CN106986894A - Simultaneously [G, P] thick dinaphthyl type derivative, its preparation method and the application of sulphur, phosphorus heteroatoms substituted diphenylamine - Google Patents

Simultaneously [G, P] thick dinaphthyl type derivative, its preparation method and the application of sulphur, phosphorus heteroatoms substituted diphenylamine Download PDF

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CN106986894A
CN106986894A CN201610038877.9A CN201610038877A CN106986894A CN 106986894 A CN106986894 A CN 106986894A CN 201610038877 A CN201610038877 A CN 201610038877A CN 106986894 A CN106986894 A CN 106986894A
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phosphorus
sulphur
dinaphthyl
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欧阳新华
米东伯
葛子义
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention provides a kind of sulphur, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative.Oxygen, phosphorus, sulphur, nitrogen heteroatom are introduced the dibenzo with condensed cyclic structure [G, P] thick two how in type structure, the carrier transport and stability of material is on the one hand added；On the other hand the controllable adjustment of triplet is realized；Meanwhile, distorted-structure is realized by introducing the phosphorus-nitrogen bonds or sulphur nitrogen key of thick atom radius, intermolecular serious pi-pi accumulation is reduced to the luminous influence under its thin-film state.Therefore, the derivative can be applied in OLED as fluorescent material.

Description

Simultaneously [G, P] thick dinaphthyl type derivative, its preparation method and the application of sulphur, phosphorus heteroatoms substituted diphenylamine
Technical field
The present invention relates to the thick dinaphthyl type technical field of structural materials of dibenzo [G, P], and in particular to simultaneously [G, P] thick dinaphthyl type derivative, its preparation method and the application of a kind of sulphur, phosphorus heteroatoms substituted diphenylamine.
Background technology
Organic electroluminescent LED (OLED) because its have energy-efficient, environmental protection, preparation technology it is simple, can large area flexible the features such as, the focus as area researches such as material, information, physics.Luminescent material is OLED core, therefore the high luminescent material of exploitation excellent performance, stability is the emphasis of OLED researchs.
For phosphorescent light-emitting materials, fluorescence OLED material more aobvious advantage in terms of cost and device stability is prepared, but fluorescence luminescent material is the problem of generally face inefficiency.In recent years, the Adachi professors of Kyushu University and South China Science ＆ Engineering University professor Ma Yuguang report the efficient thermal activation fluorescence (TADF) of acquisition and " heat shock " (hot excitons) material in succession, and new approach is opened to develop the high efficiency fluorescence OLED with actual application value.These high efficiency fluorescence OLED materials are analyzed it can be found that its molecule triplet excitons is most important.The research of relevant triplet regulation and control at present is concentrated mainly on phosphorescent light body material, but the triplet state controllable adjustment based on fluorescent material is still fresh for report.Therefore, exploitation triplet state controllable fluorescent OLED material is imperative.
Dibenzo [G, P] thick dinaphthyl is a kind of important condensed-nuclei aromatics, good electroluminescent stability and carrier transmission characteristics is shown, has caused extensive concern, such as patent document WO2008147721-A1, WO2010135403-A2, WO2011019360-A1 discloses its electroluminescence characters.However, the report on thick two naphthalene derivatives of dibenzo [G, P] is relatively fewer, and because non-dipole limits its application in OLED.
Recently, the Takuji Hatakeyam professors of Kyoto Univ Japan report a kind of dibenzo [G, P] thick dinaphthyl of utilization B-N keys substitution C-C keys in document Chem.Mater., 2014,26,6265-6271, and effectively can individually regulate and control triplet.Peking University Pei Jian professor reported in document Chem.Eur.J.2015,21,8867-8873 boron nitrogen key (B-N) substitution carbon-carbon bond (C-C) have thick thiophene type structural derivative.
But, by the B-N thick dinaphthyl type compounds replaced although can realize that the energy level part of triplet state independently regulates and controls, it is more or less the same yet with the radius of boron atom and carbon atom, so that the molecule coplanarity of the thick dinaphthyl type compound of B-N substitutions is high, intermolecular pi-pi accumulation has a strong impact on luminous under its thin-film state.In consideration of it, big thick two naphthaline derivatives of dibenzo [G, P] of exploitation planar distortion are the keys for solving this problem.
The content of the invention
For above-mentioned technical problem, the hetero atoms such as oxygen, phosphorus, sulphur, nitrogen are incorporated into the dibenzo [G with condensed cyclic structure by the present invention, P] thick two how in type structure, on the one hand make full use of thick two how the condensed ring rigid structure and superior charge-transporting of type molecule, effectively increase material carrier transport and stability；On the other hand, utilize Small disturbance of degeneracy effect of the hetero atom to its frontier orbit, effectively suppress its intramolecular list, triplet interaction, realize the controllable adjustment of its triplet, the problem of solving big on the influence of HOMO/LUMO energy levels after such material functional；Meanwhile, distorted-structure is realized to a greater degree by introducing the phosphorus-nitrogen bonds (P-N) and sulphur nitrogen key (S-N) of thick atom radius, reduces intermolecular serious pi-pi accumulation to the luminous influence under its thin-film state.
The structural formula of the phosphorus heteroatoms substituted diphenylamine that the present invention is provided simultaneously [G, P] thick dinaphthyl type derivative is any one in following structural formula 1~50：
The structural formula knot of the sulfur heteroatom substituted diphenylamine that the present invention is provided simultaneously [G, P] thick dinaphthyl type derivative is any one in following structure formula 51~100：
Compared with prior art, the present invention has the advantage that or effect：
(1) design prepares the condensed cyclic structure derivative of the hetero atoms such as oxygen-containing, phosphorus, sulphur, nitrogen substitution, can be applied to as fluorescent material in OLED, the problem of solving the carrier transport and stability of the non-condensed cyclic structure fluorescent material of traditional high triplet energy level.
