CN109970710A - The derivative preparation method and its electroluminescent application of a kind of indone and pyridine - Google Patents
The derivative preparation method and its electroluminescent application of a kind of indone and pyridine Download PDFInfo
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Abstract
The derivative preparation method and its electroluminescent application of a kind of indone and pyridine, belong to photoluminescent techniques field.These derivatives be using indone and pyridine as molecule electron-withdrawing group, and the 6,7 of electron-withdrawing group, 8, the functional group of 9 connections different structures and different conjugated degrees, synthetic method is: using 2- chloro-3-pyridyl aldehyde as raw material, by coupling, the series reactions such as oxidation, synthesis obtain different location bromo indone and pyridine luminous nucleon, then again with carbazole, triphenylamine, dimethyl acridinium carries out Suzuki coupling, and synthesis obtains target product.These derivatives have strong absorption in ultraviolet-visible light area, and its weak solution emits hyperfluorescence, and launch wavelength can be used as luminescent material applied to organic electroluminescence device between 500-650nm.
Description
Technical field
The present invention relates to the preparation methods and its electroluminescent application of a kind of indone and pyridine derivate, belong to Organic Electricity
Photoluminescence field.
Background of invention
The development of new century information technology is maked rapid progress.Efficient and accurate information collection, quick information processing are highly dense
The information of degree stores, and it is the target of people's pursuit that the information of large capacity, which is transmitted, and information high-definition is shown, information is shown
Technology plays and its important role.
Currently, more mature display has cathode-ray tube (Cathode Ray Tube, CRT), plasma to show
Device (Plasma Display Panel, PDP) and liquid crystal display (Liquid Crystal Display, LCD).Although one
They possess the excellent performance that can not be substituted in the timing phase, but these display devices all have the defects that it is different degrees of so that its
Using the demand for being unable to satisfy people.Such as: CRT is more heavy, and driving voltage is high, there is serious radiation；PDP production is complicated and more
Valuableness, LCD response speed is slow, narrow viewing angle, belongs to passive shine etc..
In contrast, organic electroluminescence device (Organic Light-emitting Diodes, OLEDs) is due to tool
Have low driving voltage, actively shine, wide viewing angle, fast-response, low in cost, simple process, it is full-color can Flexible Displays and resistance to evil
The advantages that bad environment, becomes the outstanding person in display field, and then causes the extensive concern in each field.
Earliest electroluminescent organic material is fluorescent material.But since electroluminescent particularity is to be electrically excited production
The ratio of raw singlet excitons and triplet exciton quantity is 1:3, i.e. the exciton in singlet state accounts for all exciton quantity
25%.Fluorescent material can only utilize the exciton de excitation hair for being in singlet state to realize and shine, therefore fluorescent material theoretically imitate by interior quantum
Rate highest only has 25%.Then, the discovery and research of phosphorescent glow have pushed the development of phosphor material.Not only due to phosphor material
It only can use triplet exciton de excitation hair and generate phosphorescence, can also be converted into using singlet excitons by intersystem crossing triple
State exciton realizes shining for theoretical internal quantum efficiency 100%.But the cost of phosphor material valuableness and serious exciton annihilation are existing
As limiting its development.In this context, thermotropic delayed fluorescence (Thermally Activated Delayed
Fluorescence) material (abbreviation TADF material) comes into being.
In the molecule with TADF property, molecule can use inverse intersystem crossing and convert singlet state for triplet exciton
Exciton, which is realized, to shine, and can guarantee internal quantum efficiency similar with phosphorescence in this way, and be avoided that serious exciton annihilation phenomenon.
The molecule of TADF property causes the great attention of related scientific research personnel in recent years.Such as a system of Adachi in 2012 et al. report
It arranges orange to sapphire TADF molecule, there is high luminous efficiency；The a series of of Lee in 2013 et al. report are based on disliking two
The TADF molecule of azoles kernel, obtains higher fluorescence quantum efficiency；Domestic scholars also have developed a series of be based on 2014
The TADF molecule of phosphoryl, excellent performance and novel design concept also obtain certain concern.Although big in recent years
The novel molecular of amount is developed, and still, the molecule for meeting TADF property has to take into account HOMO and LUMO electron cloud larger
The two contradictory conditions each other of the separation of degree and higher rate of irradiation constant, therefore, the TADF theory of function admirable and
Material up for deeper into research.
