CN106883203B - Derivative based on pyrene and naphthalene benzofuran, preparation method, application and device thereof - Google Patents

Derivative based on pyrene and naphthalene benzofuran, preparation method, application and device thereof Download PDF

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CN106883203B
CN106883203B CN201710059346.2A CN201710059346A CN106883203B CN 106883203 B CN106883203 B CN 106883203B CN 201710059346 A CN201710059346 A CN 201710059346A CN 106883203 B CN106883203 B CN 106883203B
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穆广园
庄少卿
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Hubei Sunshine Optoelectronics Material Co ltd
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Abstract

The invention belongs to the technical field of photoelectric material application, and particularly relates to a derivative based on pyrene and naphthobenzofuran, and a preparation method, application and a device thereof. The pyrene and naphthalene benzofuran are taken as cores of the material provided by the invention, different aromatic groups are bonded at different sites of pyrene, or a bridging structure is changed, so that a high-efficiency fluorescent luminescent material is formed.

Description

Derivative based on pyrene and naphthalene benzofuran, preparation method, application and device thereof
Technical Field
The invention belongs to the technical field of photoelectric material application, and particularly relates to a derivative based on pyrene and naphthobenzofuran, and a preparation method, application and a device thereof.
Background
In 1987, the Duncoqing cloud doctor of Kodak company in America invented an organic electroluminescent device (OLED) with a sandwich structure, and opened the application of the organic electroluminescent field, in 1990, the Cambridge university in England invented a high molecular electroluminescent device, and further expanded the field of luminescent materials, and at present, the OLED has been commercialized gradually and is praised as the next generation display.
At present, the OLED has a bottleneck, the blue light material is always a weak link, the heavy metal phosphorescent material can obtain a high-efficiency blue light device, but the synthesis cost is high, the light color cannot reach a deep blue region, the device efficiency roll-off is serious under high brightness, and the service life of the device is short. The blue light fluorescent material has the advantages of simple synthesis and purification, strong modifiability, wider energy gap, light color capable of reaching deep blue or even ultraviolet, stable device and low device efficiency under high brightness. (Zhu M., Yang C.chem Soc Rev 2013,42(12): 4963-.
The pyrene derivative can be applied to OLED luminescent materials, but due to the fact that pyrene rings are hard and have a plane structure, accumulation is easy to generate, concentration quenching is caused, photochromic red shift is caused, and efficiency is reduced.
The invention relates to a series of derivatives based on pyrene and naphthofuran, wherein the naphthobenzofuran and the pyrene are bridged to form a non-planar structure, and different groups are bonded at other positions of the pyrene to further increase a plane included angle, increase a steric effect and reduce accumulation. The naphthalene benzofuran can increase the carrier mobility of molecules, is beneficial to electron hole carrier transmission balance and recombination, is an excellent luminescent material, can be widely applied to organic light emitting diodes, obtains good effects, and is a novel material with great commercial value.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a derivative based on pyrene and naphthalene benzofuran, and a preparation method, application and a device thereof. The material takes pyrene and naphthofuran as cores, different aromatic groups are bonded at different sites of the pyrene or a bridging structure is changed to form a high-efficiency fluorescent luminescent material, the compound has high fluorescence quantum efficiency, electron hole transmission balance, excitons can efficiently perform composite luminescence in a luminescent layer, the luminescent efficiency of the same device is high, the roll-off is small, and the material can be widely applied to the field of electroluminescence.
The technical scheme provided by the invention is as follows:
the derivative based on pyrene and naphthalene benzofuran has a general structural formula shown as the following formula (I):
Figure BDA0001218086480000021
wherein R is 1 -R 3 Each independently is hydrogen, substituted or unsubstituted C 1 -C 6 Alkyl group of (2), C 1 -C 9 Silane hydrocarbon group of (2), C 6 -C 30 Aromatic group of (2), C 5 -C 35 Heterocyclic group of (A), C 6 -C 65 Polycyclic radical of (A), C 6 -C 65 Or arylene group of (C) 5 -C 65 A heteroarylene heterocyclic group of (1).
In particular, R 1 -R 3 Selected from the 2a-2m structures of formula (II) or hydrogen, R 1 -R 3 The same or different:
Figure BDA0001218086480000031
wherein, X, R 21 、R 22 、R 23 Each represents hydrogen, or C substituted or unsubstituted by deuterium, a halogen atom, cyano, nitro, amidino, hydroxyl or carbonyloxy 1 -C 20 An alkane group of (A), C 1 -C 20 Silane hydrocarbon group, substituted or unsubstituted C 6 -C 65 Aromatic group of (2), C 6 -C 65 An aromatic silane group of (A), substituted or unsubstituted C 6 -C 65 A heteroaromatic ring group of (A) or (C) 6 -C 65 P and q represent integers of 1 to 4, and represent substitution positions.