(2) using Small disturbance of degeneracy effect of the hetero atom to its frontier orbit, its intramolecular list, triplet interaction is reduced, the controllable adjustment of its triplet is realized, the problem of solving big on the influence of HOMO/LUMO energy levels after traditional material functionalization.
(3) the sulphur nitrogen key (S-N) and phosphorus-nitrogen bonds (P-N) of thick atom radius are introduced, dibenzo [G is realized to a greater degree, P] thick dinaphthyl planar distortion, reduce intermolecular serious pi-pi accumulation to the luminous influence under its thin-film state.
Above-mentioned sulphur, phosphorus heteroatoms substituted diphenylamine simultaneously [G are prepared present invention also offers one kind, P] thick dinaphthyl type derivative preparation method, its syntheti c route is as shown in Figure 1 (wherein, R1, R2 are independent of one another, it is respectively selected from one kind in diphenylamines, carbazole, N- phenyl carbazoles, benzimidazole, two indeno pyrazines, X=S or P), comprise the following steps：
(1) with 1,1 '-bis- phenyl diphenylamines or 1,1 '-bis- phenyl carbazoles are initiation material, by low temperature lithiation and combine Friedel-Crafts and react, and are aoxidized using hydrogen peroxide, the thick dinaphthyl of aniline type or the thick dinaphthyl of carbazole type of formation condensed cyclic structure.
In the step (1), described 1,1 '-bis- phenyl diphenylamines or 1,1 '-bis- phenyl carbazole sources are not limited, and are used as a kind of implementation, coupling reaction can be passed through, such as Buchwald-Hartwig is coupled or Suzuki couplings are prepared, and this method yield is high, and especially 1, the yield of 1 '-bis- phenyl diphenylamines can be up to 94%, therefore provide the guarantees of raw material for the synthesis of target product.
Course of reaction in the step (1) is specially：1 is extracted at low temperature with lithiumation thing, active hydrogen in 1 '-bis- phenyl diphenylamines on amido, add phosphorus trichloride formation halo phosphorus-nitrogen bonds, then the substituted-phenyl ortho position hydrogen atom added on metal chloride and alkali, activation 1,1 '-bis- phenyl diphenylamines, and occur substitution reaction with the halogen atom in halo phosphorus-nitrogen bonds under alkali effect, form addition peroxide in condensed cyclic structure, most backward reaction mixture to be aoxidized, form the thick dinaphthyl of aniline type；Or, 1 is extracted at low temperature with lithiumation thing, active hydrogen in 1 '-bis- phenyl carbazoles on carbazole, adds thionyl chloride formation halo sulphur nitrogen key, then adds metal chloride and alkali, activation 1, substituted-phenyl ortho position hydrogen atom on 1 '-bis- phenyl carbazoles, and occur substitution reaction with the halogen atom in halo phosphorus-nitrogen bonds under alkali effect, form condensed cyclic structure, peroxide is added in most backward reaction mixture to be aoxidized, and forms the thick dinaphthyl of carbazole type.
Wherein, the alkali is preferably one or several kinds of mixing in sodium tert-butoxide, tetramethyl piperidine, n-butanol sodium；Lithiumation thing is preferably one or several kinds of mixing in n-BuLi, tert-butyl lithium, lithium diisopropyl amido；Peroxide is preferably one or several kinds of mixing in hydrogen peroxide, dual-tert-butyl hydrogen peroxide, double normal-butyl hydrogen peroxide；Metal chloride is preferably one or several kinds of mixing in alchlor, ferric trichloride, gallium trichloride.
In the step (1), described low temperature lithiation temperature is preferably -100 DEG C~-20 DEG C.
(2) the thick dinaphthyl of aniline type made from step (1) or the thick dinaphthyl of carbazole type are subjected to bromination using NBS, synthesis can functionalization the thick dinaphthyl of intermediate double bromine substituted benzene amine type (the referred to as thick dinaphthyl of double bromobenzene amine type) or double thick dinaphthyls of bromine substituted carbazole type (the referred to as thick dinaphthyl of double bromine carbazole types).
(3) the intermediate double thick dinaphthyl of bromine substituted benzene amine type or double thick dinaphthyls of bromine substituted carbazole type are coupled by Suzuki, obtain thick two naphthalene derivatives of target product aniline type or thick two naphthalene derivatives of carbazole type.
In the step (3), as preferred, coupling reaction is carried out under catalysts conditions, described catalyst is more preferably the one or several kinds in four (triphenyl phosphorus) palladiums, dichloro two (triphenyl phosphorus) palladium, palladium etc..
Above-mentioned preparation method has the following advantages that：
(1) in step (1), initiation material 1,1 '-bis- phenyl diphenylamines or 1,1 '-bis- phenyl carbazoles source is not limited, and is readily available, the guarantee of raw material is provided for the synthesis of target product；
(2) in step (1), pass through low temperature lithiation, and combine Friedel-Crafts reaction, originally the cyclization such as derivative and phosphorus, sulphur such as diphenylamines, carbazole of non-fused ring system can be formed to the thick dinaphthyl of aniline type and the thick dinaphthyl of carbazole type of condensed cyclic structure, and involved low temperature lithiation and Friedel-Crafts reagent have high chemism in course of reaction, can obtain high yield；
(3) in step (2), NBS bromination reactions are classical organic free radical substitution reactions, it is possible to achieve high yield；
Therefore, the preparation method is simple and easy to apply, and reaction yield is very high, with large-scale production, the potentiality prepared.
