CN109678759A - Organic blue fluorescent material of a kind of D-A type based on dianthracene and its preparation method and application - Google Patents

Organic blue fluorescent material of a kind of D-A type based on dianthracene and its preparation method and application Download PDF

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CN109678759A
CN109678759A CN201811620505.2A CN201811620505A CN109678759A CN 109678759 A CN109678759 A CN 109678759A CN 201811620505 A CN201811620505 A CN 201811620505A CN 109678759 A CN109678759 A CN 109678759A
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anthracene
power supply
replaces
benzene
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胡鉴勇
张佳丽
赵振
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Shaanxi Normal University
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    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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    • C09K2211/1011—Condensed systems

Abstract

The present invention relates to a kind of organic blue fluorescent materials of the D-A type based on dianthracene and its preparation method and application, the MOLECULE DESIGN of the material be centered on benzene conjugated bridge chain come connect two anthracene luminescence units (one have donor properties group, one has the group of electrophilic characteristic), come conjugation form and the Intramolecular electron transfer path of controlled material molecule, to realize the injection balance of the carrier in OLED device application, simultaneously, further introducing in the pi-conjugated bridge chain contraposition of center benzene has donor properties group or electrophilic characteristic group, effectively π-the π between material molecule is inhibited to stack, realize material molecule high luminous quantum efficiency, a kind of organic blue fluorescent material is prepared, the thermal stability and high luminous quantum efficiency that the material has had.

Description

Organic blue fluorescent material of a kind of D-A type based on dianthracene and preparation method thereof and Using
[technical field]
The present invention relates to organic electroluminescent LED fields, and in particular to a kind of organic blue of D-A type based on dianthracene Fluorescent material and its preparation method and application.
[background technique]
Organic electroluminescent LED (Organic Light-Emitting Diodes, OLED), because it has entirely admittedly State, self-luminous, wide viewing angle, low voltage drive, can be flexible the features such as, it is considered to be a new generation's display and all solid state lighting area Most competitive technology.It is to realize full-color display and white light as organic blue light material of one of three primary colours (red, green, blue) Indispensable ingredient is illuminated, while it is also used as material of main part to prepare the doping device of feux rouges and green light.But by Generally there is wider energy gap in blue light material, thus be difficult to obtain the blue-light device of low-voltage, high efficiency and good stability.
By effort in 30 years, OLED brightness, efficiency, in terms of all achieve huge progress, produce simultaneously Industry prospect also makes first appearance.Restricting current OLED mainly has following two points without complete commercialized key factor: first is The yields of price problem, at present oled panel production is relatively low, and the cost of manufacture of vacuum evaporation process is still remote high In liquid crystal display (LCD)；Second is the life problems of blue phosphor materials, and phosphor material has high luminous efficiency, but phosphorescence Material generally requires heavy metal coordination, and synthesis is difficult, at high cost, and the service life is bad, especially these defects of blue phosphor materials Never it is resolved.Compared with blue phosphor materials, blue fluorescent material does not need expensive heavy metal coordination, synthesis letter It is single, it is at low cost, and also the service life is long, replaces blue phosphor materials with it to prepare OLED with better commercial application prospect.Cause This, the organic blue fluorescent material for developing efficient stable has more real meaning to the commercialization process for pushing OLED.
[summary of the invention]
It is an object of the invention to overcome the above-mentioned prior art, a kind of organic indigo plant of the D-A type based on dianthracene is provided Color fluorescent material and its preparation method and application, prepared material thermal stability is good and luminous quantum efficiency is high, undoped In the application of Blue OLED device, performance is excellent, external quantum efficiency (EQE) is high.
In order to achieve the above objectives, the present invention is achieved by the following scheme:
A kind of organic blue fluorescent material of D-A type based on dianthracene, the organic blue-fluorescence material of the D-A type based on dianthracene The chemical structural formula of material is as follows:
Wherein, R1For the group of donor properties, R2For the group of electrophilic characteristic, R3For donor properties group or The group of electrophilic characteristic.
Preferably, the group of donor properties is CH3、OCH3、C2H5、OC2H5Or C (CH3)3Any one of；Electrophilic is special Property group be H, F, CF3, any one of CN or CHO.
A kind of preparation method of the organic blue fluorescent material of D-A type based on dianthracene, comprising the following steps: by substance B and The bromo- 10- of 9- (4- inhales electricity and replaces) benzene anthracene carries out Suzuki coupling reaction and organic blue fluorescent material is made, and substance B is 4- [10- (4- power supply replaces) benzene anthracene] -2,5- di-substituted-phenyl borate；The disubstituted phenyl of 2,5- in substance B is 2,5- dimethyl Phenyl, 2,5- Dimethoxyphenyl, 2,5- diethyl phenyl, 2,5- diethoxy phenyl, 2,5- di-tert-butyl-phenyl, 2,5- bis- Any one of hydrogen phenyl, 2,5- difluorophenyl, bis- trifluorophenyl of 2,5-, 2,5- dicyano phenyl or 2,5- dialdehyde-based phenyl； Suction electricity substituent group in the bromo- 10- of 9- (4- inhales electricity and replaces) benzene anthracene is any one of electrophilic characteristic group, electrophilic characteristic base Group includes F, CF3, CN and CHO.
Preferably, substance B is that 4- [10- (4- power supply replaces) benzene anthracene] -2,5- bis- replaces chlorobenzene to obtain by acid esterification , specific steps include: that 4- [10- (4- power supply replaces) benzene anthracene] -2,5- bis- is replaced chlorobenzene, connection boric acid pinacol ester, acetic acid Palladium, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls, potassium acetate and 1,4- dioxane by (0.5~2) mmol:(1.5~ 6) mmol:(0.05~0.2) mmol:(0.1~0.4) mmol:(1.5~6) mmol:(25~90) mL mixing, in inert gas It is reacted 12~18 hours for 95~105 DEG C under ambient conditions, purification obtains substance B after reaction；4- [10- (4- power supply replaces) Benzene anthracene] -2,5- bis- replaces the power supply substituent group in chlorobenzene to be any one of donor properties group, donor properties group packet Include H, CH3、OCH3、C2H5、OC2H5With C (CH3)3。
Preferably, 4- [10- (4- power supply replaces) benzene anthracene] -2,5- bis- replaces chlorobenzene to be by 9- (4- power supply substituted benzene Base) -10 borate anthracenes carry out Suzuki coupling reaction and obtain, and specific preparation step includes: by 9- (4- power substituted-phenyl) - 10 borate anthracenes, 1- chlorine-4-iodine -2,5- disubstituted benzenes, tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3By (1~3) mmol: (1~3) mmol:(0.1~0.3) mmol:(40~120) mL:(10~30) mL:(40~120) mmol mixing, in inert gas Under ambient conditions, 100~110 DEG C of purifications after reaction 12~24 hours obtain 4- [10- (4- power supply replace) benzene anthracene] -2,5- bis- and take For chlorobenzene.
Preferably, 9- (4- power supply substituted-phenyl) -10 borate anthracenes are by the bromo- 10- of 9- (4- power supply replaces) benzene anthracene boron It is Esterification to obtain, specific steps include: by the bromo- 10- of 9- (4- power supply replaces) benzene anthracene, isopropyl oxygen borate, n-BuLi and THF presses (4.22~12.66) mmol:(6.32~18.96) mmol:(7.2~21.6) mmol:(50~150) mL mixing, lazy Property atmosphere under the conditions of react at room temperature, purification obtains 9- (4- power substituted-phenyl) -10 borate anthracenes after reaction.
Preferably, the bromo- 10- of 9- (4- power supply replaces) benzene anthracene is to be obtained by 9- (4- power supply replaces) benzene anthracene by bromination , specific steps include: by 9- (4- power supply replaces) benzene anthracene, N- bromo-succinimide and n,N-Dimethylformamide by (2.5 ~10) mmol:(3~12) mmol:(40~150) mL mixing, under the conditions of atmosphere of inert gases, 85~90 DEG C of reactions 1~2 are small When, purification obtains 9- (4- power supply replaces) benzene anthracene；
9- (4- power supply replaces), benzene anthracene was that 9- bromine anthracene is obtained by Suzuki coupling reaction, and specific preparation step includes: 9- bromine anthracene, 4- power supply are replaced into phenyl boric acid, tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3According to (5~20) mmol:(7.5 ~30) mmol:(0.25~1) mmol:(50~200) mL:(15~60) mL:(50~200) mmol mixing, in inert gas atmosphere Under the conditions of enclosing, 100~110 DEG C of purifications after reaction 12~24 hours obtain 9- (4- power supply replace) benzene anthracene.