Summary of the invention
The purpose of the present invention mainly introduces the group of different electron supplying capacities in the different location of indone and pyridine groups,
To adjust the luminescent properties of molecule, exploration synthesizes a series of HOMO that can be improved radiation transistion rate and make molecule
Properly sepd compound is carried out with LUMO track, to obtain the electroluminescent organic material of excellent.
The technical scheme is that a kind of indone and pyridine derivate, it is characterized in that: the general structure of the analog derivative
It is as follows:
Wherein, D is selected from: D1: carbazole, D2: diphenylamines, D3: dimethyl acridinium, the following group of structural formula:
The present invention provides a kind of preparation method for preparing indone and pyridine derivate, and specific reaction implementation steps are as follows:
By bromo indone and pyridine, intermediate M, palladium catalyst, alkali are added organic solvent, the bromo indone and pyridine,
The molar ratio of boric acid, palladium catalyst, alkali containing electron-donating group is 1:1~1.2:0.05~0.08:4~5, in nitrogen protection
Under, be heated to 60~80 DEG C reaction 12~for 24 hours.After reaction, reaction solution is poured into saturated salt solution, then respectively with two
Chloromethanes, ethyl acetate carry out liquid separation extraction, and decompression steams solvent, and crude product chromatographs to obtain target product through column.
Wherein, the palladium catalyst is tetrakis triphenylphosphine palladium, bi triphenyl phosphorus palladium chloride or [1,1'- bis- (diphenyl
Phosphino-) ferrocene] palladium chloride；The aqueous slkali is K2CO3、K3PO4、Na2CO3, CsF or Cs2CO3Solution；The solvent is first
Benzene/ethanol/water, toluene and methanol/water or glycol dimethyl ether/water.The intermediate R-Br is 5- bromopyridine -3- hexichol phosphono
One of the bromo- 5- pyrazoles yl pyridines of yl pyridines, 3-, the bromo- 5- of 3- (1,2,4- triazolyl) pyridine or the bromo- 3,3 '-bipyridyl of 5-.
The present invention provides the preparation method of a kind of indone and pyridine derivate, the indone and pyridine intermediate W of different location:
6- indone and pyridine, 7- indone and pyridine, 8- indone and pyridine, 6- indone and pyridine, preparation process the following steps are included:
Specific implementation step are as follows:
The synthesis of intermediate A: being put into 2- chloro-3-pyridyl aldehyde (5g, 35.5mmol) in there-necked flask, adds 2- bromobenzene boron
Acid or 3- bromobenzeneboronic acid or 4- bromobenzeneboronic acid (8.5g, 42.5mmol), tetrakis triphenylphosphine palladium (2.05g, 1.8mmol) He Shuding
Toluene 100mL is added in potassium alcoholate (3.98g, 35.5mmol), and ethyl alcohol 20mL makees solvent, is heated to 80 DEG C, reacts 3-4h.Reaction knot
Shu Hou pours into reaction solution in saturated sodium chloride solution, is extracted with dichloromethane (3 × 15mL), and crude product is by column chromatography point
White solid is not obtained.
The synthesis of intermediate W: the intermediate A 1 that will be obtained, A2 or A3 (5g, 19.2mmol) are added in there-necked flask, then
It is added TBHP (21ml, 153.6mmol), 50mL toluene is added and makees solvent, under nitrogen protection, be heated to 100 DEG C, react 24-
48h.After reaction, reaction solution is poured into saturated sodium chloride solution, (3 × 15mL) is extracted with dichloromethane and with anhydrous sulphur
Sour magnesium is dry, solvent is removed under reduced pressure, crude product obtains yellow solid through column chromatography for separation.