Specifically, X, R 21 、R 22 、R 23 The method comprises the following steps:
C 1 -C 20 the alkane group of (a) is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl;
unsubstituted C 6 -C 65 The aromatic group of (a) includes at least one aromatic ring, which are connected to each other by a single bond or fused, for example, phenyl, 1-naphthyl, 2-naphthyl, 3, 5-diphenylphenyl, etc.;
substituted C 6 -C 65 The aromatic group of (a) includes at least one aromatic group having at least one hydrogen atom substituted with deuterium, a halogen atom, a cyano group, a nitro group, an amidino group, a hydroxyl group or a carbonylyl group, or a non-substituted straight chain or branched C group 1 -C 20 Or said aromatic group having at least one hydrogen atom substituted by C 1 -C 20 Silane hydrocarbon group of (2)Substitutions, for example: c 1 -C 10 Alkyl-substituted aryl (toluene, ethylbenzene, o-, m-, p-cumyl, methylnaphthalene), halo (o-, m-, p-fluorobenzene, fluoronaphthalene, trifluoromethylbenzene), cyano (cyanobenzene, cyanobiphenyl), C 1 -C 10 Alkyl-substituted biphenyl radical, C 1 -C 10 Alkoxy-substituted biphenyl radicals, C 1 -C 10 Alkyl-substituted naphthalene radical, C 1 -C 10 Alkoxy substituted naphthalene group.
Preferably, X, R 21 、R 22 、R 23 C in (1) 1 -C 20 The alkane of (a) is selected from methyl, ethyl, isopropyl, tert-butyl or phenyl.
Preferably:
R 2 、R 3 independently of each other are hydrogen and C 1 -C 10 Branched or branched alkyl of R 2 And R 3 The same or different;
R 1 is hydrogen, C 1 -C 10 Branched or branched chain alkyl, phenyl, C 1 -C 10 Phenyl substituted by branched or branched alkyl, phenyl substituted by cyano, C 1 -C 5 Alkoxy-substituted phenyl, biphenyl, 1 to 6 methyl-substituted biphenyl, naphthyl, cyano-substituted naphthyl, oxyfluorenyl, phenyl-substituted dibenzofuranyl (oxyfluorenyl), 9-dimethylfluorenyl, carbazolyl (nitrofluorenyl) or 9-phenylcarbazolyl, 1 to 6C 1 -C 3 Alkyl-substituted biphenyls, mono-C 1 -C 3 Alkyl-substituted naphthyl, mono C 1 -C 3 Alkyl-substituted dibenzofuranyl, mono-C of 1 -C 3 Alkyl-substituted 9, 9-dimethylfluorenyl or mono C 1 -C 3 Alkyl-substituted carbazolyl group(s) of (a).
Some preferred pyrene and naphthalene benzofuran-based derivatives have the following structural formula:
Figure BDA0001218086480000051
Figure BDA0001218086480000061
Figure BDA0001218086480000071
Figure BDA0001218086480000081
Figure BDA0001218086480000091
Figure BDA0001218086480000101
Figure BDA0001218086480000111
the specific substituents or compounds mentioned above are only listed under the concept of the present invention, and the technical concept is mainly shown by the list, and not to limit or restrict the concept of the present invention or the scope of the claims.
The pyrene and naphthalene benzofuran provided by the invention are taken as cores, different aromatic groups are bonded at different sites of pyrene, or a bridging structure is changed, so that a high-efficiency fluorescent luminescent material is formed, the compound has high fluorescence quantum efficiency, electron hole transmission balance, efficient composite luminescence of excitons in a luminescent layer, high luminescent efficiency of the same device and small roll-off, and can be widely applied to the field of electroluminescence.
The invention also provides a preparation method of the derivative based on pyrene and naphthalene benzofuran, which comprises the following steps:
method a comprising the steps of:
Figure BDA0001218086480000112
and with
Figure BDA0001218086480000113
Suzuki reaction to obtain a derivative based on pyrene and naphthofuran;
alternatively, method B comprises the steps of:
1)
Figure BDA0001218086480000121
boration to obtain
Figure BDA0001218086480000122
2)
Figure BDA0001218086480000123
And
Figure BDA0001218086480000124
after the Suzuki reaction, alkylating the Suzuki reaction product by using a Grignard reagent to obtain a derivative based on pyrene and naphthalene benzofuran;
alternatively, method C comprises the steps of:
1)
Figure BDA0001218086480000125
completely alkylating the completely formatted reagent to obtain a dialkylated intermediate;
2) after mono-bromination of the dialkylated intermediate, with
Figure BDA0001218086480000126
Suzuki reaction to obtain a derivative based on pyrene and naphthofuran;
alternatively, method D comprises the steps of:
1)
Figure BDA0001218086480000127
reacting with substituted or unsubstituted arylboronic acid
Figure BDA0001218086480000128
Suzuki reaction to obtain a derivative based on pyrene and naphthofuran;
alternatively, method E comprises the steps of:
1)
Figure BDA0001218086480000129
completely alkylating the completely formatted reagent to obtain a dialkylated intermediate;
2) after dibromination of the dialkylated intermediate in turn with a substituted or unsubstituted arylboronic acid and
Figure BDA00012180864800001210
suzuki reaction to obtain a derivative based on pyrene and naphthofuran;
wherein:
in Process B, the alkyl substituent obtained by alkylation is C 1 -C 10 A branched or branched alkyl group of (a);
in the method C, two alkyl substituents obtained by dialkylation are respectively and independently C 1 -C 10 A branched or branched alkyl group of (a);
