CN110734453A - amine derivatives, preparation method thereof and organic light emitting diode - Google Patents

amine derivatives, preparation method thereof and organic light emitting diode Download PDF

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CN110734453A
CN110734453A CN201810806814.2A CN201810806814A CN110734453A CN 110734453 A CN110734453 A CN 110734453A CN 201810806814 A CN201810806814 A CN 201810806814A CN 110734453 A CN110734453 A CN 110734453A
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mixing
reacting
benzothiophene
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孟鸿
贺耀武
施明
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Peking University Shenzhen Graduate School
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Abstract

The invention discloses amine derivatives, a preparation method thereof and an organic light-emitting diode, wherein the molecular structure general formula of the amine derivatives is
Figure DDA0001734694170000011
Or

Description

amine derivatives, preparation method thereof and organic light emitting diode
Technical Field
The invention relates to the field of organic semiconductor materials, in particular to amine derivatives, a preparation method thereof and an organic light-emitting diode.
Background
Organic Light Emitting Diodes (OLEDs) have broad application prospects in the field of flexible display and illumination due to their advantages of low production cost and large-area fabrication, and thus research on organic semiconductor materials for OLEDs has attracted attention of researchers.
The development of organic semiconductor materials with air-stable, high hole mobility, and high luminous efficiency characteristics remains a challenge in this field [1] benzothiophene [3,2-b ] [1] benzothiophene (BTBT) as the classical semiconductor masters, which has attracted widespread interest to researchers due to its excellent device performance.
Furan derivatives have potential application prospects in the field of luminescence due to unique properties, furan is which is the simplest heterocyclic aromatic compound, and has chemical structure and electronic properties very similar to thiophene.
Thiophene derivatives have the characteristic of stronger carrier mobility, furan derivatives and furan derivatives have stronger fluorescence properties, and the furan derivatives and furan derivatives have different properties due to different structures.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide amine derivatives, a preparation method thereof, and an organic light emitting diode, and aims to solve the problem that the existing organic semiconductor material cannot achieve both high hole mobility and high fluorescence efficiency.
The technical scheme of the invention is as follows:
bases on [1]]Benzothiophene [3,2-b ]][1]Amine derivatives of benzofuran, wherein the molecular structural general formula of the amine derivatives is
Figure BDA0001734694160000021
Figure BDA0001734694160000022
Figure BDA0001734694160000023
, wherein Ar1 and Ar2 are both aryl, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 are all aryl, and R17, R18, R19 and R20 are all aryl or alkyl.
Said is based on [1]Benzothiophene [3,2-b ]][1]Amine derivatives of benzofuran, wherein the aryl group comprises
Figure BDA0001734694160000024
Figure BDA0001734694160000025
Figure BDA0001734694160000026
Wherein, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35 and R36 are all aryl or alkyl.
Said is based on [1]Benzothiophene [3,2-b ]][1]Amine derivatives of benzofuran, wherein the molecular structural formula of the amine derivatives comprises
Figure BDA0001734694160000031
Figure BDA0001734694160000032
A method for preparing amine derivatives based on [1] benzothiophene [3,2-b ] [1] benzofuran, which comprises the following steps:
mixing benzothiophene and N-bromosuccinimide, and reacting to generate 3-bromobenzothiophene;
mixing the 3-bromobenzothiophene with hydrogen peroxide, and reacting to generate benzothiophene oxide;
mixing the benzothiophene oxide with phenol, and reacting to obtain a compound with a molecular structural formula
Figure BDA0001734694160000033
intermediate;
mixing the th intermediate with diisobutylaluminum hydride, and reacting to obtain the final product with a molecular structural formulaA second intermediate of (a);
dissolving the second intermediate in glacial acetic acid, adding N-bromosuccinimide, and mixing to obtain the final product with a molecular structural formula
Figure BDA0001734694160000035
A third intermediate of (4);
reacting the third intermediate with a catalyst PdCl2(PPH3)2Mixing, reacting to obtain the molecular structural formula
Figure BDA0001734694160000041
A fourth intermediate of (4);
mixing the fourth intermediate with liquid bromine, and reacting to obtain a compound with a molecular structural formula of
Figure BDA0001734694160000042
The fifth intermediate of (4);
mixing the fifth intermediate with a diarylamine and adding Pd2(dba)3，HF4P(t-Bu)3Carrying out catalytic reaction with potassium tert-butoxide to generate a molecular structure general formula
Figure BDA0001734694160000043
Wherein, R1, R2, R3 and R4 are aryl.
A method for preparing amine derivatives based on [1] benzothiophene [3,2-b ] [1] benzofuran, which comprises the following steps:
mixing benzothiophene and N-bromosuccinimide, and reacting to generate 3-bromobenzothiophene;
mixing the 3-bromobenzothiophene with hydrogen peroxide, and reacting to generate benzothiophene oxide;
mixing the benzothiophene oxide with phenol, and reacting to obtain a compound with a molecular structural formula intermediate;
mixing the th intermediate with diisobutylaluminum hydride, and reacting to obtain the final product with a molecular structural formulaA second intermediate of (a);
dissolving the second intermediate in glacial acetic acid, adding N-bromosuccinimide, and mixing to obtain the final product with a molecular structural formula
Figure BDA0001734694160000046
A third intermediate of (4);
reacting the third intermediate with a catalyst PdCl2(PPH3)2Mixing, reacting to obtain the molecular structural formula
Figure BDA0001734694160000051
A fourth intermediate of (4);
mixing the fourth intermediate with liquid bromine, and reacting to obtain a compound with a molecular structural formula of
Figure BDA0001734694160000052
The fifth intermediate of (4);
mixing the fifth intermediate with an aryl boronic acid ester containing an aromatic amine and adding Pd (PPh)3)4Carrying out catalytic reaction to generate a molecular structure general formula
Figure BDA0001734694160000053
Wherein, Ar1, Ar2, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 are all aryl groups.
