, dinethylformamide) in, at 0 DEG C, stir 10min.By 0.050mol NBS(N-bromo-succinimide) solution in slowly add in the DMF of 10ml, at 0 DEG C, stir this mixture, carry out 6 hours.After the completion of reaction, add distilled water and ethyl acetate in the mixture, wash away DMF, and by product extraction in ethyl acetate.By organic over anhydrous MgSO 4drying, removes solvent with rotatory evaporator.Carry out column chromatography by ethyl acetate, obtain the compound of 0.045mol formula (V), it is the binary phenothiazines bromide of p-toluenesulfonyl protection, productive rate 89%.
By the compound of 0.040mol formula (V); the boronic acid compounds of 0.050mol benzo carbazole; salt of wormwood 0.120mol; be dissolved in the mixed solvent of 400mL (toluene: water=1:3), add four triphenyl phosphorus palladium 0.006mol under nitrogen protection, stirring and refluxing reacts 24 hours; reaction terminates rear cool to room temperature; separatory collected organic layer, with anhydrous magnesium sulfate drying, filters.Vacuum rotary steam removes solvent, then uses DCM and PE recrystallization column chromatography, draws 0.034mol formula VI compound, and it is the binary thiodiphenylamine of p-toluenesulfonyl protection and imidazole derivative, productive rate 85%.
To in the 500ml four-hole boiling flask that reflux is housed, drop into compound, 0.180mol potassium hydroxide, the 200ml Isosorbide-5-Nitrae-dioxane of 0.030mol formula VI, 3h is reacted at 50 DEG C, TLC determines reaction end, reacts complete, and decompression steams about major part 1,4-dioxane, with DCM and PE recrystallization, separate out a large amount of solid, suction filtration, the dry compound obtaining 0.029mol formula (VII), yield 95%.
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail below to the specific embodiment of the present invention.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Embodiment 1: the synthesis of compound 1
Under nitrogen protection, by chlorobenzene (70.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (1) 24.0mmol is obtained after drying, yield 80%.
Embodiment 2: the synthesis of compound 2
Under nitrogen protection, by chloro-for intermediate 2-4-(2-phenyl) quinoline (70.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (2) 24.0mmol is obtained after drying, yield 80%.
Embodiment 3: the synthesis of compound 3
Under nitrogen protection, by intermediate 2-chlorine phenanthrene (70.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (3) 24.0mmol is obtained after drying, yield 80%.
Embodiment 4: the synthesis of compound 4
Under nitrogen protection, by intermediate 2-chrloroanthracene (70.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (4) 24.0mmol is obtained after drying, yield 80%.
Embodiment 5: the synthesis of compound 5
Under nitrogen protection, by chloro-for intermediate 2-9, 9-dimethyl fluorene (70.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (5) 24.0mmol is obtained after drying, yield 80%.
Embodiment 6: the synthesis of compound 6
under nitrogen protection, by chloro-for intermediate 2-N-phenyl carbazole (70.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (6) 24.0mmol is obtained after drying, yield 80%.
Embodiment 7: the synthesis of compound 7
2-chlorine-4-iodine quinoline 100.0mmol; phenylo boric acid 120.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw the chloro-4-(2-phenyl of 79.0mmol white solid intermediate 2-) quinoline, productive rate 79%.
Under nitrogen protection, by chloro-for intermediate 2-4-(2-phenyl) quinoline (70.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (7) 24.0mmol is obtained after drying, yield 80%.
Embodiment 8: the synthesis of compound 8
2-chlorine-4-iodine quinoline 100.0mmol; 1-naphthalene boronic acids 110.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw the chloro-4-(1-naphthyl of 76.0mmol white solid intermediate 2-) quinoline, productive rate 76%.
Under nitrogen protection, by chloro-for intermediate 2-4-(1-naphthyl) quinoline (70.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (8) 25.3mmol is obtained after drying, yield 84%.
Embodiment 9: the synthesis of compound 9
2-chlorine-4-iodine quinoline 100.0mmol; 2-naphthalene boronic acids 130.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw the chloro-4-(2-naphthyl of 71.0mmol white solid intermediate 2-) quinoline, productive rate 71%.