Preferably, the bromo- 10- of 9- (4- inhales electricity and replaces) benzene anthracene is to be obtained by 9- (4- inhales electricity and replaces) benzene anthracene by bromination , specific steps include: by 9- (4- inhales electricity and replaces) benzene anthracene, N- bromo-succinimide and n,N-Dimethylformamide by (2.5 ~10) mmol:(3~12) mmol:(40~150) mL mixing, under the conditions of atmosphere of inert gases, 85~90 DEG C of reactions 1~2 are small When, purification obtains 9- (4- inhales electricity and replaces) benzene anthracene；
9- (4- inhales electricity and replaces) benzene anthracene is that 9- bromine anthracene is obtained by Suzuki coupling reaction, and specific preparation step includes: 9- bromine anthracene, 4- are inhaled into electric substituent group phenyl boric acid, tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3According to (5~20) mmol: (7.5~30) mmol:(0.25~1) mmol:(50~200) mL:(15~60) mL:(50~200) mmol mixing, in indifferent gas Under body ambient conditions, 100~110 DEG C of purifications after reaction 12~24 hours obtain 9- (4- inhale electricity replace) benzene anthracene.
Preferably, in Suzuki coupling reaction, catalyst, solvent and activator have been additionally added；Wherein, substance B, 9- are bromo- Ratio of the 10- (4- substituted-phenyl) between anthracene, catalyst, solvent and activator is (0.25~1) mmol:(0.21~0.84) Mmol:(0.03~0.12) mmol:(25~100) mL:(8.4~33.6) mmol；Catalyst uses tetrakis triphenylphosphine palladium；It is molten Agent uses the mixed solvent of toluene and homogeneous solvent ethyl alcohol；Activator uses K2CO3Solution；
Suzuki coupling reaction is under nitrogen gas ambient conditions, and at a temperature of 100~110 DEG C, reaction 12~24 is small When.
A kind of above-mentioned organic blue fluorescent material the answering in organic electroluminescent LED part of D-A type based on dianthracene With.
Compared with prior art, the invention has the following advantages:
The invention discloses a kind of organic blue fluorescent material of the D-A type based on dianthracene, which is anthracene derivative, energy Enough realize blue emission.The present invention connects two anthracene luminescence units using conjugated bridge chain centered on benzene, and (one with power supply The group of sub-feature, one has the group of electrophilic characteristic), regulate and control the conjugation form and Intramolecular electron transfer of organic molecule Characteristic, while realizing the balance of carrier injection in OLED device application.On the other hand, by the pi-conjugated bridge chain of center benzene Introducing has donor properties group or electrophilic characteristic group, effectively to inhibit the pi-pi accumulation between organic molecule, realizes material High luminous quantum efficiency.Two anthracene luminescence units are connected by using conjugated bridge chain centered on benzene, and (one with power supply The group of sub-feature, one has the group of electrophilic characteristic), regulate and control the conjugation form and Intramolecular electron transfer of organic molecule Characteristic, while realizing the balance of carrier injection in OLED device application；Steric hindrance is introduced on central pi-conjugated bridge chain simultaneously Group interacts to eliminate the intermolecular stacking of organic material, realizes high luminous quantum efficiency；In undoped OLED device In, blue emission is realized, it is functional, cost of manufacture can be reduced, production technology is simplified.In short, the invention has the characteristics that 1) Two anthracene luminescence units are connected as pi-conjugated bridge chain using benzene, realize the conjugation form to organic molecule, excitation state charge Transfer and OLED device application in charge injection balance regulation；2) introducing on central pi-conjugated bridge chain has supplied for electronic special The group of property or the group of electrophilic characteristic substantially increase material molecule to inhibit the π-π between organic molecule to interact Luminous quantum efficiency.
The invention also discloses a kind of preparation method of organic blue fluorescent material of the D-A type based on dianthracene, this method with Benzene is pi-conjugated bridge chain to connect two (one has the group of donor properties, and one has the group of electrophilic characteristic) anthracenes Luminescence unit is further implemented in realize the regulation of conjugation form and excitation state charge transfer path to organic molecule The injection balance of carrier in OLED device application, while the group with donor properties or suction are introduced on pi-conjugated bridge chain The group of characteristic electron improves the quantum efficiency of luminescent material molecule to inhibit the π-π between organic molecule to interact, at The organic blue fluorescent material for preparing high thermal stability, high fluorescence quantum efficiency of function；Entire synthesis process is simple, yield Height is easily purified.
The invention also discloses a kind of organic blue fluorescent materials of the D-A type based on dianthracene in organic electroluminescent LED Application in part can be successfully prepared out the undoped Nan dian Yao device of high-performance by organic blue fluorescent material；System Standby Nan dian Yao device out, under ultraviolet light, strong blue fluorescent emissions are all presented in solution or film.Such material is answered In undoped OLED, EQE (~4.99%) is much higher than theoretical calculation EQE value (~1.13%), [EQEIt is theoretical=ηeh·ηPL· ηexciton·ηout=1 × 0.15 × 0.25 × 0.3=1.13%], wherein ηehIt is the recombination rate of electrons and holes；ηPLFor net film Fluorescence quantum yield ηexcitonThe ratio of exciton；ηoutFor light transmittance.
[Detailed description of the invention]
Fig. 1 is the nuclear magnetic spectrum of organic blue fluorescent material made from the embodiment of the present invention 1.
Fig. 2 is the mass-spectrogram of organic blue fluorescent material made from the embodiment of the present invention 1.
Fig. 3 is the nuclear magnetic spectrum of organic blue fluorescent material made from the embodiment of the present invention 4.
Fig. 4 is the mass-spectrogram of organic blue fluorescent material made from the embodiment of the present invention 4.
Fig. 5 is the thermogravimetric map of anthracene derivative a made from 1-3 of the embodiment of the present invention.
Fig. 6 is absorption spectrum of organic blue fluorescent material in different solutions made from the embodiment of the present invention 1.
Fig. 7 is emission spectrum of organic blue fluorescent material in different solutions made from the embodiment of the present invention 1.
Fig. 8 is Absorption and emission spectra of organic blue fluorescent material on film made from the embodiment of the present invention 1.
Fig. 9 is electroluminescent (EL) map of device 1 produced by the present invention.
Figure 10 is Current density-voltage-brightness (Cd-V-L) graphs of device 1 produced by the present invention.
Figure 11 is that current efficiency-current density-power efficiency (CE-Cd-PE) map of device 1 produced by the present invention is bent Line.
Figure 12 is the graphs of current density-external quantum efficiency (Cd-EQE) of device 1 produced by the present invention.
[specific embodiment]
Below with reference to specific steps and attached drawing, the invention will be described in further detail:
The invention discloses a kind of organic blue fluorescent materials of the D-A type based on dianthracene and its preparation method and application；It should Invention passes through the sophisticated design to material molecule, wherein connects two anthracene mulecular luminescence units so that benzene is pi-conjugated bridge chain, comes Regulate and control the conjugation form and excitation state charge transfer path of organic molecule, realize the charge injection balance in OLED device application, Meanwhile steric group is imported in the pi-conjugated bridge chain contraposition of center benzene to inhibit the π-π stacking between organic molecule to act on, it prepares The thermal stability and high luminous quantum efficiency that organic blue fluorescent material out has had.Its chemical structural formula is as follows.
Wherein R1For the group of donor properties, R2For the group of electrophilic characteristic, R3Group or suction for donor properties The group of characteristic electron, the group of donor properties are preferably H, CH3、OCH3、C2H5、OC2H5Or C (CH3)3；Electrophilic characteristic Group is preferably F, CF3, CN or CHO；Shown in the chemical structural formula of the organic blue fluorescent material synthesized is exemplified below:
It is followed successively by compound a, compound b, compound c, compound d, compound e, compound f, compound g, compound H, compound i, compound j, compound m, compound n；R1、R2And R3It can be any one of the following table 1.
Table 1R1、R2And R3Types of radicals
R1 H、CH3、OCH3、C2H5、OC2H5Or C (CH3)3
R2 F、CF3, CN or CHO
R3 CH3、OCH3、C2H5、OC2H5、C(CH3)3、H、F、CF3, CN or CHO
Wherein compound is R1、R2、R3Any one of middle combination, above-mentioned chemical formula only enumerate a part.