A method for preparing amine derivatives based on [1] benzothiophene [3,2-b ] [1] benzofuran, which comprises the following steps:
mixing benzothiophene and N-bromosuccinimide, and reacting to generate 3-bromobenzothiophene;
mixing the 3-bromobenzothiophene with hydrogen peroxide, and reacting to generate benzothiophene oxide;
mixing the benzothiophene oxide with phenol, and reacting to obtain a compound with a molecular structural formula
Figure BDA0001734694160000055
intermediate;
mixing the th intermediate with diisobutylaluminum hydride, and reacting to obtain the final product with a molecular structural formula
Figure BDA0001734694160000056
A second intermediate of (a);
dissolving the second intermediate in glacial acetic acid, adding N-bromosuccinimide, and mixing to obtain the final product with a molecular structural formula
Figure BDA0001734694160000061
A third intermediate of (4);
reacting the third intermediate with a catalyst PdCl2(PPH3)2Mixing, reacting to obtain the molecular structural formula
Figure BDA0001734694160000062
A fourth intermediate of (4);
mixing the fourth intermediate with liquid bromine, and reacting to obtain a compound with a molecular structural formula of
Figure BDA0001734694160000063
The fifth intermediate of (4);
mixing the fifth intermediate with an aryl-substituted carbazole and adding Pd2(dba)3，HF4P(t-Bu)3Carrying out catalytic reaction with potassium tert-butoxide to generate a molecular structure general formulaWherein, R17, R18, R19 and R20 are aryl.
organic light emitting diodes, which comprises a hole function layer, wherein the hole function layer is prepared by the amine derivative based on [1] benzothiophene [3,2-b ] [1] benzofuran.
The organic light emitting diode, wherein the hole functional layer is a hole injection layer and/or a hole transport layer.
The invention has the beneficial effects that amine derivatives containing thiophene functional groups and furan functional groups simultaneously are designed by combining the characteristics that the thiophene derivatives have higher hole mobility and the furan derivatives have higher fluorescence performance, and the molecular structure of the amine derivatives is
Figure BDA0001734694160000065
Figure BDA0001734694160000071
Figure BDA0001734694160000072
, the aromatic amine group can go further steps [1]Benzothiophene [3,2-b ]][1]Hole mobility and luminous efficiency of benzofuran. The invention can effectively solve the problem of high hole migration of the existing semiconductor materialThe efficiency and the high fluorescence efficiency are not compatible.
Detailed Description
The present invention provides amine derivatives, a method for preparing the same, and an organic light emitting diode, wherein the object, technical scheme and effect of the present invention are more clear and definite, and the following step is to explain the present invention in detail.
In order to solve the problem that the high hole mobility and the high fluorescence efficiency of the existing semiconductor material cannot be obtained at the same time, the invention provides materials based on [1]]Benzothiophene [3,2-b ]][1]Amine derivatives of benzofuran, wherein the molecular structural general formula of the amine derivatives is
Figure BDA0001734694160000073
Figure BDA0001734694160000074
Figure BDA0001734694160000075
, wherein Ar1 and Ar2 are both aryl, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 are all aryl, and R17, R18, R19 and R20 are all aryl or alkyl.
Furan rings have been widely used to construct pi-conjugated molecules, furan derivatives having the advantages of (1) reduced aromaticity by replacement of the sulfur atom with oxygen, more quinoid structural features of the molecule, better delocalization of pi-electrons, and reduced oxidation potential at , resulting in an increase in HOMO orbital level, thus facilitating hole injection and transport, (2) thiophene, which contains relatively heavy sulfur atoms, resulting in fluorescence quenching due to internal conversion by heavy atoms resulting in orbital coupling, while furan semiconductors do not have the problem of fluorescence quenching due to orbital coupling, have more excellent fluorescent properties than thiophene semiconductors, and thus can be used to prepare organic semiconductor light emitting devices, including OLEDs and Organic Light Emitting Transistors (OLETs). (3) furan compounds having less aromaticity, less intermolecular pi-pi interactions, and thus having a relatively greater solubility, (4) furan is a biodegradable material, can be prepared from biorenewable raw materials, making it more suitable for large-scale applications.
According to the invention, by combining the characteristics that a thiophene derivative has high hole mobility and a furan derivative has high fluorescence performance, amine derivatives containing a thiophene functional group and a furan functional group at the same time are designed, and the aromatic amine group combined on [1] benzothiophene [3,2-b ] [1] benzofuran can further enhance the hole mobility and the luminous efficiency of [1] benzothiophene [3,2-b ] [1] benzofuran, so that the amine derivatives based on [1] benzothiophene [3,2-b ] [1] benzofuran provided by the invention can be used as the hole functional layer of an organic light-emitting diode device, the amine derivatives are prepared into a semiconductor thin film by vacuum evaporation or spin coating, and the organic light-emitting diode device with high hole mobility and high fluorescence efficiency is prepared by .
Specifically, the amine derivative provided by the invention comprises a plurality of structures, and the general formula of the molecular structure of the amine derivative is
Figure BDA0001734694160000081
When R1, R2, R3 and R4 are all aryl, and R1, R2, R3 and R4 can be the same or different groups; when the molecular structure general formula is
Figure BDA0001734694160000082
When the aromatic ring is substituted by a substituent, R5, R6, R7, R8, R9, R10, R11 and R12 are all aryl groups, and R5, R6, R7, R8, R9, R10, R11 and R12 can be the same or different groups; when the molecular structure general formula is
Figure BDA0001734694160000091
When the R13, the R14, the R15 and the R16 are all aryl groups, the R13, the R14, the R15 and the R16 can be the same or different groups, and the Ar1 and the Ar2 are aryl groups or substituted aryl groups; when the molecular structure general formula is
Figure BDA0001734694160000092
R17, R18, R19 and R20 are all aryl or alkyl groups, and R17, R18, R19 and R20 can be the same or different groups.
