Dianthracene ortho-position selective boron esterification and group post-modification method

Abstract

The invention discloses a dianthracene ortho-position selective boron esterification and group post-modification method, which realizes the ortho-position efficient boron esterification of dianthracene by taking a methoxy (cyclooctadiene) iridium dimer as a catalyst through the synergistic effect of a steric hindrance effect and a specific solvent system. A novel method which is high in regioselectivity, mild, efficient and suitable for ortho-position precise modification is provided; group post-modification is further carried out around the boron esterification intermediate, and functional groups with different push-pull electron effects, such as trifluoromethylphenyl, triisopropylsilylacetylene, 4-methoxyphenyl, pyridyl, halogen, cyano and thienyl, are introduced in a targeted design, so that a dianthracene core plane conjugated structure is reserved, and meanwhile, the functional groups with different push-pull electron effects, such as dianthracene, dianthracene and dianthracene are synthesized. The stability and the solution machinability of the material are remarkably improved, the photophysical function of the material is expanded, and a core foundation is laid for application of the dianthracene material in the fields of near-infrared photoelectricity, organic semiconductors and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic optoelectronic materials, and particularly relates to a method for ortho-position selective boron esterification and group post-modification of bisanthene. BACKGROUND

[0002] Fused-ring aromatics, as a class of important organic functional materials, have shown broad application prospects in the fields of organic photovoltaics, organic light-emitting diodes, organic field-effect transistors and other optoelectronic devices due to their highly delocalized pi-conjugated systems, excellent charge transport ability and flexible front-line molecular orbital energy level structure. As a typical representative of symmetrical fused-ring aromatics, bisanthene has an extended conjugated plane and a unique electronic structure, and its strong absorption and fluorescence emission characteristics in the visible light to near-infrared light region of 500-800 nm make it have great potential in applications such as near-infrared light detection and high-resolution fluorescence imaging.

[0003] In recent years, researchers have been committed to realizing precise control of the electronic structure of bisanthene by selective functionalization and modification of different sites of the molecule, so as to improve the material stability and solution processability and expand the functional boundaries. In the prior art, the functionalization and modification of bisanthene mainly focuses on two sites: the bay region ( bay ) and the meso position ( meso ). The bay region has a cis-conjugated diene structure, and the conjugated system can be expanded laterally through a diene addition reaction. The meso position can introduce different substituents to a certain extent to block the attack of oxygen molecules on the core skeleton of bisanthene, thereby improving the chemical stability of the molecule.

[0004] Compared with the meso position and the bay region, the ortho position ( ortho ) of bisanthene has unique structural advantages: the ortho position has less steric hindrance, and selective functionalization and modification of the ortho position can not only maximize the preservation of the planar conjugated structure and molecular symmetry of the bisanthene core to ensure its inherent charge transport performance, but also provide a new path for the construction of two-dimensional organic metal frameworks or covalent organic framework precursors through the precise introduction of active substituents. At the same time, the introduction of substituents with different electronic effects at the ortho position can develop organic optoelectronic functional materials different from meso and bay position substituted derivatives. Therefore, realizing selective functionalization of the ortho position of bisanthene and then enriching the types and functions of bisanthene derivatives has important scientific significance and practical value for perfecting the functionalization research system of bisanthene and expanding its application fields.

[0005] However, due to the relatively low electron cloud density of the ortho position of perylene, the electrophilic reactivity is significantly weaker than that of the meso and bay positions, making it difficult to selectively modify this site. In addition, the existing methods lack a general intermediate with high selectivity, high yield and applicability to various subsequent transformations, which limits the diversification and functional expansion of perylene derivatives. SUMMARY

[0006] The purpose of the present application is to solve the above technical problems, and to provide a method for selective boron esterification and group post-modification of the ortho position of perylene. This method achieves precise boron esterification of the ortho position of perylene through the synergistic effect of transition metal iridium catalysis and a specific solvent system, obtaining a general boron ester intermediate with high selectivity and high yield. Then, through cross-coupling reaction, a variety of functional groups are introduced with high selectivity. This method significantly improves the material stability and solution processability while retaining the planar conjugated structure of the perylene core and the high symmetry of the molecule, and expands its optical physical function, laying a core foundation for the application of perylene materials in the fields of near-infrared optoelectronics, organic semiconductors and photocatalysis.

[0007] The above purpose of the present application is achieved by the following technical solutions:

[0008] The present application provides a method for selective boron esterification of the ortho position of perylene, comprising the following steps:

[0009] 7,14-bis(2,4,6-trimethylphenyl)perylene (BA-Mes), pinacol diboron (B2pin2), and methoxy(cyclooctadiene)iridium dimer are dissolved in an organic solvent, and the reaction is carried out at 70-90 ℃ under inert gas protection for 40-50 h to obtain 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(pinacol borate)perylene (BAM-4Bpin);

[0010] The organic solvent is cyclohexane and / or tetrahydrofuran.

[0011] The present application realizes efficient boron esterification of the ortho position of perylene through the synergistic effect of steric hindrance and a specific solvent system, using methoxy(cyclooctadiene)iridium dimer as a catalyst, successfully synthesizing tetra(pinacol borate)substituted BAM-4Bpin, and providing a new method with high regioselectivity, mildness, high efficiency and applicability to precise modification of the ortho position. The BAM-4Bpin obtained by this method has a clear structure, good stability and applicability to various subsequent transformations, laying a synthetic foundation for the construction of perylene derivatives, and effectively expanding the application prospects of perylene materials in the fields of near-infrared optoelectronic materials, organic semiconductors and photocatalysis.