One kind indone of the present invention and pyridine derivate are applied to prepare electroluminescent device as luminescent material.
Indone of the invention and pyridine derivate, since the introducing of pyridine groups can increase the electrophilic energy of acceptor groups
Power effectively reduces lumo energy, while introducing the group of different electron supplying capacities, to adjust the forbidden bandwidth of molecule, thus
The luminosity of molecule is adjusted, and then realizes fluorescent emission of the molecule from green light to feux rouges；Also, in the difference of indone and pyridine
Position introduces electron-donating group, studies influence of the donor the position of substitution for mulecular luminescence.Wherein, with triphenylamine, carbazole and a word used for translation
Pyridine is electron-donating group, in molecule 7-TPA, 7-PhCz and 7-PhDMAC of 7 substitutions of indone and pyridine, in dilute toluene solution
Middle presence absorbs by force and fluorescence, glow peak position are respectively 618,533 and 616nm, realizes the fluorescence from green light to feux rouges
Transmitting.The calculated result of GAUSSIAN 09 shows that the molecule of whichsoever substituent group, HOMO and LUMO electron cloud are all deposited
Preferably separating.Wherein, electroluminescent device is prepared by luminescent material of 7-TPA, to open bright voltage reachable for the device minimum
3.5V, maximum current efficiency reach 2.3cd/A.
Detailed description of the invention
Fig. 1 is that compound 7-TPA passes through the HOMO being calculated of Gaussian 09 and LUMO orbit distribution figure.
Fig. 2 is that compound 7-PhCz passes through the HOMO being calculated of Gaussian 09 and LUMO orbit distribution figure.
Fig. 3 is that compound 7-PhDMAC passes through the HOMO being calculated of Gaussian 09 and LUMO orbit distribution figure.
Fig. 4 is uv-visible absorption spectra and fluorescence emission spectrum of the compound 7-TPA in toluene solution.
Fig. 5 is uv-visible absorption spectra and fluorescence emission spectrum of the compound 7-PhCz in toluene solution.
Fig. 6 is uv-visible absorption spectra and fluorescence emission spectrum of the compound 7-PhDMAC in toluene solution.
Fig. 7 is Current density-voltage-brightness curve using compound 7-TPA as the electroluminescent device of luminescent material.
Fig. 8 is using compound 7-TPA as the efficiency curve of the electroluminescent device of luminescent material.
Fig. 9 is using compound 7-TPA as the electroluminescent spectrum of the electroluminescent device of luminescent material.
Specific embodiment
Embodiment 1
It is put into 2- chloro-3-pyridyl aldehyde (5g, 35.5mmol) in there-necked flask, adds 2- bromobenzeneboronic acid or 3- bromobenzeneboronic acid
Or 4- bromobenzeneboronic acid (8.5g, 42.5mmol), tetrakis triphenylphosphine palladium (2.05g, 1.8mmol) and potassium tert-butoxide (3.98g,
35.5mmol), toluene 100mL is added, ethyl alcohol 20mL makees solvent, is heated to 80 DEG C, reacts 3-4h.After reaction, it will react
Liquid pours into saturated sodium chloride solution, is extracted with dichloromethane (3 × 15mL), and anhydrous magnesium sulfate is dry, and crude product passes through column layer
Analysis respectively obtains white solid.
A1: yield 59%, TOF-EI-MS:260.9792 [M+]；
A2: yield 63%, TOF-EI-MS:260.9778 [M+]；
A3: yield 52%, TOF-EI-MS:260.9792 [M+].
The intermediate A 1 that will be obtained, A2 or A3 (5g, 19.2mmol) are added in there-necked flask, then be added TBHP (21ml,
153.6mmol), 50mL toluene is added and makees solvent, under nitrogen protection, be heated to 100 DEG C, react 24-48h.After reaction, will
Reaction solution pours into saturated sodium chloride solution, and (3 × 15mL) is extracted with dichloromethane and is dried with anhydrous magnesium sulfate, is removed under reduced pressure
Solvent, crude product obtain yellow solid through column chromatography for separation.