Preferably, in said base [1]]Benzothiophene [3,2-b ]][1]Amine derivatives of benzofuran, wherein the aryl group in said R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 comprises
Figure BDA0001734694160000093
Figure BDA0001734694160000094
Figure BDA0001734694160000095
Wherein R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35 and R36 are all aryl or alkyl groups, preferably, the alkyl groups are heteroatom-substituted alkyl groups.
As an example, the present invention provides a composition based on [1]]Benzothiophene [3,2-b ]][1]The molecular structural formula of the amine derivative of benzofuran comprises
Figure BDA0001734694160000101
Figure BDA0001734694160000102
Based on the amine derivatives, the invention provides molecular structural general formulas
Figure BDA0001734694160000103
The process for preparing the amine derivative of (1), which comprises the steps of:
mixing benzothiophene and N-bromosuccinimide, and reacting to generate 3-bromobenzothiophene;
mixing the 3-bromobenzothiophene with hydrogen peroxide, and reacting to generate benzothiophene oxide;
mixing the benzothiophene oxide with phenol, reacting to form a moleculeStructural formula is
Figure BDA0001734694160000104
intermediate;
mixing the th intermediate with diisobutylaluminum hydride, and reacting to obtain the final product with a molecular structural formula
Figure BDA0001734694160000105
A second intermediate of (a);
dissolving the second intermediate in glacial acetic acid, adding N-bromosuccinimide, and mixing to obtain the final product with a molecular structural formula
Figure BDA0001734694160000106
A third intermediate of (4);
reacting the third intermediate with a catalyst PdCl2(PPH3)2Mixing, reacting to obtain the molecular structural formula
Figure BDA0001734694160000111
A fourth intermediate of (4);
mixing the fourth intermediate with liquid bromine, and reacting to obtain a compound with a molecular structural formula of
Figure BDA0001734694160000112
The fifth intermediate of (4);
mixing the fifth intermediate with a diarylamine and adding Pd2(dba)3，HF4P(t-Bu)3Carrying out catalytic reaction with potassium tert-butoxide to generate a molecular structure general formulaWherein, R1, R2, R3 and R4 are aryl.
As an embodiment of , the invention also provides molecular structure general formulas
Figure BDA0001734694160000114
The process for producing an amine derivative of (1), wherein the process comprises the step of：
Mixing benzothiophene and N-bromosuccinimide, and reacting to generate 3-bromobenzothiophene;
mixing the 3-bromobenzothiophene with hydrogen peroxide, and reacting to generate benzothiophene oxide;
mixing the benzothiophene oxide with phenol, and reacting to obtain a compound with a molecular structural formula
Figure BDA0001734694160000115
intermediate;
mixing the th intermediate with diisobutylaluminum hydride, and reacting to obtain the final product with a molecular structural formula
Figure BDA0001734694160000116
A second intermediate of (a);
dissolving the second intermediate in glacial acetic acid, adding N-bromosuccinimide, and mixing to obtain the final product with a molecular structural formula
Figure BDA0001734694160000121
A third intermediate of (4);
reacting the third intermediate with a catalyst PdCl2(PPH3)2Mixing, reacting to obtain the molecular structural formula
Figure BDA0001734694160000122
A fourth intermediate of (4);
mixing the fourth intermediate with liquid bromine, and reacting to obtain a compound with a molecular structural formula ofThe fifth intermediate of (4);
mixing the fifth intermediate with an aryl boronic acid ester containing an aromatic amine and adding Pd (PPh)3)4Carrying out catalytic reaction to generate a molecular structure general formula
Figure BDA0001734694160000124
Figure BDA0001734694160000125
Wherein, Ar1, Ar2, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 are all aryl groups.
As an embodiment of , the invention also provides molecular structure general formulas
Figure BDA0001734694160000126
The process for preparing the amine derivative of (1), which comprises the steps of:
mixing benzothiophene and N-bromosuccinimide, and reacting to generate 3-bromobenzothiophene;
mixing the 3-bromobenzothiophene with hydrogen peroxide, and reacting to generate benzothiophene oxide;
mixing the benzothiophene oxide with phenol, and reacting to obtain a compound with a molecular structural formula intermediate;
mixing the th intermediate with diisobutylaluminum hydride, and reacting to obtain the final product with a molecular structural formula
Figure BDA0001734694160000132
A second intermediate of (a);
dissolving the second intermediate in glacial acetic acid, adding N-bromosuccinimide, and mixing to obtain the final product with a molecular structural formula
Figure BDA0001734694160000133
A third intermediate of (4);
reacting the third intermediate with a catalyst PdCl2(PPH3)2Mixing, reacting to obtain the molecular structural formula
Figure BDA0001734694160000134
A fourth intermediate of (4);
mixing the fourth intermediate with liquid bromine, and reacting to obtain a compound with a molecular structural formula of
Figure BDA0001734694160000135
The fifth intermediate of (4);
mixing the fifth intermediate with an aryl-substituted carbazole and adding Pd2(dba)3，HF4P(t-Bu)3Carrying out catalytic reaction with potassium tert-butoxide to generate a molecular structure general formula
Figure BDA0001734694160000136
Wherein, R17, R18, R19 and R20 are aryl.
, the invention also provides kinds of organic light emitting diodes, wherein the organic light emitting diodes comprise a hole function layer, the hole function layer is prepared by adopting the amine derivatives based on [1] benzothiophene [3,2-b ] [1] benzofuran, and specifically, the hole function layer is a hole injection layer and/or a hole transport layer.