Shown in the specific synthetic route such as following formula (1) of organic blue fluorescent material of the invention:
2a in above formula is referred to3a is referred to4a is referred toIt is corresponding 2b is referred to3b is referred to4b is referred to
By taking the synthesis of compound a as an example, shown in specific synthetic route such as following formula (2):
By taking the synthesis of compound b as an example, shown in specific synthetic route such as following formula (3):
The detailed process of synthesis process the following steps are included:
Step 1, donor properties group is synthesized
1. by 5~20mmol of 9- bromine anthracene, 4- power supply substitution phenyl boric acid (2a) 7.5~30mmol, solution of potassium carbonate 15~ 60mL, 50~200mL of toluene, 15~60mL of ethyl alcohol are added to reaction flask, and wherein solution of potassium carbonate is by 50~200mmol carbonic acid Proportion in 15~60mL water is added in potassium solid；It is eventually adding 0.25~1mmol tetrakis triphenylphosphine palladium.Then system is taken out Vacuum under nitrogen protection, flows back 12~24 hours at 100~110 DEG C.After reaction, it extracts, revolving, column chromatography, recrystallization Obtain 9- (4- power supply replaces) benzene anthracene (3a)；Wherein, it powers and is substituted by any one of group of donor properties, including H, CH3、OCH3、C2H5、OC2H5With C (CH3)3。
The bromination of 9- 2. (4- power supply replaces) benzene anthracene: by 9- (4- power supply replaces) benzene anthracene 2.50~10mmol, N, N- diformazan Base formamide (DMF) 40~150mL, N- bromo-succinimide (NBS) 3~12mmol is added to reaction flask, then to system It vacuumizes, under nitrogen protection, 85~90 DEG C are reacted 1~2 hour, methanol washing reaction product, and suction filtration obtains the bromo- 10- of 9-, and (4- is supplied Electricity replaces) benzene anthracene (4a).
Step 2, the group of electrophilic characteristic is synthesized
1. by 5~20mmol of 9- bromine anthracene, 4- suction electricity substituent group phenyl boric acid (2b) 7.5~30mmol, solution of potassium carbonate 15~ 60mL, 50~200mL of toluene, 15~60mL of ethyl alcohol are added to reaction flask, and wherein solution of potassium carbonate is by 50~200mmol carbonic acid Proportion in 15~60mL water is added in potassium solid；It is eventually adding 0.25~1mmol tetrakis triphenylphosphine palladium.Then system is taken out Vacuum under nitrogen protection, flows back 12~24 hours at 100~110 DEG C.After reaction, it extracts, revolving, column chromatography, recrystallization Obtain 9- (4- inhales electricity and replaces) benzene anthracene (3b)；Wherein, electric any one of the group for being substituted by electrophilic characteristic of suction, including F, CF3、CN、CHO。
The bromination of 9- 2. (4- inhales electricity and replaces) benzene anthracene: by 9- (4- inhales electricity and replaces) benzene anthracene (3b) 2.50~10mmol, N, N- Dimethylformamide (DMF) 40~150mL, N- bromo-succinimide (NBS) 3~12mmol is added to reaction flask, then right System vacuumizes, and under nitrogen protection, 85~90 DEG C are reacted 1~2 hour, and methanol washing reaction product, suction filtration obtains the bromo- 10- of 9- (4- inhales electricity and replaces) benzene anthracene (4b).
Step 3, the synthesis process of final product
The acid esterification of the bromo- 10- of 9- 1. (4- power supply replaces) benzene anthracene: by the bromo- 10- of 9- made from step 1, (4- power supply is taken Generation) benzene anthracene (4a) 4.22~12.66mmol, isopropyl oxygen 6.32~18.96mmol of borate, 7.2~21.6mmol of n-BuLi (being added at -78 DEG C), 50~150mL of THF is added to reaction flask, then vacuumizes to system, under the protection of nitrogen, room temperature Lower stirring 8~12 hours.After reaction, it extracts, revolving, column chromatography, is recrystallized to give product 9- (4- power supply substituted-phenyl)- 10 borate anthracenes (5a).
The Suzuki coupling reaction of 9- 2. (4- power supply substituted-phenyl) -10 borate anthracenes: by 9- (4- power supply substituted-phenyl) - 10 borate anthracene (5a) 1~3mmol, 1- chlorine-4-iodine -2,5- 1~3mmol of disubstituted benzenes, tetrakis triphenylphosphine palladium 0.1~ 0.3mmol, 40~120mL of toluene, ethyl alcohol 10~30mL and K2CO340~120mL of solution (is dissolved in 10~30mL distilled water and making ) it is added to reaction flask, then system is vacuumized, under the protection of nitrogen, reacts 12~24 hours at 100~110 DEG C, instead It after answering, extracts, revolving, column chromatography, is recrystallized to give product A, 4- [10- (4- power supply replaces) benzene anthracene] -2,5- bis- replaces Chlorobenzene；The substituent group in 1- chlorine-4-iodine -2,5- disubstituted benzenes among the above is R3, R3It can be in donor properties group Any one of any or group of electrophilic characteristic, donor properties group includes H, CH3、OCH3、C2H5、OC2H5And C (CH3)3；The group of electrophilic characteristic includes F, CF3, CN and CHO.
3. the acid esterification of A reacts: by 0.5~2mmol of A, 1.5~6mmol of connection boric acid pinacol ester, acid chloride 0.05 ~0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 ' -0.1~0.4mmol of dimethoxy-biphenyl, 1.5~6mmol of potassium acetate and Isosorbide-5-Nitrae - 25~90mL of dioxane is mixed to join reaction flask, then vacuumizes to system, under the protection of nitrogen, at 95~105 DEG C Reaction 12~18 hours extracts after reaction, revolving, and column chromatography is recrystallized to give substance B；
Product B is 4- [10- (4- power supply replaces) benzene anthracene] -2,5- di-substituted-phenyl borate, wherein 2,5- is disubstituted Phenyl is respectively 2,5- 3,5-dimethylphenyl, 2,5- Dimethoxyphenyl, 2,5- diethyl phenyls, 2,5- diethoxy phenyl, and 2, 5- di-tert-butyl-phenyl, 2,5- dihydro phenyl, 2,5- difluorophenyls, 2,5- bis- trifluorophenyls, 2,5- dicyano phenyl or 2,5- Dialdehyde-based phenyl.
4. the synthesis of final product: by 0.25~1mmol of substance B, (4- inhales electricity and takes the bromo- 10- of step 2 products therefrom 4b, that is, 9- For benzene) 0.21~0.84mmol of anthracene, catalyst four (triphenyl) phosphine 0.03~0.12mmol of palladium, 15~60mL of toluene, ethyl alcohol 5~ 20mL, K2CO38.4~33.6mmol (with 5~20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, 100~110 DEG C of reflux 12~for 24 hours.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product, are Organic blue fluorescent material.
The solution of potassium carbonate of addition is so that it is converted into active reaction intermediate in order to activate borate ion.Add second Alcohol is the hydrophily in order to increase solvent, carries out reaction under homogeneous phase condition.
Intermediate product A in following example1~A10It indicates because of R3The intermediate product that group is different and synthesizes is different, B1~ B10Similarly.
Embodiment 1
Step 1 synthesizes donor properties group: 1. by 9- bromine anthracene 5mmol, 4- methoxyphenylboronic acid 7.5mmol, potassium carbonate Solution 50mmol (uses 15mL distilled water wiring solution-forming), and toluene 50mL, ethyl alcohol 15mL is added to reaction flask, is eventually adding 0.25mmol tetrakis triphenylphosphine palladium.Then system is vacuumized, under nitrogen protection, is flowed back 12 hours at 100 DEG C.Reaction terminates Afterwards, it extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=4:1), is recrystallized to give 9- (4- methoxyl group) benzene anthracene. Yield 86%.2. by 9- (4- methoxyl group) benzene anthracene 2.50mmol, n,N-Dimethylformamide (DMF) 40mL, N- bromo succinyl Imines (NBS) 3mmol is added to reaction flask, then vacuumizes to system, and under nitrogen protection, 85 DEG C are reacted 1 hour.Methanol is washed It washs, suction filtration obtains the bromo- 10- of product 9- (4- methoxyl group) benzene anthracene, yield 88%.
Step 2 synthesize electrophilic characteristic group: with step 1 [only need to by 1. 2. in 4- methoxyphenylboronic acid, 9- (4- first Oxygroup) benzene anthracene replaces with 4- cyanophenylboronic acid, 9- (4- cyano) benzene anthracene].