Brief description of the drawings
Fig. 1 is the syntheti c route schematic diagram of sulphur of the present invention, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative.
Embodiment
The present invention is described in further detail with reference to embodiment and accompanying drawing, it should be pointed out that embodiment described below is intended to be easy to the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1：
In the present embodiment, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative as shown in compound 1.
The syntheti c route of the phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative is as shown in figure 1, specific as follows；
(1) the thick dinaphthyl of aniline type：4b- azepines -12b- phosphas-dibenzo [g, p] thick two how the synthesis of -12b- oxides
The initiation material 1,1 ' of 1 molar part-bis- phenyl diphenylamines are dissolved in 250 milliliters of toluene solutions, reduction temperature is to -75 DEG C, the normal-butyl base lithium of 1 molar part is added dropwise to above-mentioned mixed system by stirring dropwise, and reaction system then is warming up into room temperature, is stirred 1 hour；
Then, reaction system is placed at -75 DEG C again, stirs 30 minutes, the phosphorus trichloride of 1 molar part is added dropwise to reaction system dropwise, be warming up to room temperature, reacted 8 hours；Reaction dissolvent is removed, mixed liquor is slowly added in the o-dichlorohenzene containing 4 molar part alchlors and 2 molar part tetramethyl piperidines, is warming up at 160 DEG C and reacts 12 hours；Room temperature is cooled to, the concentration that 4 molar parts are added into reaction mixture is 25% hydrogen peroxide, is heated to reflux；Through separation, purifying, yellow-white powder, the i.e. described thick dinaphthyl of aniline type are obtained, its yield is 56%.
Mass spectrum [M]+：363.23；Elementary analysis：C 79.33, H3.88, N 3.85, O 4.40, P 8.52, calculated value：C 79.23, H 3.91, N 3.84, O 4.47, P 8.51.
(2) double thick dinaphthyls of bromobenzene amine type：2,7- bis- bromo- 4b- azepines -12b- phosphas-dibenzo [g, p] thick two how the synthesis of -12b- oxides
How -12b- oxides are dissolved in 6 milliliters of dichloromethane and 2 milliliters of second cyanogen blend solutions above-mentioned 4b- azepines -12b- phosphas-dibenzo [g, p] thick two of 1 molar part, and the NBS powder of 2 molar parts is added in reaction system and stirred 1 hour at room temperature；After solvent is evaporated off, surplus materials smashs into powder to pieces with second cyanogen, obtains colourless powder, i.e. described double thick dinaphthyls of bromobenzene amine type, and its yield is 86%.
Mass spectrum [M]+：521.12；Elementary analysis：C 55.31, H 2.32, Br 30.67, N 2.69, O 3.07, P 5.94, calculated value：C 55.24, H 2.38, Br 30.82, N 2.63, P 6.12.
(3) synthesis of compound 1：
The bromo- 4b- azepines -12b- phosphas of above-mentioned 2,7- bis--dibenzo [g, p] thick two of 1 molar part how -12b- oxides, the potassium phosphate of the diphenylamines of 2.5 molar parts and 5 molar parts is dissolved in 15 milliliters of toluene solution；Catalyst (Pd (the PPh of 0.02 molar part3)2Cl2) add in reaction system and in 1 hour of reaction at 70 DEG C；It is then cooled to room temperature and is stopped reacting with distilled water, through separation, obtains compound 1 after purification, yield is 68%.
Mass spectrum [M]+：700.02；Elementary analysis：C 82.39, H 4.90, N 6.00, O 2.29, P 4.43, calculated value：C 82.25, H 4.96, N 6.03, O 2.14, P 4.57.
Embodiment 2：
In the present embodiment, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative as shown in compound 2.
The phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative prepare it is as follows；
(1) the thick dinaphthyl of carbazole type：14b '-azepine -14b- phosphas benzo [p] indeno [1,2,3,4-defg] thick two how the synthesis of -14b- oxides
The initiation material 1,1 ' of 1 molar part-bis- phenyl carbazoles are dissolved in 250 milliliters of toluene solution, reduction temperature is to -75 DEG C, the normal-butyl base lithium of 1 molar part is added dropwise to above-mentioned mixed system by stirring dropwise, and reaction system then is warming up into room temperature, is stirred 1 hour；
Then, reaction system is placed at -75 DEG C again, stirs 30 minutes, the phosphorus trichloride of 1 molar part is added dropwise to reaction system dropwise, be warming up to room temperature, reacted 8 hours；Reaction dissolvent is removed, mixed liquor is slowly added in the o-dichlorohenzene containing 4 molar part alchlors and 2 molar part tetramethyl piperidines, is warming up at 160 DEG C and reacts 12 hours；Room temperature is cooled to, the concentration that 4 molar parts are added into reaction mixture is 25% hydrogen peroxide, is heated to reflux；Through separation, purifying, yellow-white powder, the i.e. described thick dinaphthyl of carbazole type are obtained, its yield is 71%.
Mass spectrum [M]+：363.14；Elementary analysis：C 79.33, H 3.88, N 3.85, O 4.40, P 8.52, calculated value：C 79.28, H 3.94, N 3.92, O 4.37, P 8.42.