W1: yield 51%, TOF-EI-MS:258.9631 [M+]；
W2: yield 65%, TOF-EI-MS:258.9629 [M+]；
W3: yield 40%, TOF-EI-MS:258.9639 [M+]；
W4: yield 58%, TOF-EI-MS:258.9632 [M+].
Carbazole (10g, 59.8mmol) is respectively charged into there-necked flask, to bromo-iodobenzene (18.6g, 66mmol), potassium carbonate
It is dry to be dissolved in 50mL for (16.5g, 119.6mmol), Phen (2.154g, 12mmol), cuprous iodide (2.27g, 12mmol)
DMF in, be heated under nitrogen protection 165 DEG C reaction for 24 hours.After reaction, reaction solution is poured into saturated sodium chloride solution,
Suction filtration obtains crude product, obtains midbody compound M1, yield 78% through column chromatography for separation.
Be separately added into there-necked flask intermediate M1 (5g, 15.5mmol), connection pinacol borate (4.73g,
18.6mmol), triphenylphosphine palladium (0.545g, 0.8mmol), triphenylphosphine (0.41g, 1.6mmol), potassium acetate
(6.08g, 62mmol) is added 50mL toluene and makees solvent, under nitrogen protection, be heated to 110 DEG C of reaction 12h.After reaction, instead
Liquid is answered to pour into saturated sodium chloride solution, methylene chloride extracts (3 × 15mL), and anhydrous magnesium sulfate is dry, solvent is removed under reduced pressure, slightly
Product obtains intermediate M2, yield 65% by column chromatography for separation.
Intermediate W (1g, 3.9mmol) respectively is added respectively in there-necked flask, adds M2 (1.57g, 4.3mmol), four
25mL toluene is added in (triphenylphosphine) palladium (0.223g, 0.2mmol), 2mol/L solution of potassium carbonate (9.7ml, 69.8mmol),
5mL ethanol as solvent under nitrogen protection, is heated to 80 DEG C of reaction 12h.After reaction, reaction solution is poured into saturated brine,
Methylene chloride extracts (3 × 15mL), and anhydrous magnesium sulfate is dry, is removed under reduced pressure solvent, and crude product chromatographs to obtain yellow solid by column
Body.
6-PhCz: yield 50%, TOF-EI-MS:422.1430 [M+]；
7-PhCz: yield 64%, TOF-EI-MS:422.1426 [M+]；
8-PhCz: yield 66%, TOF-EI-MS:422.1425 [M+]；
9-PhCz: yield 53%, TOF-EI-MS:422.1428 [M+].
Embodiment 2
It is put into 2- chloro-3-pyridyl aldehyde (5g, 35.5mmol) in there-necked flask, adds 2- bromobenzeneboronic acid or 3- bromobenzeneboronic acid
Or 4- bromobenzeneboronic acid (8.5g, 42.5mmol), tetrakis triphenylphosphine palladium (2.05g, 1.8mmol) and potassium tert-butoxide (3.98g,
35.5mmol), toluene 100mL is added, ethyl alcohol 20mL makees solvent, is heated to 80 DEG C, reacts 3-4h.After reaction, it will react
Liquid pours into saturated sodium chloride solution, is extracted with dichloromethane (3 × 15mL), and crude product respectively obtains white admittedly by column chromatography
Body.
A1: yield 59%, TOF-EI-MS:260.9792 [M+]；
A2: yield 63%, TOF-EI-MS:260.9778 [M+]；
A3: yield 52%, TOF-EI-MS:260.9792 [M+].
The intermediate A 1 that will be obtained, A2 or A3 (5g, 19.2mmol) are added in there-necked flask, then be added TBHP (21ml,
153.6mmol), 50mL toluene is added and makees solvent, under nitrogen protection, be heated to 100 DEG C, react 24-48h.After reaction, will
Reaction solution pours into saturated sodium chloride solution, and (3 × 15mL) is extracted with dichloromethane and is dried with anhydrous magnesium sulfate, is removed under reduced pressure
Solvent, crude product obtain yellow solid through column chromatography for separation.