Step 3, it the synthesis process of final product: carries out in next step on the basis of step 1 3. by 9- bromo- 10- (4- methoxy Base) benzene anthracene 4.22mmol, isopropyl oxygen borate 6.32mmol, n-BuLi 7.2mmol (being added at -78 DEG C), THF 50mL It is added to reaction flask, then system is vacuumized, under the protection of nitrogen, is stirred 8 hours at room temperature.After reaction, it extracts, rotation It steams, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give -10 borate anthracene of product 9- (4- methoxyl group). Yield 80%.4. by -10 borate anthracene 1mmol, 1- chlorine-4-iodine -2,5- dimethyl benzene 1mmol of 9- (4- methoxyl group), four (triphens Base phosphine) palladium 0.1mmol, toluene 40mL, ethyl alcohol 10mL and K2CO340mmol (with 10mL distilled water wiring solution-forming) is added to reaction Bottle, then vacuumizes system, the protection of nitrogen, reacts 12 hours, after reaction, extracts, revolving at 100 DEG C, column chromatography (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A1.Yield 68%.
5. by A10.5mmol, connection pinacol borate 1.5mmol, acid chloride 0.05mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.1mmol, potassium acetate 1.5mmol, Isosorbide-5-Nitrae-dioxane 25mL is added in reaction flask, then to body System vacuumizes, the protection of nitrogen, reacts 12 hours at 90 DEG C, after reaction, extracts, revolving, column chromatography (eluant, eluent: just oneself Alkane/methylene chloride=2:1), it is recrystallized to give product B1.Yield 65%.6. obtaining end by Suzuki (Suzuki) coupling reaction Product a: by B10.25mmol, the step 2 products therefrom, that is, bromo- 10- of 9- (4- cyano) benzene anthracene 0.21mmol, four (triphen of catalyst Base) phosphine palladium 0.03mmol, toluene 15mL, ethyl alcohol 5mL, K2CO38.4mmol (uses 5mL distilled water wiring solution-forming), is added to reaction Bottle, under the protection of nitrogen, in 100 DEG C of reflux 12h.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain most Final product.Yield 50%.Nuclear magnetic resonance spectroscopy: δ=7.82-7.74 (m, 2H) NMR (400MHz), 7.56 (dd, J=38.3, 11.2,2H), 7.65-7.34 (m, 8H), 7.34-7.10 (m, 7H), 3.98 (d, J=2.4,2H), 2.30 (s, 2H), 1.99 (s, 1H), 1.97 (s, 6H), 1.99-1.13 (m, 23H) ,-0.02 (d, J=3.2,6H), nuclear magnetic spectrum is illustrated in fig. 1 shown below.Mass spectrum (m/s), molecular formula C50H35NO, theoretical value 665.27, actual value 665, mass-spectrogram is illustrated in fig. 2 shown below.
Embodiment 2
Step 1 synthesizes donor properties group: 1. by 9- bromine anthracene 10mmol, 4- methoxyphenylboronic acid 15mmol, potassium carbonate Solution 100mmol (uses 30mL distilled water wiring solution-forming), and toluene 136mL, ethyl alcohol 30mL is added to reaction flask, is eventually adding 0.5mmol tetrakis triphenylphosphine palladium.Then system is vacuumized, under nitrogen protection, 105 lower reflux 18 hours.After reaction, Extraction, revolving, column chromatograph (eluant, eluent: n-hexane/methylene chloride=4:1), are recrystallized to give 9- (4- methoxyl group) benzene anthracene.Yield 90%.2. by 9- (4- methoxyl group) benzene anthracene 5mmol, n,N-Dimethylformamide (DMF) 75mL, N- bromo-succinimide (NBS) 6mmol is added to reaction flask, then vacuumizes to system, and under nitrogen protection, 88 DEG C are reacted 1.5 hours.Methanol washing, Suction filtration obtains the bromo- 10- of product 9- (4- methoxyl group) benzene anthracene, yield 89%.
Step 2 synthesize electrophilic characteristic group: with step 1 [only need to by 1. 2. in 4- methoxyphenylboronic acid, 9- (4- first Oxygroup) benzene anthracene replaces with 4- cyanophenylboronic acid, 9- (4- cyano) benzene anthracene].
Step 3, it the synthesis process of final product: carries out in next step on the basis of step 1 3. by 9- bromo- 10- (4- methoxy Base) benzene anthracene 8.44mmol, isopropyl oxygen borate 12.64mmol, n-BuLi 14.4mmol (being added at -78 DEG C), THF100mL is added to reaction flask, then vacuumizes to system, under the protection of nitrogen, stirs 10 hours at room temperature.Reaction terminates Afterwards, it extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give product 9- (4- methoxyl group)- 10 borate anthracenes, yield 70%.4. by -10 borate anthracene 2mmol, 1- chlorine-4-iodine -2,5- dimethyl benzene of 9- (4- methoxyl group) 2mmol, tetrakis triphenylphosphine palladium 0.2mmol, toluene 80mL, ethyl alcohol 20mL and K2CO380mmol (is made into molten with 20mL distilled water Liquid) it is added to reaction flask, then system is vacuumized, the protection of nitrogen, 12 hours, after reaction, extraction are reacted at 100 DEG C It takes, rotates, column chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A1.Yield 69%.5. by A1 1mmol, connection pinacol borate 3mmol, acid chloride 0.1mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls 0.2mmol, potassium acetate 3mmol, Isosorbide-5-Nitrae-dioxane 45mL are added in reaction flask, then vacuumize to system, the guarantor of nitrogen It protecting, reacts at 95 DEG C 16 hours, after reaction, extract, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), It is recrystallized to give product B1.Yield 65%.6. obtaining final product a by Suzuki (Suzuki) coupling reaction: by B1 0.5mmol, The step 2 products therefrom, that is, bromo- 10- of 9- (4- cyano) benzene anthracene 0.42mmol, catalyst four (triphenyl) phosphine palladium 0.06mmol, toluene 30mL, ethyl alcohol 10mL, K2CO316.8mmol (uses 10mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, In 105 DEG C of reflux 18h.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 55%. Molecular formula is C50H35NO, theoretical value 665.27, actual value 665.
Embodiment 3
Step 1 synthesizes donor properties group: 1. by 9- bromine anthracene 20mmol, 4- methoxyphenylboronic acid 30mmol, potassium carbonate Solution 200mmol (uses 60mL distilled water wiring solution-forming), and toluene 200mL, ethyl alcohol 60mL is added to reaction flask, is eventually adding 1mmol tetrakis triphenylphosphine palladium.Then system is vacuumized, under nitrogen protection, is flowed back 24 hours at 110 DEG C.After reaction, Extraction, revolving, column chromatograph (eluant, eluent: n-hexane/methylene chloride=4:1), are recrystallized to give 9- (4- methoxyl group) benzene anthracene.Yield 89%.2. by 9- (4- methoxyl group) benzene anthracene 10mmol, n,N-Dimethylformamide (DMF) 150mL, N- bromo-succinimide (NBS) 12mmol is added to reaction flask, then vacuumizes to system, and under nitrogen protection, 90 DEG C are reacted 2 hours.Methanol washing, takes out Filter obtains the bromo- 10- of product 9- (4- methoxyl group) benzene anthracene, yield 90%.
Step 2 synthesize electrophilic characteristic group: with step 1 [only need to by 1. 2. in 4- methoxyphenylboronic acid, 9- (4- first Oxygroup) benzene anthracene replaces with 4- cyanophenylboronic acid, 9- (4- cyano) benzene anthracene].
Step 3, it the synthesis process of final product: carries out in next step on the basis of step 1 3. by 9- bromo- 10- (4- methoxy Base) benzene anthracene 12.66mmol, isopropyl oxygen borate 18.96mmol, n-BuLi 21.60mmol (being added at -78 DEG C), THF150mL is added to reaction flask, then vacuumizes to system, under the protection of nitrogen, stirs 12 hours at room temperature.Reaction terminates Afterwards, it extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give product 9- (4- methoxyl group)- 10 borate anthracenes, yield 68%.4. by -10 borate anthracene 3mmol, 1- chlorine-4-iodine -2,5- dimethyl benzene of 9- (4- methoxyl group) 3mmol, tetrakis triphenylphosphine palladium 0.3mmol, toluene 120mL, ethyl alcohol 30mL and K2CO3120mmol (is made into 30mL distilled water Solution) it is added to reaction flask, then system is vacuumized, the protection of nitrogen, 24 hours, after reaction, extraction are reacted at 110 DEG C It takes, rotates, column chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A1.Yield 66%.5. will A12mmol, connection pinacol borate 6mmol, acid chloride 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls 0.4mmol, potassium acetate 6mmol, Isosorbide-5-Nitrae-dioxane 90mL are added in reaction flask, then vacuumize to system, the guarantor of nitrogen It protects, reacts 18 hours, after reaction, extract, revolving at 105 DEG C, column chromatography (eluant, eluent: n-hexane/methylene chloride=2: 1), it is recrystallized to give product B1, yield 68%.6. obtaining final product a by Suzuki (Suzuki) coupling reaction: by B1 1mmol, The step 2 products therefrom, that is, bromo- 10- of 9- (4- cyano) benzene anthracene 0.84mmol, catalyst four (triphenyl) phosphine palladium 0.12mmol, toluene 60mL, ethyl alcohol 20mL, K2CO333.6mmol (uses 20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, It flows back for 24 hours at 110 DEG C.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 55%. Molecular formula is C50H35NO, theoretical value 665.27, actual value 665.
