WO2023103611A1 - Bromopyrene intermediate and derivatives thereof, preparation method, and use - Google Patents

Bromopyrene intermediate and derivatives thereof, preparation method, and use Download PDF

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WO2023103611A1
WO2023103611A1 PCT/CN2022/126686 CN2022126686W WO2023103611A1 WO 2023103611 A1 WO2023103611 A1 WO 2023103611A1 CN 2022126686 W CN2022126686 W CN 2022126686W WO 2023103611 A1 WO2023103611 A1 WO 2023103611A1
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pyrene
bromopyrene
luminescent material
tetrakis
based organic
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French (fr)
Chinese (zh)
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冯星
王晓慧
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广东工业大学
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    • C07C39/24—Halogenated derivatives
    • C07C39/40—Halogenated derivatives with at least one hydroxy group on a condensed ring system containing more than two rings
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    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
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Definitions

  • the invention belongs to the cross field of fine chemical industry and photoelectric material, and specifically relates to a class of bromopyrene intermediates and derivatives thereof, preparation methods and applications.
  • Pyrene is a common fused-ring aromatic hydrocarbon compound, and its main source is a by-product of petroleum/coal chemical industry. It has strong ⁇ -electron delocalization energy and unique blue light properties, and is widely used in organic optoelectronic devices, biosensors, Fields such as fluorescent probes have now become a popular building block for designing and synthesizing organic semiconductor materials.
  • pyrene is a strong carcinogen. If it is not fully utilized, it will cause great damage to the environment. Therefore, adhering to the idea of "turning waste into treasure, turning waste into treasure", this
  • the purpose of the invention is to design a simple synthetic method, and to develop chemical by-products into new chemical raw intermediates by optimizing the synthetic route, and to improve the yield of the synthetic route, and to accelerate the entry of such intermediates into the industrial chain and to be applied to organic semiconductors. , bioimaging and other fields.
  • the development of new pyrene-based intermediates will facilitate the development of new pyrene-based derivatives.
  • high-performance pyrenyl-based optoelectronic materials can be prepared to promote the development of pyrenyl-based functional materials.
  • the primary purpose of the present invention is to provide a bromopyrene intermediate.
  • Another object of the present invention is to provide a synthesis method of the above-mentioned bromopyrene intermediate, which has reasonable process design, high yield, mild reaction conditions and low raw material prices.
  • Another object of the invention lies in the pyrene-based luminescent material prepared based on the pyrene-based intermediate.
  • a further object of the invention is to provide the application of the above-mentioned pyrene-based functional materials.
  • a class of bromopyrene intermediates the molecular structural formula of the bromopyrene intermediates is as shown in (1):
  • R is H or OH.
  • the bromopyrene intermediate is 2-hydroxy-1,3,6,8-tetrabromopyrene or 2,7-dihydroxy-1,3,6,8-tetrabromopyrene; its molecular structure is as 1a or 1b Shown:
  • the preparation method of the bromopyrene intermediate, the bromopyrene intermediate is 2-hydroxypyrene or 2,7-dihydroxypyrene as raw material, adding a brominating agent and an organic solvent under an inert atmosphere, at 50 to 130 Heating and stirring at °C for 10-40 hours for bromination reaction to obtain 2-hydroxy-1,3,6,8-tetrabromopyrene or 2,7-dihydroxy-1,3,6,8-tetrabromopyrene.
  • the brominating agent is one or more of bromine water, N-bromosuccinimide or benzyltrimethylammonium bromide dibromide; the inert atmosphere is nitrogen or argon; the organic Solvent is more than one in nitrobenzene, dichloromethane, chloroform, acetonitrile; Described 2-hydroxypyrene or 2,7-dihydroxypyrene: the molar ratio of brominating agent is 1:(1 ⁇ 10 ).
  • a pyrene-based organic functional luminescent material the molecular structure of the pyrene-based organic functional luminescent material is shown in 2a or 2b:
  • the pyrene-based organic functional luminescent material is prepared by adding the bromopyrene intermediate into palladium catalyst, aromatic hydrocarbon boronic acid and its derivatives, inorganic base and solvent under a protective atmosphere, and catalyzing the coupling reaction by palladium at 50-100°C , were prepared by functional substitution at multiple sites of pyrene.
  • the protective atmosphere is nitrogen or argon;
  • the palladium catalyst is tetrakis(triphenylphosphine)palladium, palladium acetate, tris(tert-butylphosphine) tetrafluoroborate or tris(dibenzylideneacetone)di
  • the inorganic base is one or more of potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, and sodium hydroxide
  • the solvent is one or more of toluene, ethanol, water, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, and triethylamine;
  • the aromatic hydrocarbon boronic acid and its derivatives are 4-methoxyphenyl Boronic acid, 4-trifluoromethylphenylboronic acid, 2-thienylboronic acid, 4-trimethoxyanilinoboronic
  • the structural formula of the pyrene-based organic functional luminescent material is:
  • a pyrene-based organic functional luminescent material the molecular structure of the pyrene-based organic functional luminescent material is shown in 3a or 3b:
  • R 2 is methyl, ethyl, phenyl or benzyl
  • the pyrene-based organic functional luminescent material is to dissolve the above-mentioned pyrene-based organic functional luminescent material, the halide of the R2 substituent group and the inorganic base in an organic solvent, heat and stir at 60-80° C. for 5-12 hours, and after the reaction is completed, Cool to room temperature, extract and wash with dichloromethane, extract with saturated brine, filter after dehydration with anhydrous magnesium sulfate, perform chromatographic column separation and recrystallization after rotary evaporation;
  • the R halide substituent is methyl iodide, ethyl iodide, benzyl bromide or bromobenzene;
  • the inert atmosphere is nitrogen or argon;
  • the inorganic base is potassium carbonate, tert-butyl alcohol One or more of potassium, sodium carbonate, sodium bicarbonate, potassium bicarbonate, and sodium hydroxide;
  • the organic solvent is one or more of acetonitrile, tetrahydrofuran, dichloromethane, and ethanol;
  • R 2 substituent group halide: inorganic base molar ratio is 1:(1 ⁇ 10):(5 ⁇ 20).
  • the present invention has the following beneficial effects:
  • the organic luminescent material prepared as a precursor with the bromopyrene intermediate of the present invention by introducing a hydroxyl group at the 2- and 7-position of pyrene, the substituent group at the 1,3,6,8-position can be combined with the pyrene ring Form a large dihedral angle, effectively inhibit the interaction between molecules, improve the luminous efficiency of the target molecule, and improve its charge transport performance by balancing the charge in the molecule.
  • the introduction of hydroxyl or R 2 substituent groups can effectively Improving the hydrophilicity of target molecules is conducive to the application of such luminescent molecules in the biological field;
  • the synthetic method of the present invention has the advantages of simple experimental operation, mild reaction conditions, and high intermediate yield
  • the pyrene-based organic luminescent material of the present invention can effectively improve the solid luminous efficiency of the material, and is applied in the field of organic optoelectronics;
  • the bromopyrene intermediate and the pyrene-based organic luminescent material of the present invention can increase the hydrophilicity of the bromopyrene intermediate and the pyrene-based organic luminescent material due to the presence of hydroxyl or R substituting groups, improve the solubility of the material, and facilitate direct Applied in biological imaging and other fields.
  • Figure 1 is the HRMS chart of 2-hydroxyl-1,3,6,8-tetrabromopyrene in Example 1.
  • Figure 2 is the HRMS chart of 2,7-dihydroxy-1,3,6,8-tetrabromopyrene of Example 2.
  • Fig. 3 is a 1 H NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene in Example 3.
  • Fig. 4 is a 13 C NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene in Example 3.
  • Fig. 5 is the HRMS chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene in Example 3.
  • Fig. 6 is a single crystal structure diagram of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene in Example 3.
  • Example 7 is a 1 H NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene in Example 4.
  • Example 10 is a single crystal structure diagram of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene in Example 4.
  • Fig. 11 is a 1 H NMR chart of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene in Example 5.
  • Example 14 is a single crystal structure diagram of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene in Example 5.
  • 16 is a 13 C NMR chart of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene in Example 6.
  • FIG. 16 is a 13 C NMR chart of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene in Example 6.
  • FIG. 17 is an HRMS chart of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene of Example 6.
  • FIG. 19 is a 1 H NMR chart of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene of Example 7.
  • FIG. 19 is a 1 H NMR chart of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene of Example 7.
  • FIG. 20 is a 13 C NMR chart of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene in Example 7.
  • FIG. 20 is a 13 C NMR chart of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene in Example 7.
  • FIG. 21 is an HRMS chart of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene of Example 7.
  • Example 22 is a single crystal structure diagram of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene in Example 7.
  • FIG. 23 is a 1 H NMR chart of 1,3,6,8-tetrakis-(2-thienyl)-2,7-hydroxypyrene of Example 8.
  • FIG. 23 is a 1 H NMR chart of 1,3,6,8-tetrakis-(2-thienyl)-2,7-hydroxypyrene of Example 8.
  • 25 is an HRMS chart of 1,3,6,8-tetrakis-(2-thienyl)-2,7-hydroxypyrene of Example 8.
  • 26 is a single crystal structure diagram of 1,3,6,8-tetrakis-(2-thienyl)-2,7-hydroxypyrene in Example 8.
  • FIG. 27 is a 1 H NMR chart of 1,3,6,8-tetrakis-(4-triphenylamine)-2,7-dihydroxypyrene of Example 9.
  • FIG. 27 is a 1 H NMR chart of 1,3,6,8-tetrakis-(4-triphenylamine)-2,7-dihydroxypyrene of Example 9.
  • FIG. 29 is an HRMS chart of 1,3,6,8-tetrakis-(4-triphenylamine)-2,7-dihydroxypyrene of Example 9.
  • Example 30 is a 1 H NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene in Example 10.
  • Example 31 is a 13 C NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene in Example 10.
  • 33 is a single crystal structure diagram of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene in Example 10.
  • Figure 34 is the 1,3,6,8-tetrasubstituted-2,7-dihydroxy-pyrene derivatives, 1,3,6,8 obtained from bromopyrene intermediates in Examples 3, 4, 5, 6, and 10 - UV-vis and fluorescence spectra of tetrasubstituted-2-hydroxy-pyrene derivatives and 1,3,6,8-tetrasubstituted-2-methoxy-pyrene derivatives.