The preparation of [1] benzothiophene [3,2-b ] [1] benzofuran-based derivatives of the present invention is illustrated by the following specific examples in steps:
example 1
N2,N2,N7,N7-tetraphenyl [1]]Benzothiophene [3,2-b ]][1]The synthetic process of the benzofuran-2, 7-diamine comprises the following steps:
Figure BDA0001734694160000141
the preparation method comprises the following specific steps:
20g (150mmol) of benzothiophene were dissolved in 150mL of chloroform, 33.2g (186mmol, 1.25 equivalents) were added portionwise at 0 ℃ and, after completion of the addition, the reaction was allowed to proceed at 0 ℃ for 4h, after which the temperature was raised to room temperature and stirring was continued for 24 h. Adding 60mL of chloroform, washing with a sodium thiosulfate aqueous solution, saturated sodium carbonate and water respectively, drying an organic phase with anhydrous magnesium sulfate, concentrating, and carrying out column chromatography to obtain the 3-bromobenzothiophene.
Dissolving 10g (46mmol) of 3-bromobenzothiophene in 80mL of dichloromethane and 80mL of trifluoroacetic acid solution, stirring at room temperature for 5 minutes, adding 4mL of 35% hydrogen peroxide, stirring until the raw materials completely react, neutralizing with saturated sodium carbonate solution to be neutral, separating liquid, washing an organic phase with saturated sodium bicarbonate and water, drying over anhydrous magnesium sulfate, concentrating, and carrying out column chromatography to obtain a compound 3-bromobenzothiophene-1-oxygen.
2.3g (10mmol) of 3-bromobenzothiophene-1-oxide, 3.4g (20mmol) of phenol, 2.76g (20mmol) of potassium carbonate and 30mL of anhydrous DMF are stirred at 70 ℃ for reaction overnight, cooled to room temperature, concentrated, the residue is dissolved in 50mL of dichloromethane, washed with saturated brine and water, the organic phase is dried over anhydrous magnesium sulfate, concentrated and subjected to column chromatography to obtain 3-phenoxybenzothiophene-1-oxide.
Dissolving 2.54g (8mmol) of 3-phenoxybenzothiophene-1-oxygen in 50mL of anhydrous toluene, slowly dropwise adding diisobutylaluminum hydride (16mmol,13mL of 20% toluene solution) at 0 ℃, stirring at 65 ℃ after adding, reacting until the raw materials disappear, cooling to 0 ℃, neutralizing with 2M sodium hydroxide aqueous solution, extracting with dichloromethane for three times, combining organic phases, washing the organic phases to the center with water, drying over anhydrous magnesium sulfate, concentrating, and carrying out column chromatography to obtain the 3-phenoxybenzothiophene.
1.82g.6(6mmol) of 3-phenoxybenzothiophene was dissolved in 30mL of glacial acetic acid, 1.2g (6.6mmol) of NBS was added, stirring was carried out for 10 minutes, and the reaction was continued at 55 ℃ for 2 h. Cooling to room temperature, adding 80mL of ice water, extracting with ethyl acetate for three times, combining organic phases, washing the organic phases with saturated sodium carbonate, saturated brine and water, drying over anhydrous magnesium sulfate, and carrying out column chromatography to obtain the 2-bromo-3-phenoxybenzothiophene.
1.51g (4mmol) of 2-bromo-3-phenoxybenzothiophene and 0.67g (8mmol) of sodium acetate were dissolved in 80ml of N, N-dimethylacetamide, and 0.14g (0.2mmol) of PdCl were added under nitrogen2(PPh3)2Stirring overnight at 140 deg.C, cooling to room temperature, adding 200mL of 1mol/L hydrochloric acid, extracting with 500mL of ethyl acetate and n-hexane (volume ratio 1:1), washing the organic phase with saturated brine and water, drying over anhydrous magnesium sulfate, concentrating, and subjecting to column chromatography to obtain the target compound [ 1%]Benzothiophene [3,2-b ]][1]A benzofuran.
[1] benzothiophene [3,2-b ] [1] benzofuran (4.48g,20mmol) was dissolved in 250mL chloroform at 0 ℃ in 100mL chloroform solution containing liquid bromine (9.6g, 60mmol), the chloroform solution of liquid bromine was added dropwise until the reaction of the starting material was completed, and saturated aqueous sodium thiosulfate solution was added to reduce excess liquid bromine. Washing the organic phase with saturated sodium bicarbonate water solution, drying, and performing column chromatography with petroleum ether as eluent to obtain 2, 7-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran.
2, 7-dibromo [1]]Benzothiophene [3,2-b ]][1]Benzofuran (1.9g,5mmol) and diphenylamine (2.63g,15mmol) were dissolved in 100mL of toluene, and after removing oxygen in the system, a catalytic amount of Pd was added2(dba)3，HF4P(t-Bu)3And potassium tert-butoxide (1.68g,15mmol) are heated and reacted under the protection of inert gas until the reaction of the raw materials is finished; cooling to room temperature, washing with saturated brine and water, drying over anhydrous sodium sulfate, concentrating, and subjecting the residue to column chromatography using petroleum ether and dichloromethane as eluent to obtain N2,N2,N7,N7-tetraphenyl [1]]Benzothiophene [3,2-b ]][1]Benzofuran-2, 7-diamines.
Example 2
N2,N7-diphenyl-N2,N7Di (1-naphthyl) [1]]Benzothiophene [3,2-b ]][1]The synthetic process of the benzofuran-2, 7-diamine comprises the following steps:
Figure BDA0001734694160000161
the preparation method comprises the following steps:
20g (150mmol) of benzothiophene were dissolved in 150mL of chloroform, 33.2g (186mmol, 1.25 equivalents) were added portionwise at 0 ℃ and, after completion of the addition, the reaction was allowed to proceed at 0 ℃ for 4h, after which the temperature was raised to room temperature and stirring was continued for 24 h. Adding 60mL of chloroform, washing with a sodium thiosulfate aqueous solution, saturated sodium carbonate and water respectively, drying an organic phase with anhydrous magnesium sulfate, concentrating, and carrying out column chromatography to obtain the 3-bromobenzothiophene.