W1: yield 51%, TOF-EI-MS:258.9631 [M+]；
W2: yield 65%, TOF-EI-MS:258.9629 [M+]；
W3: yield 40%, TOF-EI-MS:258.9639 [M+]；
W4: yield 58%, TOF-EI-MS:258.9632 [M+].
It is separately added into intermediate W (1g 3.9mmol) in there-necked flask, adds triphenylamine boric acid (1.34g
4.6mmol), tetrakis triphenylphosphine palladium (0.223g 0.2mmol), 2mol/L solution of potassium carbonate (9.7ml 69.8mmol), are dissolved in
Toluene/ethanol=5:1, under nitrogen protection, 80 DEG C of reaction 12h.After reaction, reaction solution is poured into saturated brine, dichloro
Methane extracts 3 times (3 × 15mL), and anhydrous magnesium sulfate is dry, and crude product passes through column Chromatographic purification Orange red solid.
6-TPA: yield 52%, TOF-EI-MS:424.1586 [M+]；
7-TPA: yield 69%, TOF-EI-MS:424.1578 [M+]；
8-TPA: yield 68%, TOF-EI-MS:424.1583 [M+]；
9-TPA: yield 54%, TOF-EI-MS:424.1584 [M+].
Embodiment 3
It is put into 2- chloro-3-pyridyl aldehyde (5g, 35.5mmol) in there-necked flask, adds 2- bromobenzeneboronic acid or 3- bromobenzeneboronic acid
Or 4- bromobenzeneboronic acid (8.5g, 42.5mmol), tetrakis triphenylphosphine palladium (2.05g, 1.8mmol) and potassium tert-butoxide (3.98g,
35.5mmol), toluene 100mL is added, ethyl alcohol 20mL makees solvent, is heated to 80 DEG C, reacts 3-4h.After reaction, it will react
Liquid pours into saturated sodium chloride solution, is extracted with dichloromethane (3 × 15mL), and anhydrous magnesium sulfate is dry, and crude product passes through column layer
Analysis respectively obtains white solid.
A1: yield 59%, TOF-EI-MS:260.9792 [M+]；
A2: yield 63%, TOF-EI-MS:260.9778 [M+]；
A3: yield 52%, TOF-EI-MS:260.9792 [M+].
The intermediate A 1 that will be obtained, A2 or A3 (5g, 19.2mmol) are added in there-necked flask, then be added TBHP (21ml,
153.6mmol), 50mL toluene is added and makees solvent, under nitrogen protection, be heated to 100 DEG C, react 24-48h.After reaction, will
Reaction solution pours into saturated sodium chloride solution, and (3 × 15mL) is extracted with dichloromethane and is dried with anhydrous magnesium sulfate, is removed under reduced pressure
Solvent, crude product obtain yellow solid through column chromatography for separation.
W1: yield 51%, TOF-EI-MS:258.9631 [M+]；
W2: yield 65%, TOF-EI-MS:258.9629 [M+]；
W3: yield 40%, TOF-EI-MS:258.9639 [M+]；
W4: yield 58%, TOF-EI-MS:258.9632 [M+].
9,9- dimethyl acridinium (1g, 4.78mmol) is packed into there-necked flask, to bromo-iodobenzene (1.48g, 5.26mmol), vinegar
Sour palladium (0.14g, 0.15mmol), cesium carbonate (3.89g, 11.93mmol), tri-tert-butylphosphine tetrafluoroborate (0.044g,
0.15mmol), it is added in 30mL dry toluene, under nitrogen protection, is heated to 130 DEG C of reaction 12h.After reaction, it will react
Liquid pours into saturated brine, then carries out liquid separation extraction with methylene chloride, ethyl acetate respectively, and decompression steams solvent, crude product
It chromatographs to obtain intermediate M3, yield 63% through column.