Under nitrogen protection, by chloro-for intermediate 2-4-(2-naphthyl) quinoline (65.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5.0mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (9) 24.8mmol is obtained after drying, yield 82.7%.
Embodiment 10: the synthesis of compound 10
2-chlorine-4-iodine quinoline 100.0mmol; 4-biphenylboronic acid 130.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw 69.0mmol white solid intermediate 4-([1,1'-biphenyl]-4-base)-2-chloroquinoline, productive rate 69%.
Under nitrogen protection, by intermediate 4-([1, 1'-biphenyl]-4-base)-2-chloroquinoline (65.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (10) 26.0mmol is obtained after drying, yield 83%.
Embodiment 11: the synthesis of compound 11
2-chlorine-4-iodine quinoline 100.0mmol; 3-biphenylboronic acid 140.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw 72.0mmol white solid intermediate 4-([1,1'-biphenyl]-3-base)-2-chloroquinoline, productive rate 72%.
Under nitrogen protection, by intermediate 4-([1, 1'-biphenyl]-3-base)-2-chloroquinoline (68.0mmol), binary thiodiphenylamine imidazole derivative intermediate (32.0mmol), three (dibenzalacetone) two palladium (1.6mmol), sodium tert-butoxide (128.0mmol), tri-butyl phosphine (6.4mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (11) 23.9mmol is obtained after drying, yield 75%.
Embodiment 12: the synthesis of compound 12
2-chlorine-4-iodine quinoline 100.0mmol; the luxuriant and rich with fragrance boric acid 120.0mmol of 9-; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw the chloro-4-(9-phenanthryl of 73.0mmol white solid intermediate 2-) quinoline, productive rate 73%.
Under nitrogen protection, by chloro-for intermediate 2-4-(9-phenanthryl) quinoline (68.0mmol), binary thiodiphenylamine imidazole derivative intermediate (32.0mmol), three (dibenzalacetone) two palladium (1.6mmol), sodium tert-butoxide (128.0mmol), tri-butyl phosphine (6.4mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (12) 22.5mmol is obtained after drying, yield 70%.
Embodiment 13: the synthesis of compound 13
2-chlorine-4-iodine quinazoline 100.0mmol; phenylo boric acid 120.0mmol; salt of wormwood 120.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw the chloro-4-(2-phenyl of 78.0mmol white solid intermediate 2-) quinazoline, productive rate 78%.
Under nitrogen protection, by chloro-for intermediate 2-4-(2-phenyl) quinazoline (70.0mmol), binary thiodiphenylamine imidazole derivative intermediate (32mmol), three (dibenzalacetone) two palladium (1.6mmol), sodium tert-butoxide (128.0mmol), tri-butyl phosphine (6.4mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (13) 22.5mmol is obtained after drying, yield 70%.
Embodiment 14: the synthesis of compound 14
2-chlorine-4-iodine quinazoline 100.0mmol; 1-naphthalene boronic acids 130.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw the chloro-4-(1-naphthyl of 75.0mol white solid intermediate 2-) quinazoline, productive rate 75%.
Under nitrogen protection, by chloro-for intermediate 2-4-(1-naphthyl) quinazoline (69.0mmol), binary thiodiphenylamine imidazole derivative intermediate (31.0mmol), three (dibenzalacetone) two palladium (1.6mmol), sodium tert-butoxide (124.0mmol), tri-butyl phosphine (6.2mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (14) 22.7mmol is obtained after drying, yield 73%.
Embodiment 15: the synthesis of compound 15
2-chlorine-4-iodine quinazoline 100.0mmol; 2-naphthalene boronic acids 120.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw the chloro-4-(2-naphthyl of 70.0m1mol white solid intermediate 2-) quinazoline, productive rate 71%.
Under nitrogen protection, by chloro-for intermediate 2-4-(2-naphthyl) quinazoline (65.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (15) 21.8mmol is obtained after drying, yield 73%.
Embodiment 16: the synthesis of compound 16
2-chlorine-4-iodine quinazoline 100.0mmol; 2-naphthalene boronic acids 120.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw the chloro-4-(2-naphthyl of 70.0mmol white solid intermediate 2-) quinazoline, productive rate 70%.