in the method D, the substituted aryl boric acid is cyano-substituted phenyl boric acid, C 1 -C 5 Alkoxy-substituted phenylboronic acids, biphenylboronic acids, 1 to 6 methyl-substituted biphenylboronic acids, naphthylboronic acids, cyano-substituted naphthylboronic acids, dibenzofuranylboronic acids, phenyl-substituted dibenzofuranylboronic acids, 9-dimethylfluorenylboronic acids, carbazolyl or 9-phenylcarbazolyl boronic acids, 1 to 6C 1 -C 3 Alkyl-substituted biphenylboronic acids, mono-C 1 -C 3 Alkyl-substituted naphthyl boronic acids, mono C 1 -C 3 Alkyl-substituted dibenzofuranylboronic acids, monoc 1 -C 3 Alkyl-substituted 9, 9-dimethylfluorenylboronic acid or mono C 1 -C 3 Alkyl-substituted carbazolylboronic acid of (a);
in Process E, the two alkyl substituents obtained by dialkylation are each independently C 1 -C 10 Is branched orBranched alkyl, substituted aryl boronic acids being phenyl boronic acids substituted by cyano groups, C 1 -C 5 Alkoxy-substituted phenylboronic acids, biphenylboronic acids, 1 to 6 methyl-substituted biphenylboronic acids, naphthylboronic acids, cyano-substituted naphthylboronic acids, dibenzofuranylboronic acids, phenyl-substituted dibenzofuranylboronic acids, 9-dimethylfluorenylboronic acids, carbazolyl or 9-phenylcarbazolyl boronic acids, 1 to 6C 1 -C 3 Alkyl-substituted biphenylboronic acids, mono-C 1 -C 3 Alkyl-substituted naphthyl boronic acids, mono C 1 -C 3 Alkyl-substituted dibenzofuranylboronic acids, monoc 1 -C 3 Alkyl-substituted 9, 9-dimethylfluorenylboronic acids or mono C 1 -C 3 Alkyl-substituted carbazolylboronic acids of (a).
The synthesis of short-circuit lines by the above methods A-E is based on derivatives of pyrene and naphthalene benzofurans.
The invention also provides application of the derivative based on pyrene and naphthofuran as an electroluminescent layer material in an organic electroluminescent device.
The compounds provided by the invention have high fluorescence quantum efficiency, electron hole transmission balance, efficient composite luminescence of exciton energy in a luminescent layer, high luminescent efficiency of the same device, small roll-off and wide application in the field of electroluminescence.
The invention also provides an electroluminescent device comprising a pair of electrodes and an organic light-emitting medium arranged between the pair of electrodes, wherein the organic light-emitting medium contains at least one compound provided by the invention.
The device provided by the invention takes the derivative based on pyrene and naphthofuran as a material, and has high luminous efficiency and small roll-off.
Drawings
Fig. 1 is a structural view of an electroluminescent device provided by the present invention.
Detailed Description
The principles and features of the present invention are described below, and the examples are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1: the invention provides 1 as an example, which can be synthesized by the following method.
Figure BDA0001218086480000141
Adding 2-bromonaphthalene [2,3-b ] into a 100ml three-neck bottle]2.97g of benzofuran, 2.71g of phenylboronic acid, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and protection of nitrogen, and reacting at 80 ℃ for 12 hours. TLC showed the reaction was complete. The toluene was spun off, ethanol, the aqueous phase was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated and the product 1 was obtained by column chromatography in 80% yield. MALDI TOF MS (M +1) theoretical value 419.13, found value [ M +1] + 419.13。
Example 2: the present invention provides 4 as an example, which can be synthesized by the following method.
Figure BDA0001218086480000151
Adding 2.97g of 2-bromonaphthalene [2,3-b ] benzofuran and 50ml of anhydrous tetrahydrofuran into a 100ml three-necked bottle, replacing air, reducing the temperature to-78 ℃ under the protection of nitrogen and ethanol, slowly dropwise adding n-butyllithium (2.5mol/L and 4ml), stirring for 2h, reducing the temperature to-78 ℃ again, slowly dropwise adding 2.3g of trimethyl borate, heating to room temperature after dropwise adding, and stirring for 12 h. TLC shows that the reaction is complete, water is added for quenching, tetrahydrofuran is spun off, 60ml dichloromethane solution is added, saturated sodium sulfite aqueous solution is added for washing, washing is carried out, anhydrous sodium sulfate is dried, concentration and recrystallization are carried out, and the white solid product 2-naphthalene [2,3-b ] benzofuran boric acid is obtained, wherein the yield is 86%.
2.8g of 2-naphthalene [2,3-b ] benzofuran boronic acid, 3.6g of 1, 6-dibromopyrene, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and reaction at 80 ℃ for 12 hours under the protection of nitrogen. TLC showed the reaction was complete. Toluene was removed by evaporation, ethanol was added, the aqueous phase was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and the product, 2- (6-bromo-1-pyrenyl) naphthalene [2,3-b ] benzofuran, was obtained by column chromatography in 66% yield.
Adding 2- (6-bromo-1-pyrenyl) naphthalene [2,3-b ] into a 100ml three-necked bottle]Benzofuran 2.4g, anhydrous tetrahydrofuran 50ml, grignard reagent of tert-butyl bromide 1.1 times added under ice bath, reaction at room temperature for 2 hours, ammonium chloride solution quenching, dichloromethane extraction of aqueous phase, organic phase combination, drying with anhydrous sodium sulfate, concentration, by column chromatography to obtain product 4 with 76% yield. MALDI TOF MS (M +1) theoretical value 475.20, found value [ M +1] + 475.19。
Example 3: the invention provides 8 as an example, which can be synthesized by the following method.