[0012] Furthermore, the molar ratio of 7,14-bis(2,4,6-trimethylphenyl)bisanthracene to pinacol diboronate is 1:(8-12).

[0013] Furthermore, the molar ratio of the 7,14-bis(2,4,6-trimethylphenyl)bisanthracene to the methoxy(cyclooctadiene)iridium dimer is 1:(0.1-1).

[0014] Furthermore, the molar ratio of the methoxy(cyclooctadiene) iridium dimer to 4,4'-di-tert-butyl-2,2'-dipyridine is (0.4-0.6):1.

[0015] Furthermore, the inert gas is argon or nitrogen.

[0016] Furthermore, when the solvent is a mixture of cyclohexane and tetrahydrofuran, the volume ratio of cyclohexane to tetrahydrofuran is (0.5-1.5):1.

[0017] Furthermore, the reaction also includes a separation and purification step after completion.

[0018] Furthermore, the separation and purification includes the steps of column chromatography purification and recrystallization.

[0019] Furthermore, the eluent for column chromatography is dichloromethane, and the solvent for recrystallization is a mixture of petroleum ether and ethyl acetate.

[0020] In a specific embodiment, BA-Mes, B2pin2, methoxy(cyclooctadiene)iridium dimer and 4,4'-di-tert-butyl-2,2'-dipyridine were dissolved in an organic solvent and refluxed and stirred at 70-90 °C under inert gas protection for 40-50 h. After the reaction was cooled to room temperature, the reaction solution was purified by short column chromatography to obtain a blue-green solid, which was then recrystallized to obtain BAM-4Bpin.

[0021] A second aspect of the present invention provides a method for ortho-selective stepwise boron esterification of bis(anthracene), comprising the following steps:

[0022] (1) 7,14-bis(2,4,6-trimethylphenyl)bisanthracene, pinacol diborate, methoxy(cyclooctadiene)iridium dimer and 4,4'-di-tert-butyl-2,2'-dipyridine are dissolved in an organic solvent and reacted at 70-90 °C under inert gas protection for 20-30 h to obtain 7,14-bis(2,4,6-trimethylphenyl)-2,5,9-tris(pinacol diborate)bisanthracene (BAM-3Bpin); the organic solvent is cyclohexane and / or tetrahydrofuran;

[0023] (2) 7,14-bis(2,4,6-trimethylphenyl)-2,5,9-tris(pinacolyl borate)bisanthracene, pinacolyl borate, methoxy(cyclooctadiene)iridium dimer and 4,4'-di-tert-butyl-2,2'-dipyridine are dissolved in an organic solvent and reacted at 70-90 °C under inert gas protection for 40-50 h to obtain 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(pinacolyl borate)bisanthracene; the organic solvent is cyclohexane and / or tetrahydrofuran.

[0024] Further, in step (1), the molar ratio of 7,14-bis(2,4,6-trimethylphenyl)bisanthracene to pinacol diboronate is 1:(8-12).

[0025] Further, in step (1), the molar ratio of 7,14-bis(2,4,6-trimethylphenyl)bisanthracene to methoxy(cyclooctadiene)iridium dimer is 1:(0.1-1).

[0026] Further, in step (1), the molar ratio of the methoxy(cyclooctadiene) iridium dimer to 4,4'-di-tert-butyl-2,2'-dipyridine is (0.4-0.6):1.

[0027] Further, in step (1), the inert gas is argon or nitrogen.

[0028] Further, in step (1), the volume ratio of cyclohexane to tetrahydrofuran is (0.5-1.5):1.

[0029] Furthermore, in step (1), after the reaction is completed, a separation and purification step is also included.

[0030] Further, in step (1), the separation and purification includes column chromatography purification, vacuum distillation and recrystallization.

[0031] Further, in step (1), the eluent for column chromatography is dichloromethane, and the solvent for recrystallization is a mixture of petroleum ether and ethyl acetate.

[0032] Further, in step (2), the molar ratio of 7,14-bis(2,4,6-trimethylphenyl)-2,5,9-tris(pinacolyl borate)bis(anthracene) to pinacolyl borate is 1:(2-4).

[0033] Further, in step (2), the molar ratio of 7,14-bis(2,4,6-trimethylphenyl)-2,5,9-tris(pinacolyl borate)bis(anthracene) to methoxy(cyclooctadiene)iridium dimer is 1:(0.1-0.5).

[0034] Further, in step (2), the molar ratio of the methoxy(cyclooctadiene) iridium dimer to 4,4'-di-tert-butyl-2,2'-dipyridine is (0.4-0.6):1.

[0035] Furthermore, in step (2), the inert gas is argon or nitrogen.

[0036] Further, in step (2), the volume ratio of cyclohexane to tetrahydrofuran is (0.5-1.5):1.

[0037] Furthermore, in step (2), after the reaction is completed, a separation and purification step is also included.

[0038] Furthermore, in step (2), the separation and purification includes column chromatography purification, vacuum distillation and recrystallization.

[0039] Further, in step (2), the eluent for column chromatography is dichloromethane, and the solvent for recrystallization is a mixture of petroleum ether and ethyl acetate.