Embodiment 4
In steps 1 and 2 and step 3 3. with embodiment 1.
4. by -10 borate anthracene 1mmol, 1- chlorine-4-iodine -2,5- dimethoxy benzene 1mmol of 9- (4- methoxyl group), four (three Phenylphosphine) palladium 0.1mmol, toluene 40mL, ethyl alcohol 10mL and K2CO340mmol (with 10mL distilled water wiring solution-forming) is added to instead Bottle is answered, then system is vacuumized, the protection of nitrogen is reacted at 100 DEG C 12 hours, after reaction, extracted, revolving, column layer It analyses (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A2.Yield 69%.5. by A20.5mmol joins boric acid Pinacol ester 1.5mmol, acid chloride 0.05mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.1mmol, potassium acetate 1.5mmol, Isosorbide-5-Nitrae-dioxane 25mL are added in reaction flask, then vacuumize to system, the protection of nitrogen, react at 95 DEG C It 12 hours, after reaction, extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give production Object B2.Yield 65%.
6. obtaining final product b by Suzuki (Suzuki) coupling reaction: by B20.25mmol, step 2 products therefrom, that is, 9- Bromo- 10- (4- cyano) benzene anthracene 0.21mmol, catalyst four (triphenyl) phosphine palladium 0.03mmol, toluene 15mL, ethyl alcohol 5mL, K2CO3 8.4mmol (uses 5mL distilled water wiring solution-forming), reaction flask is added to, under the protection of nitrogen, in 100 DEG C of reflux 12h.Reaction knot Shu Hou, methanol hot wash filter, re crystallization from toluene, and distillation obtains final product.Yield 52%.Nuclear magnetic resonance spectroscopy: NMR δ=8.01-7.89 (m, 14H) (400MHz) δ=NMR (400MHz), 7.85-7.77 (m, 5H), 7.60 (dd, J=5.2, 4.3,5H),7.56–7.37(m,24H),7.29–7.20(m,23H),7.20–7.11(m,21H),3.98(s,7H),3.57(s, 14H), 2.34 (s, 13H), 1.76-1.58 (m, 2H), 1.41 (d, J=123.3,54H), 0.06 (s, 1H), 0.02-- 0.05 (m,15H).Nuclear magnetic spectrum is illustrated in fig. 2 shown below.Mass spectrum (m/s), molecular formula C50H35NO3, theoretical value 697.26, actual value is 696.5 mass-spectrogram is illustrated in fig. 4 shown below.
Embodiment 5
In steps 1 and 2 and step 3 3. with embodiment 2.
4. by -10 borate anthracene 2mmol, 1- chlorine-4-iodine -2,5- dimethoxy benzene 2mmol of 9- (4- methoxyl group), four (three Phenylphosphine) palladium 0.2mmol, toluene 80mL, ethyl alcohol 20mL and K2CO380mmol (with 20mL distilled water wiring solution-forming) is added to instead Bottle is answered, then system is vacuumized, the protection of nitrogen is reacted at 100 DEG C 12 hours, after reaction, extracted, revolving, column layer It analyses (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A2.Yield 69%.5. by A21mmol, connection boric acid frequency Any alcohol ester 3mmol, acid chloride 0.1mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.2mmol, potassium acetate 3mmol, Isosorbide-5-Nitrae-dioxane 45mL is added in reaction flask, is then vacuumized to system, the protection of nitrogen, is reacted 16 hours at 100 DEG C, After reaction, it extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give product B2.It produces Rate 65%.6. obtaining final product b by Suzuki (Suzuki) coupling reaction: by B20.5mmol, step 2 products therefrom, that is, 9- Bromo- 10- (4- cyano) benzene anthracene 0.42mmol, catalyst four (triphenyl) phosphine palladium 0.06mmol, toluene 30mL, ethyl alcohol 10mL, K2CO316.8mmol (uses 10mL distilled water wiring solution-forming), reaction flask is added to, under the protection of nitrogen, in 105 DEG C of reflux 18h. After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 55%.Molecular formula is C50H35NO3, theoretical value 697.26, actual value 696.5.
Embodiment 6
In steps 1 and 2 and step 3 3. with embodiment 3.
4. by -10 borate anthracene 3mmol, 1- chlorine-4-iodine -2,5- dimethoxy benzene 3mmol of 9- (4- methoxyl group), four (three Phenylphosphine) palladium 0.3mmol, toluene 120mL, ethyl alcohol 30mL and K2CO3120mmol (with 30mL distilled water wiring solution-forming) is added to Then reaction flask vacuumizes system, the protection of nitrogen, reacts 24 hours, after reaction, extracts, revolving, column at 110 DEG C It chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A2.Yield 66%.5. by A22mmol joins boric acid Pinacol ester 6mmol, acid chloride 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.4mmol, potassium acetate 6mmol, Isosorbide-5-Nitrae-dioxane 90mL are added in reaction flask, then vacuumize to system, the protection of nitrogen, react at 105 DEG C It 18 hours, after reaction, extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give production Object B2.Yield 68%.6. obtaining final product b by Suzuki (Suzuki) coupling reaction: by B21mmol, step 2 products therefrom are The bromo- 10- of 9- (4- cyano) benzene anthracene 0.84mmol, catalyst four (triphenyl) phosphine palladium 0.12mmol, toluene 60mL, ethyl alcohol 20mL, K2CO333.6mmol (uses 20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, flows back for 24 hours at 110 DEG C. After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 55%.Molecular formula is C50H35NO3, theoretical value 697.26, actual value 696.5.
Embodiment 7
In steps 1 and 2 and step 3 3. with embodiment 1.
4. by -10 borate anthracene 1mmol, 1- chlorine-4-iodine -2,5- diethylbenzene 1mmol of 9- (4- methoxyl group), four (triphens Base phosphine) palladium 0.1mmol, toluene 40mL, ethyl alcohol 10mL and K2CO340mmol (with 10mL distilled water wiring solution-forming) is added to reaction Bottle, then vacuumizes system, the protection of nitrogen, reacts 12 hours, after reaction, extracts, revolving at 100 DEG C, column chromatography (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A3.Yield 69%.5. by A30.5mmol, connection boric acid frequency Any alcohol ester 1.5mmol, acid chloride 0.05mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.1mmol, potassium acetate 1.5mmol, Isosorbide-5-Nitrae-dioxane 25mL are added in reaction flask, then vacuumize to system, the protection of nitrogen, react at 90 DEG C It 12 hours, after reaction, extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give production Object B3.Yield 65%.6. obtaining final product c by Suzuki (Suzuki) coupling reaction: by B30.25mmol, step 2 products therefrom That is the bromo- 10- of 9- (4- cyano) benzene anthracene 0.21mmol, catalyst four (triphenyl) phosphine palladium 0.03mmol, toluene 15mL, ethyl alcohol 5mL, K2CO38.4mmol (uses 5mL distilled water wiring solution-forming), reaction flask is added to, under the protection of nitrogen, in 100 DEG C of reflux 12h.Instead After answering, methanol hot wash is filtered, re crystallization from toluene, and distillation obtains final product.Yield 52%.Molecular formula is C52H39NO, Theoretical value is 693.30, actual value 693.
Embodiment 8
In steps 1 and 2 and step 3 3. with embodiment 1.