Under nitrogen protection, by chloro-for intermediate 2-4-(2-naphthyl) quinazoline (64.0mmol), binary thiodiphenylamine imidazole derivative intermediate (29.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (116.0mmol), tri-butyl phosphine (5.8mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (16) 23.0mmol is obtained after drying, yield 79%.
Embodiment 17: the synthesis of compound 17
2-chlorine-4-iodine quinazoline 100.0mmol; 3-biphenylboronic acid 110.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw 71.0mmol white solid intermediate 4-([1,1'-biphenyl]-3-base)-2-chloro-quinazoline, productive rate 71%.
Under nitrogen protection, by intermediate 4-([1, 1'-biphenyl]-3-base)-2-chloro-quinazoline (66.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (17) 23.6mmol is obtained after drying, yield 77%.
Embodiment 18: the synthesis of compound 18
2-chlorine-4-iodine quinazoline 100.0mmol; the luxuriant and rich with fragrance boric acid 120.0mmol of 9-; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw the chloro-4-(9-phenanthryl of 68.0mmol white solid intermediate 2-) quinazoline, productive rate 68%.
Under nitrogen protection, by chloro-for intermediate 2-4-(9-phenanthryl) quinazoline (65.0mmol), binary thiodiphenylamine imidazole derivative intermediate (29.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (116.0mmol), tri-butyl phosphine (5.8mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (18) 22.5mmol is obtained after drying, yield 78%.
Embodiment 19: the synthesis of compound 19
2-chlorine-4-iodine pyrido [2; 3-d] pyrimidine 100.0mmol, phenylo boric acid 130.0mmol, salt of wormwood 300.0mmol; be dissolved in 400L(toluene: water=3:1) in solvent; add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection, stirring and refluxing reacts 24 hours, and reaction terminates separatory under rear normal temperature; cross silica gel funnel; by dichloromethane rinse, be spin-dried for solvent, recrystallization.Draw the chloro-4-phenylpyridine of 77.0mmol white solid intermediate 2-also [2,3-d] pyrimidine, productive rate 77%.
Under nitrogen protection, by chloro-for intermediate 2-4-phenylpyridine also [2, 3-d] pyrimidine (65.0mmol), binary thiodiphenylamine imidazole derivative intermediate (29.0mmol), three (dibenzalacetone) two palladium (1.45mmol), sodium tert-butoxide (116.0mmol), tri-butyl phosphine (5.8mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (19) 22.5mmol is obtained after drying, yield 78%.
Embodiment 20: the synthesis of compound 20
2-chlorine-4-iodine pyrido [2; 3-d] pyrimidine 100.0mmol, 1-naphthalene boronic acids 120.0mmol, salt of wormwood 300.0mmol; be dissolved in 400L(toluene: water=3:1) in solvent; add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection, stirring and refluxing reacts 24 hours, and reaction terminates separatory under rear normal temperature; cross silica gel funnel; by dichloromethane rinse, be spin-dried for solvent, recrystallization.Draw the chloro-4-(1-naphthyl of 74.0mmol white solid intermediate 2-) pyrido [2,3-d] pyrimidine, productive rate 74%.
Under nitrogen protection, by chloro-for intermediate 2-4-(1-naphthyl) pyrido [2, 3-d] pyrimidine (70.0mmol), binary thiodiphenylamine imidazole derivative intermediate (33.0mmol), three (dibenzalacetone) two palladium (1.7mmol), sodium tert-butoxide (132.0mmol), tri-butyl phosphine (6.6mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (20) 23.7mmol is obtained after drying, yield 72%.
Embodiment 21: the synthesis of compound 21
2-chlorine-4-iodine pyrido [2; 3-d] pyrimidine 100.0mmol, 2-naphthalene boronic acids 130.0mmol, salt of wormwood 300.0mmol; be dissolved in 400L(toluene: water=3:1) in solvent; add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection, stirring and refluxing reacts 24 hours, and reaction terminates separatory under rear normal temperature; cross silica gel funnel; by dichloromethane rinse, be spin-dried for solvent, recrystallization.Draw the chloro-4-(2-naphthyl of 73.0mmol white solid intermediate 2-) pyrido [2,3-d] pyrimidine, productive rate 73%.