Figure BDA0001218086480000161
Adding 3.6g of 1, 6-dibromopyrene and 50ml of anhydrous tetrahydrofuran into a 100ml three-necked bottle, adding 1.1 times of Grignard reagent of isopropyl bromide under ice bath, reacting for 2 hours at room temperature, adding ammonium chloride solution for quenching, extracting an aqueous phase by dichloromethane, combining organic phases, drying by anhydrous sodium sulfate, concentrating, and obtaining a product of 1, 6-diisopropylpyrene by column chromatography with the yield of 86%.
Adding 2.97g of 1, 6-diisopropyl pyrene into a 100ml three-necked flask, adding 1.05 times of liquid bromine, stirring at room temperature for reaction for 4 hours, quenching the reaction by using a sodium thiosulfate aqueous solution, extracting by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating and recrystallizing to obtain the 3-bromo-1, 6-diisopropyl pyrene with the yield of 62%.
2-naphthalene [2,3-b ]]2.8g of benzofuran boric acid, 4.1g of 3-bromo-1, 6-diisopropyl pyrene, 0.05g of tetratriphenylphosphine palladium, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and reaction at 80 ℃ for 12 hours under the protection of nitrogen. TLC showed the reaction was complete. The toluene was spun off, ethanol, the aqueous phase was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and the product was obtained by column chromatography in 56% yield. MALDI TOF MS (M +1) theoretical value 503.23, found value [ M +1] + 503.22。
Example 4: the present invention provides 11 as an example, which can be synthesized by the following method.
Figure BDA0001218086480000171
Adding 3.6g of 1, 6-dibromopyrene and 50ml of anhydrous tetrahydrofuran into a 100ml three-necked bottle, adding 1.1 times of Grignard reagent of tert-butyl bromide under ice bath, reacting at room temperature for 2 hours, adding ammonium chloride solution for quenching, extracting an aqueous phase by dichloromethane, combining organic phases, drying by anhydrous sodium sulfate, concentrating, and obtaining a product 1, 6-di-tert-butylpyrene with the yield of 81% by column chromatography.
Adding 3.17g of 1, 6-di-tert-butylpyrene into a 100ml three-necked flask, adding 2.1 times of liquid bromine, stirring at room temperature for reaction for 4 hours, quenching the reaction by using a sodium thiosulfate aqueous solution, extracting by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating, recrystallizing to obtain the 1, 6-dibromo-3, 8-di-tert-butylpyrene with the yield of 81 percent.
1.3g of phenylboronic acid, 4.7g of 1, 6-dibromo-3, 8-di-tert-butylpyrene, 0.05g of tetratriphenylphosphine palladium, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and the like are reacted for 6 hours at 80 ℃ under the protection of nitrogen. TLC showed the reaction was complete. Toluene and ethanol are removed by spinning, the water phase is extracted by dichloromethane, the organic phases are combined, dried by anhydrous sodium sulfate and concentrated, and the product 1-bromo-3, 8-di-tert-butyl-6-phenylpyrene is obtained by column chromatography with the yield of 51%.
2-naphthalene [2,3-b ]]2.8g of benzofuran boric acid, 4.8g of 1-bromo-3, 8-di-tert-butyl-6-phenylpyrene, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and a nitrogen protection reaction at 80 ℃ for 12 hours. TLC showed the reaction was complete. The toluene was spun off, ethanol, the aqueous phase was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated and the product was obtained by column chromatography in 51% yield. MALDI TOF MS (M +1) theoretical value 607.2922, found value [ M +1] + 607.2921。
Example 5: the invention provides 15 as an example, which can be synthesized by the following method.
Figure BDA0001218086480000181
1.3g of p-cyanobenzene boronic acid, 3.6g of 1, 6-dibromopyrene, 0.05g of palladium tetrakistriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol and 30ml of water are reacted for 6 hours at 80 ℃ under the protection of nitrogen. TLC showed the reaction was complete. Toluene and ethanol are removed by spinning, the water phase is extracted by dichloromethane, the organic phases are combined, dried by anhydrous sodium sulfate and concentrated, and the product 1-bromo-6-p-cyanophenylpyrene is obtained by column chromatography with the yield of 66%.
1-bromo-6-p-cyanophenylpyrene 3.8g, 2-naphthalene [2,3-b ]]2.8g of benzofuranboronic acid, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and reaction for 12 hours at 80 ℃ under the protection of nitrogen. TLC showed the reaction was complete. Toluene was removed by evaporation, ethanol was added, the aqueous phase was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated and the product was obtained by column chromatography in 49% yield. MALDI TOF MS (M +1) theoretical value 520.16, found value [ M +1] + 520.16。
Example 6: the 18 of the present invention can be synthesized by the following method.
Figure BDA0001218086480000191
1.3g of m-methoxyphenylboronic acid, 3.6g of 1, 6-dibromopyrene, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol and 30ml of water are reacted for 6 hours at 80 ℃ under the protection of nitrogen. TLC showed the reaction was complete. Toluene and ethanol are removed by spinning, the water phase is extracted by dichloromethane, the organic phases are combined, dried by anhydrous sodium sulfate and concentrated, and the product 1-bromo-6-m-methoxyphenyl pyrene is obtained by column chromatography with the yield of 57%.