  • Fig. 1 is the high-resolution mass spectrum of 2-hydroxyl-1,3,6,8-tetrabromopyrene obtained in this example, as can be seen from Fig. 1, bromopyrene intermediate 2-hydroxyl-1,3,6 ,8-Tetrabromopyrene.
  • Figure 2 is the high-resolution mass spectrum of 2,7-dihydroxy-1,3,6,8-tetrabromopyrene obtained in this example, as can be seen from Figure 2, the bromopyrene intermediate 2,7-dihydroxy -1,3,6,8-Tetrabromopyrene.
  • Fig. 3 is the 1 H NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene obtained in this example.
  • Figure 4 is the 13 C NMR figure of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene obtained in this example, and
  • Figure 5 is the 1,3,8 obtained in this example The HRMS figure of 6,8-tetra-(4-methoxyphenyl)-2-hydroxypyrene
  • Figure 6 is the 1,3,6,8-tetra-(4-methoxyphenyl obtained in this example )-2-hydroxypyrene single crystal structure diagram, as can be seen from Figure 3-6, 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene organic blue light material was successfully prepared.
  • Fig. 7 is the 1 H NMR figure of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene obtained in this embodiment, and Fig. 8 obtained in this embodiment 1, The 13 C NMR figure of 3,6,8-tetra-(4-methoxyphenyl)-2,7 dihydroxypyrene, Figure 9 is the 1,3,6,8-tetra-(4 The HRMS figure of -methoxyphenyl)-2,7-dihydroxypyrene, Fig.
  • 1,3,6,8-tetra-(4-methoxyphenyl)-2,7 that this embodiment obtains -Single crystal structure of dihydroxypyrene, as can be seen from Figure 7-10, 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene was successfully prepared, and the prepared 1,3,6,8-Tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene is a blue light material.
  • Figure 11 is the 1 H NMR figure of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene obtained in the present example
  • Figure 12 is the 1,3 obtained in the present example , 6,8-tetra-(4-trifluoromethylphenyl)-2-hydroxypyrene 13 C NMR figure
  • Figure 13 is the 1,3,6,8-tetra-(4-three The HRMS figure of fluoromethylphenyl)-2-hydroxypyrene
  • FIG. As can be seen from Figures 11-14, 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene organic blue light material was successfully prepared.
  • Figure 15 is the 1 H NMR figure of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene obtained in this example, and Figure 16 is obtained in this example
  • Figure 17 is the 1,3,6,8-
  • Figure 18 is the 1,3,6,8-tetra-(4-trifluoromethylbenzene obtained in this embodiment base)-2,7-dihydroxypyrene single crystal structure, as can be seen from Figures 15-18, 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7 - Dihydroxypyrene organic blue light material.
  • Figure 19 is the 1 H NMR figure of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene obtained in this example, and Figure 20 is the 1,3,6,8 obtained in this example - The 13 C NMR figure of tetrakis-(2-thienyl)-2-hydroxypyrene, Figure 21 is the 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene obtained in this embodiment HRMS diagram, Figure 22 is the single crystal structure diagram of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene obtained in this example, as can be seen from Figures 19-22, successfully prepared 1, 3,6,8-Tetrakis-(2-thienyl)-2-hydroxypyrene.
  • Figure 23 is the 1 H NMR figure of 1,3,6,8-tetrakis-(2-thienyl)-2,7-dihydroxypyrene obtained in this example, and Figure 24 is the 1,3,8-dihydroxypyrene obtained in this example.
  • Figure 25 is the 1,3,6,8-tetra-(2-thienyl) obtained in this example -HRMS diagram of 2,7-dihydroxypyrene
  • Figure 26 is the single crystal structure diagram of 1,3,6,8-tetrakis-(2-thienyl)-2,7-dihydroxypyrene obtained in this example, It can be seen from Figures 23-26 that 1,3,6,8-tetrakis-(2-thienyl)-2,7-dihydroxypyrene was successfully prepared.
  • Figure 27 is the 1 H NMR figure of 1,3,6,8-tetrakis-(4-trimethoxyaniline)-2,7-dihydroxypyrene obtained in this example, and Figure 28 is the 1, The 13 C NMR figure of 3,6,8-tetra-(4-trimethoxyaniline)-2,7-dihydroxypyrene, Figure 29 is the 1,3,6,8-tetra-(4 The HRMS figure of -trimethoxyaniline)-2,7-dihydroxypyrene, as can be seen from Figures 27-29, successfully prepared 1,3,6,8-tetrakis-(4-trimethoxyaniline)-2,7 - dihydroxypyrene.
  • Figure 30 is the 1 H NMR figure of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene obtained in this example, and Figure 31 is the 1 obtained in this example , 3,6,8-tetra-(4-methoxyphenyl)-2-methoxy-pyrene 13 C NMR figure, Figure 32 is the 1,3,6,8-tetra- The HRMS figure of (4-methoxyphenyl)-2-methoxy-pyrene, Figure 33 is the 1,3,6,8-tetra-(4-methoxyphenyl)-2 obtained in this example -Single crystal structure diagram of methoxy-pyrene, as can be seen from Figures 30-33, 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene was successfully prepared.
  • Figure 34 is the 1,3,6,8-tetrasubstituted-2,7-dihydroxy-pyrene derivatives, 1,3,6,8 obtained from bromopyrene intermediates in Examples 3, 4, 5, 6, and 10 - UV-vis and fluorescence spectra of tetrasubstituted-2-hydroxy-pyrene derivatives and 1,3,6,8-tetrasubstituted-2-methoxy-pyrene derivatives.
  • 3a is 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene
  • 3b is 1,3,6,8-tetrakis-(4-trifluoromethane phenyl)-2,7-dihydroxypyrene
  • 4a is 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene
  • 4b is 1,3,6,8- Tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene
  • 5 is 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene.
  • the maximum emission wavelength of 3a, 3b, 4a, 4b and 5 in tetrahydrofuran solution is 426-432nm, and these four types of luminescent materials are all blue light materials.

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Abstract

The present invention belongs to the field of the synthesis of fine chemical intermediates, and discloses a bromopyrene intermediate and derivatives thereof, a preparation method, and use. The bromopyrene intermediate has a molecular structural formula as shown in (1), wherein R is H or OH. In the present invention, 2-hydroxypyrene or 2,7-dihydroxypyrene is used as a raw material and is subjected to boration, hydroxylation and bromination reactions to prepare a bromopyrene intermediate; and then functional substitution is separately performed at a plurality of sites of pyrene by means of a palladium-catalyzed coupling reaction, so as to prepare a pyrene-based organic functional light-emitting material. In the present invention, the raw materials used in the method are easy to purchase and low in price, and the preparation method is simple, is mild in terms of reaction conditions, has low requirements for equipment, and is suitable for industrial production. The pyrene-based organic light-emitting material of the present invention can, due to the introduction of a hydroxyl/R2 substituent group, effectively improve the hydrophilicity of a target molecule, thus facilitating the use of this type of light-emitting molecule in the biological field.

Description

一类溴芘中间体及其衍生物、制备方法和应用A class of bromopyrene intermediates and derivatives thereof, preparation methods and applications 技术领域technical field
本发明属于精细化工和光电材料交叉领域，具体涉及一类溴芘中间体及其衍生物、制备方法和应用。The invention belongs to the cross field of fine chemical industry and photoelectric material, and specifically relates to a class of bromopyrene intermediates and derivatives thereof, preparation methods and applications.
背景技术Background technique
芘是一种常见的稠环芳香烃化合物，其主要来源是石油/煤化工的副产品，具有较强的π-电子离域能和独特的蓝光性质，被广泛应用于有机光电器件、生物传感器、荧光探针等领域，现在已经成为一种设计和合成有机半导体材料的流行砌块。Pyrene is a common fused-ring aromatic hydrocarbon compound, and its main source is a by-product of petroleum/coal chemical industry. It has strong π-electron delocalization energy and unique blue light properties, and is widely used in organic optoelectronic devices, biosensors, Fields such as fluorescent probes have now become a popular building block for designing and synthesizing organic semiconductor materials.
中间体的设计与合成对开发新型功能材料至关重要。截止目前，已经有至少12种新型芘基中间体得以开发，如1,3,6,8-四溴芘、2,7-二叔丁基-4,5,9,10-四溴芘、2,7-芘硼酸、4,5,9,10-芘四醌等都得到了广泛的关注和应用，特别是自从1937年以较为简单的方法成功合成1,3,6,8-四溴芘后，基于此中间体，多达1900余种新型芘衍生物被开发，极大的丰富了有机半导体材料库，促进了有机半导体科学的发展。The design and synthesis of intermediates are crucial to the development of new functional materials. So far, at least 12 new pyrene-based intermediates have been developed, such as 1,3,6,8-tetrabromopyrene, 2,7-di-tert-butyl-4,5,9,10-tetrabromopyrene, 2,7-pyrene boronic acid, 4,5,9,10-pyrene tetraquinone, etc. have been widely concerned and applied, especially since the successful synthesis of 1,3,6,8-tetrabromo After pyrene, more than 1,900 new pyrene derivatives have been developed based on this intermediate, which greatly enriches the library of organic semiconductor materials and promotes the development of organic semiconductor science.
另一方面，芘作为煤化工工业的副产品，是一类强致癌物质，如不充分利用，将对环境产生极大地破坏，因此，秉承“变废为宝，变废为宝”的思路，本发明旨在设计一种简便的合成方法，并通过优化合成路线，将化工副产品开发成新型化工原中间体，并提高合成路线的产率，加速推进这类中间体进入工业链，应用于有机半导体、生物成像等领域。新型芘基中间体的开发将便于开发新型的芘基衍生物，通过调控分子结构，制备高性能的芘基光电材料，促进芘基功能材料的发展。On the other hand, as a by-product of the coal chemical industry, pyrene is a strong carcinogen. If it is not fully utilized, it will cause great damage to the environment. Therefore, adhering to the idea of "turning waste into treasure, turning waste into treasure", this The purpose of the invention is to design a simple synthetic method, and to develop chemical by-products into new chemical raw intermediates by optimizing the synthetic route, and to improve the yield of the synthetic route, and to accelerate the entry of such intermediates into the industrial chain and to be applied to organic semiconductors. , bioimaging and other fields. The development of new pyrene-based intermediates will facilitate the development of new pyrene-based derivatives. By adjusting the molecular structure, high-performance pyrenyl-based optoelectronic materials can be prepared to promote the development of pyrenyl-based functional materials.