Under nitrogen protection, by chloro-for intermediate 2-4-(2-naphthyl) pyrido [2, 3-d] pyrimidine (68.0mmol), binary thiodiphenylamine imidazole derivative intermediate (32.0mmol), three (dibenzalacetone) two palladium (1.6mmol), sodium tert-butoxide (128.0mmol), tri-butyl phosphine (6.4mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (21) 24.0mmol is obtained after drying, yield 75%.
Embodiment 22: the synthesis of compound 22
2-chlorine-4-iodine pyrido [2; 3-d] pyrimidine 100.0mmol, 4-biphenylboronic acid 120.0mmol, salt of wormwood 300.0mmol; be dissolved in 400L(toluene: water=3:1) in solvent; add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection, stirring and refluxing reacts 24 hours, and reaction terminates separatory under rear normal temperature; cross silica gel funnel; by dichloromethane rinse, be spin-dried for solvent, recrystallization.Draw the chloro-4-(2-naphthyl of 77.0mmol white solid intermediate 2-) pyrido [2,3-d] pyrimidine, productive rate 77%.
Under nitrogen protection, by chloro-for intermediate 2-4-(2-naphthyl) pyrido [2, 3-d] pyrimidine (70.0mmol), binary thiodiphenylamine imidazole derivative intermediate (32.0mmol), three (dibenzalacetone) two palladium (1.6mmol), sodium tert-butoxide (128.0mmol), tri-butyl phosphine (6.4mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (22) 22.6mmol is obtained after drying, yield 71%.
Embodiment 23: the synthesis of compound 23
2-chlorine-4-iodine pyrido [2; 3-d] pyrimidine 100.0mmol, 3-biphenylboronic acid 120.0mmol, salt of wormwood 300.0mmol; be dissolved in 400L(toluene: water=3:1) in solvent; add tetra-triphenylphosphine palladium 0.01mol under nitrogen protection, stirring and refluxing reacts 24 hours, and reaction terminates separatory under rear normal temperature; cross silica gel funnel; by dichloromethane rinse, be spin-dried for solvent, recrystallization.Draw 71.0mmol white solid intermediate 4-([1,1'-biphenyl]-3-base)-2-chloropyridine also [2,3-d] pyrimidine, productive rate 71%.
Under nitrogen protection, by intermediate 4-([1, 1'-biphenyl]-3-base)-2-chloropyridine also [2, 3-d] pyrimidine (67.0mmol), binary thiodiphenylamine imidazole derivative intermediate (31.0mmol), three (dibenzalacetone) two palladium (1.6mmol), sodium tert-butoxide (124.0mmol), tri-butyl phosphine (6.2mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (23) 21.6mmol is obtained after drying, yield 70%.
Embodiment 24: the synthesis of compound 24
2-chlorine-4-iodine pyrido [2; 3-d] pyrimidine 100.0mmol, 9-luxuriant and rich with fragrance boric acid 130.0mmol, salt of wormwood 300.0mmol; be dissolved in 400L(toluene: water=3:1) in solvent; add tetra-triphenylphosphine palladium 0.01mol under nitrogen protection, stirring and refluxing reacts 24 hours, and reaction terminates separatory under rear normal temperature; cross silica gel funnel; by dichloromethane rinse, be spin-dried for solvent, recrystallization.Draw the chloro-4-(9-phenanthryl of 68.0mmol white solid intermediate 2-) pyrido [2,3-d] pyrimidine, productive rate 68%.
Under nitrogen protection, by chloro-for intermediate 2-4-(9-phenanthryl) pyrido [2, 3-d] pyrimidine (60.0mmol), binary thiodiphenylamine imidazole derivative intermediate (27.0mmol), three (dibenzalacetone) two palladium (1.4mmol), sodium tert-butoxide (108.0mmol), tri-butyl phosphine (5.4mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (24) 20.8mmol is obtained after drying, yield 77%.
Embodiment 25: the synthesis of compound 25
2-chlorine-4-iodine pteridine 100.0mmol; phenylo boric acid 130.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw 77.0mmol white solid intermediate 2-chloro-4-phenyl pteridine, productive rate 77%.