[0040] A third aspect of the present invention provides a method for modification after selectively functionalizing a dianthracene group at the ortho position, comprising the following steps:

[0041] The 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(pinacolyl borate)bis(anthracene), a compound containing the functionalized group R, prepared by the method described in the first or second aspect, were dissolved in a solvent with a palladium catalyst and coupled together at 80-90 °C under an inert gas atmosphere for 10-20 h to obtain the compound with the following structural formula: Bisanthrabenzyl derivatives;

[0042] The functional group R is (4-Trifluoromethylphenyl) (triisopropylsilylethynyl) (4-Methoxyphenyl) (aniline), halogen, cyano, naphthyl, phenanthryl, anthracene, thiophene, pyridyl, furanyl or benzothiophene; the palladium catalyst is tetra(triphenylphosphine)palladium, 1,1'-bis(diphenylphosphine)ferrocene palladium chloride, palladium acetate, palladium chloride or tris(dibenzylideneacetone)dipalladium.

[0043] This invention leverages the four borate ester active sites of BAM-4Bpin to efficiently introduce various functionalized groups through multiple cross-coupling reactions, such as Suzuki-Miyaura coupling and sage coupling. These functionalized groups include trifluoromethylphenyl, triisopropylsilylethynyl, 4-methoxyphenyl, cyano, naphthyl, phenanthryl, anthraceneyl, thiophene, pyridyl, furanyl, and benzothiopheneyl groups. The introduction of aryl and alkynyl groups effectively expands the π-conjugated system of bisanthracite, shifting its absorption and emission spectra towards the near-infrared region. Electron-withdrawing groups such as trifluoromethylphenyl significantly enhance the chemical stability and antioxidant properties of bisanthracite derivatives. Heterocyclic groups such as pyridyl and thiophene can regulate the charge transport properties of the molecule and its responsiveness to external stimuli (such as acid-base interactions and metal ion coordination), further expanding the application scenarios of the material.

[0044] Further, the molar ratio of 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(boranoyl ester)bis(anthracene) to the compound containing the functionalized group R is 1:(4-16).

[0045] Further, the molar ratio of 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(pinacolyl borate)bis(anthracene) to the palladium catalyst is (2-8):1.

[0046] Furthermore, the compound containing the functional group R is p-bromotrifluorotoluene, (2-bromoethynyl)triisopropylsilane, 4-bromoanisole, cuprous cyanide, 2-bromothiophene, 4-bromobenzamine, 4-bromobenzaldehyde, 2-bromofuran, or 2-bromopyrrole.

[0047] Furthermore, the inert gas is argon or nitrogen.

[0048] Further, the solvent is a mixed solvent of toluene, ethanol and potassium carbonate aqueous solution or a mixed solvent of 1,4-dioxane and potassium carbonate aqueous solution; the volume ratio of toluene, ethanol and potassium carbonate aqueous solution is (800-1200):(400-600):(10-25), and the concentration of potassium carbonate aqueous solution is 1-3 M; the volume ratio of 1,4-dioxane and potassium carbonate aqueous solution is 1000:(10-25), and the concentration of potassium carbonate aqueous solution is 1-3 M.

[0049] Furthermore, the reaction also includes a separation and purification step after completion.

[0050] Furthermore, the separation and purification includes the steps of extraction, column chromatography separation, and recrystallization.

[0051] Furthermore, the column chromatography separation uses a mixed solvent of petroleum ether and dichloromethane as the eluent, with a volume ratio of petroleum ether to dichloromethane of (8-12):1; the recrystallization solvent is a mixed solvent of dichloromethane and methanol with a volume ratio of 1:7. This mixed solvent is a typical two-phase system for coupling reactions, with toluene serving as the organic phase to dissolve the substrate, ethanol as a co-solvent to enhance the compatibility of the two phases, and potassium carbonate aqueous solution as a base to promote the reaction.

[0052] Compared with the prior art, the above-described technical solution of the present invention has the following advantages:

[0053] 1. This invention achieves high regioselectivity by leveraging the steric hindrance effect and the synergistic effect of the iridium catalytic system, specifically introducing borate pinacol ester groups at the ortho position of bis(anthracene) to effectively avoid side reactions in the meso or bay regions. At the same time, the ortho substitution mode has minimal interference with the planarity and molecular structural symmetry of the bis(anthracene) core skeleton, which is beneficial for maintaining the excellent π-electron delocalization and photoelectric properties of the molecule.

[0054] 2. The BAM-4Bpin intermediate prepared by this invention has strong versatility and can efficiently participate in various cross-coupling reactions such as the Suzuki reaction and the sage coupling reaction. It successfully introduces diverse functional groups such as trifluoromethylphenyl, triisopropylsilylethynyl, 4-methoxyphenyl, aniline, halogen, cyano, naphthyl, phenanthryl, anthraceneyl, thiophene, pyridyl, furanyl, or benzothiophene. By introducing different functional groups, precise control over the molecular photophysical properties and chemical stability can be achieved. The aryl and alkynyl groups expand the π-conjugated system, causing the absorption / emission spectrum to redshift to the near-infrared region. The electron-withdrawing groups such as trifluoromethylphenyl and triisopropylsilylethynyl lower the energy of the highest occupied molecular orbital, improve molecular stability, and expand the application scenarios of the material in the fields of imaging and detection.

[0055] 3. The preparation method provided by the present invention has excellent process feasibility. The reaction conditions of each step are mild, the raw materials are readily available, the operation is controllable, the separation and purification steps are simple and efficient, no complex equipment is required, and it has the potential for large-scale production. Attached Figure Description

[0056] Figure 1 This is a schematic diagram of the median, adjacent, and bay sites of bis(anthracene).

[0057] Figure 2 The reaction equation for the preparation of BAM-4Bpin in Example 1.

