Bisanthene aromatic ring bay region C-H nucleophilic substitution reaction method and application thereof

Abstract

The invention provides a bissanthin aromatic ring bay region C-H nucleophilic substitution reaction method and application thereof, and belongs to the field of organic synthesis methodology. According to the reaction, bissanthin is used as a raw material, dichloromethane and acetonitrile are used as solvents, and the bissanthin is oxidized by nitrite hexafluorotellurate and respectively reacts with nucleophilic reagents such as carbon anions, oxygen-containing reagents, sulfur-containing reagents, chlorine-containing reagents, nitrogen-containing reagents, phosphorus-containing reagents and cyano groups in one step to synthesize a series of bissanthin bay area modified functionalized products; when the reaction method is further applied to the nucleophilic substitution reaction of two molecules, namely perylene (Perylene) and N, N '-di (1, 3-diisopropyl benzene)-3, 4, 9, 10-perylene dicarboximide (PDI), good universality is shown, and the reaction method can be applied to the nucleophilic substitution reaction of two molecules, namely perylene (Perylene) and N, N'-di (1, 3-diisopropyl benzene)-3, 4, 9, 10-perylene dicarboximide (PDI). The method is mild in reaction condition, does not need to introduce transition metal as a catalyst, is easy in product separation and purification, and has the advantages of low cost, high efficiency and greenness; the series of functionalized derivatives constructed by the method can provide important intermediates for synthesis of larger polycyclic aromatic hydrocarbon molecules of the system; the method has a good industrial production prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis methodology, and specifically relates to a bisanthene aromatic ring bay area CH nucleophilic substitution reaction method and application thereof. Background Art

[0002] Polycyclic aromatic hydrocarbons (PAHs) can be regarded as nanographene fragments or structural units, usually showing unique properties, and have attracted much attention in the fields of organic light, electricity, and magnetism, showing broad application prospects. Functional group modification of polycyclic aromatic hydrocarbons with specific structures is the key to the design and synthesis of polycyclic aromatic hydrocarbon molecules. In particular, when synthesizing polycyclic aromatic hydrocarbon molecules with novel structures, it is often necessary to introduce functional groups at their special positions. Typical methods for functional modification of polycyclic aromatic hydrocarbons include electrophilic substitution reactions of aromatic ring CH bonds, or coupling reactions involving transition metals. The electrophilic substitution reactions of aromatic ring CH bonds are characterized by multiple reactive sites and poor selectivity. When reacting with electrophilic reagents with weak electrophilicity, it is often necessary to introduce electron-donating groups on the aromatic ring to activate the aromatic ring; coupling reactions involving transition metals provide a powerful means for the expansion of polycyclic aromatic hydrocarbon molecules, but their synthesis generally requires the provision of precursors containing halogen sources, and transition metals are also required as catalysts. When produced on a large scale, the cost is high and it also brings potential pollution. Bisanthene, abbreviated as BA, is an important polycyclic aromatic hydrocarbon structural unit. Its molecular structure is composed of two anthracene molecules connected by three single bonds. It has a classic two-dimensional planar structure, with both zigzag edges and bay region structures. It is an ideal structural unit for constructing organic magnetic molecules and near-infrared dyes, and can be chemically modified to synthesize higher-order polycyclic aromatic hydrocarbons. However, it is very difficult to directly modify bisanthene in the bay region to introduce functional groups, and CH electrophilic substitution occurs preferentially at other positions, such as the peri position. It can be seen that achieving highly selective regional CH bond functionalization is a challenge for the synthesis technology of conjugated polycyclic aromatic hydrocarbons. Summary of the invention

[0003] Based on the above background technology, the present invention provides a method for the nucleophilic substitution reaction of CH based on the high regioselectivity of bisanthene, synthesizes a series of different functionalized derivatives modified by the bay region of bisanthene, so as to achieve the regioselectivity of the CH bond activation of the aromatic ring, solve the problem of the difficulty of modifying the bay region of bisanthene, and further apply this method to the nucleophilic substitution reaction of CH in the bay region of molecular systems such as perylene and N,N′-di(1,3-diisopropylbenzene)-3,4,9,10-perylene dicarboximide (PDI) to construct its functionalized product, provide a path for the activation and regioselectivity of the CH bond of conjugated condensed aromatic hydrocarbons, and enrich the family library of functionalized derivatives of classic condensed aromatic hydrocarbons such as bisanthene. The method of the present invention has simple steps, mild reaction conditions, high efficiency, high selectivity, and has prospects for industrial production. The present invention can be implemented by the following scheme:

[0004] (1) Reaction with carbon anion nucleophiles: Bisanthene is used as the starting material and dissolved in a certain volume of a mixed solution of dichloromethane and acetonitrile at room temperature. Under the protection of an inert gas, a certain amount of nitrosohexafluorotellurate (NOSbF 6 ), slowly stirred for 3 minutes to obtain its cationic free radical intermediate, which was reacted with n-butyl lithium, phenyl lithium, carborane lithium reagent, diethyl malonate, cyano and other active methylene carbon anions, carbon-carbon triple bond carbon anions and other carbon anion nucleophilic reagents to synthesize a series of bisanthene derivatives, as follows:

[0005] (2) Reaction with heteroatom nucleophiles: Bisanthene is used as the starting material and dissolved in a certain volume of a mixed solution of dichloromethane and acetonitrile at room temperature. Under the protection of an inert gas, a certain amount of nitrosohexafluorotellurate (NOSbF 6 ), slowly stirred for 3 minutes to obtain its cationic free radical intermediate, which was reacted with sodium methoxide to obtain methoxy-type BA functionalized derivatives; reacted with sodium methyl mercaptan and sodium thiophenol to obtain sulfur-containing BA functionalized derivatives; reacted with lithium reagent of diphenylphosphine to obtain phosphine-containing BA functionalized derivatives; reacted with chlorine source to produce chlorine-containing BA functionalized products; reacted with nitrogen nucleophiles such as n-butylamine, aniline and benzylamine to synthesize nitrogen-doped BA derivatives, as follows:

[0006] (3) Application of the reaction method: Using this nucleophilic substitution reaction method, the reaction substrates are expanded to molecules such as perylene and N,N′-bis(1,3-diisopropylbenzene)-3,4,9,10-perylene dicarboximide (PDI). Perylene and N,N′-bis(1,3-diisopropylbenzene)-3,4,9,10-perylene dicarboximide (PDI) are used as the initial raw materials. They are dissolved in a certain volume of a mixed solution of dichloromethane and acetonitrile at room temperature. Under the protection of an inert gas, a certain amount of nitric acid hexafluorotellurate (NO 2 Sb 6 ), slowly stirred for 3 minutes to obtain its cationic free radical intermediate, and a certain amount of methoxy and cyano nucleophilic reagents were added to synthesize the corresponding functionalized derivatives, as follows:

[0007] Compared with the prior art, the present invention has the following advantages and technical effects: (1) The present invention discloses for the first time a method for the nucleophilic substitution reaction of CH in the bay region of the aromatic ring of bisanthene, and applies this method to the nucleophilic substitution reaction of molecules such as perylene and N,N′-bis(1,3-diisopropylbenzene)-3,4,9,10-perylene dicarboximide (PDI), providing an effective path for the synthesis of functionalized products of such compounds, showing good universality and strong applicability; (2) The present invention realizes the modification of the CH bond in the bay region of bisanthene without introducing expensive transition metal catalysts, overcoming the problems of poor activity and reaction site selectivity of traditional aromatic compound CH bond modification reactions, and has the advantages of being green, low-cost and having a specific reaction site selectivity; (3) The synthesis process of the present invention is simple, the reaction rate is fast, the yield of the target compound is high, and it is easy to industrialize. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 It is the basic technical route map of the reaction of the present invention.

[0009] Figure 2 This is the H NMR spectrum of compound BA-Bu.

[0010] Figure 3 This is the H NMR spectrum of compound BA-CCPh.

[0011] Figure 4 This is the H NMR spectrum of compound BA-THF.

[0012] Figure 5 This is the H NMR spectrum of the compound BA-Carborane.

[0013] Figure 6 This is the H NMR spectrum of compound BA-BESEYZ.

[0014] Figure 7 This is the H NMR spectrum of compound BA-OMe.

[0015] Figure 8 It is the compound BA-SCH 3 H NMR spectrum.

[0016] Fig. 9 This is the H-NMR spectrum of compound BA-SPh.

[0017] Fig.10 This is the H NMR spectrum of the compound BA-imide.

[0018] Fig.11 This is the H NMR spectrum of compound BA-2Cl.

[0019] Fig.12 This is the H NMR spectrum of compound BA-CN.

[0020] Fig.13 This is the H NMR spectrum of compound BA-2CN.

[0021] Fig.14 This is the H NMR spectrum of compound BA-5-2CN.

[0022] Fig.15 This is the H NMR spectrum of compound BA-6-2CN.

[0023] Fig.16 This is the H NMR spectrum of compound BA-6-CNCOOR.

[0024] Fig.17 This is the H NMR spectrum of compound BA-6-Me-EA.