Under nitrogen protection, by chloro-for intermediate 2-4-phenyl pteridine (65.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (25) 24.6mmol is obtained after drying, yield 82%.
Embodiment 26: the synthesis of compound 26
2-chlorine-4-iodine pteridine 100.0mmol; 1-naphthalene boronic acids 140.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw the chloro-4-(1-naphthyl of 73.0mmol white solid intermediate 2-) pteridine, productive rate 73%.
Under nitrogen protection, by chloro-for intermediate 2-4-(1-naphthyl) pteridine (65.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (26) 23.5mmol is obtained after drying, yield 78%.
Embodiment 27: the synthesis of compound 27
2-chlorine-4-iodine pteridine 100.0mmol; 2-naphthalene boronic acids 140.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw the chloro-4-(2-naphthyl of 74.0mmol white solid intermediate 2-) pteridine, productive rate 74%.
Under nitrogen protection, by chloro-for intermediate 2-4-(2-naphthyl) pteridine (64.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (27) 22.8mmol is obtained after drying, yield 76%.
Embodiment 28: the synthesis of compound 28
2-chlorine-4-iodine pteridine 100.0mmol; 4-biphenylboronic acid 140.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw 72.0mmol white solid intermediate 4-([1,1'-biphenyl]-4-base)-2-pteridine, productive rate 72%.
Under nitrogen protection, by intermediate 4-([1, 1'-biphenyl]-4-base)-2-pteridine (66.0mmol), binary thiodiphenylamine imidazole derivative intermediate (31.0mmol), three (dibenzalacetone) two palladium (1.6mmol), sodium tert-butoxide (124.0mmol), tri-butyl phosphine (6.2mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (28) 23.4mmol is obtained after drying, yield 75%.
Embodiment 29: the synthesis of compound 29
2-chlorine-4-iodine pteridine 100.0mmol; 3-biphenylboronic acid 140.0mmol; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw 73.0mmol white solid intermediate 4-([1,1'-biphenyl]-3-base)-2-pteridine, productive rate 73%.
Under nitrogen protection, by intermediate 4-([1, 1'-biphenyl]-3-base)-2-pteridine (65.0mmol), binary thiodiphenylamine imidazole derivative intermediate (30.0mmol), three (dibenzalacetone) two palladium (1.5mmol), sodium tert-butoxide (120.0mmol), tri-butyl phosphine (6.0mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (29) 22.7mmol is obtained after drying, yield 76%.
Embodiment 30: the synthesis of compound 30
2-chlorine-4-iodine pteridine 100.0mmol; the luxuriant and rich with fragrance phenylo boric acid 120.0mmol of 9-; salt of wormwood 300.0mmol, is dissolved in 400L(toluene: water=3:1) in solvent, add tetra-triphenylphosphine palladium 10.0mmol under nitrogen protection; stirring and refluxing reacts 24 hours; reaction terminates separatory under rear normal temperature, crosses silica gel funnel, by dichloromethane rinse; be spin-dried for solvent, recrystallization.Draw the chloro-4-(9-phenanthryl of 71.0mmol white solid intermediate 2-) pteridine, productive rate 71%.
Under nitrogen protection, by chloro-for intermediate 2-4-(9-phenanthryl) pteridine (62.0mmol), binary thiodiphenylamine imidazole derivative intermediate (28.0mmol), three (dibenzalacetone) two palladium (1.4mmol), sodium tert-butoxide (112.0mmol), tri-butyl phosphine (5.6mmol), 500ml toluene dissolves, 110 DEG C of back flow reaction 24 hours, reaction end is determined with thin-layer chromatography (TLC), react complete, be cooled to room temperature, cross silica gel funnel, DCM rinses, be spin-dried for, methylene dichloride, sherwood oil recrystallization, suction filtration, compound (30) 20.3mmol is obtained after drying, yield 73%.