发明内容Contents of the invention
本发明的首要目的是提供一种溴芘中间体。The primary purpose of the present invention is to provide a bromopyrene intermediate.
本发明的另一目的在于提供上述溴芘中间体的合成方法，该方法工艺设计合理、收率高、反应条件温和、原料价格低廉。Another object of the present invention is to provide a synthesis method of the above-mentioned bromopyrene intermediate, which has reasonable process design, high yield, mild reaction conditions and low raw material prices.
发明的再一目的在于基于芘基中间体制得的芘基发光材料。Another object of the invention lies in the pyrene-based luminescent material prepared based on the pyrene-based intermediate.
发明的进一步目的在于提供上述芘基功能材料的应用。A further object of the invention is to provide the application of the above-mentioned pyrene-based functional materials.
本发明的目的通过下述技术方案实现：The object of the present invention is achieved through the following technical solutions:
一类溴芘中间体，所述溴芘中间体的分子结构式如(1)所示：A class of bromopyrene intermediates, the molecular structural formula of the bromopyrene intermediates is as shown in (1):
Figure PCTCN2022126686-appb-000001
Figure PCTCN2022126686-appb-000001
其中，R为H或者OH。Wherein, R is H or OH.
所述的溴芘中间体为2-羟基-1,3,6,8-四溴芘或2,7-二羟基-1,3,6,8-四溴芘；其分子结构式如1a或1b所示：The bromopyrene intermediate is 2-hydroxy-1,3,6,8-tetrabromopyrene or 2,7-dihydroxy-1,3,6,8-tetrabromopyrene; its molecular structure is as 1a or 1b Shown:
Figure PCTCN2022126686-appb-000002
Figure PCTCN2022126686-appb-000002
所述的溴芘中间体的制备方法，所述溴芘中间体是以2-羟基芘或2,7-二羟基芘为原料，在惰性气氛下加入溴化剂和有机溶剂，在50～130℃加热搅拌10～40h进行溴代反应，制得2-羟基-1,3,6,8-四溴芘或2,7-二羟基-1,3,6,8-四溴芘。The preparation method of the bromopyrene intermediate, the bromopyrene intermediate is 2-hydroxypyrene or 2,7-dihydroxypyrene as raw material, adding a brominating agent and an organic solvent under an inert atmosphere, at 50 to 130 Heating and stirring at ℃ for 10-40 hours for bromination reaction to obtain 2-hydroxy-1,3,6,8-tetrabromopyrene or 2,7-dihydroxy-1,3,6,8-tetrabromopyrene.
优选地，所述溴化剂为溴水、N-溴代琥珀酰亚胺或苄基三甲基溴化铵二溴中的一种以上；所述惰性气氛为氮气或者氩气；所述有机溶剂为硝基苯、二氯甲烷、三氯甲烷、乙腈中的一种以上；所述的2-羟基芘或2,7-二羟基芘:溴化剂的摩尔比为1:(1～10)。Preferably, the brominating agent is one or more of bromine water, N-bromosuccinimide or benzyltrimethylammonium bromide dibromide; the inert atmosphere is nitrogen or argon; the organic Solvent is more than one in nitrobenzene, dichloromethane, chloroform, acetonitrile; Described 2-hydroxypyrene or 2,7-dihydroxypyrene: the molar ratio of brominating agent is 1:(1～10 ).
一种芘基有机功能发光材料，所述的芘基有机功能发光材料的分子结构通式如2a或2b所示：A pyrene-based organic functional luminescent material, the molecular structure of the pyrene-based organic functional luminescent material is shown in 2a or 2b:
Figure PCTCN2022126686-appb-000003
Figure PCTCN2022126686-appb-000003
其中，R 1为
Figure PCTCN2022126686-appb-000004
where R1 is
Figure PCTCN2022126686-appb-000004
所述芘基有机功能发光材料是在保护气氛下，将所述的溴芘中间体加入钯催化剂、芳香烃硼酸及其衍生物、无机碱和溶剂，在50～100℃通过钯催化偶联反应，分别在芘的多个位点进行功能化取代制备得到。The pyrene-based organic functional luminescent material is prepared by adding the bromopyrene intermediate into palladium catalyst, aromatic hydrocarbon boronic acid and its derivatives, inorganic base and solvent under a protective atmosphere, and catalyzing the coupling reaction by palladium at 50-100°C , were prepared by functional substitution at multiple sites of pyrene.
优选地，所述保护气氛为氮气或者氩气；所述钯催化剂为四(三苯基膦)钯、醋酸钯、四氟硼酸三(叔丁基膦)或三(二亚苄基丙酮)二钯、二氯双(三苯基膦)合钯中的一种及以上，所述无机碱为碳酸钾、碳酸钠、碳酸氢钠、碳酸氢钾、氢氧化钠中的一种及以上；所述溶剂为甲苯、乙醇、水、四氢呋喃、N,N-二甲基甲酰胺、乙腈、三乙胺中的一种及以上；所述芳香烃硼酸及其衍生物为4-甲氧基苯基硼酸、4-三氟甲基苯基硼酸、2-噻吩基硼酸、4-三甲氧基苯胺基硼酸酯；所述2-羟基-1,3,6,8-四溴芘或2,7-二羟基-1,3,6,8-四溴芘:芳香烃硼酸及其衍生物:钯催化剂:无机碱的摩尔比为1:(4～10):(0.05～0.2):(5～20)。Preferably, the protective atmosphere is nitrogen or argon; the palladium catalyst is tetrakis(triphenylphosphine)palladium, palladium acetate, tris(tert-butylphosphine) tetrafluoroborate or tris(dibenzylideneacetone)di One or more of palladium, dichlorobis(triphenylphosphine) palladium, and the inorganic base is one or more of potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, and sodium hydroxide; The solvent is one or more of toluene, ethanol, water, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, and triethylamine; the aromatic hydrocarbon boronic acid and its derivatives are 4-methoxyphenyl Boronic acid, 4-trifluoromethylphenylboronic acid, 2-thienylboronic acid, 4-trimethoxyanilinoboronic acid ester; the 2-hydroxy-1,3,6,8-tetrabromopyrene or 2,7 -Dihydroxy-1,3,6,8-tetrabromopyrene: aromatic hydrocarbon boronic acid and its derivatives: palladium catalyst: the molar ratio of inorganic base is 1: (4 ~ 10): (0.05 ~ 0.2): (5 ~ 20).
所述的芘基有机功能发光材料的结构式为：The structural formula of the pyrene-based organic functional luminescent material is:
Figure PCTCN2022126686-appb-000005
Figure PCTCN2022126686-appb-000005
Figure PCTCN2022126686-appb-000006
Figure PCTCN2022126686-appb-000006
一种芘基有机功能发光材料，所述的芘基有机功能发光材料的分子结构通式如3a或3b所示：A pyrene-based organic functional luminescent material, the molecular structure of the pyrene-based organic functional luminescent material is shown in 3a or 3b:
Figure PCTCN2022126686-appb-000007
Figure PCTCN2022126686-appb-000007
其中，R 2为甲基、乙基、苯基或苄基； Wherein, R 2 is methyl, ethyl, phenyl or benzyl;
所述芘基有机功能发光材料是将上述的芘基有机功能发光材料、R 2取代基团的卤化物和无机碱溶解在有机溶剂中，在60～80℃加热搅拌5～12h，反应结束后冷却至室温，用二氯甲烷萃取洗涤，饱和食盐水萃取，无水硫酸镁除水后过滤，旋蒸后进行色谱柱分离并重结晶制得； The pyrene-based organic functional luminescent material is to dissolve the above-mentioned pyrene-based organic functional luminescent material, the halide of the R2 substituent group and the inorganic base in an organic solvent, heat and stir at 60-80° C. for 5-12 hours, and after the reaction is completed, Cool to room temperature, extract and wash with dichloromethane, extract with saturated brine, filter after dehydration with anhydrous magnesium sulfate, perform chromatographic column separation and recrystallization after rotary evaporation;
优选地，所述R 2取代基团的卤化物为碘甲烷、碘乙烷、苄基溴或溴苯；所述惰性气氛为氮气或氩气；所述无机碱为碳酸钾、叔丁基醇钾、碳酸钠、碳酸氢钠、碳酸氢钾、氢氧化钠中的一种以上；所述有机溶剂为乙腈、四氢呋喃、二氯甲烷、乙醇中的一种以上；所述的芘基有机功能发光材料:R 2取代基团的卤化物: 无机碱的摩尔比为1:(1～10):(5～20)。 Preferably, the R halide substituent is methyl iodide, ethyl iodide, benzyl bromide or bromobenzene; the inert atmosphere is nitrogen or argon; the inorganic base is potassium carbonate, tert-butyl alcohol One or more of potassium, sodium carbonate, sodium bicarbonate, potassium bicarbonate, and sodium hydroxide; the organic solvent is one or more of acetonitrile, tetrahydrofuran, dichloromethane, and ethanol; the pyrene-based organic functional light emitting Material: R 2 substituent group halide: inorganic base molar ratio is 1:(1~10):(5~20).
所述的芘类发光材料在有机电子学或生物领域中的应用。The application of the pyrene-based luminescent material in the field of organic electronics or biology.