[0058] Figure 3 The matrix-assisted laser desorption / ionization time-of-flight mass spectrum (MALDI-TOF spectrum) of BAM-4Bpin prepared in Example 1 is shown.

[0059] Figure 4The MALDI-TOF spectrum of 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(triisopropylsilylethynyl)bisanthracene prepared in Example 8 is shown.

[0060] Figure 5 The MALDI-TOF spectrum of 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-methoxyphenyl)bisanthracene prepared in Example 9 is shown.

[0061] Figure 6 The UV-Vis absorption spectra of BAM-4Bpin prepared in Example 1, 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-trifluoromethylphenyl)bisanthracite prepared in Example 7, and 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-methoxyphenyl)bisanthracite prepared in Example 9 are shown.

[0062] Figure 7 The fluorescence emission spectra of BAM-4Bpin prepared in Example 1, 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-trifluoromethylphenyl)bisanthracite prepared in Example 7, and 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-methoxyphenyl)bisanthracite prepared in Example 9 are shown.

[0063] Figure 8 The MALDI-TOF spectrum of 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-benzaldehyde)bisanthracene prepared in Example 10 is shown. Detailed Implementation

[0064] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0065] A schematic diagram of the long-axis median, ortho, and short-axis bay sites of bis(thiazoline) is shown below. Figure 1 As shown, the present invention provides a method for ortho-selective boron esterification of bis(anthracene), comprising the following steps:

[0066] BA-Mes, B2pin2, methoxy(cyclooctadiene) iridium dimer, and 4,4'-di-tert-butyl-2,2'-dipyridine were dissolved in an organic solvent and reacted at 70-90 °C under inert gas protection for 40-50 h to obtain BAM-4Bpin; the organic solvent was cyclohexane and / or tetrahydrofuran.

[0067] This invention also provides a method for post-modification with ortho- and ortho-functionalized groups of bis(anthracene), comprising the following steps:

[0068] BAM-4Bpin, a compound containing a functionalized group R, and a palladium catalyst were dissolved in a solvent and coupled together at 80-90 °C under inert gas protection for 10-20 h to obtain the structure with the following formula: The derivatives are bis(anthracene) derivatives (Mes is 2,4,6-trimethylphenyl); the functional group R is 4-trifluoromethylphenyl, triisopropylsilylethynyl, 4-methoxyphenyl, aniline, halogen, cyano, naphthyl, phenanthryl, anthracene, thiophene, pyridyl, furanyl, or benzothiophene; the palladium catalyst is tetrakis(triphenylphosphine)palladium, 1,1'-bis(diphenylphosphine)ferrocene palladium chloride, palladium acetate, palladium chloride, or tris(dibenzylideneacetone)dipalladium.

[0069] This invention successfully achieved efficient ortho-boronization of bis(anthracene) to synthesize the key intermediate BAM-4Bpin, which is a tetra(pinacol borate) substituted group. Further post-modification of this boronized intermediate was carried out, with targeted design and introduction of functional groups with different push-pull electron effects, such as trifluoromethylphenyl, triisopropylsilylethynyl, 4-methoxyphenyl, pyridyl, halogen, cyano, and thiophene groups. This provides a general and efficient method for post-modification, laying a solid molecular design foundation for the development of high-performance, high-stability bis(anthracene) optoelectronic materials.

[0070] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0071] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, and the materials and reagents used are commercially available.

[0072] Example 1

[0073] A method for ortho-selective boron esterification of bis(anthracene) includes the following steps, and the reaction equation is as follows: Figure 2 As shown:

[0074] 67.2 mg (0.115 mmol) of 7,14-bis(2,4,6-trimethylphenyl)bis(anthracene) (BA-Mes), 337 mg (1.33 mmol) of pinacol diborate (B2pin2), 74.1 mg (0.113 mmol) of methoxy(cyclooctadiene) iridium dimer and 61.3 mg (0.226 mmol) of 4,4'-di-tert-butyl-2,2'-dipyridine were added to a 25 mL reaction tube. Under argon protection, 2.5 mL of dry cyclohexane and 3.5 mL of tetrahydrofuran were added, and the mixture was heated to 85 °C and reacted for 48 h. After the reaction was completed, the reaction solution was subjected to column chromatography using dichloromethane as the eluent. The blue-green eluent was collected and distilled under reduced pressure to obtain a crude solid product. The crude product was recrystallized multiple times with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 1:7. After filtration and drying, 17.6 mg of the blue-green solid product 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(boranoyl ester)bis(anthracene) (BAM-4Bpin) was obtained, with a yield of 43%. The NMR data of the product are as follows: 1 H NMR (400 MHz, Tol- d 8,298K) delta 9.25 (s, 4H), 8.28 (s, 4H), 6.88 (s, 4H), 2.19 (s, 6H), 2.02 (s, 12H), 0.97 (s, 48H).

[0075] The MALDI-TOF spectrum of the product is as follows Figure 3 As shown, its characteristic peak appears at a mass-to-charge ratio of approximately 1091-1092, which matches the theoretical molecular weight of the target BAM-4Bpin molecule, confirming the successful synthesis of BAM-4Bpin. The main peak has the highest signal intensity and no obvious impurity peaks, with only adjacent small peaks caused by differences in isotopic abundance, indicating that the obtained product has high purity.