(2) double thick dinaphthyls of bromine carbazole type：2,7- bis- bromo- 14b '-azepine -14b- phosphas benzo [p] indeno [1,2,3,4-defg] thick two how the synthesis of -14b- oxides
The above-mentioned 14b ' of 1 molar part-azepine -14b- phosphas benzo [p] indeno [1,2,3,4-defg] thick two how -14b- oxides are dissolved in 6 milliliters of dichloromethane and 2 milliliters of second cyanogen blend solutions, and the NBS powder of 2 molar parts is added among reaction system and stirring 1 hour at room temperature；After solvent is evaporated off, surplus materials smashs into powder to pieces with second cyanogen, obtains colourless powder, i.e. described double thick dinaphthyls of bromine carbazole type, and its yield is 89%.
Mass spectrum [M]+：521.21；Elementary analysis：C 55.31, H 2.32, Br 30.67, N 2.69, O 3.07, P5.94, calculated value：C 55.19, H 2.39, Br 30.64, N 2.73, O 3.14, P 5.87.
(3) synthesis of compound 2：
The bromo- 14b ' of above-mentioned 2, the 7- bis- of 1 molar part-azepine -14b- phosphas benzo [p] indeno [1,2,3,4-defg] thick two how -14b- oxides, the potassium phosphate of the diphenylamines of 2.5 molar parts and 5 molar parts is dissolved in 15 milliliters of toluene solution；0.02 part of catalyst (Pd (PPh3)2Cl2) add in reaction system and in 1 hour of reaction at 70 DEG C；It is then cooled to room temperature and is stopped reacting with distilled water, through separation, obtains compound 2 after purification, yield is 63%.
Mass spectrum [M]+：698.11；Elementary analysis：C 82.62, H 4.62, N 6.02, O 2.29, P 4.44, calculated value：C 82.58, H 4.69, N 5.98, O 2.34, P 4.12.
Embodiment 3：
In the present embodiment, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative as shown in compound 11.
The phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative prepare it is as follows；
(1) the thick dinaphthyl of aniline type：4b- azepines -12b- phosphas-dibenzo [g, p] thick two how the synthesis of -12b- oxides
By the initiation material 1 of 1 molar part, 1 '-bis- phenyl diphenylamines are dissolved in 250 milliliters of toluene solution, in at -75 DEG C, it is put into low-temp reaction bath and handles 30 minutes, then 1 part of tert-butyl lithium hexane solution is added dropwise in reaction system, then reaction system is warming up at room temperature, stirred 1 hour；
Then, reaction system is placed at -75 DEG C again and handled 30 minutes, the phosphorus trichloride pentane solution of 1 molar part is added dropwise in reaction system, is warming up to after room temperature, react 8 hours；Solvent is removed, mixed liquor is slowly added in the o-dichlorohenzene containing 4 molar part alchlors and 2 molar part tetramethyl piperidines, is warming up at 160 DEG C and reacts 12 hours；Room temperature is cooled to, the concentration that 4 molar parts are added into reaction mixture is 25% hydrogen peroxide, is heated to reflux；Through separation, purifying, yellow-white powder, the i.e. described thick dinaphthyl of aniline type are obtained, its yield is 62%.
Mass spectrum [M]+：363.23；Elementary analysis：C 79.33, H3.88, N 3.85, O 4.40, P 8.52, calculated value：C 79.23, H 3.91, N 3.84, O 4.47, P 8.51.
(2) double thick dinaphthyls of bromobenzene amine type：2,7- bis- bromo- 4b- azepines -12b- phosphas-dibenzo [g, p] thick two how the synthesis of -12b- oxides
How -12b- oxides are dissolved in 6 milliliters of dichloromethane and 2 milliliters of second cyanogen blend solutions above-mentioned 4b- azepines -12b- phosphas-dibenzo [g, p] thick two of 1 molar part, and the NBS powder of 2 molar parts is added among reaction system and stirred 1 hour at room temperature；After solvent is evaporated off, surplus materials smashs into powder to pieces with second cyanogen, obtains colourless powder, i.e. described thick two naphthalene compound of double bromobenzene amine type, and its yield is 86%.
Mass spectrum [M]+：521.12；Elementary analysis：C 55.31, H 2.32, Br 30.67, N 2.69, O 3.07, P 5.94, calculated value：C 55.24, H 2.38, Br30.82, N 2.63, P 6.12.
(3) synthesis of compound 11
The bromo- 4b- azepines -12b- phosphas of above-mentioned 2, the 7- bis- of 1 molar part-dibenzo [g, p] thick two how -12b- oxides, the potassium phosphate of the diphenylamines of 1.25 molar parts, the carbazole of 1.25 molar parts and 5 molar parts is dissolved in 15 milliliters of toluene solution；Catalyst (Pd (the PPh of 0.02 molar part3)2Cl2) add in reaction system and in 1 hour of reaction at 70 DEG C；It is cooled to after room temperature and is stopped reacting with distilled water, through separation, obtains compound 11 after purification, yield is 66%.
Mass spectrum [M]+：698.02；Elementary analysis：C 82.62, H 4.62, N 6.02, O 2.29, P 4.44, calculated value：C 82.59, H 4.65, N 5.98, O 2.33, P 4.41.
Embodiment 4：
In the present embodiment, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative as shown in compound 12.
The phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative prepare it is as follows；
(1) the thick dinaphthyl of carbazole type：14b '-azepine -14b- phosphas benzo [p] indeno [1,2,3,4-defg] thick two how the synthesis of -14b- oxides
By the initiation material 1 of 1 molar part, 1 '-diphenyl carbazole is dissolved in 250 milliliters of toluene solution, in at -75 DEG C, it is put into low-temp reaction bath and handles 30 minutes, then 1 part of tert-butyl lithium hexane solution is added dropwise in reaction system, reaction system is then warming up to room temperature, 1 hour is stirred；
Then, reaction system is placed at -75 DEG C again and is put into low-temp reaction bath processing 30 minutes, the phosphorus trichloride solution of 1 molar part is added dropwise in reaction system, is warming up to after room temperature, 8 hours are reacted；After solvent is removed, mixed liquor is slowly added in the o-dichlorohenzene containing 4 molar part alchlors and 2 molar part tetramethyl piperidines, is warming up at 160 DEG C and reacts 12 hours；Room temperature is cooled to, the concentration that 4 molar parts are added into reaction mixture is 25% hydrogen peroxide, is heated to reflux；Through separation, purifying, yellow-white powder, the i.e. described thick dinaphthyl of carbazole type are obtained, its yield is 52%.
Mass spectrum [M]+：363.14；Elementary analysis：C 79.33, H 3.88, N 3.85, O 4.40, P 8.52, calculated value：C 79.28, H 3.94, N 3.92, O 4.37, P 8.42.
(2) double thick dinaphthyls of bromine carbazole type：2,7- bis- bromo- 14b '-azepine -14b- phosphas benzo [p] indeno [1,2,3,4-defg] thick two how the synthesis of -14b- oxides
The above-mentioned 14b ' of 1 molar part-azepine -14b- phosphas benzo [p] indeno [1,2,3,4-defg] thick two how -14b- oxides are dissolved in 6 milliliters of dichloromethane and 2 milliliters of second cyanogen blend solutions, and the NBS powder of 2 molar parts is added among reaction system and stirring 1 hour at room temperature；After solvent is evaporated off, surplus materials smashs into powder to pieces with second cyanogen, obtains colourless powder, i.e. described thick two naphthalene derivatives of double bromine carbazole types, and its yield is 89%.Mass spectrum [M]+：521.21；Elementary analysis：C 55.31, H 2.32, Br 30.67, N 2.69, O 3.07, P5.94, calculated value：C 55.19, H 2.39, Br, 30.64, N 2.73, O 3.14, P 5.87.
(3) synthesis of compound 12
1 molar part above-mentioned 2, the bromo- 14b ' of 7- bis--azepine -14b- phosphas benzo [p] indeno [1,2,3,4-defg] thick two how -14b- oxides, the potassium phosphate of the diphenylamines of 1.25 molar parts, the carbazole of 1.25 molar parts and 5 molar parts is dissolved in 15 milliliters of toluene solution；Catalyst (Pd (the PPh of 0.02 molar part3)2Cl2) add in reaction system and in 1 hour of reaction at 70 DEG C；It is cooled to after room temperature and is stopped reacting with distilled water, through separation, obtain compound 12 after purification, its yield is 69%.Mass spectrum [M]+：696.02；Elementary analysis：C 82.86, H 4.35, N 6.04, O 2.30, P 4.45, calculated value：C 82.84, H 4.39, N 6.01, O 2.35, P 4.35.
Embodiment 5：
In the present embodiment, sulfur heteroatom substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative as shown in compound 51.
The sulfur heteroatom substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative prepare it is as follows；
(1) the thick dinaphthyl of hexichol amine type：4b- azepines -12b- thias-dibenzo [g, p] thick two how the synthesis of -12b- Oxide intermediates
By the initiation material 1 of 1 molar part, 1 '-diphenyl diphenylamines is dissolved in 250 milliliters of toluene solution, in at -75 DEG C, it is put into low-temp reaction bath and handles 30 minutes, then the tert-butyl lithium hexane solution of 1 molar part is added dropwise in reaction system, reaction system is then warming up to room temperature, 1 hour is stirred；
Then, reaction system is placed at -75 DEG C again and is put into low-temp reaction bath processing 30 minutes, the thionyl chloride solution of 1 molar part is added dropwise in reaction system, is warming up to after room temperature, 8 hours are reacted；Mixed liquor is slowly added in the o-dichlorohenzene containing 4 molar part alchlors and 2 molar part tetramethyl piperidines, is warming up at 160 DEG C and reacts 12 hours；Room temperature is cooled to, the concentration that 4 molar parts are added into reaction mixture is 25% hydrogen peroxide, is heated to reflux；Through separation, purifying, yellow-white powder, the i.e. described thick dinaphthyl of hexichol amine type are obtained, its yield is 71%.
Mass spectrum [M]+：367.23；Elementary analysis：C 78.45, H4.66, N 3.81, O 4.35, S 8.73, calculated value：C 78.37, H 4.69, N 3.80, O 4.39, S 8.69.
(2) double thick dinaphthyls of bromine hexichol amine type：2,7- bis- bromo- 4b- azepines -12b- thias-dibenzo [g, p] thick two how the synthesis of -12b- oxides
How -12b- oxides are dissolved in 6 milliliters of dichloromethane and 2 milliliters of second cyanogen blend solutions above-mentioned 4b- azepines -12b- thias-dibenzo [g, p] thick two of 1 molar part, and the NBS powder of 2 molar parts is added among reaction system and stirred 1 hour at room temperature；After solvent is evaporated off, surplus materials smashs into powder to pieces with second cyanogen, obtains colourless powder, i.e. described double thick dinaphthyls of bromine hexichol amine type, and its yield is 84%.Mass spectrum [M]+：525.12；Elementary analysis：C 54.88, H 2.88, Br, 30.42, N 2.67, O 3.05, S 6.10, calculated value：C 54.83, H 2.92, Br 30.41, N 2.64, O 3.12, S 6.01.