Dissolving 10g (46mmol) of 3-bromobenzothiophene in 80mL of dichloromethane and 80mL of trifluoroacetic acid solution, stirring at room temperature for 5 minutes, adding 4mL of 35% hydrogen peroxide, stirring until the raw materials completely react, neutralizing with saturated sodium carbonate solution to be neutral, separating liquid, washing an organic phase with saturated sodium bicarbonate and water, drying over anhydrous magnesium sulfate, concentrating, and carrying out column chromatography to obtain a compound 3-bromobenzothiophene-1-oxygen.
2.3g (10mmol) of 3-bromobenzothiophene-1-oxide, 3.4g (20mmol) of phenol, 2.76g (20mmol) of potassium carbonate and 30mL of anhydrous DMF are stirred at 70 ℃ for reaction overnight, cooled to room temperature, concentrated, the residue is dissolved in 50mL of dichloromethane, washed with saturated brine and water, the organic phase is dried over anhydrous magnesium sulfate, concentrated and subjected to column chromatography to obtain 3-phenoxybenzothiophene-1-oxide.
Dissolving 2.54g (8mmol) of 3-phenoxybenzothiophene-1-oxygen in 50mL of anhydrous toluene, slowly dropwise adding diisobutylaluminum hydride (16mmol,13mL of 20% toluene solution) at 0 ℃, stirring at 65 ℃ after adding, reacting until the raw materials disappear, cooling to 0 ℃, neutralizing with 2M sodium hydroxide aqueous solution, extracting with dichloromethane for three times, combining organic phases, washing the organic phases to the center with water, drying over anhydrous magnesium sulfate, concentrating, and carrying out column chromatography to obtain the 3-phenoxybenzothiophene.
1.82g (6mmol) of 3-phenoxybenzothiophene was dissolved in 30mL of glacial acetic acid, 1.2g (6.6mmol) of NBS was added thereto, and the reaction was stirred for 10 minutes and further stirred at 55 ℃ for 2 hours. Cooling to room temperature, adding 80mL of ice water, extracting with ethyl acetate for three times, combining organic phases, washing the organic phases with saturated sodium carbonate, saturated brine and water, drying over anhydrous magnesium sulfate, and carrying out column chromatography to obtain the 2-bromo-3-phenoxybenzothiophene.
1.51g (4mmol) of 2-bromo-3-phenoxybenzothiophene and 0.67g (8mmol) of sodium acetate were dissolved in 80ml of N, N-dimethylacetamide, and 0.14g (0.2mmol) of PdCl were added under nitrogen2(PPh3)2,Stirring at 140 deg.C overnight, cooling to room temperature, adding 200mL of 1mol/L hydrochloric acid, extracting with 500mL of ethyl acetate and n-hexane (volume ratio 1:1), washing the organic phase with saturated brine and water, drying over anhydrous magnesium sulfate, concentrating, and subjecting to column chromatography to obtain the final product [ 1%]Benzothiophene [3,2-b ]][1]A benzofuran.
[1] benzothiophene [3,2-b ] [1] benzofuran (4.48g,20mmol) was dissolved in 250mL chloroform at 0 ℃ in 100mL chloroform solution containing liquid bromine (9.6g, 60mmol), the chloroform solution of liquid bromine was added dropwise until the reaction of the starting material was completed, and saturated aqueous sodium thiosulfate solution was added to reduce excess liquid bromine. Washing the organic phase with saturated sodium bicarbonate water solution, drying, and performing column chromatography with petroleum ether as eluent to obtain 2, 7-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran.
2, 7-dibromo [1]]Benzothiophene [3,2-b ]][1]Benzofuran (1.9g,5mmol) and phenyl-1-naphthylamine (3.28g,15mmol) were dissolved in 100mL of toluene, and after removing oxygen in the system, a catalytic amount of Pd was added2(dba)3，HF4P(t-Bu)3And potassium tert-butoxide (1.68g,15mmol) are heated and reacted under the protection of inert gas until the reaction of the raw materials is finished; cooling to room temperature, washing with saturated saline water and water, drying over anhydrous sodium sulfate, concentrating, and subjecting the residue to column chromatography with petroleum ether and dichloromethane as eluent to obtain N2,N7-diphenyl-N2,N7Di (1-naphthyl) [1]]Benzothiophene [3,2-b ]][1]Benzofuran-2, 7-diamines.
Example 3
2, 7-bis (3, 5-diphenylamino) phenyl-1-yl [1]]Benzothiophene [3,2-b ]][1]The synthetic process of benzofuran is as follows:
Figure BDA0001734694160000171
the preparation method comprises the following steps:
20g (150mmol) of benzothiophene were dissolved in 150mL of chloroform, 33.2g (186mmol, 1.25 equivalents) were added portionwise at 0 ℃ and, after completion of the addition, the reaction was allowed to proceed at 0 ℃ for 4h, after which the temperature was raised to room temperature and stirring was continued for 24 h. Adding 60mL of chloroform, washing with a sodium thiosulfate aqueous solution, saturated sodium carbonate and water respectively, drying an organic phase with anhydrous magnesium sulfate, concentrating, and carrying out column chromatography to obtain the 3-bromobenzothiophene.
Dissolving 10g (46mmol) of 3-bromobenzothiophene in 80mL of dichloromethane and 80mL of trifluoroacetic acid solution, stirring at room temperature for 5 minutes, adding 4mL of 35% hydrogen peroxide, stirring until the raw materials completely react, neutralizing with saturated sodium carbonate solution to be neutral, separating liquid, washing an organic phase with saturated sodium bicarbonate and water, drying over anhydrous magnesium sulfate, concentrating, and carrying out column chromatography to obtain a compound 3-bromobenzothiophene-1-oxygen.