1-bromo-6-m-methoxyphenyl pyrene 3.9g, 2-naphthalene [2,3-b ]]2.8g of benzofuranboronic acid, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and reaction for 12 hours at 80 ℃ under the protection of nitrogen. TLC showed the reaction was complete. The toluene was spun off, ethanol, the aqueous phase was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated and the product was obtained by column chromatography in 61% yield. MALDI TOF MS (M +1) theoretical value 525.17, found value [ M +1] + 525.16。
Example 7: the 29 described in the present invention can be synthesized by the following method.
Figure BDA0001218086480000192
Referring to example 6, [1,1' -biphenyl ] -2-boronic acid 2.1g, 1, 6-dibromopyrene 3.6g, palladium tetratriphenylphosphine 0.05g, potassium carbonate 4g, toluene 30ml, ethanol 15ml, water 30ml, under nitrogen protection, were reacted at 80 ℃ for 6 hours. TLC showed the reaction was complete. Toluene and ethanol are removed by spinning, the water phase is extracted by dichloromethane, the organic phases are combined, dried by anhydrous sodium sulfate and concentrated, and an intermediate product 1- ([1,1' -diphenyl ] -2-yl) -6-bromopyrene is obtained by column chromatography with the yield of 57%.
1- ([1,1' -Diphenyl group)]-2-yl) -6-bromopyrene 4.3g, 2-naphthalene [2,3-b]2.8g of benzofuranboronic acid, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and reaction for 12 hours at 80 ℃ under the protection of nitrogen. TLC showed the reaction was complete. Toluene was removed, ethanol was extracted with dichloromethane, the aqueous phases were combined, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to give product 29 in 63% yield. MALDI TOF MS (M +1) theoretical value 571.19, found value [ M +1] + 571.19。
Example 8: the present invention provides 45 as an example, which can be synthesized by the following method.
Figure BDA0001218086480000201
Referring to example 6, 1.9g of 1-naphthalene boronic acid, 3.6g of 1, 6-dibromopyrene, 0.05g of tetratriphenylphosphine palladium, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and a nitrogen atmosphere were reacted at 80 ℃ for 6 hours. TLC showed the reaction was complete. Toluene and ethanol are removed by spinning, the water phase is extracted by dichloromethane, the organic phases are combined, dried by anhydrous sodium sulfate and concentrated, and an intermediate product 1-bromo-6-naphthyl pyrene is obtained by column chromatography with the yield of 52%.
1-bromo-6-naphthylpyrene 4.0g, 2-naphthalene [2,3-b ]]2.8g of benzofuran boric acid, 0.05g of palladium tetrakistriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and a nitrogen protection reaction at 80 ℃ for 12 hours. TLC showed the reaction was complete. Is screwed offToluene, ethanol, extraction of the aqueous phase with dichloromethane, combination of the organic phases, drying over anhydrous sodium sulfate, concentration and column chromatography gave the product 45 in 52% yield. MALDI TOF MS (M +1) theoretical value 547.18, found value [ M +1] + 537.18。
Example 9: the present invention provides 48 as an example, which can be synthesized by the following method.
Figure BDA0001218086480000211
Reference example 2.1g of 8-cyano-1-naphthalene boronic acid, 3.6g of 1, 6-dibromopyrene, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and a nitrogen atmosphere were reacted at 80 ℃ for 6 hours. TLC showed the reaction was complete. Toluene and ethanol are removed by spinning, the water phase is extracted by dichloromethane, the organic phases are combined, dried by anhydrous sodium sulfate and concentrated, and an intermediate product 1-bromo-6- [1- (8-phenyl) naphthyl ] pyrene is obtained by column chromatography with the yield of 43%.
1-bromo-6- [1- (8-phenyl) naphthyl]Pyrene 4.3g, 2-naphthalene [2,3-b ]]2.8g of benzofuran boric acid, 0.05g of palladium tetrakistriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and a nitrogen protection reaction at 80 ℃ for 12 hours. TLC showed the reaction was complete. The toluene was removed by evaporation, the ethanol was extracted with dichloromethane, the aqueous phases were combined, dried over anhydrous sodium sulfate, concentrated and the product was obtained by column chromatography in 52% yield. MALDI TOF MS (M +1) theoretical value 569.17, found value [ M +1] + 569.17。
Example 10: the 55 provided by the invention is an example, and can be synthesized by the following method.
Figure BDA0001218086480000221
2.3g of 4-dibenzofuran boric acid, 4.7g of 1, 6-dibromo-3, 8-di-tert-butylpyrene, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and reaction at 80 ℃ for 6 hours under the protection of nitrogen. TLC showed the reaction was complete. Toluene was removed by rotation, ethanol was added, the aqueous phase was extracted with methylene chloride, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and the product 1-bromo-3, 8-di-tert-butyl-6- (4-dibenzofuranyl) pyrene was obtained by column chromatography in 43% yield.
2-naphthalene [2,3-b ]]2.8g of benzofuranboronic acid, 5.6g of 1-bromo-3, 8-di-tert-butyl-6- (4-dibenzofuranyl) pyrene, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and a nitrogen protection atmosphere, and reacting at 80 ℃ for 12 hours. TLC showed the reaction was complete. Toluene was removed, ethanol was extracted with dichloromethane, the aqueous phases were combined, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to give the product 55 in 31% yield. MALDI TOF MS (M +1) theoretical value 699.31, found value [ M +1] + 699.31。
Example 11: the 57 provided by the present invention is an example, which can be synthesized by the following method.