本发明2-羟基-1,3,6,8-四溴芘和2,7-二羟基-1,3,6,8-四溴芘的合成步骤如(I)和(II)所示：The synthesis steps of 2-hydroxy-1,3,6,8-tetrabromopyrene and 2,7-dihydroxy-1,3,6,8-tetrabromopyrene of the present invention are shown in (I) and (II):
Figure PCTCN2022126686-appb-000008
Figure PCTCN2022126686-appb-000008
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1.以本发明的溴芘中间体为前驱体制备的有机发光材料，通过在芘的2-和7-位引入羟基，使得1,3,6,8-位的取代基团能够与芘环形成较大的二面角，有效抑制分子间的相互作用，提升目标分子的发光效率，通过平衡分子内的电荷，提高其电荷传输性能，此外，羟基或者R 2取代基团的引入能够有效的提高目标分子的亲水性，有利于将这类发光分子应用于生物领域； 1. The organic luminescent material prepared as a precursor with the bromopyrene intermediate of the present invention, by introducing a hydroxyl group at the 2- and 7-position of pyrene, the substituent group at the 1,3,6,8-position can be combined with the pyrene ring Form a large dihedral angle, effectively inhibit the interaction between molecules, improve the luminous efficiency of the target molecule, and improve its charge transport performance by balancing the charge in the molecule. In addition, the introduction of hydroxyl or R 2 substituent groups can effectively Improving the hydrophilicity of target molecules is conducive to the application of such luminescent molecules in the biological field;
2.本发明的合成方法具有实验操作简单、反应条件温和、中间体产率高等优点；2. The synthetic method of the present invention has the advantages of simple experimental operation, mild reaction conditions, and high intermediate yield;
3.本发明的芘基有机发光材料能够有效地提高材料的固体发光效率，应用于有机光电领域；3. The pyrene-based organic luminescent material of the present invention can effectively improve the solid luminous efficiency of the material, and is applied in the field of organic optoelectronics;
4.本发明的溴芘中间体和芘基有机发光材料由于羟基或者R 2取代基团的存在，能够增加溴芘中间体和芘基有机发光材料的亲水性能，提高材料的溶解度，便于直接应用于生物成像等领域。 4. The bromopyrene intermediate and the pyrene-based organic luminescent material of the present invention can increase the hydrophilicity of the bromopyrene intermediate and the pyrene-based organic luminescent material due to the presence of hydroxyl or R substituting groups, improve the solubility of the material, and facilitate direct Applied in biological imaging and other fields.
附图说明Description of drawings
图1为实施例1的2-羟基-1,3,6,8-四溴芘的HRMS图。Figure 1 is the HRMS chart of 2-hydroxyl-1,3,6,8-tetrabromopyrene in Example 1.
图2为实施例2的2,7-二羟基-1,3,6,8-四溴芘的HRMS图。Figure 2 is the HRMS chart of 2,7-dihydroxy-1,3,6,8-tetrabromopyrene of Example 2.
图3为实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的 1H NMR图。 Fig. 3 is a 1 H NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene in Example 3.
图4为实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的 13C NMR图。 Fig. 4 is a 13 C NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene in Example 3.
图5为实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的HRMS图。Fig. 5 is the HRMS chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene in Example 3.
图6为实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的单晶结构图。Fig. 6 is a single crystal structure diagram of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene in Example 3.
图7为实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘 1H NMR图。 7 is a 1 H NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene in Example 4.
图8为实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的 13C NMR图。 8 is a 13 C NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene in Example 4. FIG.
图9为实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的HRMS图。9 is the HRMS chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene of Example 4.
图10为实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的单晶结构图。10 is a single crystal structure diagram of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene in Example 4.
图11为实施例5的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的 1HNMR图。 Fig. 11 is a 1 H NMR chart of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene in Example 5.
图12为实施例5的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的 13C NMR图。 12 is a 13 C NMR chart of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene in Example 5. FIG.
图13为实施例5的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的HRMS图。13 is the HRMS chart of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene of Example 5.
图14为实施例5的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的单晶结构图。14 is a single crystal structure diagram of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene in Example 5.
图15为实施例6的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的 1H NMR图。 15 is a 1 H NMR chart of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene of Example 6. FIG.
图16为实施例6的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的 13C NMR图。 16 is a 13 C NMR chart of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene in Example 6. FIG.
图17为实施例6的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的HRMS图。17 is an HRMS chart of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene of Example 6. FIG.
图18为实施例6的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的单晶结构图。18 is a single crystal structure diagram of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene in Example 6.
图19为实施例7的1,3,6,8-四-(2-噻吩基)-2-羟基芘的 1H NMR图。 19 is a 1 H NMR chart of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene of Example 7. FIG.
图20为实施例7的1,3,6,8-四-(2-噻吩基)-2-羟基芘的 13C NMR图。 20 is a 13 C NMR chart of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene in Example 7. FIG.
图21为实施例7的1,3,6,8-四-(2-噻吩基)-2-羟基芘的HRMS图。21 is an HRMS chart of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene of Example 7. FIG.
图22为实施例7的1,3,6,8-四-(2-噻吩基)-2-羟基芘的单晶结构图。22 is a single crystal structure diagram of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene in Example 7.
图23为实施例8的1,3,6,8-四-(2-噻吩基)-2,7-羟基芘的 1HNMR图。 23 is a 1 H NMR chart of 1,3,6,8-tetrakis-(2-thienyl)-2,7-hydroxypyrene of Example 8. FIG.
图24为实施例8的1,3,6,8-四-(2-噻吩基)-2,7-羟基芘的 13C NMR图。 24 is a 13 C NMR chart of 1,3,6,8-tetrakis-(2-thienyl)-2,7-hydroxypyrene in Example 8. FIG.
图25为实施例8的1,3,6,8-四-(2-噻吩基)-2,7-羟基芘的HRMS图。25 is an HRMS chart of 1,3,6,8-tetrakis-(2-thienyl)-2,7-hydroxypyrene of Example 8. FIG.
图26为实施例8的1,3,6,8-四-(2-噻吩基)-2,7-羟基芘的单晶结构图。26 is a single crystal structure diagram of 1,3,6,8-tetrakis-(2-thienyl)-2,7-hydroxypyrene in Example 8.
图27为实施例9的1,3,6,8-四-(4-三苯胺)-2,7-二羟基芘的 1H NMR图。 27 is a 1 H NMR chart of 1,3,6,8-tetrakis-(4-triphenylamine)-2,7-dihydroxypyrene of Example 9. FIG.
图28为实施例9的1,3,6,8-四-(4-三苯胺)-2,7-二羟基芘的 13C NMR图。 28 is a 13 C NMR chart of 1,3,6,8-tetrakis-(4-triphenylamine)-2,7-dihydroxypyrene in Example 9. FIG.
图29为实施例9的1,3,6,8-四-(4-三苯胺)-2,7-二羟基芘的HRMS图。29 is an HRMS chart of 1,3,6,8-tetrakis-(4-triphenylamine)-2,7-dihydroxypyrene of Example 9. FIG.
图30为实施例10的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的 1H NMR图。 30 is a 1 H NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene in Example 10.
图31为实施例10的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的 13C NMR图。 31 is a 13 C NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene in Example 10.
图32为实施例10的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的HRMS图。32 is the HRMS chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene of Example 10.
图33为实施例10的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的单晶结构图。33 is a single crystal structure diagram of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene in Example 10.
图34为实施例3、4、5、6、10由溴芘中间体得到的1,3,6,8-四取代-2,7-二羟基-芘衍生物、1,3,6,8-四取代-2-羟基-芘衍生物和1,3,6,8-四取代-2-甲氧基-芘衍生物的UV-vis和荧光光谱图。Figure 34 is the 1,3,6,8-tetrasubstituted-2,7-dihydroxy-pyrene derivatives, 1,3,6,8 obtained from bromopyrene intermediates in Examples 3, 4, 5, 6, and 10 - UV-vis and fluorescence spectra of tetrasubstituted-2-hydroxy-pyrene derivatives and 1,3,6,8-tetrasubstituted-2-methoxy-pyrene derivatives.
具体实施方式Detailed ways
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。The content of the present invention will be further described below in conjunction with specific examples, but it should not be construed as a limitation of the present invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
实施例1 2-羟基-1,3,6,8-四溴芘的制备The preparation of embodiment 1 2-hydroxyl-1,3,6,8-tetrabromopyrene
1.根据文献报道的方法(Chem.Commun.,2005,2172～2174，Chem.Eur.J.2012,18,5022～5035)，将芘逐步进行硼酸酯化和羟基化，得到2-羟基芘。1. According to the method reported in the literature (Chem.Commun., 2005, 2172～2174, Chem.Eur.J.2012, 18, 5022～5035), pyrene is gradually boronated and hydroxylated to obtain 2-hydroxy Pyrene.
2.在氮气的保护下，将2-羟基芘(1eq.)和15～50mL硝基苯加入250ml的双颈瓶中，室温搅拌10分钟后加入溴水(4～10eq.)，混合溶液在120℃条件下强力搅拌24h。室温冷却后，将混合物过滤，乙醇冲洗三次，得到浅棕色粉末，产率约为92％，其合成路线如式(1)所示。2. Under the protection of nitrogen, add 2-hydroxypyrene (1eq.) and 15-50mL nitrobenzene into a 250ml double-neck flask, stir at room temperature for 10 minutes, then add bromine water (4-10eq.), and the mixed solution is in Stir vigorously at 120°C for 24h. After cooling at room temperature, the mixture was filtered and washed with ethanol three times to obtain a light brown powder with a yield of about 92%. The synthetic route is shown in formula (1).
Figure PCTCN2022126686-appb-000009
Figure PCTCN2022126686-appb-000009
图1为本实施例得到的2-羟基-1,3,6,8-四溴芘的高分辨质谱图，从图1可知，成功制备出溴芘中间体2-羟基-1,3,6,8-四溴芘。Fig. 1 is the high-resolution mass spectrum of 2-hydroxyl-1,3,6,8-tetrabromopyrene obtained in this example, as can be seen from Fig. 1, bromopyrene intermediate 2-hydroxyl-1,3,6 ,8-Tetrabromopyrene.
实施例2 2,7-二羟基-1,3,6,8-四溴芘的制备Example 2 Preparation of 2,7-dihydroxy-1,3,6,8-tetrabromopyrene
1.根据文献报道的方法(Chem.Commun.,2005,2172～2174，Chem.Eur.J.2012,18,5022～5035)，将芘逐步进行硼酸酯化和羟基化，得到2,7-二羟基芘。1. According to the method reported in the literature (Chem.Commun., 2005, 2172～2174, Chem.Eur.J.2012, 18, 5022～5035), pyrene is gradually boronated and hydroxylated to obtain 2,7 - dihydroxypyrene.
2.在氮气的保护下，将2,7-二羟基芘(1eq.)和15～50mL硝基苯加入250ml 的双颈瓶中，室温搅拌10分钟后加入溴水(4～10eq.)，混合溶液在120℃条件下强力搅拌24h。室温冷却后，将混合物过滤，乙醇冲洗三次，得到浅绿色粉末，产率约为95％，其合成路线如式(2)所示。2. Under the protection of nitrogen, add 2,7-dihydroxypyrene (1eq.) and 15-50mL nitrobenzene into a 250ml double-necked bottle, stir at room temperature for 10 minutes, then add bromine water (4-10eq.), The mixed solution was vigorously stirred at 120 °C for 24 h. After cooling at room temperature, the mixture was filtered and washed with ethanol three times to obtain a light green powder with a yield of about 95%. The synthetic route is shown in formula (2).