(3) synthesis of compound 51
The bromo- 4b- azepines -12b- thias of above-mentioned 2, the 7- bis- of 1 molar part-dibenzo [g, p] thick two how -12b- oxides, the potassium phosphate of the diphenylamines of 2.5 molar parts and 5 molar parts is dissolved in 15 milliliters of toluene solution；Catalyst (Pd (the PPh of 0.02 molar part3)2Cl2) add in reaction system and in 1 hour of reaction at 70 DEG C；It is then cooled to room temperature and is stopped reacting with distilled water, through separation, obtains compound 51, yield 62% after purification.Mass spectrum [M]+：701.02；Elementary analysis：C 82.14, H 5.03, N 5.99, O 2.28, S 4.57, calculated value：C 82.11, H 5.23, N 5.97, O 2.32, S 4.33.
Embodiment 6：
In the present embodiment, sulfur heteroatom substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative as shown in compound 52.
The sulfur heteroatom substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative prepare it is as follows；
(1) the thick dinaphthyl of carbazole type：14b '-azepine -14b- thias benzo [p] indeno [1,2,3,4-defg] thick two how the synthesis of -14b- oxides
By the initiation material 1 of 1 molar part, 1 '-diphenyl carbazole is dissolved in 250 milliliters of toluene solution, in at -75 DEG C, it is put into low-temp reaction bath and handles 30 minutes, then the tert-butyl lithium hexane solution of 1 molar part is added dropwise in reaction system, reaction system is then warming up to room temperature, 1 hour is stirred；
Then, reaction system is placed at -75 DEG C again and is put into low-temp reaction bath processing 30 minutes, the thionyl chloride solution of 1 molar part is added dropwise in reaction system, is warming up to after room temperature, 8 hours are reacted；Mixed liquor is slowly added in the o-dichlorohenzene containing 4 molar part alchlors and 2 molar part tetramethyl piperidines, is warming up at 160 DEG C and reacts 12 hours；Room temperature is cooled to, the concentration that 4 molar parts are added into reaction mixture is 25% hydrogen peroxide, is heated to reflux；Through separation, purifying, yellow-white powder, the i.e. described thick dinaphthyl of carbazole type are obtained, its yield is 84%.Mass spectrum [M]+：365.12；Elementary analysis：C 78.88, H 4.14, N 3.83, O 4.38, S8.77, calculated value：C 78.84, H 4.17, N 3.82, O 4.42, S 8.72.
(2) double thick dinaphthyls of bromine carbazole type：2,7- bis- bromo- 14b '-azepine -14b- thias benzo [p] indeno [1,2,3,4-defg] thick two how the synthesis of -14b- oxides
The above-mentioned 14b ' of 1 molar part-azepine -14b- thias benzo [p] indeno [1,2,3,4-defg] thick two how -14b- oxides are dissolved in 6 milliliters of dichloromethane and 2 milliliters of second cyanogen blend solutions, and the NBS powder of 2 molar parts is added among reaction system and stirring 1 hour at room temperature；After solvent is evaporated off, surplus materials smashs into powder to pieces with second cyanogen, obtains colourless powder, i.e. described double thick dinaphthyls of bromine carbazole type, and its yield is 87%.Mass spectrum [M]+：523.16；Elementary analysis：C 55.09, H 2.50, Br 30.54, N 2.68, O 3.06, S 6.13, calculated value：C 55.01, H 2.53, Br 30.52, N 2.67, O 3.14, S 6.06.
(3) synthesis of compound 52
The bromo- 14b ' of above-mentioned 2, the 7- bis- of 1 molar part-azepine -14b- thias benzo [p] indeno [1,2,3,4-defg] thick two how -14b- oxides, the diphenylamines of 2.5 molar parts and 5 parts of potassium phosphate are dissolved in 15 milliliters of toluene solution；Catalyst (Pd (the PPh of 0.02 molar part3)2Cl2) add in reaction system and in 1 hour of reaction at 70 DEG C；It is cooled to after room temperature and is stopped reacting with distilled water, through separation, obtains compound 52 after purification, yield is 55%.Mass spectrum [M]+：700.14；Elementary analysis：C 82.38, H 4.75, N 6.00, O 2.29, S 4.58, calculated value：C 82.33, H 4.79, N 5.98, O 2.34, S 4.49.
Embodiment 7：
In the present embodiment, sulfur heteroatom substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative as shown in compound 61.
The sulfur heteroatom substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative prepare it is as follows；
(1) the thick dinaphthyl of hexichol amine type：4b- azepines -12b- thias-dibenzo [g, p] thick two how the synthesis of -12b- oxides
By the initiation material 1 of 1 molar part, 1 '-diphenyl diphenylamines is dissolved in 250 milliliters of toluene solution, in at -75 DEG C, it is put into low-temp reaction bath and handles 30 minutes, then the tert-butyl lithium hexane solution of 1 molar part is added dropwise in reaction system, reaction system is then warming up to room temperature, 1 hour is stirred；
Then, reaction system is placed at -75 DEG C again and is put into low-temp reaction bath processing 30 minutes, the thionyl chloride solution of 1 molar part is added dropwise in reaction system, is warming up to after room temperature, 8 hours are reacted；Mixed liquor is slowly added in the o-dichlorohenzene containing 4 molar part alchlors and 2 molar part tetramethyl piperidines, is warming up at 160 DEG C and reacts 12 hours；Room temperature is cooled to, the concentration that 4 molar parts are added into reaction mixture is 25% hydrogen peroxide, is heated to reflux；Through separation, purifying, yellow-white powder, the i.e. described thick dinaphthyl of hexichol amine type are obtained, its yield is 71%.