[0025] Fig.18 This is the H NMR spectrum of compound BA-Pyo-1.

[0026] Fig.19 This is the H NMR spectrum of compound BA-Pyo-2.

[0027] Fig. 20 This is the H NMR spectrum of compound BA-Pyo-3.

[0028] Fig.21 This is the H NMR spectrum of compound BA-Pyd-2.

[0029] Fig. 22 This is the H NMR spectrum of compound BA-PO.

[0030] Fig.23This is the H NMR spectrum of the compound Per-OMe.

[0031] Fig.24 This is the H NMR spectrum of the compound Per-CN.

[0032] Fig.25 It is the compound PDI-SCH 3 H NMR spectrum. DETAILED DESCRIPTION

[0033] In order to facilitate the understanding of the present invention, the present invention will be described in more detail below. However, it should be understood that the embodiments are only for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0034] Example 1

[0035] Synthesis route of compound BA:

[0036] Synthesis process of compound BA: BA is the raw material used in the present invention. Its synthesis process refers to the literature that has been reported (Konishi A et al., Chemistry Letters, 2013, 42(6): 592-594). The synthesis process is as follows: in an air environment, anthrone, i.e., compound 1 (3 g, 15.6 mmol) and potassium carbonate (14.28 g, 100 mmol) are added to a 250 mL double-necked reaction bottle, 180 mL of acetone is added, and the temperature is slowly raised to 50° C. for reaction for 18 hours. After the reaction was completed, the solvent of the reaction solution was removed by vacuum distillation, 50 mL of deionized water was added to dissolve it, 80 mL of dichloromethane was added for extraction, and the extraction was repeated 3 times. The extracts were combined and the dichloromethane was removed by vacuum distillation to obtain a solid crude product, which was separated and purified by silica gel chromatography (eluent was dichloromethane: petroleum ether = 1:1) to obtain about 2.4 g of light yellow solid (compound 2), with a yield of 40%; under an inert atmosphere, compound 2 (1 g, 2.58 mmol) was added to a 150 mL double-necked reaction bottle, 50 mL of dry tetrahydrofuran solution (re-distilled) was added to the reaction bottle, and liquid nitrogen freezing-evacuation / ventilation-thawing was performed to remove water and oxygen. This operation was repeated 3 times. When the system temperature returned to room temperature, the reaction solution was placed in an ice water bath, and 2-mesitylene magnesium bromide (1 mol / L, 16 mL), react at 0°C for 36 hours, quench the reaction solution with glacial acetic acid, and remove the reaction solvent under reduced pressure using a rotary evaporator; add 80 mL of glacial acetic acid solution to the reaction bottle in which the solvent has been removed, sodium iodide (2.6 g, 17.0 mmol) and sodium hypophosphite monohydrate (2.3 g, 21.7 mmol), slowly raise the temperature to 118°C, and react for 2 hours. After the reaction is completed, remove the solvent glacial acetic acid by reduced pressure distillation, extract with 50 mL of dichloromethane and 30 mL of water, repeat the extraction 3 times, separate the organic phase, and then dry with anhydrous sodium sulfate to obtain a crude product.The crude solid was separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:5) to obtain about 1.2 g of a light pink solid compound (compound 3) with a yield of 80%. Under an inert atmosphere, compound 3 (0.232 g, 0.4 mmol), DDQ (0.443 g, 1.92 mmol), and scandium trifluoromethanesulfonate (1.30 g, 2.63 mmol) were added to a 150 mL double-necked reaction bottle, 50 mL of dry chlorobenzene solution (re-distillation is required) was added to the reaction bottle, and liquid nitrogen was used for freezing-evacuation / ventilation-thawing to remove water and oxygen. This operation was repeated 3 times. When the system temperature returned to room temperature, the reaction liquid temperature was slowly raised to 132 ° C and stirred for 36 hours. After the reaction was completed, 5 mL of hydrazine hydrate was added to quench the reaction solution, and the reaction solvent was removed under reduced pressure using a rotary evaporator to obtain a crude product. The crude product solid was separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:3) to obtain about 0.128 g (BA) of a blue solid compound with a yield of 55%.