Figure PCTCN2022126686-appb-000010
Figure PCTCN2022126686-appb-000010
图2为本实施例得到的2,7-二羟基-1,3,6,8-四溴芘的高分辨质谱图，从图2可知，成功制备出溴芘中间体2,7-二羟基-1,3,6,8-四溴芘。Figure 2 is the high-resolution mass spectrum of 2,7-dihydroxy-1,3,6,8-tetrabromopyrene obtained in this example, as can be seen from Figure 2, the bromopyrene intermediate 2,7-dihydroxy -1,3,6,8-Tetrabromopyrene.
实施例3 1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的制备Example 3 Preparation of 1,3,6,8-tetra-(4-methoxyphenyl)-2-hydroxypyrene
在氮气的保护下，将实施例1的2-羟基-1,3,6,8-四溴芘(1eq.)和4-甲氧基苯基硼酸(4～8eq.)、碳酸钾(10～20eq.)加入100ml的双颈瓶中，溶解在体积比为5：1：1的甲苯、乙醇和水的混合溶液(8～20mL)中，加入四(三苯基膦)钯(0.05～0.2eq.)，在90℃下强力搅拌24h，反应京结束后冷却至室温，用二氯甲烷萃取洗涤三次，饱和食盐水萃取一次，旋蒸后进行色谱柱分离，得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘，产率约为70％，其合成路线如式(3)所示。Under the protection of nitrogen, 2-hydroxyl-1,3,6,8-tetrabromopyrene (1eq.) and 4-methoxyphenylboronic acid (4～8eq.), potassium carbonate (10 ～20eq.) into a 100ml double-necked flask, dissolved in a mixed solution (8～20mL) of toluene, ethanol and water with a volume ratio of 5:1:1, and added tetrakis(triphenylphosphine)palladium (0.05～ 0.2eq.), stirred vigorously at 90°C for 24h, cooled to room temperature after the reaction was completed, extracted and washed with dichloromethane three times, extracted once with saturated brine, and separated by chromatographic column after rotary evaporation to obtain the target product 1,3, The yield of 6,8-tetra-(4-methoxyphenyl)-2-hydroxypyrene is about 70%, and its synthetic route is shown in formula (3).
Figure PCTCN2022126686-appb-000011
Figure PCTCN2022126686-appb-000011
图3为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的 1H NMR图。图4为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的 13C NMR图，图5为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的HRMS图，图6为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘的单晶结构图，从图3-6可知，成功制备出1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘有机蓝光材料。 Fig. 3 is the 1 H NMR chart of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene obtained in this example. Figure 4 is the 13 C NMR figure of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene obtained in this example, and Figure 5 is the 1,3,8 obtained in this example The HRMS figure of 6,8-tetra-(4-methoxyphenyl)-2-hydroxypyrene, Figure 6 is the 1,3,6,8-tetra-(4-methoxyphenyl obtained in this example )-2-hydroxypyrene single crystal structure diagram, as can be seen from Figure 3-6, 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene organic blue light material was successfully prepared.
实施例4 1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的制备Example 4 Preparation of 1,3,6,8-tetra-(4-methoxyphenyl)-2,7-dihydroxypyrene
在氮气的保护下，将实施例2的2,7-二羟基-1,3,6,8-四溴芘(1eq.)和4-甲氧基苯基硼酸(4～8eq.)、碳酸钾(10～20eq.)加入100mL的双颈瓶中，加入四氢呋喃(8～20mL)和四(三苯基膦)钯(0.05～0.2eq.)，在90℃下强力搅拌24h，反应结束后冷却至室温，用二氯甲烷萃取洗涤三次，饱和食盐水萃取一次，旋蒸后进行色谱柱分离和重结晶，得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘，产率约为47％，其合成路线如式(4)所示。Under the protection of nitrogen, the 2,7-dihydroxy-1,3,6,8-tetrabromopyrene (1eq.) and 4-methoxyphenylboronic acid (4~8eq.) of Example 2, carbonic acid Add potassium (10~20eq.) into a 100mL double-necked flask, add tetrahydrofuran (8~20mL) and tetrakis(triphenylphosphine)palladium (0.05~0.2eq.), stir vigorously at 90°C for 24h, after the reaction Cool to room temperature, extract and wash with dichloromethane three times, extract once with saturated brine, and perform chromatographic column separation and recrystallization after rotary evaporation to obtain the target product 1,3,6,8-tetra-(4-methoxyphenyl )-2,7-dihydroxypyrene, the yield is about 47%, and its synthetic route is shown in formula (4).
Figure PCTCN2022126686-appb-000012
Figure PCTCN2022126686-appb-000012
图7为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的 1H NMR图，图8本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2,7二羟基芘的 13C NMR图，图9为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的HRMS图，图10为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘的单晶结构图，从图7-10可知，成功制备出1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘，所制备的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘是蓝光材料。 Fig. 7 is the 1 H NMR figure of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene obtained in this embodiment, and Fig. 8 obtained in this embodiment 1, The 13 C NMR figure of 3,6,8-tetra-(4-methoxyphenyl)-2,7 dihydroxypyrene, Figure 9 is the 1,3,6,8-tetra-(4 The HRMS figure of -methoxyphenyl)-2,7-dihydroxypyrene, Fig. 10 is the 1,3,6,8-tetra-(4-methoxyphenyl)-2,7 that this embodiment obtains -Single crystal structure of dihydroxypyrene, as can be seen from Figure 7-10, 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene was successfully prepared, and the prepared 1,3,6,8-Tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene is a blue light material.
实施例5 1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的制备Example 5 Preparation of 1,3,6,8-tetra-(4-trifluoromethylphenyl)-2-hydroxypyrene
在氮气的保护下，将实施例1的2-羟基-1,3,6,8-四溴芘(1eq.)和4-三氟甲基苯基硼酸(4～8eq.)、碳酸钾(10～20eq.)加入100mL的双颈瓶中，溶解在体积比为4：1的四氢呋喃和水的混合溶液(8～20mL)中，加入Pd 2(dba) 3(0.05～0.2eq.)和(t-Bu) 3PBF 4(0.2～0.8eq.)，在90℃下强力搅拌24h，反应结束后冷却至室温，用二氯甲烷萃取洗涤三次，饱和食盐水萃取一次，旋蒸进行色谱柱分离并重结晶，得到目标产物1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘，产率约为65％，其合成路线如式(5)所示。 Under the protection of nitrogen, 2-hydroxyl-1,3,6,8-tetrabromopyrene (1eq.) and 4-trifluoromethylphenylboronic acid (4～8eq.), potassium carbonate ( 10~20eq.) into a 100mL double-necked bottle, dissolved in a mixed solution (8~20mL) of tetrahydrofuran and water with a volume ratio of 4:1, and added Pd 2 (dba) 3 (0.05~0.2eq.) and (t-Bu) 3 PBF 4 (0.2～0.8eq.), vigorously stirred at 90°C for 24h, cooled to room temperature after the reaction, extracted and washed with dichloromethane three times, extracted once with saturated saline, and rotary evaporated for chromatographic column Separate and recrystallize to obtain the target product 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene, the yield is about 65%, and its synthetic route is shown in formula (5) .
Figure PCTCN2022126686-appb-000013
Figure PCTCN2022126686-appb-000013
图11为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的 1H NMR图，图12为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的 13C NMR图，图13为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的HRMS图，图14为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘的单晶结构图，从图11-14可知，成功制备出1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘有机蓝光材料。 Figure 11 is the 1 H NMR figure of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene obtained in the present example, and Figure 12 is the 1,3 obtained in the present example , 6,8-tetra-(4-trifluoromethylphenyl)-2-hydroxypyrene 13 C NMR figure, Figure 13 is the 1,3,6,8-tetra-(4-three The HRMS figure of fluoromethylphenyl)-2-hydroxypyrene, FIG. As can be seen from Figures 11-14, 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene organic blue light material was successfully prepared.
实施例6 1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的制备Example 6 Preparation of 1,3,6,8-tetra-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene
在氮气的保护下，将实施例2的2,7-二羟基-1,3,6,8-四溴芘(1eq.)和4-三氟甲基苯基硼酸(4～8eq.)、碳酸钾(10～20eq.)加入100mL的双颈瓶中，溶解在体积比为4：1的四氢呋喃和水的混合溶液(8～20mL)中，加入Pd 2(dba) 3(0.05～0.2eq.)和(t-Bu) 3PBF 4(0.2～0.8eq.)，在90℃下强力搅拌24h，反应结束后冷却至室温，用乙酸乙酯萃取洗涤三次，饱和食盐水萃取一次，旋蒸后进行色谱柱分离并重结晶，得到目标产物1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘，产率约为38％，其合成路线如式(6)所示。 Under the protection of nitrogen, 2,7-dihydroxy-1,3,6,8-tetrabromopyrene (1eq.) and 4-trifluoromethylphenylboronic acid (4～8eq.) of Example 2, Potassium carbonate (10~20eq.) was added to a 100mL double-neck flask, dissolved in a mixed solution (8~20mL) of tetrahydrofuran and water with a volume ratio of 4:1, and Pd 2 (dba) 3 (0.05~0.2eq .) and (t-Bu) 3 PBF 4 (0.2～0.8eq.), stirred vigorously at 90°C for 24h, cooled to room temperature after the reaction, extracted and washed with ethyl acetate three times, extracted once with saturated saline, and rotary evaporated After separation by chromatographic column and recrystallization, the target product 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene was obtained with a yield of about 38%. The synthetic route As shown in formula (6).
Figure PCTCN2022126686-appb-000014
Figure PCTCN2022126686-appb-000014
图15为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的 1H NMR图，图16为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的 13C NMR图，图17为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二 羟基芘的HRMS图，图18为本实施例得到的1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘的单晶结构图，从图15-18可知，成功制备出1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘有机蓝光材料。 Figure 15 is the 1 H NMR figure of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene obtained in this example, and Figure 16 is obtained in this example The 13 C NMR figure of 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene, Figure 17 is the 1,3,6,8- The HRMS figure of four-(4-trifluoromethylphenyl)-2,7-dihydroxypyrene, Figure 18 is the 1,3,6,8-tetra-(4-trifluoromethylbenzene obtained in this embodiment base)-2,7-dihydroxypyrene single crystal structure, as can be seen from Figures 15-18, 1,3,6,8-tetrakis-(4-trifluoromethylphenyl)-2,7 - Dihydroxypyrene organic blue light material.