2.3g (10mmol) of 3-bromobenzothiophene-1-oxide, 3.4g (20mmol) of phenol, 2.76g (20mmol) of potassium carbonate and 30mL of anhydrous DMF are stirred at 70 ℃ for reaction overnight, cooled to room temperature, concentrated, the residue is dissolved in 50mL of dichloromethane, washed with saturated brine and water, the organic phase is dried over anhydrous magnesium sulfate, concentrated and subjected to column chromatography to obtain 3-phenoxybenzothiophene-1-oxide.
Dissolving 2.54g (8mmol) of 3-phenoxybenzothiophene-1-oxygen in 50mL of anhydrous toluene, slowly dropwise adding diisobutylaluminum hydride (16mmol,13mL of 20% toluene solution) at 0 ℃, stirring at 65 ℃ after adding, reacting until the raw materials disappear, cooling to 0 ℃, neutralizing with 2M sodium hydroxide aqueous solution, extracting with dichloromethane for three times, combining organic phases, washing the organic phases to the center with water, drying over anhydrous magnesium sulfate, concentrating, and carrying out column chromatography to obtain the 3-phenoxybenzothiophene.
1.82g.6(6mmol) of 3-phenoxybenzothiophene was dissolved in 30mL of glacial acetic acid, 1.2g (6.6mmol) of NBS was added, stirring was carried out for 10 minutes, and the reaction was continued at 55 ℃ for 2 h. Cooling to room temperature, adding 80mL of ice water, extracting with ethyl acetate for three times, combining organic phases, washing the organic phases with saturated sodium carbonate, saturated brine and water, drying over anhydrous magnesium sulfate, and carrying out column chromatography to obtain the 2-bromo-3-phenoxybenzothiophene.
1.51g (4mmol) of 2-bromo-3-phenoxybenzothiophene and 0.67g (8mmol) of sodium acetate were dissolved in 80ml of N, N-dimethylacetamide, and 0.14g (0.2mmol) of PdCl were added under nitrogen2(PPh3)2Stirring overnight at 140 deg.C, cooling to room temperature, adding 200mL of 1mol/L hydrochloric acid, extracting with 500mL of ethyl acetate and n-hexane (volume ratio 1:1), washing the organic phase with saturated brine and water, drying over anhydrous magnesium sulfate, concentrating, and subjecting to column chromatography to obtain the target compound [ 1%]Benzothiophene [3,2-b ]][1]A benzofuran.
[1] benzothiophene [3,2-b ] [1] benzofuran (4.48g,20mmol) was dissolved in 250mL chloroform at 0 ℃ in 100mL chloroform solution containing liquid bromine (9.6g, 60mmol), the chloroform solution of liquid bromine was added dropwise until the reaction of the starting material was completed, and saturated aqueous sodium thiosulfate solution was added to reduce excess liquid bromine. Washing the organic phase with saturated sodium bicarbonate water solution, drying, and performing column chromatography with petroleum ether as eluent to obtain 2, 7-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran.
1.9g (5mmol) of 2, 7-dibromo [1] are reacted]Benzothiophene [3,2-b ]][1]Benzofuran and 8.07g (15mmol,3 equivalents) of 3, 5-diphenylaminophen-1-ylboronic acidThe pinacol ester was dissolved in 50mL of toluene, 10mL of 2M potassium carbonate aqueous solution was added, nitrogen was purged for 30min, and Pd (PPh) was added3)4(2% equiv.) stirring at 110 ℃ for 24h under nitrogen, the reaction mixture poured into 100mL of methanol, filtered, and the solid washed with hydrochloric acid and water. Obtaining 2, 7-di (3, 5-diphenylamino) phenyl-1-yl [1] by high vacuum sublimation]Benzothiophene [3,2-b ]][1]A benzofuran.
Example 4
2, 7-bis (9H-carbazolyl) [1]]Benzothiophene [3,2-b ]][1]The synthetic process of the benzofuran-2, 7-diamine comprises the following steps:
Figure BDA0001734694160000191
the preparation method comprises the following steps:
20g (150mmol) of benzothiophene were dissolved in 150mL of chloroform, 33.2g (186mmol, 1.25 equivalents) were added portionwise at 0 ℃ and, after completion of the addition, the reaction was allowed to proceed at 0 ℃ for 4h, after which the temperature was raised to room temperature and stirring was continued for 24 h. Adding 60mL of chloroform, washing with a sodium thiosulfate aqueous solution, saturated sodium carbonate and water respectively, drying an organic phase with anhydrous magnesium sulfate, concentrating, and carrying out column chromatography to obtain the 3-bromobenzothiophene.
Dissolving 10g (46mmol) of 3-bromobenzothiophene in 80mL of dichloromethane and 80mL of trifluoroacetic acid solution, stirring at room temperature for 5 minutes, adding 4mL of 35% hydrogen peroxide, stirring until the raw materials completely react, neutralizing with saturated sodium carbonate solution to be neutral, separating liquid, washing an organic phase with saturated sodium bicarbonate and water, drying over anhydrous magnesium sulfate, concentrating, and carrying out column chromatography to obtain a compound 3-bromobenzothiophene-1-oxygen.
2.3g (10mmol) of 3-bromobenzothiophene-1-oxide, 3.4g (20mmol) of phenol, 2.76g (20mmol) of potassium carbonate and 30mL of anhydrous DMF are stirred at 70 ℃ for reaction overnight, cooled to room temperature, concentrated, the residue is dissolved in 50mL of dichloromethane, washed with saturated brine and water, the organic phase is dried over anhydrous magnesium sulfate, concentrated and subjected to column chromatography to obtain 3-phenoxybenzothiophene-1-oxide.