[0076] Example 2

[0077] A method for ortho-selective boron esterification of bis(anthracene) includes the following steps:

[0078] One equivalent (eq) of BA-Mes, 12 eq of B2pin2, 0.5 eq of methoxy(cyclooctadiene)iridium dimer, and 1 eq of 4,4'-di-tert-butyl-2,2'-dipyridine were added to a 25 mL reaction tube. Under argon protection, 6 mL of a mixed solvent of dry cyclohexane and tetrahydrofuran (v / v ratio) at a ratio of 0.66:1 was added, and the mixture was heated to 90 °C for 48 h. After the reaction was completed, the reaction solution was separated by column chromatography using dichloromethane as the eluent. The blue-green eluent was collected and distilled under reduced pressure to obtain a crude solid product. The crude product was recrystallized multiple times using a mixed solvent of petroleum ether and ethyl acetate (v / v ratio) at a ratio of 1:7. After filtration and drying, the blue-green solid product BAM-4Bpin was obtained, with a yield of 16%.

[0079] Example 3

[0080] A method for ortho-selective boron esterification of bis(anthracene) includes the following steps:

[0081] One eq of BA-Mes, 12 eq of B2pin2, 0.5 eq of methoxy(cyclooctadiene)iridium dimer, and one eq of 4,4'-di-tert-butyl-2,2'-dipyridine were added to a 25 mL reaction tube. Under argon protection, 6 mL of a mixed solvent of dry cyclohexane and tetrahydrofuran (v / v ratio) at 0.77:1 was added, and the mixture was heated to 90 °C for 48 h. After the reaction was completed, the reaction solution was separated by column chromatography using dichloromethane as the eluent. The blue-green eluent was collected and distilled under reduced pressure to obtain a crude solid product. The crude product was recrystallized multiple times using a mixed solvent of petroleum ether and ethyl acetate (v / v ratio) at 1:7. After filtration and drying, the blue-green solid product BAM-4Bpin was obtained, with a yield of 43%.

[0082] Example 4

[0083] A method for ortho-selective boron esterification of bis(anthracene) includes the following steps:

[0084] One eq of BA-Mes, 12 eq of B2pin2, 0.5 eq of methoxy(cyclooctadiene)iridium dimer, and one eq of 4,4'-di-tert-butyl-2,2'-dipyridine were added to a 25 mL reaction tube. Under argon protection, dry tetrahydrofuran solvent was added, and the mixture was heated to 80 °C for 48 h. After the reaction was completed, the reaction solution was separated by column chromatography using dichloromethane as the eluent. The blue-green eluent was collected and distilled under reduced pressure to obtain a crude solid product. The crude product was recrystallized multiple times with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 1:7. After filtration and drying, the blue-green solid product BAM-4Bpin was obtained, with a yield of 30%.

[0085] Example 5

[0086] A method for ortho-selective boron esterification of bis(anthracene) includes the following steps:

[0087] One eq of BA-Mes, 12 eq of B2pin2, 0.5 eq of methoxy(cyclooctadiene)iridium dimer, and one eq of 4,4'-di-tert-butyl-2,2'-dipyridine were added to a 25 mL reaction tube. Under argon protection, dry cyclohexane solvent was added, and the mixture was heated to 80 °C for 48 h. After the reaction was completed, the reaction solution was separated by column chromatography using dichloromethane as the eluent. The blue-green eluent was collected and distilled under reduced pressure to obtain a crude solid product. The crude product was recrystallized multiple times with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 1:7. After filtration and drying, the blue-green solid product BAM-4Bpin was obtained, with a yield of 34%.

[0088] Example 6

[0089] A method for ortho-selective boron esterification of bis(anthracene) includes the following steps:

[0090] (1) 1 eq BA-Mes, 8 eq B2pin2, 0.2 eq methoxy(cyclooctadiene)iridium dimer and 0.4 eq 4,4'-di-tert-butyl-2,2'-dipyridine were added to a 25 mL reaction tube. Under argon protection, 6 mL of dry tetrahydrofuran solvent was added, and the mixture was heated to 70 °C for 24 h. After the reaction, the reaction solution was separated by column chromatography using dichloromethane as the eluent. The eluent was collected and distilled under reduced pressure to obtain a solid crude product. The crude product was recrystallized multiple times with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 1:7. After filtration and drying, the solid product BAM-3Bpin was obtained with a yield of 32%. The NMR data of the product were as follows: 1 H NMR (400 MHz, CDCl3, 298 K) delta 8.65 (s, 2H), 8.60 (s, 2H),8.37 (s, 2H), 7.68 (s, 1H), 7.63 (s, 2H), 7.11 (s, 4H), 2.49 (s, 6H), 1.59(s, 12H), 1.38 - 1.34 (m, 36H).

[0091] (2) 1 eq BAM-3Bpin, 2 eq B2pin2, 0.1 eq methoxy(cyclooctadiene) iridium dimer and 0.2 eq 4,4'-di-tert-butyl-2,2'-dipyridine were added to a 25 mL reaction tube. Under argon protection, 6 mL of a 1:1 mixture of dry cyclohexane and tetrahydrofuran was added, and the mixture was heated to 90 °C for 48 h. After the reaction was completed, the reaction solution was separated by column chromatography using dichloromethane as the eluent. The blue-green eluent was collected and distilled under reduced pressure to obtain a crude solid product. The crude product was recrystallized multiple times using a 1:7 mixture of petroleum ether and ethyl acetate. After filtration and drying, the blue-green solid product BAM-4Bpin was obtained with a yield of 91%.