By fast atom bombardment mass spectroscopy(FABMS) (FABMS) method, carry out the ultimate analysis of compound.The results are shown in Table 2, and wherein MS/FAB (M+) is the molecular weight recorded by FABMS:
Table 2
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Comparing embodiment 1
Using the compound of chemical formula a as light emitting host material, the compound of chemical formula b is as dopant material, the 2-TNATA (4 that chemical formula c represents, 4,4-tri-(N-naphthyl)-N-phenyl amino)-triphenylamine) as hole-injecting material, α-NPD (the N that chemical formula d represents, N '-two (naphthyl)-N, N '-diphenylbenzidine) as hole mobile material, make the organic luminescent device of structure below: ITO/2-TNATA (80nm)/α-NPD (30nm)/compound a+compound b (30nm, wherein b content is 8%)/Al q 3(30nm)/LiF (0.5nm)/Al (60nm).Wherein, Alq 3oxine aluminium.
Chemical formula a chemical formula b
Corning(is healthy and free from worry) society 15 Ω/cm2 (1000) ITO glass substrate is cut into the size of 50mm*50mm*0.7mm.Subsequently in microwave, successively at acetone, Virahol, cleans 15 minutes in pure water respectively, in ultraviolet, clean 30 minutes again.At the 2-TNATA of thereon vacuum evaporation 80 nm thickness, form hole injection layer.Above hole injection layer, the α-NPD of vacuum evaporation 30 nm thickness, defines hole transporting layer.The compound that above hole transporting layer, the chemical formula a of vacuum evaporation 30nm thickness represents and the compound that chemical formula b represents (doping rate 8%), define luminescent layer.The Alq of vacuum evaporation 30 nm thickness above luminescent layer 3, define electron supplying layer.Vacuum evaporation LiF 0.5 nm (electron injection) and Al 60 nm successively above electron supplying layer, has made organic luminescent device.In this comparing embodiment 1 and following Application Example 1-30, the EL evaporator adopting DOV company to manufacture carries out vacuum evaporation.
Application Example 1-30:
Adopt as the method in comparative example 1, make the organic luminescent device with structure below, difference is as luminescent layer compound, what replace compound a to adopt is compound 1-30:ITO/2-TNATA (80nm)/α-NPD (the 30nm)/binary thiodiphenylamine imidazole derivative intermediate 1 ~ 30+ compound b that represent in preparation example] (25nm, wherein b content is 8.0%)/Alq 3(30nm) organic luminescent device of the structure of/LiF (0.5nm)/Al (60nm).
Measure embodiment 1: the luminescent properties of comparative sample and sample 1-30
Under similarity condition, measure the sample of comparing embodiment 1 and the sample of Application Example 1-30.Measure and adopt KEITHLEY Keithley 235 type source measuring unit, SpectrascanPR650 spectral scan colourimeter, to evaluate driving voltage, luminosity, luminous efficiency, glow color.The results are shown in Table 3:
Table 3
Represented by table 3, above-mentioned sample shows glow color for green in 500-520nm wavelength region.The sample of Application Example 1 to 30 compares with the sample of comparing embodiment 1, uses binary thiodiphenylamine the organic luminescent device of imidazole derivative can have the efficiency of lower driving voltage, higher brightness and Geng Gao.
Although the present invention's exemplary embodiment has carried out special description, but should be appreciated that those of ordinary skill in the art can carry out the change in various forms and details to it when not departing from the spirit of the present invention and scope that following patent requirement limits.

Claims (9)

1. contain binary thiodiphenylamine and an imidazole derivative, have the green glow material of main part of superior luminescence performance, hole-injecting material or hole mobile material, is characterized in that, general formula of molecular structure is:
（1）
In general formula (1), A is selected from the alkyl that R is 1 ~ 40 carbon atom, has the aryl of carbonatoms 1 ~ 40, the heterocyclic radical of carbon atom numerical digit 1 ~ 40, or A substituting group is general formula (2).
（2）
Wherein, X, Y, Z, W represent carbon atom or nitrogen-atoms.R represents hydrogen atom, D atom, replacement and unsubstituted C 1-C 30alkyl, replacement and unsubstituted C 3-C 30cycloalkyl, replacement and unsubstituted C 1-C 30alkoxyl group, replacement and unsubstituted C 5-C 30aryloxy, replacement and unsubstituted C 5-C 30arylthio, replacement and unsubstituted C 5-C 30aryl, by C 5-C 30the amino that aryl replaces, replacement and unsubstituted C 4-C 40heteroaryl, replacement and unsubstituted C 6-C 40condensation polycyclic base, halogen atom, cyano group, nitro, hydroxyl and carboxyl.