Dissolving 2.54g (8mmol) of 3-phenoxybenzothiophene-1-oxygen in 50mL of anhydrous toluene, slowly dropwise adding diisobutylaluminum hydride (16mmol,13mL of 20% toluene solution) at 0 ℃, stirring at 65 ℃ after adding, reacting until the raw materials disappear, cooling to 0 ℃, neutralizing with 2M sodium hydroxide aqueous solution, extracting with dichloromethane for three times, combining organic phases, washing the organic phases to the center with water, drying over anhydrous magnesium sulfate, concentrating, and carrying out column chromatography to obtain the 3-phenoxybenzothiophene.
1.82g.6(6mmol) of 3-phenoxybenzothiophene was dissolved in 30mL of glacial acetic acid, 1.2g (6.6mmol) of NBS was added, stirring was carried out for 10 minutes, and the reaction was continued at 55 ℃ for 2 h. Cooling to room temperature, adding 80mL of ice water, extracting with ethyl acetate for three times, combining organic phases, washing the organic phases with saturated sodium carbonate, saturated brine and water, drying over anhydrous magnesium sulfate, and carrying out column chromatography to obtain the 2-bromo-3-phenoxybenzothiophene.
1.51g (4mmol) of 2-bromo-3-phenoxybenzothiophene and 0.67g (8mmol) of sodium acetate were dissolved in 80ml of N, N-dimethylacetamide, and 0.14g (0.2mmol) of PdCl were added under nitrogen2(PPh3)2Stirring overnight at 140 deg.C, cooling to room temperature, adding 200mL of 1mol/L hydrochloric acid, extracting with 500mL of ethyl acetate and n-hexane (volume ratio 1:1), washing the organic phase with saturated brine and water, drying over anhydrous magnesium sulfate, concentrating, and subjecting to column chromatography to obtain the target compound [ 1%]Benzothiophene [3,2-b ]][1]A benzofuran.
[1] benzothiophene [3,2-b ] [1] benzofuran (4.48g,20mmol) was dissolved in 250mL chloroform at 0 ℃ in 100mL chloroform solution containing liquid bromine (9.6g, 60mmol), the chloroform solution of liquid bromine was added dropwise until the reaction of the starting material was completed, and saturated aqueous sodium thiosulfate solution was added to reduce excess liquid bromine. Washing the organic phase with saturated sodium bicarbonate water solution, drying, and performing column chromatography with petroleum ether as eluent to obtain 2, 7-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran.
2, 7-dibromo [1]]Benzothiophene [3,2-b ]][1]Benzofuran (1.9g,5mmol) and carbazole (2.5g,15mmol) were dissolved in 100mL of toluene, and after removing oxygen in the system, a catalytic amount of Pd was added2(dba)3，HF4P(t-Bu)3And potassium tert-butoxide (1.68g,15mmol) are heated and reacted under the protection of inert gas until the reaction of the raw materials is finished; then cooled to room temperature, washed with saturated brine and water, dried over anhydrous sodium sulfate, concentrated, and the residue was washed with petroleum ether and dichloromethaneThe eluent column chromatography is carried out to obtain 2, 7-di (9H-carbazolyl) [1]Benzothiophene [3,2-b ]][1]Benzofuran-2, 7-diamines.
Example 5
Device preparation and performance test:
and masking the silicon wafer by using a semiconductor mask, selecting a proper substrate temperature, and preparing the film under high vacuum. And controlling the evaporation rate of the semiconductor material, and carrying out evaporation on an electrode by using an electrode mask after the film is prepared, wherein the electrode material is Au. And testing the performance of the prepared organic light-emitting diode device by using a semiconductor analyzer. Testing Id-Vg and Id-Vd curves using the following formula Id＝(W/2L)μTFTCi(Vg-Vth)2The calculation of the mobility was performed.
The conventional materials DPh-BTBT and the amine derivative materials prepared in embodiments 1 to 4 of the present invention are respectively used to prepare the same organic thin film transistor device, and the hole mobility and the fluorescence quantum efficiency of the organic thin film transistor device are respectively tested, and the results are as follows:
compound (I) Hole mobility Fluorescence quantum yield
DPh-BTBT 0.36-0.46cm2V-1s-1 18％
Example 1 0.32-0.44cm2V-1s-1 48％
Example 2 0.34-0.48cm2V-1s-1 55％
Example 3 0.40-0.51cm2V-1s-1 58％
Example 4 0.41-0.53cm2V-1s-1 49％
As is clear from the above experimental results, the base of [1] prepared according to the present invention]Benzothiophene [3,2-b ]][1]Amine derivatives of benzofuran and related compounds
Figure BDA0001734694160000211
The (DPh-BTBT) materials have higher hole mobility, but compared with the existing DPh-BTBT materials, the material provided by the invention has higher fluorescence efficiency.
In summary, the thiophene derivative has the characteristics of high hole mobility and the furan derivative has high fluorescence performance, amine derivatives containing thiophene functional groups and furan functional groups are designed, and the molecular structure of the amine derivative is
Figure BDA0001734694160000221
Figure BDA0001734694160000222
Figure BDA0001734694160000223
, the aromatic amine group can go further steps [1]Benzo (b) isThiophene [3,2-b ]][1]Hole mobility and luminous efficiency of benzofuran. The amine derivative provided by the invention can be used for preparing a hole functional layer of an organic light-emitting diode, so that the problem that the organic light-emitting diode device has high hole mobility and high fluorescence efficiency is solved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (8)

1, bases on [1]]Benzothiophene [3,2-b ]][1]The benzofuran amine derivative is characterized in that the molecular structural general formula of the benzofuran amine derivative is shown in the specification
Figure FDA0001734694150000011
Figure FDA0001734694150000012
Figure FDA0001734694150000013
, wherein Ar1 and Ar2 are both aryl, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 are all aryl, and R17, R18, R19 and R20 are all aryl or alkyl.