[0092] Example 7

[0093] A method for post-modification with ortho-selective functionalized groups of bis(anthracene) includes the following steps:

[0094] 4.8 mg (4.6 μmol) of BAM-4Bpin prepared in Example 1, 5.1 μL (37 μmol) of p-bromotrifluorotoluene, and 1.0 mg (1.4 μmol) of 1,1'-bis(diphenylphosphine)ferrocene palladium chloride were added to a 25 mL reaction tube. Under an argon atmosphere, 1 mL of dry toluene, 0.5 mL of ethanol, and 6 μL of 2 M potassium carbonate aqueous solution were added. The mixture was heated to 85 °C and reacted for 16 h. After the reaction was completed, the reaction solution was extracted multiple times with ethyl acetate. The combined organic phases were collected and the solvent was removed by vacuum distillation to obtain a solid mixture. The solid mixture was then separated by column chromatography using a 10:1 (v / v) mixture of petroleum ether and dichloromethane as the eluent. The eluent corresponding to the second band was collected to obtain the crude product. The crude product was recrystallized from a mixed solvent of dichloromethane and methanol to give 1.3 mg of solid product 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-trifluoromethylphenyl)bis(anthracene), with the structural formula [insert structural formula here]. The yield was 25%, and the NMR data of the product were as follows: 1 H NMR (400 MHz, Tol- d 8,298 K) delta 8.57 (s, 4H), 7.87 (s, 4H), 7.56 - 7.53 (m, 8H), 7.45 - 7.47 (m, 8H), 7.20 (s, 4H), 2.38 (s, 6H), 2.21 (s, 12H).

[0095] Example 8

[0096] A method for post-modification with ortho-selective functionalized groups of bis(anthracene) includes the following steps:

[0097] 10.0 mg (9.17 μmol) of BAM-4Bpin prepared in Example 1, 9.1 μL (38 μmol) of (2-bromoethynyl)triisopropylsilane, and 2.1 mg (1.8 μmol) of tetrakis(triphenylphosphine)palladium were added to a 25 mL reaction tube. Under an argon atmosphere, 1 mL of dry toluene, 0.5 mL of ethanol, and 18 μL of 2 M potassium carbonate aqueous solution were added. The mixture was heated to 80 °C and reacted for 16 h. After the reaction was completed, the reaction solution was extracted multiple times with ethyl acetate. The combined organic phases were collected and the solvent was removed by vacuum distillation to obtain a solid mixture. The solid mixture was then separated by column chromatography using a 10:1 (v / v) mixture of petroleum ether and dichloromethane as the eluent. The eluent corresponding to the third band was collected and the crude product was obtained by vacuum distillation. The crude product was recrystallized from a mixed solvent of dichloromethane and methanol in a volume ratio of 1:7 to give 2.1 mg of a blue solid product, 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(triisopropylsilylethynyl)bis(anthracene), with the structural formula [insert structural formula here]. The yield was 18%, and the NMR data of the product were as follows: 1 H NMR (400 MHz, Tol- d 8,298 K) delta 8.33 (s, 4H), 7.76 (s, 4H), 6.85 (s, 4H), 2.25 (s, 6H), 1.89 (s, 12H), 1.17 - 1.21 (m, 84H).

[0098] The MALDI-TOF spectrum of the product is as follows Figure 4 As shown, its characteristic peak appears at a mass-to-charge ratio of approximately 1308-1310, which is consistent with the theoretical molecular weight of the target 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(triisopropylsilylethynyl)bisanthracene molecule, confirming the successful synthesis of the product. The main peak signal intensity is high and there are only adjacent small peaks caused by differences in isotopic abundance, with no obvious impurity peaks, indicating that the obtained product has high purity.

[0099] Example 9

[0100] A method for post-modification with ortho-selective functionalized groups of bis(anthracene) includes the following steps:

[0101] 4.8 mg (4.6 μmol) of BAM-4Bpin prepared in Example 1, 6.0 μL (73 μmol) of 4-bromoanisole, and 1.0 mg (1.4 μmol) of 1,1'-bis(diphenylphosphine)ferrocene palladium chloride were added to a 25 mL reaction tube. 1 mL of dry toluene, 0.5 mL of ethanol, and 6 μL of 2 M potassium carbonate aqueous solution were added. The mixture was heated to 85 °C and reacted for 16 h. After the reaction, the reaction solution was extracted multiple times with ethyl acetate. The combined organic phases were collected, and the solvent was removed by vacuum distillation to obtain a solid mixture. This solid mixture was then separated by column chromatography using a 10:1 (v / v) mixture of petroleum ether and dichloromethane as the eluent. The eluent corresponding to the fourth band was collected. The crude product was recrystallized from a mixed solvent of dichloromethane and methanol in a volume ratio of 1:7 to give 1.1 mg of solid product 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-methoxyphenyl)bis(anthracene), with the structural formula [structure omitted]. The yield was 25%, and the NMR data of the product were as follows: 1 H NMR (400 MHz, CDCl3, 298 K) delta 8.58 (s, 4H), 7.59 - 7.62 (m,8H), 7.39 (s, 4H), 7.12 (s, 4H), 7.05 - 7.02 (m, 8H), 3.89 (s, 12H), 2.47 (s,6H), 1.98 (s, 12H).

[0102] The MALDI-TOF spectrum of the product is as follows Figure 5 As shown, its characteristic peak appears at a mass-to-charge ratio of approximately 10¹⁰-10¹¹, which is consistent with the theoretical molecular weight of the target 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-methoxyphenyl)bis(anthracene) molecule, confirming the successful synthesis of the product. The main peak signal intensity is high and there are only adjacent small peaks caused by differences in isotopic abundance, with no obvious impurity peaks, indicating that the obtained product has high purity.