Figure BDA0001218086480000231
Adding 2.97g of 1, 6-diisopropyl pyrene into a 100ml three-necked flask, adding 2.1 times of liquid bromine, stirring at room temperature for reaction for 4 hours, quenching the reaction by using a sodium thiosulfate aqueous solution, extracting by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating, recrystallizing to obtain the 1, 6-dibromo-3, 8-diisopropyl pyrene with the yield of 67 percent.
2.5g of 9, 9-dimethyl-1-fluorenylboronic acid, 3.1g of (6-phenyldiphenyl [ b, d ] furan-4-yl) boronic acid, 0.05g of palladium tetrakistriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and protection of nitrogen, and the reaction is carried out at 80 ℃ for 12 hours. TLC showed the reaction was complete. Toluene was removed by evaporation, ethanol was added, the aqueous phase was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and the product, 4- (6-bromo-3, 8-diisopropylpyrene-1-yl) -6-phenyldibenzo [ b, d ] furan, was obtained by column chromatography with a yield of 44%.
2-naphthalene [2,3-b ]]Benzofuran boronic acid 2.8g, 4- (6-bromo-3, 8-diisopropylpyrene-1-yl) -6-phenyldibenzo [ b, d]6.1g of furan, 0.05g of palladium tetrakistriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol and 30ml of water are reacted for 12h at 80 ℃ under the protection of nitrogen. TLC showed the reaction was complete. Removing toluene and ethanol, extracting water phase with dichloromethane, mixing organic phases, and removing impuritiesDried over sodium sulfate, concentrated and column chromatographed to give 66 in 39% yield. MALDI TOF MS (M +1) theoretical value 745.30, found value [ M +1] + 745.30。
Example 12: 66 provided by the present invention is an example, which can be synthesized by the following method.
Figure BDA0001218086480000241
Adding 2.97g of 1, 6-diisopropyl pyrene into a 100ml three-necked flask, adding 2.1 times of liquid bromine, stirring and reacting for 4 hours at room temperature, quenching the reaction by using a sodium thiosulfate aqueous solution, extracting by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating and recrystallizing to obtain the 1, 6-dibromo-3, 8-diisopropyl pyrene with the yield of 67 percent.
2.5g of 9, 9-dimethyl-1-fluorenylboronic acid, 3.8g of 1, 6-dibromo-3, 8-diisopropylpyrene, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and protection of nitrogen gas are reacted at 80 ℃ for 12 hours. TLC showed the reaction was complete. Toluene and ethanol are removed by spinning, the water phase is extracted by dichloromethane, the organic phases are combined, dried by anhydrous sodium sulfate and concentrated, and the product 1-bromo-3, 8-diisopropyl-6- (1-9, 9-dimethylfluorenyl) pyrene is obtained by column chromatography with the yield of 51%.
2-naphthalene [2,3-b ]]2.8g of benzofuran boric acid, 5.5g of 1-bromo-3, 8-diisopropyl-6- (1-9, 9-dimethylfluorenyl) pyrene, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and reaction at 80 ℃ for 12h under the protection of nitrogen. TLC showed the reaction was complete. The toluene was spun off, ethanol, the aqueous phase was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated and the product was obtained by column chromatography in 39% yield. MALDI TOF MS (M +1) theoretical value 697.33, found value [ M +1] + 697.32。
Example 13: the 79 provided by the invention is an example, and can be synthesized by the following method.
Figure BDA0001218086480000251
3.2g of 9-phenyl-3-carbazole boric acid, 4.7g of 1, 6-dibromo-3, 8-di-tert-butylpyrene, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and reaction at 80 ℃ for 6 hours under the protection of nitrogen. TLC showed the reaction was complete. Toluene and ethanol are removed by spinning, a water phase is extracted by dichloromethane, organic phases are combined, dried by anhydrous sodium sulfate and concentrated, and a product 1-bromo-3, 8-di-tert-butyl-6- (3-9-phenylcarbazolyl) pyrene is obtained by column chromatography with the yield of 43%.
2-naphthalene [2,3-b ]]2.8g of benzofuranboronic acid, 6.4g of 1-bromo-3, 8-di-tert-butyl-6- (3-9-phenylcarbazolyl) pyrene, 0.05g of palladium tetrakistriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and reaction at 80 ℃ for 12 hours under the protection of nitrogen. TLC showed the reaction was complete. Toluene was removed by evaporation, ethanol was added, the aqueous phase was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated and the product was obtained by column chromatography in 31% yield. MALDI TOF MS (M +1) theoretical value 774.37, found value [ M +1] + 774.37。
Example 14: the 88 provided by the invention is an example, which can be synthesized by the following method.
Figure BDA0001218086480000261
Referring to example 4, 3.6g of 1, 6-dibromopyrene and 50ml of anhydrous tetrahydrofuran were added to a 100ml three-necked flask, 1.1-fold Grignard reagent of t-butyl bromide was added under ice bath, reacted at room temperature for 2 hours, quenched by adding ammonium chloride solution, the aqueous phase was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and the product 1, 6-di-t-butylpyrene was obtained by column chromatography in 80% yield.