实施例7 1,3,6,8-四-(2-噻吩基)-2-羟基芘的制备Example 7 Preparation of 1,3,6,8-tetra-(2-thienyl)-2-hydroxypyrene
在氮气的保护下，将实施例1的2-羟基-1,3,6,8-四溴芘(1eq.)和2-噻吩基硼酸(4～8eq.)、碳酸钾(10～20eq.)加入100mL的双颈瓶中，溶解在体积比为4：1的四氢呋喃和水的混合溶液(8～20mL)中，加入Pd 2(dba) 3(0.05～0.2eq.)和(t-Bu) 3PBF 4(0.2～0.8eq.)，在90℃下强力搅拌24h，反应结束后冷却至室温，用二氯甲烷萃取洗涤三次，饱和食盐水萃取一次，旋蒸后进行色谱柱分离并重结晶，得到目标产物1,3,6,8-四-(2-噻吩基)-2-羟基芘，产率约为72％，其合成路线如式(7)所示。 Under the protection of nitrogen, the 2-hydroxyl-1,3,6,8-tetrabromopyrene (1eq.) and 2-thienylboronic acid (4～8eq.), potassium carbonate (10～20eq.) ) into a 100mL double-necked flask, dissolved in a mixed solution (8-20mL) of tetrahydrofuran and water with a volume ratio of 4:1, and added Pd 2 (dba) 3 (0.05-0.2eq.) and (t-Bu ) 3 PBF 4 (0.2～0.8eq.), vigorously stirred at 90°C for 24h, cooled to room temperature after the reaction, extracted and washed with dichloromethane three times, extracted once with saturated saline, separated by chromatographic column and recrystallized after rotary evaporation , to obtain the target product 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene with a yield of about 72%, and its synthetic route is shown in formula (7).
Figure PCTCN2022126686-appb-000015
Figure PCTCN2022126686-appb-000015
图19为本实施例得到的1,3,6,8-四-(2-噻吩基)-2-羟基芘的 1H NMR图，图20为本实施例得到的1,3,6,8-四-(2-噻吩基)-2-羟基芘的 13C NMR图，图21为本实施例得到的1,3,6,8-四-(2-噻吩基)-2-羟基芘的HRMS图，图22为本实施例得到的1,3,6,8-四-(2-噻吩基)-2-羟基芘的单晶结构图，从图19-22可知，成功制备出1,3,6,8-四-(2-噻吩基)-2-羟基芘。 Figure 19 is the 1 H NMR figure of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene obtained in this example, and Figure 20 is the 1,3,6,8 obtained in this example - The 13 C NMR figure of tetrakis-(2-thienyl)-2-hydroxypyrene, Figure 21 is the 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene obtained in this embodiment HRMS diagram, Figure 22 is the single crystal structure diagram of 1,3,6,8-tetrakis-(2-thienyl)-2-hydroxypyrene obtained in this example, as can be seen from Figures 19-22, successfully prepared 1, 3,6,8-Tetrakis-(2-thienyl)-2-hydroxypyrene.
实施例8 1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘的制备Example 8 Preparation of 1,3,6,8-tetra-(2-thienyl)-2,7-dihydroxypyrene
在氮气的保护下，将实施例2的2,7-二羟基-1,3,6,8-四溴芘(1eq.)和2-噻吩基硼酸(4～8eq.)、碳酸钾(10～20eq.)加入100ml的双颈瓶中，溶解在体积比为4：1的四氢呋喃和水的混合溶液(8～20mL)中，加入Pd 2(dba) 3(0.05～0.2eq.)和(t-Bu) 3PBF 4(0.2～0.8eq.)，在90℃下强力搅拌24h，反应结束后冷却至室温，用二氯甲烷萃取洗涤三次，饱和食盐水萃取一次，旋蒸后进行色谱柱分离并重结晶，得到目标产物1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘，产率约为40％，其合成路线如式(8)所示。 Under the protection of nitrogen, 2,7-dihydroxyl-1,3,6,8-tetrabromopyrene (1eq.) and 2-thienylboronic acid (4～8eq.), potassium carbonate (10 ~20eq.) into a 100ml double-necked flask, dissolved in a mixed solution (8~20mL) of tetrahydrofuran and water with a volume ratio of 4:1, and added Pd 2 (dba) 3 (0.05~0.2eq.) and ( t-Bu) 3 PBF 4 (0.2～0.8eq.), vigorously stirred at 90°C for 24h, cooled to room temperature after the reaction, extracted and washed with dichloromethane three times, extracted once with saturated saline, and carried out chromatographic column after rotary evaporation After separation and recrystallization, the target product 1,3,6,8-tetrakis-(2-thienyl)-2,7-dihydroxypyrene was obtained with a yield of about 40%. The synthetic route is shown in formula (8).
Figure PCTCN2022126686-appb-000016
Figure PCTCN2022126686-appb-000016
图23为本实施例得到的1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘的 1H NMR图，图24为本实施例得到的1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘的 13C NMR图，图25为本实施例得到的1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘的HRMS图，图26为本实施例得到的1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘的单晶结构图，从图23-26可知，成功制备出1,3,6,8-四-(2-噻吩基)-2,7-二羟基芘。 Figure 23 is the 1 H NMR figure of 1,3,6,8-tetrakis-(2-thienyl)-2,7-dihydroxypyrene obtained in this example, and Figure 24 is the 1,3,8-dihydroxypyrene obtained in this example. The 13 C NMR chart of 6,8-tetra-(2-thienyl)-2,7-dihydroxypyrene, Figure 25 is the 1,3,6,8-tetra-(2-thienyl) obtained in this example -HRMS diagram of 2,7-dihydroxypyrene, Figure 26 is the single crystal structure diagram of 1,3,6,8-tetrakis-(2-thienyl)-2,7-dihydroxypyrene obtained in this example, It can be seen from Figures 23-26 that 1,3,6,8-tetrakis-(2-thienyl)-2,7-dihydroxypyrene was successfully prepared.
实施例9 1,3,6,8-四-(4-三甲氧基苯胺)-2,7-二羟基芘的制备Example 9 Preparation of 1,3,6,8-tetra-(4-trimethoxyaniline)-2,7-dihydroxypyrene
在氮气的保护下，将实施例2的2,7-二羟基-1,3,6,8-四溴芘(1eq.)和4-三甲氧基苯胺基硼酸酯(4～8eq.)、碳酸钾(10～20eq.)加入100mL的双颈瓶中，溶解在体积比为5：1：1的甲苯、乙醇和水的混合溶液(8～20mL)中，加入四(三苯基膦)钯(0.05～0.2eq.)，在90℃下强力搅拌24h，反应结束后冷却至室温，用二氯甲烷萃取洗涤三次，饱和食盐水萃取一次，旋蒸后进行色谱柱分离，得到目标产物1,3,6,8-四-(4-三甲氧基苯胺)-2,7-二羟基芘，产率约为50％，其合成路线如式(9)所示。Under the protection of nitrogen, the 2,7-dihydroxyl-1,3,6,8-tetrabromopyrene (1eq.) and 4-trimethoxyanilino borate (4～8eq.) , Potassium carbonate (10~20eq.) was added to a 100mL double-neck flask, dissolved in a mixed solution (8~20mL) of toluene, ethanol and water with a volume ratio of 5:1:1, and tetrakis(triphenylphosphine) was added ) palladium (0.05～0.2eq.), stirred vigorously at 90°C for 24h, cooled to room temperature after the reaction, extracted and washed three times with dichloromethane, extracted once with saturated saline, and separated by chromatographic column after rotary evaporation to obtain the target product 1,3,6,8-Tetrakis-(4-trimethoxyaniline)-2,7-dihydroxypyrene has a yield of about 50%, and its synthetic route is shown in formula (9).
Figure PCTCN2022126686-appb-000017
Figure PCTCN2022126686-appb-000017
图27为本实施例得到的1,3,6,8-四-(4-三甲氧基苯胺)-2,7-二羟基芘的 1H NMR图，图28为本实施例得到的1,3,6,8-四-(4-三甲氧基苯胺)-2,7-二羟基芘的 13C NMR图，图29为本实施例得到的1,3,6,8-四-(4-三甲氧基苯胺)-2,7-二 羟基芘的HRMS图，从图27-29可知，成功制备出1,3,6,8-四-(4-三甲氧基苯胺)-2,7-二羟基芘。 Figure 27 is the 1 H NMR figure of 1,3,6,8-tetrakis-(4-trimethoxyaniline)-2,7-dihydroxypyrene obtained in this example, and Figure 28 is the 1, The 13 C NMR figure of 3,6,8-tetra-(4-trimethoxyaniline)-2,7-dihydroxypyrene, Figure 29 is the 1,3,6,8-tetra-(4 The HRMS figure of -trimethoxyaniline)-2,7-dihydroxypyrene, as can be seen from Figures 27-29, successfully prepared 1,3,6,8-tetrakis-(4-trimethoxyaniline)-2,7 - dihydroxypyrene.
实施例10 1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的制备Example 10 Preparation of 1,3,6,8-tetra-(4-methoxyphenyl)-2-methoxy-pyrene
在氮气的保护下，将实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘(1eq.)和碘甲烷(1～10eq.)、碳酸钾(10～20eq.)加入100mL的双颈瓶中，溶解在乙腈(5～20mL)中，加热回流，强力搅拌12h，反应结束后冷却至室温，用二氯甲烷萃取洗涤三次，饱和食盐水萃取一次，无水硫酸镁除水后过滤，旋蒸后进行色谱柱分离并重结晶，得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘，产率约为70％，其合成路线如式(10)所示。Under the protection of nitrogen, the 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene (1eq.) and iodomethane (1~10eq.), carbonic acid Potassium (10-20eq.) was added to a 100mL double-necked flask, dissolved in acetonitrile (5-20mL), heated to reflux, stirred vigorously for 12 hours, cooled to room temperature after the reaction, extracted and washed with dichloromethane three times, saturated saline Extracted once, filtered with anhydrous magnesium sulfate to remove water, separated by chromatographic column after rotary evaporation and recrystallized to obtain the target product 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy -pyrene, the yield is about 70%, and its synthetic route is shown in formula (10).