[0103] The UV-Vis absorption spectra of BAM-4Bpin prepared in Example 1, 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-trifluoromethylphenyl)bisphenethracene prepared in Example 7, and 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-methoxyphenyl)bisphenethracene prepared in Example 9 are shown below. Figure 6 As shown, the test solvent was dichloromethane, and the temperature was 298 K. c 实施例1 =1.2×10 -5mol / L, c 实施例7 =0.5×10 -5 mol / L, c 实施例9 =0.6×10 -5 mol / L; the three bis-anthracene derivatives all exhibited characteristic absorption peaks in the ultraviolet-visible-near-infrared region (300-800 nm), and showed significant differences in the position of the maximum absorption peak due to different substituents. These differences reflect that the optical band gap and absorption characteristics of this type of material can be effectively adjusted by introducing different substituents.

[0104] The fluorescence emission spectra of BAM-4Bpin prepared in Example 1, 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-trifluoromethylphenyl)bisphenethracene prepared in Example 7, and 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-methoxyphenyl)bisphenethracene prepared in Example 9 are shown below. Figure 7 As shown, the temperature was 298 K, dichloromethane was used as the solvent, and the excitation wavelength was 380 nm. All three bis-anthracene derivatives showed obvious fluorescence emission peaks in the visible-near infrared region (600-800 nm), and the derivatives with different substituents showed significant spectral differences. These differences reflect the regulatory role of the electronic effect of the substituents on the fluorescence properties of the bis-anthracene parent nucleus, and also indicate that the luminescence properties of this type of material can be precisely adjusted by changing the substituents.

[0105] Example 10

[0106] A method for post-modification with ortho-selective functionalized groups of bis(anthracene) includes the following steps:

[0107] 5.1 mg (4.7 μmol) of BAM-4Bpin prepared in Example 1, 6.9 μL (69.2 μmol) of 4-bromobenzaldehyde, and 1.0 mg (1.4 μmol) of 1,1'-bis(diphenylphosphine)ferrocene palladium chloride were added to a 25 mL reaction tube. Under an argon atmosphere, 1 mL of dry toluene, 0.5 mL of ethanol, and 6 μL of 2 M potassium carbonate aqueous solution were added. The mixture was heated to 85 °C and reacted for 16 h. After the reaction was completed, the reaction solution was extracted multiple times with ethyl acetate, and the combined organic phases were collected. The solvent was removed by vacuum distillation to obtain a solid mixture. The solid mixture was then separated by column chromatography using a 10:1 (v / v) mixture of petroleum ether and dichloromethane as the eluent. The eluent corresponding to the fourth band was collected. The crude product was recrystallized from a mixed solvent of dichloromethane and methanol in a volume ratio of 1:7 to obtain 1.1 mg of solid product 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-aldehydebenzyl)bis(anthracene), with the structural formula [structure omitted]. The yield was 23%, and the NMR data of the product were as follows: 1 H NMR (400 MHz, CDCl3, 298 K) delta 10.08 (s, 4H), 8.61 (s, 4H), 7.99 - 8.02 (m, 8H), 7.79 - 7.81 (m, 8H), 7.51 (s, 4H), 7.14 (s, 4H), 2.47 (s, 6H), 1.56 (s, 12H).

[0108] The MALDI-TOF spectrum of the product is as follows Figure 8 As shown, its characteristic peak appears at a mass-to-charge ratio of approximately 1002-1003, which is consistent with the theoretical molecular weight of the target 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(4-aldehydebenzyl)bisanthracene molecule, confirming the successful synthesis of the product. The main peak signal intensity is high and there are only adjacent small peaks caused by differences in isotopic abundance, with no obvious impurity peaks, indicating that the obtained product has high purity.

[0109] Comparative Example 1

[0110] One eq of BA-Mes, 12 eq of B2pin2, 0.5 eq of methoxy(cyclooctadiene)iridium dimer, and one eq of 4,4'-di-tert-butyl-2,2'-dipyridine were added to a 25 mL reaction tube. Under argon protection, a mixed solvent of mesitylene and methyl tert-butyl ether (v / v) in a 2:1 ratio was added, and the mixture was heated to 80 °C for 48 h. After the reaction was completed, the reaction solution was separated by column chromatography using dichloromethane as the eluent. The eluent was collected and distilled under reduced pressure to obtain a crude solid product. The crude product was recrystallized multiple times using a mixed solvent of petroleum ether and ethyl acetate (v / v), filtered, and dried. Analysis showed that BAM-4Bpin was not obtained.

[0111] Comparative Example 2

[0112] One eq of BA-Mes, 12 eq of B2pin2, 0.5 eq of methoxy(cyclooctadiene)iridium dimer, and one eq of 3,4,7,8-tetramethyl-1,10-phenanthroline were added to a 25 mL reaction tube. Under argon protection, dry cyclohexane solvent was added, and the mixture was heated to 80 °C for 48 h. After the reaction, the reaction solution was separated by column chromatography using dichloromethane as the eluent. The eluent was collected and distilled under reduced pressure to obtain a crude solid product. The crude product was recrystallized multiple times using a mixed solvent of petroleum ether and ethyl acetate in a 1:7 volume ratio. Analysis revealed that BAM-4Bpin was not obtained.