Adding 3.17g of 1, 6-di-tert-butylpyrene into a 100ml three-necked flask, adding 2.1 times of liquid bromine, stirring at room temperature for reaction for 4 hours, quenching the reaction by using a sodium thiosulfate aqueous solution, extracting by using ethyl acetate, combining organic phases, drying by using anhydrous sodium sulfate, concentrating, recrystallizing to obtain the 1, 6-dibromo-3, 8-di-tert-butylpyrene with the yield of 82%.
1.65g of 2-methoxyphenylboronic acid, 4.7g of 1, 6-dibromo-3, 8-di-tert-butylpyrene, 0.05g of tetratriphenylphosphine palladium, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and reaction at 80 ℃ for 6 hours under the protection of nitrogen. TLC showed the reaction was complete. Toluene and ethanol are removed by spinning, the water phase is extracted by dichloromethane, the organic phases are combined, dried by anhydrous sodium sulfate and concentrated, and the product 1-bromo-3, 8-di-tert-butyl-6-methoxy-2-phenylpyrene is obtained by column chromatography with the yield of 52%.
2-naphthalene [2,3-b ]]2.8g of benzofuran boric acid, 5.1g of 1-bromo-3, 8-di-tert-butyl-6-methoxy-2-phenylpyrene, 0.05g of palladium tetratriphenylphosphine, 4g of potassium carbonate, 30ml of toluene, 15ml of ethanol, 30ml of water and reaction at 80 ℃ for 12 hours under the protection of nitrogen. TLC showed the reaction was complete. Toluene was removed by evaporation, ethanol was added, the aqueous phase was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, concentrated and the product was purified by column chromatography to give 88 in 53% yield. MALDI TOF MS (M +1) theoretical value 621.31, found value [ M +1] + 621.30。
Example 15: 1 as a light emitting layer.
This example demonstrates performance verification of 1 an electroluminescent device prepared as a luminescent material. The ITO (indium tin oxide) glass was successively cleaned with ultrasound in a detergent and deionized water for 30 minutes. Then vacuum-dried for 2 hours (105 ℃), then the ITO glass was put into a plasma reactor for oxygen plasma treatment for 5 minutes, transferred into a vacuum chamber to prepare an organic film and a metal electrode, then a layer of molybdenum trioxide, which is a hole injection material, was prepared at 10nm by a vacuum evaporation method, then a 70nm thick hole transport material, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC), was evaporated, and then a 12nm light-emitting layer, 1: 6% of compound 1: 4,4 '-bis (9-ethyl-3-carbazole vinyl) -1,1' -biphenyl (BCzVBi), evaporating 1,3, 5-tri [ (3-pyridyl) -3-phenyl ] benzene (TmPyPB) by 20nm to serve as an electron transport layer, and finally evaporating a layer of 1nm LiF and 100nm Al.
Aluminum is used as the cathode of the device, the anode of direct current is added to the ITO (indium tin oxide) layer, the cathode is added to the metal layer, and bright and uniform deep blue light emitted from the ITO (indium tin oxide) layer can be obtained, the CIE color coordinate is (0.15,0.06), the starting voltage is 2.78V, and the maximum brightness is 15840cd/m 2 The maximum current efficiency was 8.82 cd/A. The experimental device has the structure that: ITO (indium tin oxide)/MoO 3 (10nm)//TAPC(70nm)/1：wt6％BCzVBi(12nm)/TMPYPB(20nm)/LiF(1nm)/Al(100nm)。
Example 16: 4 as a light emitting layer.
This example demonstrates 4 performance verification of an electroluminescent device prepared as a light emitting material. The ITO (indium tin oxide) glass was successively cleaned with ultrasound in a detergent and deionized water for 30 minutes. Then vacuum-dried for 2 hours (105 ℃), then the ITO glass was put into a plasma reactor for oxygen plasma treatment for 5 minutes, transferred into a vacuum chamber to prepare an organic film and a metal electrode, then a layer of molybdenum trioxide, which is a hole injection material, was prepared at 10nm by a vacuum evaporation method, then a 70nm thick hole transport material, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC), was evaporated, and then a 12nm light-emitting layer, 4: 6% of compound 1, was vacuum-evaporated: 4,4 '-bis (9-ethyl-3-carbazolevinyl) -1,1' -biphenyl (BCzVBi), evaporating 1,3, 5-tri [ (3-pyridyl) -3-phenyl ] benzene (TmPyPB) by 20nm as an electron transport layer, and finally evaporating a layer of LiF with the thickness of 1nm and Al with the thickness of 100 nm.
Aluminum is used as the cathode of the device, the anode of direct current is added to the ITO (indium tin oxide) layer, the cathode is added to the metal layer, and bright and uniform deep blue light emitted from the ITO (indium tin oxide) layer can be obtained, the CIE color coordinate is (0.15,0.07), the starting voltage is 2.88V, and the maximum brightness is 13760cd/m 2 The maximum current efficiency was 7.83 cd/A. The experimental device has the structure that: ITO (indium tin oxide)/MoO 3 (10nm)//TAPC(70nm)/4：wt 6％BCzVBi(12nm)/TMPYPB(20nm)/LiF(1nm)/Al(100nm)。
The compounds 1, 4, 8, 11, 15, 18, 29, 45, 48, 55, 57, 66, 79 and 88 are used for preparing devices with the same structure, and the device performances are shown in the following table 1. The table 1 shows that part of the compounds are expressed in the organic electroluminescent device, and the data in the table show that the material is outstanding when being used as a fluorescent object, and is a luminescent material with a wide application prospect.