Be separately added into there-necked flask intermediate M3 (5g, 15.5mmol), connection pinacol borate (4.73g,
18.6mmol), triphenylphosphine palladium (0.545g, 0.8mmol), triphenylphosphine (0.41g, 1.6mmol), potassium acetate
(6.08g, 62mmol), is dissolved in toluene, the lower 110 DEG C of reactions 12h of nitrogen protection.After reaction, reaction solution pours into saturation chlorine
Change in sodium solution, is spin-dried for sample preparation；It chromatographs to obtain intermediate M4, yield 54% by column.
It is sequentially added in 100mL two-mouth bottle intermediate W (1g 3.9mmol), 4- (9,9- dimethyl acridinium -10- base) benzene
Borate M4 (1.89g 4.6mmol), toluene (30mL), ethyl alcohol (6mL), wet chemical (2M, 9.7ml 69.8mmol)
With catalyst tetrakis triphenylphosphine palladium ((0.223g 0.2mmol).It is stirred at reflux 8h under nitrogen atmosphere.It is cold to the end of reacting
But it to room temperature, and is diluted with deionized water (20mL), separates organic layer, (3 × 20mL) is extracted with dichloromethane in water phase benefit.Merge
Organic layer is successively washed using saturated sodium-chloride water solution (50mL), and anhydrous magnesium sulfate is dry and filters.Vacuum distillation removes molten
After agent, obtained solid petroleum ether and ethyl acetate column chromatography, obtained solid are recrystallized three times repeatedly using chloroform/methanol, are obtained
Pulverulent solids.
6-PhDMAC: yield 50%, TOF-EI-MS:464.1892 [M+]；
7-PhDMAC: yield 62%, TOF-EI-MS:464.1897 [M+]；
8-PhDMAC: yield 50%, TOF-EI-MS:464.1893 [M+]；
9-PhDMAC: yield 50%, TOF-EI-MS:464.1889 [M+]
Embodiment 4
The embodiment 1 calculated by 09 program of Gauss is to the indone in embodiment 3 and the HOMO and LUMO of pyridine derivate
Cloud Distribution is as shown in Figs. 1-3.It can be seen that the series compound from HOMO the and LUMO Cloud Distribution figure of molecule
HOMO electron cloud is all distributed in carbazole, and on triphenylamine or acridine group, and LUMO electron cloud is then all distributed in electrophilic indenes
On ketone and pyridine groups.Meanwhile HOMO and LUMO have while separate again part overlapping again.
Embodiment 5
Under room temperature, using dry toluene as solvent, solution concentration is 1 × 10-5Mol/L determines 7- at room temperature
The uv-visible absorption spectra and fluorescence spectrum of TPA, 7-PhCz and 7-PhDMAC, as Figure 4-Figure 6.It can from Fig. 4
Out, compound 7-TPA has a strong absorption within the scope of 280-500nm, and the strong absorption at 300nm and 350nm belongs to compound
n-π*With π-π*The absorption of transition, and the strong absorption at 450nm belongs to the absorption of Intramolecular electron transfer state.It can be with from Fig. 5
Find out, compound 7-PhCz has strong absorption at 290-300nm, and the absorption at this belongs to the π-π of carbazole*Transition, 340nm are left
Right absorption peak belongs to the n- π of carbazole*Transition, and the weak absorbing peak in 410nm or so then belongs to Intramolecular electron transfer
The absorption of state.From fig. 6 it can be seen that 7-PhCz has strong absorption at 300nm, the absorption at this belongs to intramolecular conjugation knot
π-the π of structure*Transition, and the weak absorbing at 420nm then belongs to the absorption peak of Intramolecular electron transfer.All due to three molecules
It is to the molecule of receptor type, so it is with apparent Intramolecular electron transfer.Figures 4-6 it can be seen that three molecules are in first
Stronger fluorescent emission is shown in benzene weak solution, glow peak position is respectively 618,533 and 616nm, luminescent color point
It Wei not feux rouges, green light and feux rouges.By changing fluorescent emission of the different electron-donating group realizations from green light to feux rouges.