Figure PCTCN2022126686-appb-000018
Figure PCTCN2022126686-appb-000018
图30为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的 1H NMR图，图31为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的 13C NMR图，图32为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的HRMS图，图33为本实施例得到的1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘的单晶结构图，从图30-33可知，成功制备出1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘。 Figure 30 is the 1 H NMR figure of 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene obtained in this example, and Figure 31 is the 1 obtained in this example , 3,6,8-tetra-(4-methoxyphenyl)-2-methoxy-pyrene 13 C NMR figure, Figure 32 is the 1,3,6,8-tetra- The HRMS figure of (4-methoxyphenyl)-2-methoxy-pyrene, Figure 33 is the 1,3,6,8-tetra-(4-methoxyphenyl)-2 obtained in this example -Single crystal structure diagram of methoxy-pyrene, as can be seen from Figures 30-33, 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene was successfully prepared.
图34为实施例3、4、5、6、10由溴芘中间体得到的1,3,6,8-四取代-2,7-二羟基-芘衍生物、1,3,6,8-四取代-2-羟基-芘衍生物和1,3,6,8-四取代-2-甲氧基-芘衍生物的UV-vis和荧光光谱图。其中，3a为1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘，3b为1,3,6,8-四-(4-三氟甲基苯基)-2,7-二羟基芘，4a为1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘，4b为1,3,6,8-四-(4-三氟甲基苯基)-2-羟基芘，5为1,3,6,8-四-(4-甲氧基苯基)-2-甲氧基-芘。从图34可知，3a，3b，4a，4b和5在四氢呋喃溶液中最大发射波长处于426-432nm，这四类发光材料均是蓝光材料。Figure 34 is the 1,3,6,8-tetrasubstituted-2,7-dihydroxy-pyrene derivatives, 1,3,6,8 obtained from bromopyrene intermediates in Examples 3, 4, 5, 6, and 10 - UV-vis and fluorescence spectra of tetrasubstituted-2-hydroxy-pyrene derivatives and 1,3,6,8-tetrasubstituted-2-methoxy-pyrene derivatives. Among them, 3a is 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene, 3b is 1,3,6,8-tetrakis-(4-trifluoromethane phenyl)-2,7-dihydroxypyrene, 4a is 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene, 4b is 1,3,6,8- Tetrakis-(4-trifluoromethylphenyl)-2-hydroxypyrene, 5 is 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-methoxy-pyrene. It can be seen from Fig. 34 that the maximum emission wavelength of 3a, 3b, 4a, 4b and 5 in tetrahydrofuran solution is 426-432nm, and these four types of luminescent materials are all blue light materials.
实施例11 1,3,6,8-四-(4-甲氧基苯基)-2,7-二甲氧基-芘的制备Example 11 Preparation of 1,3,6,8-tetra-(4-methoxyphenyl)-2,7-dimethoxy-pyrene
在氮气的保护下，将实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘(1eq.)和碘甲烷(2～20eq.)、碳酸钾(10～20eq.)加入100mL的双颈瓶中， 溶解在乙腈(5～20mL)中，加热回流，强力搅拌12h，反应结束后冷却至室温，用二氯甲烷萃取洗涤三次，饱和食盐水萃取一次，无水硫酸镁除水后过滤，旋蒸后进行色谱柱分离并重结晶，得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2,7-甲氧基-芘，产率约为80％，其合成路线如式(11)所示。Under the protection of nitrogen, the 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene (1eq.) and iodomethane (2～20eq. ), potassium carbonate (10~20eq.) into a 100mL double-necked flask, dissolved in acetonitrile (5~20mL), heated to reflux, stirred vigorously for 12h, cooled to room temperature after the reaction, extracted and washed with dichloromethane three times, Saturated brine was extracted once, anhydrous magnesium sulfate dehydrated, filtered, chromatographic column separation and recrystallization after rotary evaporation to obtain the target product 1,3,6,8-tetrakis-(4-methoxyphenyl)-2, 7-methoxy-pyrene, the yield is about 80%, and its synthetic route is shown in formula (11).
Figure PCTCN2022126686-appb-000019
Figure PCTCN2022126686-appb-000019
实施例12 1,3,6,8-四-(4-甲氧基苯基)-2-乙氧基-芘的制备Example 12 Preparation of 1,3,6,8-tetra-(4-methoxyphenyl)-2-ethoxy-pyrene
在氮气的保护下，将实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘(1eq.)和碘乙烷(1～10eq.)、叔丁基醇钾(10～20eq.)加入100mL的双颈瓶中，溶解在四氢呋喃(5～20mL)中，加热回流，强力搅拌12h，反应结束后冷却至室温，用二氯甲烷萃取洗涤三次，饱和食盐水萃取一次，无水硫酸镁除水后过滤，旋蒸后进行色谱柱分离并重结晶，得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2-乙氧基-芘，产率约为80％，其合成路线如式(12)所示。Under the protection of nitrogen, the 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene (1eq.) and iodoethane (1～10eq.) of Example 3, Add potassium tert-butylate (10~20eq.) into a 100mL double-necked flask, dissolve in tetrahydrofuran (5~20mL), heat to reflux, stir vigorously for 12h, cool to room temperature after the reaction, extract and wash with dichloromethane three times , extracted once with saturated brine, filtered after dehydration with anhydrous magnesium sulfate, separated by chromatographic column after rotary evaporation and recrystallized to obtain the target product 1,3,6,8-tetrakis-(4-methoxyphenyl)-2 -Ethoxy-pyrene, the yield is about 80%, and its synthetic route is shown in formula (12).
Figure PCTCN2022126686-appb-000020
Figure PCTCN2022126686-appb-000020
实施例13 1,3,6,8-四-(4-甲氧基苯基)-2,7-二乙氧基-芘的制备Example 13 Preparation of 1,3,6,8-tetra-(4-methoxyphenyl)-2,7-diethoxy-pyrene
在氮气的保护下，将实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘(1eq.)和碘乙烷(2～20eq.)、叔丁基醇钾(10～20eq.)加入100mL的双颈瓶中，溶解在乙腈(5～20mL)中，加热回流，强力搅拌12h，反应结束后冷却至室温，用二氯甲烷萃取洗涤三次，饱和食盐水萃取一次，无水硫酸镁除水后过滤，旋蒸后进行色谱柱分离并重结晶，得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2,7-甲氧基-芘，产率约为75％，其合成路线如式(13)所示。Under the protection of nitrogen, 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene (1eq.) and iodoethane (2～20eq .), Potassium tert-butyl alkoxide (10~20eq.) was added to a 100mL double-necked flask, dissolved in acetonitrile (5~20mL), heated to reflux, stirred vigorously for 12h, cooled to room temperature after the reaction, and dichloromethane Extract and wash three times, extract once with saturated saline, filter after dehydration with anhydrous magnesium sulfate, and perform chromatographic column separation and recrystallization after rotary evaporation to obtain the target product 1,3,6,8-tetra-(4-methoxyphenyl )-2,7-methoxy-pyrene, the yield is about 75%, and its synthetic route is shown in formula (13).
Figure PCTCN2022126686-appb-000021
Figure PCTCN2022126686-appb-000021
实施例14 1,3,6,8-四-(4-甲氧基苯基)-2-苄氧基-芘的制备Example 14 Preparation of 1,3,6,8-tetra-(4-methoxyphenyl)-2-benzyloxy-pyrene
在氮气的保护下，将实施例3的1,3,6,8-四-(4-甲氧基苯基)-2-羟基芘(1eq.)和苄基溴(2～20eq.)、叔丁基醇钾(10～20eq.)加入100mL的双颈瓶中，溶解在乙腈(5～20mL)中，加热回流，强力搅拌12h，反应结束后冷却至室温，用二氯甲烷萃取洗涤三次，饱和食盐水萃取一次，无水硫酸镁除水后过滤，旋蒸后进行色谱柱分离并重结晶，得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2-苄氧基-芘，产率约为63％，其合成路线如式(14)所示。Under the protection of nitrogen, the 1,3,6,8-tetrakis-(4-methoxyphenyl)-2-hydroxypyrene (1eq.) and benzyl bromide (2～20eq.) of Example 3, Add potassium tert-butyl alkoxide (10~20eq.) into a 100mL double-neck flask, dissolve in acetonitrile (5~20mL), heat to reflux, stir vigorously for 12h, cool to room temperature after the reaction, extract and wash with dichloromethane three times , extracted once with saturated brine, filtered after dehydration with anhydrous magnesium sulfate, separated by chromatographic column after rotary evaporation and recrystallized to obtain the target product 1,3,6,8-tetrakis-(4-methoxyphenyl)-2 -benzyloxy-pyrene, the yield is about 63%, and its synthetic route is shown in formula (14).
Figure PCTCN2022126686-appb-000022
Figure PCTCN2022126686-appb-000022
实施例15 1,3,6,8-四-(4-甲氧基苯基)-2,7-二苄氧基-芘的制备Example 15 Preparation of 1,3,6,8-tetra-(4-methoxyphenyl)-2,7-dibenzyloxy-pyrene
在氮气的保护下，将实施例4的1,3,6,8-四-(4-甲氧基苯基)-2,7-二羟基芘(1eq.)和苄基溴(2～20eq.)、叔丁基醇钾(10～20eq.)加入100mL的双颈瓶中，溶解在乙腈(5～20mL)中，加热回流，强力搅拌12h，反应结束后冷却至室温，用二氯甲烷萃取洗涤三次，饱和食盐水萃取一次，无水硫酸镁除水后过滤，旋蒸后进行色谱柱分离并重结晶，得到目标产物1,3,6,8-四-(4-甲氧基苯基)-2,7-二苄氧基-芘，产率约为51％，其合成路线如式(15)所示。Under the protection of nitrogen, 1,3,6,8-tetrakis-(4-methoxyphenyl)-2,7-dihydroxypyrene (1eq.) and benzyl bromide (2～20eq .), Potassium tert-butyl alkoxide (10~20eq.) was added to a 100mL double-necked flask, dissolved in acetonitrile (5~20mL), heated to reflux, stirred vigorously for 12h, cooled to room temperature after the reaction, and dichloromethane Extract and wash three times, extract once with saturated saline, filter after dehydration with anhydrous magnesium sulfate, and perform chromatographic column separation and recrystallization after rotary evaporation to obtain the target product 1,3,6,8-tetra-(4-methoxyphenyl )-2,7-dibenzyloxy-pyrene, the yield is about 51%, and its synthetic route is shown in formula (15).