4. by -10 borate anthracene 1mmol, 1- chlorine-4-iodine -2,5- diethoxybenzene 1mmol of 9- (4- methoxyl group), four (three Phenylphosphine) palladium 0.1mmol, toluene 40mL, ethyl alcohol 10mL and K2CO340mmol (with 10mL distilled water wiring solution-forming) is added to instead Bottle is answered, then system is vacuumized, the protection of nitrogen is reacted at 100 DEG C 12 hours, after reaction, extracted, revolving, column layer It analyses (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A4.Yield 69%.5. by A40.5mmol joins boric acid Pinacol ester 1.5mmol, acid chloride 0.05mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.1mmol, potassium acetate 1.5mmol, Isosorbide-5-Nitrae-dioxane 25mL are added in reaction flask, then vacuumize to system, the protection of nitrogen, react at 90 DEG C It 12 hours, after reaction, extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give production Object B4.Yield 65%.6. obtaining final product d by Suzuki (Suzuki) coupling reaction: by B40.25mmol, step 2 products therefrom That is the bromo- 10- of 9- (4- cyano) benzene anthracene 0.21mmol, catalyst four (triphenyl) phosphine palladium 0.03mmol, toluene 15mL, ethyl alcohol 5mL, K2CO38.4mmol (uses 5mL distilled water wiring solution-forming), reaction flask is added to, under the protection of nitrogen, in 100 DEG C of reflux 12h.Instead After answering, methanol hot wash is filtered, re crystallization from toluene, and distillation obtains final product.Yield 55%.Molecular formula is C52H39NO3, Theoretical value is 725.29, actual value 725.
Embodiment 9
In steps 1 and 2 and step 3 3. with embodiment 1.
4. by -10 borate anthracene 1mmol, 1- chlorine-4-iodine -2,5- di-tert-butyl 1mmol of 9- (4- methoxyl group), four (three Phenylphosphine) palladium 0.1mmol, toluene 40mL, ethyl alcohol 10mL and K2CO340mmol (with 10mL distilled water wiring solution-forming) is added to instead Bottle is answered, then system is vacuumized, the protection of nitrogen is reacted at 100 DEG C 12 hours, after reaction, extracted, revolving, column layer It analyses (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A5.Yield 69%.5. by A50.5mmol joins boric acid Pinacol ester 1.5mmol, acid chloride 0.05mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.1mmol, potassium acetate 1.5mmol, Isosorbide-5-Nitrae-dioxane 25mL are added in reaction flask, then vacuumize to system, the protection of nitrogen, react at 90 DEG C It 12 hours, after reaction, extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give production Object B5.Yield 65%.6. obtaining final product e by Suzuki (Suzuki) coupling reaction: by B50.25mmol, step 2 products therefrom That is the bromo- 10- of 9- (4- cyano) benzene anthracene 0.21mmol, catalyst four (triphenyl) phosphine palladium 0.03mmol, toluene 15mL, ethyl alcohol 5mL, K2CO38.4mmol (uses 5mL distilled water wiring solution-forming), reaction flask is added to, under the protection of nitrogen, in 100 DEG C of reflux 12h.Instead After answering, methanol hot wash is filtered, re crystallization from toluene, and distillation obtains final product.Yield 50%.Molecular formula is C48H29NO, Theoretical value is 635.22, actual value 635.
Embodiment 10
In steps 1 and 2 and step 3 3. with embodiment 1.
4. by -10 borate anthracene 1mmol, 1- chlorine-4-iodine benzene 1mmol of 9- (4- methoxyl group), tetrakis triphenylphosphine palladium 0.1mmol, toluene 40mL, ethyl alcohol 10mL and K2CO340mmol (with 10mL distilled water wiring solution-forming) is added to reaction flask, then System is vacuumized, the protection of nitrogen, reacts 12 hours, after reaction, extract, revolving at 100 DEG C, column chromatography (eluant, eluent: N-hexane/methylene chloride=1:1), it is recrystallized to give product A6.Yield 69%.5. by A60.5mmol joins pinacol borate 1.5mmol, acid chloride 0.05mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.1mmol, potassium acetate 1.5mmol, Isosorbide-5-Nitrae-dioxane 25mL is added in reaction flask, is then vacuumized to system, the protection of nitrogen, is reacted 12 hours at 90 DEG C, After reaction, it extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give product B6.It produces Rate 65%.6. obtaining final product f by Suzuki (Suzuki) coupling reaction: by B60.25mmol, step 2 products therefrom, that is, 9- Bromo- 10- (4- cyano) benzene anthracene 0.21mmol, catalyst four (triphenyl) phosphine palladium 0.03mmol, toluene 15mL, ethyl alcohol 5mL, K2CO38.4mmol (uses 5mL distilled water wiring solution-forming), reaction flask is added to, under the protection of nitrogen, in 100 DEG C of reflux 12h.Instead After answering, methanol hot wash is filtered, re crystallization from toluene, and distillation obtains final product.Yield 50%.Molecular formula is C48H31NO, Theoretical value is 637.24, actual value 637.
Embodiment 11
In steps 1 and 2 and step 3 3. with embodiment 1.
4. by -10 borate anthracene 1mmol, 1- chlorine-4-iodine difluorobenzene 1mmol of 9- (4- methoxyl group), tetrakis triphenylphosphine palladium 0.1mmol, toluene 40mL, ethyl alcohol 10mL and K2CO340mmol (with 10mL distilled water wiring solution-forming) is added to reaction flask, then System is vacuumized, the protection of nitrogen, reacts 12 hours, after reaction, extract, revolving at 100 DEG C, column chromatography (eluant, eluent: N-hexane/methylene chloride=1:1), it is recrystallized to give product A7.Yield 69%.5. by A70.5mmol joins pinacol borate 1.5mmol, acid chloride 0.05mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.1mmol, potassium acetate 1.5mmol, Isosorbide-5-Nitrae-dioxane 25mL is added in reaction flask, is then vacuumized to system, the protection of nitrogen, is reacted 12 hours at 90 DEG C, After reaction, it extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give product B7.It produces Rate 65%.6. obtaining final product g by Suzuki (Suzuki) coupling reaction: by B70.25mmol, step 2 products therefrom, that is, 9- Bromo- 10- (4- cyano) benzene anthracene 0.21mmol, catalyst four (triphenyl) phosphine palladium 0.03mmol, toluene 15mL, ethyl alcohol 5mL, K2CO38.4mmol (uses 5mL distilled water wiring solution-forming), reaction flask is added to, under the protection of nitrogen, in 100 DEG C of reflux 12h.Instead After answering, methanol hot wash is filtered, re crystallization from toluene, and distillation obtains final product.Yield 58%.Molecular formula is C48H29F2NO, Theoretical value is 673.22, actual value 673.
Embodiment 12
In steps 1 and 2 and step 3 3. with embodiment 1.
4. by two trifluoromethylbenzene 1mmol of -10 borate anthracene 1mmol, 1- chlorine-4-iodine of 9- (4- methoxyl group), four (triphenyls Phosphine) palladium 0.1mmol, toluene 40mL, ethyl alcohol 10mL and K2CO340mmol (with 10mL distilled water wiring solution-forming) is added to reaction flask, Then system is vacuumized, the protection of nitrogen, reacts 12 hours, after reaction, extract, revolving at 100 DEG C, column chromatography (is washed De- agent: n-hexane/methylene chloride=1:1), it is recrystallized to give product A8.Yield 69%.5. by A80.5mmol, where is connection boric acid frequency Alcohol ester 1.5mmol, acid chloride 0.05mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.1mmol, potassium acetate 1.5mmol, Isosorbide-5-Nitrae-dioxane 25mL are added in reaction flask, then vacuumize to system, the protection of nitrogen, react at 90 DEG C It 12 hours, after reaction, extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give production Object B8.Yield 65%.6. obtaining final product h by Suzuki (Suzuki) coupling reaction: by B80.25mmol, step 2 products therefrom That is the bromo- 10- of 9- (4- cyano) benzene anthracene 0.21mmol, catalyst four (triphenyl) phosphine palladium 0.03mmol, toluene 15mL, ethyl alcohol 5mL, K2CO38.4mmol (uses 5mL distilled water wiring solution-forming), reaction flask is added to, under the protection of nitrogen, in 100 DEG C of reflux 12h.Instead After answering, methanol hot wash is filtered, re crystallization from toluene, and distillation obtains final product.Yield 56%.Molecular formula is C48H29F2NO, Theoretical value is 673.22, actual value 673.
Embodiment 13
In steps 1 and 2 and step 3 3. with embodiment 1.