Mass spectrum [M]+：367.23；Elementary analysis：C 78.45, H4.66, N 3.81, O 4.35, S 8.73, calculated value：C 78.37, H 4.69, N 3.80, O 4.39, S 8.69.
(2) double thick dinaphthyls of bromine hexichol amine type：2,7- bis- bromo- 4b- azepines -12b- thias-dibenzo [g, p] thick two how the synthesis of -12b- oxides
How -12b- oxides are dissolved in 6 milliliters of dichloromethane and 2 milliliters of second cyanogen blend solutions the above-mentioned 4b- azepines -12b- thias-dibenzo [g, p] thick two of 1 molar part, and the NBS powder of 2 molar parts is added among reaction system and stirred 1 hour at room temperature；After solvent is evaporated off, surplus materials smashs into powder to pieces with second cyanogen, obtains colourless powder, i.e. described double thick dinaphthyls of bromine hexichol amine type, and its yield is 84%.Mass spectrum [M]+：525.12；Elementary analysis：C 54.88, H 2.88, Br, 30.42, N 2.67, O 3.05, S 6.10, calculated value：C 54.83, H 2.92, Br 30.41, N 2.64, O 3.12, S 6.01.
(3) synthesis of compound 61
The bromo- 4b- azepines -12b- thias of above-mentioned 2, the 7- bis- of 1 molar part-dibenzo [g, p] thick two how -12b- oxides, the potassium phosphate of the diphenylamines of 1.25 molar parts, the carbazole of 1.25 molar parts and 5 molar parts is dissolved in 15 milliliters of toluene solution；0.02 part of catalyst (Pd (PPh3)2Cl2) add in reaction system and in 1 hour of reaction at 70 DEG C；It is then cooled to room temperature and is stopped reacting with distilled water, through separation, obtains compound 61 after purification, yield is 54%.Mass spectrum [M]+：700.02；Elementary analysis：C 82.38, H 4.75, N 6.00, O 2.29, S 4.58, calculated value：C 82.34, H 4.77, N 5.96, O 2.33, S 4.2.
Embodiment 8：
In the present embodiment, sulfur heteroatom substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative as shown in compound 62.
The sulfur heteroatom substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative prepare it is as follows；
(1) the thick dinaphthyl of carbazole type：14b '-azepine -14b- thias benzo [p] indeno [1,2,3,4-defg] thick two how the synthesis of -14b- oxides
By the initiation material 1 of 1 molar part, 1 '-diphenyl carbazole is dissolved in 250 milliliters of toluene solution, in at -75 DEG C, it is put into low-temp reaction bath and handles 30 minutes, then the tert-butyl lithium hexane solution of 1 molar part is added dropwise in reaction system, reaction system is then warming up to room temperature, 1 hour is stirred；
Then, reaction system is placed at -75 DEG C again and is put into low-temp reaction bath processing 30 minutes, the thionyl chloride solution of 1 molar part is added dropwise in reaction system, is warming up to after room temperature, 8 hours are reacted；Mixed liquor is slowly added in the o-dichlorohenzene containing 4 molar part alchlors and 2 molar part tetramethyl piperidines, is warming up at 160 DEG C and reacts 12 hours；Room temperature is cooled to, the concentration that 4 molar parts are added into reaction mixture is 25% hydrogen peroxide, is heated to reflux.Through separation, purifying, yellow-white powder, the i.e. described thick dinaphthyl of carbazole type are obtained, its yield is 67%.
Mass spectrum [M]+：365.12；Elementary analysis：C 78.88, H 4.14, N 3.83, O 4.38, S8.77, calculated value：C 78.84, H 4.17, N 3.82, O 4.42, S 8.72.
Mass spectrum [M]+：365.12；Elementary analysis：C 78.88, H 4.14, N 3.83, O 4.38, S 8.77, calculated value：C 78.84, H 4.17, N 3.82, O 4.42, S 8.72.
(2) double thick dinaphthyls of bromine carbazole type：2,7- bis- bromo- 14b '-azepine -14b- thias benzo [p] indeno [1,2,3,4-defg] thick two how the synthesis of -14b- oxides
The above-mentioned 14b ' of 1 molar part-azepine -14b- thias benzo [p] indeno [1,2,3,4-defg] thick two how -14b- oxides are dissolved in 6 milliliters of dichloromethane and 2 milliliters of second cyanogen blend solutions, and the NBS powder of 2 molar parts is added among reaction system and stirring 1 hour at room temperature；After solvent is evaporated off, surplus materials smashs into powder to pieces with second cyanogen, obtains colourless powder, i.e. described double thick dinaphthyls of bromine carbazole type, and its yield is 87%.Mass spectrum [M]+：523.16；Elementary analysis：C 55.09, H 2.50, Br 30.54, N 2.68, O 3.06, S 6.13, calculated value：C 55.01, H 2.53, Br 30.52, N 2.67, O 3.14, S 6.06.
(3) synthesis of compound 62
1 molar part above-mentioned 2, the bromo- 14b ' of 7- bis--azepine -14b- thias benzo [p] indeno [1,2,3,4-defg] thick two how -14b- oxides, the potassium phosphate of the diphenylamines of 1.25 molar parts, the carbazole of 1.25 molar parts and 5 molar parts is dissolved in 15 milliliters of toluene solution；Catalyst (Pd (the PPh of 0.02 molar part3)2Cl2) add in reaction system and in 1 hour of reaction at 70 DEG C；It is then cooled to room temperature and is stopped reacting with distilled water, through separation, obtain compound 62 after purification, its yield is 55%.Mass spectrum [M]+：698.14；Elementary analysis：C 82.61, H 4.48, N6.02, O 2.29, S 4.59, calculated value：C 82.59, H 4.51, N 6.01, O 2.33, S 4.49.