2. The method according to claim 1 and based on [1]]Benzothiophene [3,2-b ]][1]Amine derivatives of benzofuran, characterized in that said aryl group comprises
Figure FDA0001734694150000015
Wherein, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35 and R36 are all aryl or alkyl.
3. The method according to claim 1 and based on [1]]Benzothiophene [3,2-b ]][1]Amine derivatives of benzofuran, characterized in that the molecular structure of said amine derivatives comprises
Figure FDA0001734694150000021
4, A method for preparing amine derivatives based on [1] benzothiophene [3,2-b ] [1] benzofuran, which comprises the steps of:
mixing benzothiophene and N-bromosuccinimide, and reacting to generate 3-bromobenzothiophene;
mixing the 3-bromobenzothiophene with hydrogen peroxide, and reacting to generate benzothiophene oxide;
mixing the benzothiophene oxide with phenol, and reacting to obtain a compound with a molecular structural formula
Figure FDA0001734694150000022
intermediate;
mixing the th intermediate with diisobutylaluminum hydride, and reacting to obtain the final product with a molecular structural formula
Figure FDA0001734694150000023
A second intermediate of (a);
dissolving the second intermediate in glacial acetic acid, adding N-bromosuccinimide, and mixing to obtain the final product with a molecular structural formula
Figure FDA0001734694150000024
A third intermediate of (4);
reacting the third intermediate with a catalyst PdCl2(PPH3)2Mixing, reacting to obtain the molecular structural formula
Figure FDA0001734694150000031
A fourth intermediate of (4);
mixing the fourth intermediate with liquid bromine, and reacting to obtain a compound with a molecular structural formula of
Figure FDA0001734694150000032
The fifth intermediate of (4);
mixing the fifth intermediate with a diarylamine and adding Pd2(dba)3，HF4P(t-Bu)3Carrying out catalytic reaction with potassium tert-butoxide to generate a molecular structure general formula
Figure FDA0001734694150000033
Wherein, R1, R2, R3 and R4 are aryl.
5, A method for preparing amine derivatives based on [1] benzothiophene [3,2-b ] [1] benzofuran, which comprises the steps of:
mixing benzothiophene and N-bromosuccinimide, and reacting to generate 3-bromobenzothiophene;
mixing the 3-bromobenzothiophene with hydrogen peroxide, and reacting to generate benzothiophene oxide;
mixing the benzothiophene oxide with phenol, and reacting to obtain a compound with a molecular structural formula intermediate;
mixing the th intermediate with diisobutylaluminum hydride, and reacting to obtain the final product with a molecular structural formula
Figure FDA0001734694150000035
A second intermediate of (a);
dissolving the second intermediate in glacial acetic acid, adding N-bromosuccinimide, and mixing to obtain the final product with a molecular structural formula
Figure FDA0001734694150000036
A third intermediate of (4);
reacting the third intermediate with a catalyst PdCl2(PPH3)2Mixing, reacting to obtain the molecular structural formula
Figure FDA0001734694150000041
A fourth intermediate of (4);
mixing the fourth intermediate with liquid bromine, and reacting to obtain a compound with a molecular structural formula of
Figure FDA0001734694150000042
The fifth intermediate of (4);
mixing the fifth intermediate with an aryl boronic acid ester containing an aromatic amine and adding Pd (PPh)3)4Carrying out catalytic reaction to generate a molecular structure general formula
Figure FDA0001734694150000043
Figure FDA0001734694150000044
Wherein, Ar1, Ar2, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 are all aryl groups.
6, A method for preparing amine derivatives based on [1] benzothiophene [3,2-b ] [1] benzofuran, which is characterized by comprising the steps of:
mixing benzothiophene and N-bromosuccinimide, and reacting to generate 3-bromobenzothiophene;
mixing the 3-bromobenzothiophene with hydrogen peroxide, and reacting to generate benzothiophene oxide;
mixing the benzothiophene oxide with phenol, and reacting to obtain a compound with a molecular structural formula
Figure FDA0001734694150000045
intermediate;
intermediate said thThe mixture is mixed with diisobutyl aluminum hydride and reacts to generate a molecular structural formulaA second intermediate of (a);
dissolving the second intermediate in glacial acetic acid, adding N-bromosuccinimide, and mixing to obtain the final product with a molecular structural formula
Figure FDA0001734694150000051
A third intermediate of (4);
reacting the third intermediate with a catalyst PdCl2(PPH3)2Mixing, reacting to obtain the molecular structural formula
Figure FDA0001734694150000052
A fourth intermediate of (4);
mixing the fourth intermediate with liquid bromine, and reacting to obtain a compound with a molecular structural formula of
Figure FDA0001734694150000053
The fifth intermediate of (4);
mixing the fifth intermediate with an aryl-substituted carbazole and adding Pd2(dba)3，HF4P(t-Bu)3Carrying out catalytic reaction with potassium tert-butoxide to generate a molecular structure general formula
Figure FDA0001734694150000054
Wherein, R17, R18, R19 and R20 are aryl.
An organic light emitting diode of , comprising a hole function layer, wherein the hole function layer is prepared by using the amine derivative based on [1] benzothiophene [3,2-b ] [1] benzofuran as claimed in any of claims 1 to 3 and .
8. The organic light-emitting diode according to claim 7, wherein the hole function layer is a hole injection layer and/or a hole transport layer.
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CN115490703A (en) * 2021-06-17 2022-12-20 广东阿格蕾雅光电材料有限公司 Synthetic method of BTBF
CN115490702A (en) * 2021-06-17 2022-12-20 广东阿格蕾雅光电材料有限公司 Synthetic method of BTBF arylamine derivative
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