4. by -10 borate anthracene 1mmol, 1- chlorine-4-iodine dicyanobenzenes 1mmol of 9- (4- methoxyl group), four (triphenylphosphines) Palladium 0.1mmol, toluene 40mL, ethyl alcohol 10mL and K2CO340mmol (with 10mL distilled water wiring solution-forming) is added to reaction flask, so System is vacuumized afterwards, the protection of nitrogen, reacts 12 hours, after reaction, extract, revolving at 100 DEG C, column chromatography (elution Agent: n-hexane/methylene chloride=1:1), it is recrystallized to give product A9.Yield 69%.5. by A90.5mmol joins boric acid pinacol Ester 1.5mmol, acid chloride 0.05mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.1mmol, potassium acetate 1.5mmol, Isosorbide-5-Nitrae-dioxane 25mL are added in reaction flask, then vacuumize to system, the protection of nitrogen, react at 90 DEG C It 12 hours, after reaction, extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give production Object B9.Yield 65%.6. obtaining final product i by Suzuki (Suzuki) coupling reaction: by B90.25mmol, step 2 products therefrom That is the bromo- 10- of 9- (4- cyano) benzene anthracene 0.21mmol, catalyst four (triphenyl) phosphine palladium 0.03mmol, toluene 15mL, ethyl alcohol 5mL, K2CO38.4mmol (uses 5mL distilled water wiring solution-forming), reaction flask is added to, under the protection of nitrogen, in 100 DEG C of reflux 12h.Instead After answering, methanol hot wash is filtered, re crystallization from toluene, and distillation obtains final product.Yield 56%.Molecular formula is C50H29N3O, Theoretical value is 687.23, actual value 687.
Embodiment 14
In steps 1 and 2 and step 3 3. with embodiment 1.
4. by -10 borate anthracene 1mmol, 1- chlorine-4-iodine dialdehyde-based benzene 1mmol of 9- (4- methoxyl group), four (triphenylphosphines) Palladium 0.1mmol, toluene 40mL, ethyl alcohol 10mL and K2CO340mmol (with 10mL distilled water wiring solution-forming) is added to reaction flask, so System is vacuumized afterwards, the protection of nitrogen, reacts 12 hours, after reaction, extract, revolving at 100 DEG C, column chromatography (elution Agent: n-hexane/methylene chloride=1:1), it is recrystallized to give product A10.Yield 69%.5. by A100.5mmol, where is connection boric acid frequency Alcohol ester 1.5mmol, acid chloride 0.05mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.1mmol, potassium acetate 1.5mmol, Isosorbide-5-Nitrae-dioxane 25mL are added in reaction flask, then vacuumize to system, the protection of nitrogen, react at 90 DEG C It 12 hours, after reaction, extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give production Object B10.Yield 65%.6. obtaining final product j by Suzuki (Suzuki) coupling reaction: by B100.25mmol is produced obtained by step 2 The bromo- 10- of object, that is, 9- (4- cyano) benzene anthracene 0.21mmol, catalyst four (triphenyl) phosphine palladium 0.03mmol, toluene 15mL, ethyl alcohol 5mL, K2CO38.4mmol (uses 5mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, flows back at 100 DEG C 12h.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 56%.Molecular formula is C50H31NO3, theoretical value 693.23, actual value 693.
Embodiment 15
With embodiment 1.(1. middle 4- methoxyphenylboronic acid, the 4- cyano base phenyl boric acid of steps 1 and 2 need to only be replaced with respectively 4- methylphenylboronic acid, 4- fluorobenzoic boric acid, then corresponding functional group is also substituted accordingly in following step)
Embodiment 16
With embodiment 1.(1. middle 4- methoxyphenylboronic acid, the 4- methoxyphenylboronic acid of steps 1 and 2 need to only be replaced with respectively 4. 1- chlorine-4-iodine -2,5- dimethyl benzene in is replaced with 1- chlorine-4-iodine-by 4- ethyl phenyl boric acid, 4- trifluoromethylbenzene boronic acid 2,5- dimethyl benzenes, then the involved functional group for needing to be replaced also is substituted accordingly in following step)
Embodiment 17
With embodiment 1.(1. middle 4- methoxyphenylboronic acid, the 4- methoxyphenylboronic acid of steps 1 and 2 need to only be replaced with respectively 4- ethoxybenzene boric acid, phenyl boric acid, then the involved functional group for needing to be replaced also is substituted accordingly in following step)
Embodiment 18
With embodiment 1.(1. middle 4- methoxyphenylboronic acid, the 4- methoxyphenylboronic acid of steps 1 and 2 need to only be replaced with respectively 4. 1- chlorine-4-iodine -2,5- dimethyl benzene in is replaced with chlorine-4-iodine -2 1- by 4- tert-butylbenzeneboronic acid, 4- aldehyde radical phenyl boric acid, 5- dimethyl benzene, then the involved functional group for needing to be replaced also is substituted accordingly in following step)
After tested, the thermogravimetric map of the target product a of above-described embodiment 1-3 is as shown in Fig. 5, can obtain from thermogravimetric map The thermal decomposition temperature of a is 370 DEG C out, illustrates that material a has good thermal stability.
After tested, the target product a of above-described embodiment 1-3 is respectively in hexamethylene, toluene and 1,2- dichloroethane solution (~10-6mol L-1) and UV absorption and fluorescence emission spectrum on film: Fig. 6 and Fig. 7 has made from embodiment 1-3 respectively Machine blue fluorescent material is the Absorption and emission spectra in different solutions；Fig. 8 is respectively organic blue made from embodiment 1-3 Absorption (square) and transmitting (triangle) spectrum of the fluorescent material in film: as can be drawn from Figure 6, a is in different solvents Absorption peak is respectively 357/373/395,355/377/397,356/378/398nm, and the feature that these peaks are from anthracene is inhaled Receive peak.It does not change a lot from the polarity of solvent is ascending, illustrates that the dipole moment of molecule ground state varies less.From Fig. 7 It can be concluded that emission peak of the e in different solvents is respectively 413,420,423nm, wherein with the increase of solvent polarity have it is red Move phenomenon, and acromion gradually weakens, due in excitation state intramolecular dipole moment variation.As can be drawn from Figure 8, e It absorbs and emission peak is respectively the characteristic absorption and emission peak that these peaks 361/380/401,426nm are from anthracene.
Application examples 1
The preparation of organic electroluminescence device 1
The present embodiment prepares organic electroluminescence device 1 by the following method:
A) it cleans ITO (tin indium oxide) glass: using dish washing liquid, deionized water, THF, isopropanol solvent ultrasonic cleaning respectively Ito glass is distinguished 20 minutes, then handles 10 minutes in plasma cleaner, and sheet resistance is 15-20 Ω/sq；
B) the vacuum evaporation hole transmission layer NPB on anode ito glass, with a thickness of 30nm；
C) the vacuum evaporation electronic barrier layer TCTA on hole transmission layer NPB, with a thickness of 10nm.
D) on electronic barrier layer TCTA, vacuum evaporation luminescent layer compound a, with a thickness of 20nm；
E) on luminescent layer, TPBi of the vacuum evaporation as electron transfer layer, with a thickness of 40nm；
F) on electron transfer layer, vacuum evaporation electron injecting layer LiF, with a thickness of 1nm；
G) on electron injecting layer, vacuum evaporation cathode Al, with a thickness of 100nm.
The structure of organic electroluminescence device 1 be successively lamination ITO (110nm) */NPB (30nm)/TCTA (10nm)/ EML:[a(20nm)]/TPBi(40nm)/LiF(1nm)/Al(100nm)。
Wherein material molecule structural formula used in device 1 (luminescent layer is compound a) is as shown in table 2 below:
Material molecule structural formula used in 2 device 1 of table
After tested, shine (EL) map, Current density-voltage-brightness (Cd-V-L) graphs, the electric current of device 1 are close Degree-current efficiency (Cd-CE-PE), current density-external quantum efficiency (Cd-EQE) graphs respectively as Fig. 9, Figure 10, Shown in Figure 11, Figure 12: as can be drawn from Figure 9: device 1 comes from shining for material a, and the spectrum under different current densities It is constant, illustrate that its electroluminescent spectrum has good stability.As can be drawn from Figure 11: the maximum current efficiency of device 1 is 9.33Cd/A is obtained from Figure 11,12: the efficiency roll-off very little of device 1 illustrates that device efficiency stability is good.
The photoelectric properties parameter of device 1 is as shown in table 3 below
The photoelectric parameter of 3 electroluminescent device 1 of table
In upper table, [a] device name, [b] luminescent layer, [c] represents ignition voltage, and [d] represents maximum current efficiency, [e] Maximum power efficiency is represented, [f] represents maximum external quantum efficiency, and [g] represents the maximum internal quantum effect in 500cd/A Rate, [h] represent excitation purity coordinate (CIE).
Organic assembly ignition voltage based on material of the present invention is 3.6V, realizes the undoped blue of low voltage drive OLED device.Organic luminescent device of the invention can be used in Electrophtography photosensor, flat-panel screens, duplicator, printing The light sources such as machine, LCD backlight source, timer and various luminescent devices, various display devices, various marks, various biographies Sensor, various doorplates etc..