2. binary thiodiphenylamine according to claim 1 imidazole derivative, wherein, preferred A substituting group is phenyl, 1-naphthyl, phenanthryl, anthryl, 9,9-dimethyl fluorenyls, N-phenyl carbazole base, or in general formula 2, when , , , , R substituent is phenyl, 1-naphthyl, 2-naphthyl, 4-xenyl, 3-xenyl, 9-phenanthryl.
3. according to claim 1 and 2 containing binary thiodiphenylamine imidazole derivative, be at least one of compound shown in following chemical formula:
， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， 。
4. as described in claim 1 ~ 3 containing binary thiodiphenylamine a preparation method for imidazole derivative, it is characterized in that, comprise the steps:
Step S1: add binary thiodiphenylamine and the muriate of imidazoles intermediate, described A group, catalyzer, alkali and solvent in the reaction vessel after degassed;
Step S2: raise temperature of reaction and reflux, fully reacting;
Step S3: filter, washing, recrystallization obtains described binary thiodiphenylamine and imidazole derivative.
5. preparation method according to claim 4, is characterized in that, binary thiodiphenylamine in described step S1 the synthesis of imidazole derivative, comprises the steps:
Step M1: add thiodiphenylamine, p-methyl benzene sulfonic chloride in the reactor, alkali lye, normal temperature refluxes, extract, filter, wash, revolve steamings, crystallization, drying obtains the phenothiazine compound that p-toluenesulfonyl is protected;
Step M2: be dissolved in solvent by the phenothiazine compound that described p-toluenesulfonyl is protected, stirs the solution adding N-bromo-succinimide at 0 DEG C, after reaction terminates, and washing, the phenothiazines bromo-derivative that dry, purification obtains p-toluenesulfonyl protection;
Step M3: the phenothiazines bromo-derivative that p-toluenesulfonyl is protected, 3-boronate thiodiphenylamine, palladium, tri-butyl phosphine, cesium carbonate, is dissolved in solvent, at 120 DEG C stirring reaction fully after, washing, dry, purifying obtains the binary phenothiazine compound of p-toluenesulfonyl protection;
Step M4: the binary phenothiazine compound that p-toluenesulfonyl is protected, and four triphenyl phosphorus palladiums, salt of wormwood, the benzoglyoxaline of boronation, be dissolved in solvent, after 110 DEG C of sufficient reactings, washing, dry, purify the binary thiodiphenylamine glyoxaline compound that obtain p-toluenesulfonyl protection;
Step M5: the binary thiodiphenylamine protect p-toluenesulfonyl glyoxaline compound and potassium hydroxide, is dissolved in Isosorbide-5-Nitrae-dioxane, 50 DEG C of backflows fully after reaction suction filtration, dryings obtain required binary thiodiphenylamine and the intermediate of imidazole derivative.
6. preparation method according to claim 4, is characterized in that, the muriate of the A group in described step S1, if general formula according to claim 12 class muriate, is that the boric acid replaced by 2-chlorine-4-iodine base quinoline derivatives and R is prepared from.
7. preparation method according to claim 4, is characterized in that, the muriatic preparation method of the A group in described step S1, comprises the steps:
Step N1: add 2-chlorine-4-iodine base quinoline derivatives in the reaction vessel after degassed, boric acid, salt of wormwood and solvent that described R group replaces;
Step N2: backflow, fully reacts;
Step N3: through extraction, washing, dry, column chromatography purification obtains can for step S1 A group muriate directly.
8. an organic luminescent device, the one or more organic compound layers comprising the first electrode, the second electrode and be placed between described two electrodes, it is characterized in that, at least one organic compound layer comprise at least one as any one of claim 1 ~ 3 define containing binary thiodiphenylamine imidazole derivative.
9. according to any one of claim 1 ~ 3 containing binary thiodiphenylamine the application of imidazole derivative in organic electroluminescence device, it is characterized in that, described containing binary thiodiphenylamine and imidazole derivative is used as phosphorescence green material of main part, hole-injecting material or hole mobile material in described organic electroluminescence device.
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