By the sulphur in above-described embodiment 1-8, phosphorus heteroatoms substituted diphenylamine, simultaneously [G, P] thick dinaphthyl type derivative is as the emitting layer material of organic electroluminescence device, and when applying appropriate external voltage, the performance for measuring the electroluminescent device is as shown in table 1.
Table 1：(guest materials is Ir (PPy) to organic electroluminescence device in embodiment 1-83) performance table
Technical scheme is described in detail embodiment described above, the preparation method of other involved derivatives is similar with corresponding embodiment method in the present invention, corresponding diphenylamines or/and carbazole are simply substituted for N- phenyl -3- carbazole boric acid, 1- phenyl -2- benzimidazole boric acid, 6,6,12,12- tetraethyl -8- phenyl -6,12- bis- (indane) simultaneously [1,2-b:1 ', 2 '-e] pyrazine -2- boric acid.Simultaneously; it should be understood that above-described preparation method is only the specific embodiment of the present invention; it is not intended to limit the invention, all any modifications made in the spirit of the present invention, supplement or similar fashion are substituted etc., it should be included in the scope of the protection.

Claims (10)

1. sulphur, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative, it is characterized in that：Structural formula is any one in following structural formula 1~100：
2. the preparation method of sulphur as claimed in claim 1, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative, it is characterized in that：Comprise the following steps：
(1) with 1,1 '-bis- phenyl diphenylamines or 1,1 '-bis- phenyl carbazoles are initiation material, by low temperature lithiation and combine Friedel-Crafts and react, and are aoxidized using hydrogen peroxide, the thick dinaphthyl of aniline type or the thick dinaphthyl of carbazole type of formation condensed cyclic structure；
(2) the thick dinaphthyl of aniline type made from step (1) or the thick dinaphthyl of carbazole type are subjected to bromination using NBS, synthesis can functionalization the intermediate double thick dinaphthyl of bromine substituted benzene amine type or double thick dinaphthyls of bromine substituted carbazole type；
(3) the intermediate double thick dinaphthyl of bromine substituted benzene amine type or double thick dinaphthyls of bromine substituted carbazole type are coupled by Suzuki, obtain thick two naphthalene derivatives of target product aniline type or thick two naphthalene derivatives of carbazole type.
3. in the preparation method of sulphur as claimed in claim 2, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative, the step (1), low temperature lithiation temperature is -100 DEG C~-20 DEG C.
4. in the preparation method of sulphur as claimed in claim 2, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative, the step (1), 1,1 '-bis- phenyl diphenylamines or 1,1 '-bis- phenyl carbazoles are made by coupling reaction.
5. in the preparation method of sulphur, phosphorus heteroatoms substituted diphenylamine as described in claim 2,3 or 4 simultaneously [G, P] thick dinaphthyl type derivative, the step (1), course of reaction is specially：1 is extracted at low temperature with lithiumation thing, active hydrogen in 1 '-bis- phenyl diphenylamines on amido, add phosphorus trichloride formation halo phosphorus-nitrogen bonds, then the substituted-phenyl ortho position hydrogen atom added on metal chloride and alkali, activation 1,1 '-bis- phenyl diphenylamines, and occur substitution reaction with the halogen atom in halo phosphorus-nitrogen bonds under alkali effect, form addition peroxide in condensed cyclic structure, most backward reaction mixture to be aoxidized, form the thick dinaphthyl of aniline type；Or, 1 is extracted at low temperature with lithiumation thing, active hydrogen in 1 '-bis- phenyl carbazoles on carbazole, adds thionyl chloride formation halo sulphur nitrogen key, then adds metal chloride and alkali, activation 1, substituted-phenyl ortho position hydrogen atom on 1 '-bis- phenyl carbazoles, and occur substitution reaction with the halogen atom in halo phosphorus-nitrogen bonds under alkali effect, form condensed cyclic structure, peroxide is added in most backward reaction mixture to be aoxidized, and forms the thick dinaphthyl of carbazole type.
6. the preparation method of sulphur as claimed in claim 5, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative, described alkali is one or several kinds of mixing in sodium tert-butoxide, tetramethyl piperidine, n-butanol sodium.
7. the preparation method of sulphur as claimed in claim 5, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative, described lithiumation thing is one or several kinds of mixing in n-BuLi, tert-butyl lithium, lithium diisopropyl amido.
8. the preparation method of sulphur as claimed in claim 5, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative, described peroxide is one or several kinds of mixing in hydrogen peroxide, dual-tert-butyl hydrogen peroxide, double normal-butyl hydrogen peroxide；
Preferably, described metal chloride is one or several kinds of mixing in alchlor, ferric trichloride, gallium trichloride.
9. sulphur, phosphorus heteroatoms substituted diphenylamine as described in claim 2,3 or 4 simultaneously [G, P] thick dinaphthyl type derivative preparation method, in the step (3), coupling reaction is carried out under catalysts conditions, described catalyst is the one or several kinds in four (triphenyl phosphorus) palladiums, dichloro two (triphenyl phosphorus) palladium, palladium.
10. sulphur as claimed in claim 1, phosphorus heteroatoms substituted diphenylamine simultaneously [G, P] thick dinaphthyl type derivative as fluorescent material application.
CN201610038877.9A 2016-01-20 2016-01-20 Simultaneously [G, P] thick dinaphthyl type derivative, its preparation method and the application of sulphur, phosphorus heteroatoms substituted diphenylamine Pending CN106986894A (en)

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Application publication date: 20170728