Materials synthesis prepared by the present invention is at low cost, yield is high, the features such as being easily purified, under solution or filminess all Strong blue fluorescent emissions are presented.Material prepared by the present invention is applied in OLED device, and blue emission is realized, maximum EQE is 4.99%.Material prepared by the present invention has centainly in organic photoelectrics fields such as organic display, organic solid-state illuminations Application value and market prospects.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of organic blue fluorescent material of D-A type based on dianthracene, it is characterised in that: the D-A type based on dianthracene is organic The chemical structural formula of blue fluorescent material is as follows:
Wherein, R1For the group of donor properties, R2For the group of electrophilic characteristic, R3For the group or suction electricity of donor properties The group of sub-feature.
2. the organic blue fluorescent material of a kind of D-A type based on dianthracene according to claim 1, it is characterised in that: power supply The group of sub-feature is H, CH3、OCH3、C2H5、OC2H5Or C (CH3)3Any one of；The group of electrophilic characteristic is F, CF3、 Any one of CN or CHO.
3. a kind of preparation method of the organic blue fluorescent material of D-A type based on dianthracene, it is characterised in that: the following steps are included: Substance B and the bromo- 10- of 9- (4- inhales electricity and replaces) benzene anthracene are carried out Suzuki coupling reaction and organic blue fluorescent material, substance B are made For 4- [10- (4- power supply replaces) benzene anthracene] -2,5- di-substituted-phenyl borate；The disubstituted phenyl of 2,5- in substance B is 2, 5- 3,5-dimethylphenyl, 2,5- Dimethoxyphenyl, 2,5- diethyl phenyl, 2,5- diethoxy phenyl, 2,5- di-tert-butyl In base, 2,5- dihydro phenyl, 2,5- difluorophenyl, bis- trifluorophenyl of 2,5-, 2,5- dicyano phenyl or 2,5- dialdehyde-based phenyl It is any；Suction electricity substituent group in the bromo- 10- of 9- (4- inhales electricity and replaces) benzene anthracene is any one of electrophilic characteristic group, is inhaled Characteristic electron group includes H, F, CF3, CN and CHO.
4. the preparation method of the organic blue fluorescent material of the D-A type according to claim 3 based on dianthracene, feature exist In: substance B is that 4- [10- (4- power supply replaces) benzene anthracene] -2,5- bis- replaces chlorobenzene to obtain by acid esterification, specific steps packet It includes: 4- [10- (4- power supply replaces) benzene anthracene] -2,5- two is replaced into chlorobenzene, connection boric acid pinacol ester, acid chloride, 2- dicyclohexyl Phosphine -2 ', 6 '-dimethoxy-biphenyls, potassium acetate and 1,4- dioxane press (0.5~2) mmol:(1.5~6) mmol:(0.05 ~0.2) mmol:(0.1~0.4) mmol:(1.5~6) mmol:(25~90) mL mixing, 95 under the conditions of atmosphere of inert gases ~105 DEG C are reacted 12~18 hours, and purification obtains substance B after reaction；4- [10- (4- power supply replaces) benzene anthracene] -2,5- two Replacing the power supply substituent group in chlorobenzene is any one of donor properties group, and donor properties group includes CH3、OCH3、 C2H5、OC2H5With C (CH3)3。
5. the preparation method of the organic blue fluorescent material of the D-A type according to claim 4 based on dianthracene, feature exist In: 4- [10- (4- power supply replaces) benzene anthracene] -2,5- two replaces chlorobenzene to be by 9- (4- power supply substituted-phenyl) -10 borate anthracenes Carry out what Suzuki coupling reaction obtained, specific preparation step includes: by 9- (4- power supply substituted-phenyl) -10 borate anthracenes, 1- Chlorine-4-iodine -2,5- disubstituted benzenes, tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3By (1~3) mmol:(1~3) mmol: (0.1~0.3) mmol:(40~120) mL:(10~30) mL:(40~120) mmol mixing, under the conditions of atmosphere of inert gases, 100~110 DEG C of purifications after reaction 12~24 hours obtain 4- [10- (4- power supply replace) benzene anthracene] -2,5- two and replace chlorobenzene.
6. the preparation method of the organic blue fluorescent material of the D-A type according to claim 5 based on dianthracene, feature exist In: 9- (4- power supply substituted-phenyl) -10 borate anthracenes are obtained by the bromo- 10- of 9- (4- power supply replaces) benzene anthracene acid esterification, Specific steps include: by the bromo- 10- of 9- (4- power supply replace) benzene anthracene, isopropyl oxygen borate, n-BuLi and THF by (4.22~ 12.66) mmol:(6.32~18.96) mmol:(7.2~21.6) mmol:(50~150) mL mixing, in atmosphere of inert gases item It is reacted at room temperature under part, purification obtains 9- (4- power supply substituted-phenyl) -10 borate anthracenes after reaction.
7. the preparation method of the organic blue fluorescent material of the D-A type according to claim 6 based on dianthracene, feature exist In: the bromo- 10- of 9- (4- power supply replaces) benzene anthracene is to be obtained by 9- (4- power supply replaces) benzene anthracene by bromination, specific steps packet It includes: by 9- (4- power supply replaces) benzene anthracene, N- bromo-succinimide and N,N-dimethylformamide by (2.5~10) mmol:(3 ~12) mmol:(40~150) mL mixing, under the conditions of atmosphere of inert gases, 85~90 DEG C are reacted 1~2 hour, and purification obtains The bromo- 10- of 9- (4- power supply replaces) benzene anthracene；
9- (4- power supply replaces), benzene anthracene was that 9- bromine anthracene is obtained by Suzuki coupling reaction, and specific preparation step includes: by 9- Bromine anthracene, 4- power supply replace phenyl boric acid, tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3According to (5~20) mmol:(7.5~30) Mmol:(0.25~1) mmol:(50~200) mL:(15~60) mL:(50~200) mmol mixing, in atmosphere of inert gases item Under part, 100~110 DEG C of purifications after reaction 12~24 hours obtain 9- (4- power supply replace) benzene anthracene.
8. the preparation method of the organic blue fluorescent material of the D-A type according to claim 3 based on dianthracene, feature exist In: the bromo- 10- of 9- (4- inhales electricity and replaces) benzene anthracene is to be obtained by 9- (4- inhales electricity and replaces) benzene anthracene by bromination, specific steps packet It includes: by 9- (4- inhales electricity and replaces) benzene anthracene, N- bromo-succinimide and N,N-dimethylformamide by (2.5~10) mmol:(3 ~12) mmol:(40~150) mL mixing, under the conditions of atmosphere of inert gases, 85~90 DEG C are reacted 1~2 hour, and purification obtains The bromo- 10- of 9- (4- inhales electricity and replaces) benzene anthracene；
9- (4- inhales electricity and replaces) benzene anthracene is that 9- bromine anthracene is obtained by Suzuki coupling reaction, and specific preparation step includes: by 9- Bromine anthracene, 4- inhale electric substituent group phenyl boric acid, tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3According to (5~20) mmol:(7.5~ 30) mmol:(0.25~1) mmol:(50~200) mL:(15~60) mL:(50~200) mmol mixing, in atmosphere of inert gases Under the conditions of, 100~110 DEG C of purifications after reaction 12~24 hours obtain 9- (4- inhale electricity replace) benzene anthracene.
9. the preparation method of the organic blue fluorescent material of the D-A type according to claim 3 based on dianthracene, feature exist In: in Suzuki coupling reaction, it has been additionally added catalyst, solvent and activator；Wherein, the bromo- 10- of substance B, 9- (4- substituted benzene Base) ratio between anthracene, catalyst, solvent and activator is (0.25~1) mmol:(0.21~0.84) mmol:(0.03~ 0.12) mmol:(25~100) mL:(8.4~33.6) mmol；Catalyst uses tetrakis triphenylphosphine palladium；Solvent using toluene and The mixed solvent of homogeneous solvent ethyl alcohol；Activator uses K2CO3Solution；
Suzuki coupling reaction at a temperature of 100~110 DEG C, is reacted 12~24 hours under nitrogen gas ambient conditions.
10. the organic blue fluorescent material of a kind of D-A type based on dianthracene as described in claim 1 is in organic electroluminescent LED Application in part.
CN201811620505.2A 2018-12-28 2018-12-28 Organic blue fluorescent material of a kind of D-A type based on dianthracene and its preparation method and application Pending CN109678759A (en)

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