TABLE 1 device fundamental Properties of some of the Compounds
Figure BDA0001218086480000281
Figure BDA0001218086480000291
From the above, the organic light-emitting device prepared from the organic electroluminescent material based on pyrene and naphthalene benzofuran provided by the invention has low starting voltage, high brightness, high external quantum efficiency, and adjustable light color to deep blue light, and has important application value in constructing blue light organic light-emitting materials.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.

Claims (4)

1. Derivatives based on pyrene and naphthalene benzofurans, characterized in that they have the general structural formula:
Figure FDA0003755417260000011
wherein R is 2 、R 3 Are respectively and independently 2a-2f structure, R 2 And R 3 The same or different:
Figure FDA0003755417260000012
R 1 is phenyl, cyano-substituted phenyl, C 1 -C 5 Alkoxy-substituted phenyl, biphenyl, dibenzofuranyl, phenyl-substituted dibenzofuranyl, 9-dimethylfluorenyl, carbazolyl, 9-phenylcarbazolyl, 1 to 6C 1 -C 3 Alkyl-substituted biphenyls, mono-C of 1 -C 3 Alkyl-substituted dibenzofuranyl, mono-C of 1 -C 3 Alkyl-substituted 9, 9-dimethylfluorenyl or mono C 1 -C 3 Alkyl of (2)A substituted carbazolyl group.
2. A method for preparing pyrene and naphthalene benzofuran based derivatives according to claim 1, wherein:
method a comprising the steps of:
Figure FDA0003755417260000013
and
Figure FDA0003755417260000014
suzuki reaction to obtain a derivative based on pyrene and naphthofuran;
alternatively, method B comprises the steps of:
1)
Figure FDA0003755417260000015
boration to obtain
Figure FDA0003755417260000016
2)
Figure FDA0003755417260000017
And
Figure FDA0003755417260000018
after Suzuki reaction, alkylating the Suzuki by using a Grignard reagent to obtain a derivative based on pyrene and naphthalene benzofuran;
alternatively, method C comprises the steps of:
1)
Figure FDA0003755417260000021
completely alkylating the completely formatted reagent to obtain a dialkylated intermediate;
2) after mono-bromination of the dialkylated intermediate, with
Figure FDA0003755417260000022
Suzuki reaction to obtain a derivative based on pyrene and naphthalene benzofuran;
alternatively, method D comprises the steps of:
1)
Figure FDA0003755417260000023
reacting with substituted or unsubstituted arylboronic acid
Figure FDA0003755417260000024
Suzuki reaction to obtain a derivative based on pyrene and naphthofuran;
alternatively, method E comprises the steps of:
1)
Figure FDA0003755417260000025
completely alkylating the completely formatted reagent to obtain a dialkylated intermediate;
2) after the dialkylated intermediate is dibrominated, the intermediate is then reacted sequentially with a substituted or unsubstituted arylboronic acid and
Figure FDA0003755417260000026
suzuki reaction to obtain a derivative based on pyrene and naphthalene benzofuran;
wherein:
in the method B, the alkyl substituent obtained by alkylation is of a 2a-2f structure;
in the method C, two alkyl substituent groups obtained by dialkylation are respectively and independently 2a-2f structures;
in the method D, the substituted aryl boric acid is cyano-substituted phenyl boric acid, C 1 -C 5 Alkoxy-substituted phenylboronic acids, biphenylboronic acids, dibenzofuranylboronic acids, phenyl-substituted dibenzofuranylboronic acids, 9-dimethylfluorenylboronic acids, carbazolylboronic acids, 9-phenylcarbazolylboronic acids, 1 to 6C 1 -C 3 Alkyl-substituted biphenylboronic acids, mono-C 1 -C 3 Alkyl-substituted dibenzofuranylboronic acids, monoc 1 -C 3 Alkyl-substituted 9, 9-dimethylfluorenylboronic acids or mono C 1 -C 3 Alkyl-substituted carbazolylboronic acid of (a);
in the method E, two alkyl substituents obtained by dialkylation are respectively and independently 2a-2f structures, and the substituted aryl boric acid is cyano-substituted phenyl boric acid and C 1 -C 5 Alkoxy-substituted phenylboronic acids, biphenylboronic acids, dibenzofuranylboronic acids, phenyl-substituted dibenzofuranylboronic acids, 9-dimethylfluorenylboronic acids, carbazolylboronic acids, 9-phenylcarbazolylboronic acids, 1 to 6C 1 -C 3 Alkyl-substituted biphenylboronic acids, mono-C 1 -C 3 Alkyl-substituted dibenzofuranylboronic acids, mono-C 1 -C 3 Alkyl-substituted 9, 9-dimethylfluorenylboronic acids or mono C 1 -C 3 Alkyl-substituted carbazolylboronic acid of (a).
3. Use of the pyrene and naphthalene benzofuran based derivatives according to claim 1, wherein: as the electroluminescent layer material in the organic electroluminescent device.
4. An electroluminescent device comprising a pair of electrodes and an organic light-emissive medium disposed between the pair of electrodes, characterized in that: the organic light-emitting medium contains at least one derivative selected from the derivatives according to claim 1.
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