Embodiment 6
Using 7-TPA as luminescent material, material based on CBP prepares electroluminescent device ITO/ according to following device architecture
PEDOT:PSS/TAPC (20nm)/7-TPA:CBP (10wt%, 20nm)/TmPyPB (40nm)/LiF (1nm)/Al.Wherein,
PEDOT:PSS and LiF makees respectively as hole, electron injection material, TAPC as hole mobile material, TmPyPB (2.78eV)
For electron-transport and hole barrier materials.
Current density-voltage-brightness (J-V-B) curve and efficiency curve of the device are as shown in Figure 7 and Figure 8, You Tuke
Know, the bright voltage that opens of the device is 3.5V, when brightness is 9.647cd/m2When, it is 2.3cd/ which, which obtains maximum current efficiency,
A, when brightness is 3.264cd/m2When, it is 2.0lm/W which, which obtains maximum power efficiency,.The electroluminescent spectrum of the device is such as
Shown in Fig. 9.From electroluminescent spectrum as can be seen that the glow peak of the device only has the glow peak of guest materials 7-TPA, do not lead
Body material or other glow peaks.
In conclusion the series indone and pyridine derivate introduce different electron-donating groups in identical the position of substitution can
Realize the fluorescent emission from green light to feux rouges；It is larger that the calculated result of Gauss 09 shows that HOMO and the LUMO electron cloud of molecule have
The separation of degree, to guarantee that molecule has the energy level difference of lesser singlet state and triplet.Excellent electroluminescent of the Series Molecules
Light-emitting data shows molecule radiation transistion rate with higher.
Claims (5)
1. a kind of indone and pyridine derivate, it is characterised in that: the general structure of the analog derivative is as follows:
Wherein, D is used with flowering structure:
2. the preparation method of one kind indone according to claim 1 and pyridine derivate, which is characterized in that including following step
It is rapid:
By bromo indone and organic solvent, the bromo indone and pyridine is added in pyridine, intermediate M, palladium catalyst, alkali: containing confession
The boric acid of electron group: palladium catalyst: the molar ratio of alkali is 1:1-1.2:0.05-0.08:4-5, under nitrogen protection, heating
To 80-130 DEG C of reaction 12-24h；After reaction, reaction solution is poured into saturated salt solution, then respectively with methylene chloride,
Ethyl acetate carries out liquid separation extraction, and decompression steams solvent, and crude product chromatographs to obtain target product through column；
The palladium catalyst is tetrakis triphenylphosphine palladium, bi triphenyl phosphorus palladium chloride or [two cyclopentadienyl of 1,1'- bis- (diphenylphosphinos)
Iron] palladium chloride；The aqueous slkali is K2CO3、K3PO4、Na2CO3, CsF or Cs2CO3Solution；The solvent be toluene/ethanol/
Water mixed solution, toluene and methanol/water mixed solution or glycol dimethyl ether/water mixed solution；
The intermediate M is 4- (9H- carbazole -9- base) borate ester, 4- boric acid triphenylamine, 4- (9,9- dimethyl acridinium -10-
One of base) borate ester.