[0113] In summary, this invention achieves selective boron esterification at the ortho position of bis(anthracene), overcoming the technical limitation of traditional methods that can only modify bay areas. Specifically, using 7,14-bis(2,4,6-trimethylphenyl)bis(anthracene) as the reaction substrate, employing a methoxy(cyclooctadiene) iridium dimer as an iridium catalyst, and combining it with a specific ligand of 4,4'-di-tert-butyl-2,2'-dipyridine, a highly selective CH pinacol boron esterification reaction is completed in a solvent system of cyclohexane and / or tetrahydrofuran. Through multi-step synthesis, a universal intermediate BAM-4Bpin with four ortho-boron ester groups is obtained. This intermediate can be further efficiently converted into bis(anthracene) derivatives containing various substituents such as trifluoromethylphenyl, triisopropylsilylethynyl, 4-methoxyphenyl, pyridyl, halogen, cyano, and thiophene, providing a novel pathway for the functionalization of this type of polycyclic aromatic hydrocarbon.

[0114] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art should understand that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A method for ortho-selective boron esterification of bis(anthracene), characterized in that, Includes the following steps: 7,14-bis(2,4,6-trimethylphenyl)bisanthracene, pinacol borate, methoxy(cyclooctadiene)iridium dimer, and 4,4'-di-tert-butyl-2,2'-dipyridine were dissolved in an organic solvent and reacted at 70-90 °C under inert gas protection for 40-50 h to obtain 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(pinacol borate)bisanthracene; The organic solvent is cyclohexane and / or tetrahydrofuran.

2. The method according to claim 1, characterized in that, The molar ratio of 7,14-bis(2,4,6-trimethylphenyl)bisanthracene to pinacol diboronate is 1:(8-12).

3. The method according to claim 1, characterized in that, The molar ratio of 7,14-bis(2,4,6-trimethylphenyl)bis(anthracene) to methoxy(cyclooctadiene)iridium dimer is 1:(0.1-1); the molar ratio of the methoxy(cyclooctadiene)iridium dimer to 4,4'-di-tert-butyl-2,2'-dipyridine is (0.4-0.6):

1.

4. The method according to claim 1, characterized in that, When the solvent is a mixture of cyclohexane and tetrahydrofuran, the volume ratio of cyclohexane to tetrahydrofuran is (0.5-1.5):

1.

5. The method according to claim 1, characterized in that, After the reaction is completed, a separation and purification step is also included; the separation and purification includes column chromatography purification, vacuum distillation and recrystallization.

6. A method for ortho-selective boron esterification of bis(anthracene), characterized in that, Includes the following steps: (1) 7,14-bis(2,4,6-trimethylphenyl)bisanthracene, pinacol diborate, methoxy(cyclooctadiene)iridium dimer and 4,4'-di-tert-butyl-2,2'-dipyridine are dissolved in an organic solvent and reacted at 70-90 °C under inert gas protection for 20-30 h to obtain 7,14-bis(2,4,6-trimethylphenyl)-2,5,9-tris(pinacol diborate)bisanthracene; the organic solvent is cyclohexane and / or tetrahydrofuran; (2) 7,14-bis(2,4,6-trimethylphenyl)-2,5,9-tris(pinacolyl borate)bisanthracene, pinacolyl borate, methoxy(cyclooctadiene)iridium dimer and 4,4'-di-tert-butyl-2,2'-dipyridine are dissolved in an organic solvent and reacted at 70-90 °C under inert gas protection for 40-50 h to obtain 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(pinacolyl borate)bisanthracene; the organic solvent is cyclohexane and / or tetrahydrofuran.

7. A method for post-modification with ortho- and ortho-functionalized groups of bis(anthracene), characterized in that, Includes the following steps: The 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(pinacolyl borate)bis(anthracene), a compound containing the functionalized group R, prepared by the method according to any one of claims 1-6, were dissolved in a solvent with a palladium catalyst and coupled to the solution for 10-20 h at 80-90 °C under an inert gas atmosphere to obtain the compound with the following structural formula: Bisanthrabenzyl derivatives; The functional group R is , , , Halogen, cyano, naphthyl, phenanthryl, anthracene, thiophene, pyridyl, furanyl or benzothiophene; the palladium catalyst is tetra(triphenylphosphine)palladium, 1,1'-bis(diphenylphosphine)ferrocene palladium chloride, palladium acetate, palladium chloride or tris(dibenzylideneacetone)dipalladium.

8. The method according to claim 7, characterized in that, The molar ratio of 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(pinacolyl borate)bisanthracene to the compound containing the functionalized group R is 1:(4-16); the molar ratio of 7,14-bis(2,4,6-trimethylphenyl)-2,5,9,12-tetra(pinacolyl borate)bisanthracene to the palladium catalyst is (2-8):

1.

9. The method according to claim 7, characterized in that, The compound containing the functional group R is p-bromotrifluorotoluene, (2-bromoethynyl)triisopropylsilane, 4-bromoanisole, cuprous cyanide, 2-bromothiophene, 4-bromobenzamine, 4-bromobenzaldehyde, 2-bromofuran, or 2-bromopyrrole.

10. The method according to claim 7, characterized in that, The solvent is a mixed solvent of toluene, ethanol and potassium carbonate aqueous solution or a mixed solvent of 1,4-dioxane and potassium carbonate aqueous solution; the volume ratio of toluene, ethanol and potassium carbonate aqueous solution is (800-1200):(400-600):(10-25), and the concentration of potassium carbonate aqueous solution is 1-3 M; the volume ratio of 1,4-dioxane and potassium carbonate aqueous solution is 1000:(10-25), and the concentration of potassium carbonate aqueous solution is 1-3 M.

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