Figure PCTCN2022126686-appb-000023
Figure PCTCN2022126686-appb-000023
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations and modifications made without departing from the spirit and principles of the present invention Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (8)

  1. 一类溴芘中间体，其特征在于，所述溴芘中间体的分子结构式如(1)所示：A class of bromopyrene intermediates, characterized in that the molecular structural formula of the bromopyrene intermediates is as shown in (1):
    Figure PCTCN2022126686-appb-100001
    Figure PCTCN2022126686-appb-100001
    其中，R为H或者OH。Wherein, R is H or OH.
  2. 根据权利要求1所述的溴芘中间体的制备方法，其特征在于，所述溴芘中间体是以2-羟基芘或2,7-二羟基芘为原料，在惰性气氛下加入溴化剂和有机溶剂，在50～130℃加热搅拌10～40h进行溴代反应，制得2-羟基-1,3,6,8-四溴芘或2,7-二羟基-1,3,6,8-四溴芘。The preparation method of bromopyrene intermediate according to claim 1, is characterized in that, described bromopyrene intermediate is to take 2-hydroxypyrene or 2,7-dihydroxypyrene as raw material, add brominating agent under inert atmosphere and an organic solvent, heated and stirred at 50-130°C for 10-40 hours for bromination reaction to obtain 2-hydroxy-1,3,6,8-tetrabromopyrene or 2,7-dihydroxy-1,3,6, 8-Tetrabromopyrene.
  3. 根据权利要求2所述的溴芘中间体的制备方法，其特征在于，所述溴化剂为溴水、N-溴代琥珀酰亚胺或苄基三甲基溴化铵二溴中的一种以上；所述惰性气氛为氮气或者氩气；所述有机溶剂为硝基苯、二氯甲烷、三氯甲烷、乙腈中的一种以上；所述的2-羟基芘或2,7-二羟基芘:溴化剂的摩尔比为1:(1～10)。The preparation method of bromopyrene intermediate according to claim 2, is characterized in that, the bromination agent is one of bromine water, N-bromosuccinimide or benzyltrimethylammonium bromide dibromide The inert atmosphere is nitrogen or argon; the organic solvent is more than one of nitrobenzene, dichloromethane, chloroform, and acetonitrile; the 2-hydroxypyrene or 2,7-bis The molar ratio of hydroxypyrene:brominating agent is 1:(1～10).
  4. 一种芘基有机功能发光材料，其特征在于，所述的芘基有机功能发光材料的分子结构通式如2a或2b所示：A pyrene-based organic functional luminescent material, characterized in that the general molecular structure formula of the pyrene-based organic functional luminescent material is shown in 2a or 2b:
    Figure PCTCN2022126686-appb-100002
    Figure PCTCN2022126686-appb-100002
    其中，R 1为
    Figure PCTCN2022126686-appb-100003
    where R1 is
    Figure PCTCN2022126686-appb-100003
    所述的芘基有机功能发光材料是在保护气氛下，将权利要求1所述的溴芘中间体加入钯催化剂、芳香烃硼酸及其衍生物、无机碱和溶剂，在50～100℃通过钯催化偶联反应，分别在芘的多个位点进行功能化取代制备得到。The pyrene-based organic functional luminescent material is to add the bromopyrene intermediate described in claim 1 into palladium catalyst, aromatic hydrocarbon boronic acid and its derivatives, inorganic base and solvent under protective atmosphere, and pass palladium at 50-100°C Catalyzed coupling reaction, prepared by functional substitution at multiple sites of pyrene.
  5. 根据权利要求4所述的芘基有机功能发光材料，其特征在于，所述保护气氛为氮气或者氩气；所述钯催化剂为四(三苯基膦)钯、醋酸钯、四氟硼酸三(叔丁基膦)或三(二亚苄基丙酮)二钯、二氯双(三苯基膦)合钯中的一种及以上，所述无机碱为碳酸钾、碳酸钠、碳酸氢钠、碳酸氢钾、氢氧化钠中的一种及以上；所述溶剂为甲苯、乙醇、水、四氢呋喃、N,N-二甲基甲酰胺、乙腈、三乙胺中的一种及以上；所述芳香烃硼酸及其衍生物为4-甲氧基苯基硼酸、4-三氟甲基苯基硼酸、2-噻吩基硼酸、4-三甲氧基苯胺基硼酸酯；所述2-羟基-1,3,6,8-四溴芘或2,7-二羟基-1,3,6,8-四溴芘:芳香烃硼酸及其衍生物:钯催化剂:无机碱的摩尔比为1:(4～10):(0.05～0.2):(5～20)。The pyrene-based organic functional luminescent material according to claim 4, wherein the protective atmosphere is nitrogen or argon; the palladium catalyst is tetrakis (triphenylphosphine) palladium, palladium acetate, tris(tetrafluoroborate) tert-butylphosphine) or three (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium and one or more, the inorganic base is potassium carbonate, sodium carbonate, sodium bicarbonate, One or more of potassium bicarbonate and sodium hydroxide; the solvent is one or more of toluene, ethanol, water, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, and triethylamine; the Aromatic hydrocarbon boronic acid and derivatives thereof are 4-methoxyphenylboronic acid, 4-trifluoromethylphenylboronic acid, 2-thienylboronic acid, 4-trimethoxyanilinoboronic acid ester; the 2-hydroxy- The molar ratio of 1,3,6,8-tetrabromopyrene or 2,7-dihydroxy-1,3,6,8-tetrabromopyrene: aromatic hydrocarbon boronic acid and its derivatives: palladium catalyst: inorganic base is 1: (4～10):(0.05～0.2):(5～20).
  6. 一种芘基有机功能发光材料，其特征在于，所述的芘基有机功能发光材料的分子结构通式如3a或3b所示：A pyrene-based organic functional luminescent material, characterized in that the general molecular structure formula of the pyrene-based organic functional luminescent material is as shown in 3a or 3b:
    Figure PCTCN2022126686-appb-100004
    Figure PCTCN2022126686-appb-100004
    其中，R 2为甲基、乙基、苯基或苄基； Wherein, R 2 is methyl, ethyl, phenyl or benzyl;
    所述芘基有机功能发光材料是将权利要求4或5所述的芘基有机功能发光材料、R 2取代基团的卤化物和无机碱溶解在有机溶剂中搅拌，在60～80℃加热5～12h，反应结束后冷却至室温，用二氯甲烷萃取洗涤，饱和食盐水萃取，无水硫酸镁除水后过滤，旋蒸后进行色谱柱分离并重结晶制得。 The pyrene-based organic functional luminescent material is that the pyrene-based organic functional luminescent material described in claim 4 or 5, the halide of the R substituent group and the inorganic base are dissolved in an organic solvent and stirred, and heated at 60 to 80°C for 5 After ~12h, cool to room temperature after the reaction, extract and wash with dichloromethane, extract with saturated brine, filter with anhydrous magnesium sulfate to remove water, perform chromatographic column separation and recrystallization after rotary evaporation.
  7. 根据权利要求6所述的芘基有机功能发光材料，其特征在于，所述R 2取代基团的卤化物为碘甲烷、碘乙烷、苄基溴或溴苯；所述惰性气氛为氮气或氩气；所述无机碱为碳酸钾、叔丁基醇钾、碳酸钠、碳酸氢钠、碳酸氢钾、氢氧化钠中的一种以上；所述有机溶剂为乙腈、四氢呋喃、二氯甲烷、乙醇中的一种以上； 所述的芘基有机功能发光材料:R 2取代基团的卤化物:无机碱的摩尔比为1:(1～10):(5～20)。 The pyrene-based organic functional luminescent material according to claim 6, wherein the halide of the R substituting group is methyl iodide, ethyl iodide, benzyl bromide or bromobenzene; the inert atmosphere is nitrogen or Argon; the inorganic base is more than one of potassium carbonate, potassium tert-butyl alkoxide, sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide; the organic solvent is acetonitrile, tetrahydrofuran, dichloromethane, More than one of ethanol; The molar ratio of the pyrene-based organic functional luminescent material: the halide of the R 2 substituent group: the inorganic base is 1: (1-10): (5-20).
  8. 权利要求4-7任一项所述的芘类发光材料在有机电子学或生物领域中的应用。The application of the pyrene-based luminescent material described in any one of claims 4-7 in the field of organic electronics or biology.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101003508A (en) * 2006-01-16 2007-07-25 Lg电子株式会社 Electron transport compound and organic light emitting device comprising the same
CN101768436A (en) * 2008-12-30 2010-07-07 乐金显示有限公司 Organic light emitting material and organic light emitting device using the same
CN107004776A (en) * 2014-12-31 2017-08-01 Sfc株式会社 With high efficiency and long-life organic illuminating element
CN111477765A (en) * 2019-01-23 2020-07-31 三星显示有限公司 Organic light emitting device
CN114149307A (en) * 2021-12-07 2022-03-08 广东工业大学 Bromopyrene intermediate and derivative, preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101003508A (en) * 2006-01-16 2007-07-25 Lg电子株式会社 Electron transport compound and organic light emitting device comprising the same
CN101768436A (en) * 2008-12-30 2010-07-07 乐金显示有限公司 Organic light emitting material and organic light emitting device using the same
CN107004776A (en) * 2014-12-31 2017-08-01 Sfc株式会社 With high efficiency and long-life organic illuminating element
CN111477765A (en) * 2019-01-23 2020-07-31 三星显示有限公司 Organic light emitting device
CN114149307A (en) * 2021-12-07 2022-03-08 广东工业大学 Bromopyrene intermediate and derivative, preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
RUNGE, FRANZ; MECKELBURG, ARNO: "Auffindung und Synthese von 4.9-Dimethyl-pyren", EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, WILEY - V C H VERLAG GMBH & CO. KGAA, vol. 86, no. 3, 31 March 1953 (1953-03-31), pages 373 - 376, XP009546812, ISSN: 1099-0682, DOI: 10.1002/cber.19530860311 *
TREIBS WILHELM, MOBIUS GUNTER: "UBER METHYLPYRENE, I Der EinfluB der Methylgruppe in 4-Stellung auf die direkte Substitution", JUSTUS LIEBIGS ANNALEN DER CHEMIE, vol. 619, no. 1, 11 August 1958 (1958-08-11), pages 122 - 136, XP093070731, DOI: 10.1002/jlac.19586190113 *

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