3. the preparation method of one kind indone according to claim 2 and pyridine derivate, it is characterised in that: the intermediate
The synthetic method of M comprises the steps of:
(1) preparation method of 4- (9H- carbazole -9- base) phenyl boric acid
It is respectively charged into carbazole in there-necked flask, to bromo-iodobenzene, potassium carbonate, Phen, cuprous iodide, is dissolved in DMF, nitrogen is protected
Protect lower 165 DEG C of reactions 20-24h；The carbazole: to bromo-iodobenzene: potassium carbonate: Phen: the molar ratio of cuprous iodide is 1:
1.0-1.2:0.05-0.2:2-4:0.05-0.2；After reaction, reaction solution is poured into saturated sodium chloride solution, is filtered, very
Sky is dry, obtains crude product, chromatographs to obtain midbody compound M1 through column；
Intermediate M1, connection pinacol borate, triphenylphosphine palladium, triphenylphosphine, acetic acid are separately added into there-necked flask
Potassium is dissolved in toluene, 100-120 DEG C of reaction 12-16h under nitrogen protection；The intermediate M1: connection pinacol borate: three
Phenylphosphine palladium chloride: triphenylphosphine: the molar ratio of potassium acetate is 1:1.1-1.5:0.05-0.08:0.1-0.16:4-6；Instead
After answering, reaction solution is poured into saturated sodium chloride solution, methylene chloride extraction, and anhydrous magnesium sulfate is dry；Crude product passes through column
Chromatography obtains intermediate M2；
(2) preparation method of 4- (9,9-dimethylacridan -10- base) phenyl boric acid
9,9-dimethylacridan is packed into there-necked flask, to bromo-iodobenzene, palladium acetate, cesium carbonate, tri-tert-butylphosphine tetrafluoroborate
It is dissolved in dry toluene, under nitrogen protection, 110-130 DEG C of reaction 20-24h；The 9,9-dimethylacridan, to bromo-iodobenzene,
Palladium acetate, tri-tert-butylphosphine tetrafluoroborate, cesium carbonate molar ratio be 1.0-1.2:1:0.05-0.08:0.15-0.24:
5-10；After reaction, reaction solution is poured into saturated brine, is then extracted, is subtracted with methylene chloride, ethyl acetate respectively
Pressure steams solvent, and crude product chromatographs to obtain intermediate M3 through column；
Intermediate M3, connection pinacol borate, triphenylphosphine palladium, triphenylphosphine, acetic acid are separately added into there-necked flask
Potassium is dissolved in toluene, 100-120 DEG C of reaction 12-16h under nitrogen protection；The intermediate M1, connection pinacol borate, three
Phenylphosphine palladium chloride, triphenylphosphine, potassium acetate molar ratio be 1:1.1-1.5:0.05-0.08:0.1-0.16:4-6；Instead
After answering, reaction solution is poured into saturated sodium chloride solution, methylene chloride extraction, and anhydrous magnesium sulfate is dry；Crude product passes through column
Chromatography obtains intermediate M4.
4. the preparation method of one kind indone according to claim 2 and pyridine derivate, it is characterised in that: the intermediate
The synthetic method of W comprises the steps of:
The synthesis of bromo indone and pyridine:
2- chloro-3-pyridyl aldehyde, bromo phenyl boric acid, potassium tert-butoxide, tetrakis triphenylphosphine palladium are added in three-necked flask, first is added
Benzene: ethyl alcohol volume ratio is 5:1 mixed solution as solvent, the 2- chloro-3-pyridyl aldehyde: bromo phenyl boric acid: potassium tert-butoxide: four
The molar ratio of (triphenylphosphine) palladium is 1:1-1.2:1-2:0.05-0.08, under nitrogen protection, is heated to 80-100 DEG C, reacts 4-
6h or so；After reaction, reaction solution is poured into saturated brine, is then divided respectively with methylene chloride, ethyl acetate
Liquid extraction, crude product chromatograph to obtain intermediate white solid A through column；
Intermediate A is weighed in three-necked flask, TBHP solution is added, the molar ratio of intermediate W1:TBHP is 1:3-8, and first is added
Benzene makees solvent, under nitrogen protection, is heated to 100 DEG C, reacts 24-48h；After reaction, reaction solution is poured into saturated salt solution
In, liquid separation extraction then is carried out with methylene chloride, ethyl acetate respectively, crude product chromatographs to obtain intermediate yellow solid W through column.
5. the application of one kind indone according to claim 1 and pyridine derivate, it is characterised in that: the derivative conduct
Luminescent material is used to prepare electroluminescent device.
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| CN102903854A (en) * | 2012-09-27 | 2013-01-30 | 电子科技大学 | White-light organic electroluminescent device and production method thereof |
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