[0037] Example 2

[0038] Synthesis route of compound BA-Bu:

[0039] Synthesis process of compound BA-Bu: Under an inert atmosphere, weigh the raw material BA (60 mg, 0.09 mmol) into a 50 mL double-necked reaction bottle, add NOSbF 6 (26.6 mg, 0.1 mmol), add ultra-dry dichloromethane (re-evaporated) and ultra-dry acetonitrile 12 mL (volume ratio of 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, slowly add n-butyl lithium solution (2.5 mol / L in Hexane, 210 uL) at -78°C, and react at -78°C for 10 minutes. After the reaction is completed, quench the reaction solution with 1 mL of saturated ammonium chloride solution; remove the reaction solvent under reduced pressure in an inert atmosphere to obtain a crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:5), and a blue solid compound of about 40.4 mg (BA-Bu) is obtained with a yield of 70%. 1 H NMR (600 MHz, (CD 3 ) 2 CO) δ 8.53 (t, J = 7.6 Hz,2H), 7.93 (d, J = 7.5 Hz, 1H), 7.55-7.49 (m, 4H), 7.26 (d, J = 4.8 Hz, 3H), 7.22(d,J = 8.6 Hz, 1H), 7.18 (s, 4H), 3.31-3.21 (m, 2H), 2.45 (s, 6H), 2.14 (t, J =8.1 Hz, 2H), 2.00-1.96 (m, 2H), 1.86 (d, J = 5.0 Hz, 12H), 1.04 (t, J = 7.4 Hz,3H). 13 C NMR (151 MHz, CDCl 3 ) δ 138.57, 137.90, 137.87, 137.32, 135.00, 134.95,134.64, 132.70, 132.39, 131.43, 130.99, 130.89, 129.98, 128.61, 128.58,127.67, 127.56, 127.22, 126.87, 126.66, 126.41, 126.31, 125.91, 125.71,125.66, 125.61, 125.45, 125.30, 125.07, 120.58, 120.20, 36.01, 32.98, 23.17,21.41, 20.12, 14.16. HRMS(APCI) m / z: Calcd for C 50 H 42 , 643.3321; Found:643.33561.

[0040] Example 3

[0041] Synthesis route of compound BA-CCPh:

[0042] Synthesis process of compound BA-CCPh: Under an inert atmosphere, weigh the raw material BA (60 mg, 0.1 mmol) into a 50 mL double-necked reaction bottle, add NOSbF 6(26.6 mg, 0.1 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 12 mL (volume ratio of 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, slowly add the prepared lithium phenylacetylene solution (0.85 mol / L in THF, 400 uL) at 0°C, and react at 0°C for 1 hour. After the reaction is completed, quench the reaction solution with 1 mL saturated ammonium chloride solution; remove the reaction solvent under reduced pressure, extract with 20 mL dichloromethane and 20 mL water, repeat the extraction 3 times, separate the organic phase, and then dry with anhydrous sodium sulfate to obtain a crude product. The crude solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:4), and a blue solid compound of about 27.44 mg (BA-CCPh) is obtained with a yield of 40%. 1 H NMR (600MHz, CDCl 3 ): δ9.92 (d, J = 6.0 Hz, 1H),8.36 (d, J = 6.0 Hz, 2H), 7.64 (d, J = 6.0 Hz, 2H), 7.51 (d, J = 6.0 Hz, 1H), 7.50(t, J = 6.0 Hz, 1H), 7.36-7.43 (m, 6H),7.30 (d, J = 6.0 Hz, 1H), 7.18 (d, J = 12.0Hz, 2H), 7.12 (s, 4H), 2.48 (s, 6H), 1.89 (s, 12H). 13 C NMR (150 MHz, CDCl 3): δ137.71, 137.68, 137.36, 137.39, 135.98, 134.80, 134.68, 134.57, 133.78,133.35, 132.60, 132.44, 131.94, 131.78, 131.69, 131.33, 131.23, 130.75,128.60, 128.53, 128.42, 127.18, 127.12,127.00, 126.70, 126.51, 126.15,125.96, 125.56, 125.40, 124.71, 123.82, 120.75, 120.56, 115.79, 94.61, 21.06,19.98; HRMS(APCI) m / z: Calcd for C 52 H 38 [M+H] + : 687.2974, Found: 687.30423.

[0043] Example 4

[0044] Synthesis route of compound BA-THF:

[0045] Synthesis process of compound BA-THF: Under air environment, weigh the raw material BA (60 mg, 0.1 mmol) and potassium tert-butoxide (44.8 mg, 0.4 mmol) in a 50 mL double-necked reaction bottle, add 10 mL of ultra-dry tetrahydrofuran, react at 66°C for 12 hours, after the reaction, remove the reaction solvent under reduced pressure, extract with 20 mL of dichloromethane and 20 mL of water, repeat the extraction 3 times, separate the organic phase, and then dry with anhydrous sodium sulfate to obtain a crude product. The crude solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:3), and a blue solid compound of about 23.1 mg is obtained, with a yield of 35% (BA-THF). The process of the reaction is that in a strong alkaline environment, the hydrogen at the a-position of tetrahydrofuran is pulled out to form a carbon anion, which attacks the bay area of ​​BA to form the final product. 1 H NMR (600 MHz, CDCl 3 ): δ8.37 (d, J =12.0Hz, 2H), 7.60 (dd, J =12Hz, 6.0Hz, 2H), 7.41-7.46 (m, 3H), 7.31-7.35 (m, 4H), 7.12 (d,J = 12.0 Hz, 4H ), 5.41 (t, J = 6.0 Hz, 1H), 4.25-4.29 (m, 1H), 3.95-3.99 (m, 1H), 2.59-2.63 (m, 1H), 2.46 (d, J = 7.2Hz, 6H), 2.28-2.33 (m, 2H), 2.22-2.25 (m, 1H), 1.87 (dd, J = 24Hz, 6.0Hz, 12H); 13 C NMR (150 MHz, CDCl 3 ): δ137.91, 137.82, 137.68, 137.56, 137.23,137.18, 134.79, 134.72, 134.68,134.62, 132.51, 131.70, 131.02, 130.26, 128.97,128.48, 128.46, 128.42,128.35, 127.36, 126.90, 126.75, 126.62, 126.38, 126.08,125.84, 125.59,125.40, 125.32, 125.21, 120.46, 120.30, 78.47, 69.16, 34.90, 29.68, 21.23,19.99, 19.93. HRMS(APCI) m / z: Calcd for C 52 H 38 [M+H] + : 657.3079, Found: 657.31455(error).

[0046] Example 5

[0047] Synthesis route of compound BA-BESEYZ:

[0048] Synthesis process of compound BA-BESEYZ: Under an inert atmosphere, diethyl malonate (80 mg, 0.5 mmol) was weighed, and 0.5 mL of lithium diisopropylamide (LDA) (2.0 M in THF) was slowly added dropwise, and the reaction was carried out at 0°C for 2 hours; the raw material BA (60 mg, 0.1 mmol) was weighed and placed in a 50 mL double-necked reaction bottle, and NOSbF 6(26.6 mg, 0.1 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 12 mL (volume ratio of 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple; at 0°C, add the diethyl malonate solution after LDA reaction to the BA solution oxidized by hexafluorotelluric acid for 5 hours. After the reaction is completed, quench the reaction solution with 1 mL saturated ammonium chloride solution; remove the reaction solvent under reduced pressure, extract with 20 mL dichloromethane and 20 mL water, repeat the extraction 3 times, separate the organic phase, and then dry with anhydrous sodium sulfate to obtain a crude product. The crude solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:3), and about 30.1 mg of a blue solid compound (BA-BESEYZ) is obtained with a yield of 41%. 1 H NMR (600 MHz, (CD 3 ) 2 CO): δ8.57 (d, J = 6.0 Hz, 2H), 7.83 (d, J = 6.0 Hz, 2H), 7.56 (t, J = 6.0 Hz, 2H), 7.37(d, J = 6.0 Hz, 2H), 7.20(s, 4H), 7.18 (d, J = 6.0 Hz, 2H), 4.32(q, J = 6.0 Hz,4H),2.47(s, 6H),1.94(s, 12H),1.31(t, J = 6.0 Hz 3H); 13 C NMR (150 MHz, CDCl 3 ): δ167.9, 139.11, 137.70, 137.37, 137.85, 135.85, 134.76, 133.66, 133.25,132.85, 131.05, 129.98, 129.94, 128.46, 127.19, 127.04, 126.44, 126.03,125.73, 124.39, 122.12, 120.07, 73.55, 62.62, 21.32, 20.17, 14.08;HRMS(APCI)m / z: Calcd for C 53 H 42 O 4 [M+H] + : 743.3083, Found: 743.3154.

[0049] Example 6

[0050] Synthesis route of compound BA-OMe:

[0051] Synthesis process of compound BA-OMe: Under an inert atmosphere, weigh the raw material BA (60 mg, 0.1 mmol) into a 50 mL double-necked reaction bottle, add NOSbF 6 (26.6 mg, 0.1 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 12 mL (volume ratio of 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, add sodium methoxide solid (54 mg, 1 mmol) at 40°C and react at 40°C for 1 hour. After the reaction is completed, remove the reaction solvent under reduced pressure, extract with 20 mL dichloromethane and 20 mL water, repeat the extraction 3 times, separate the organic phase, and then dry with anhydrous sodium sulfate to obtain a crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:4), and a blue solid compound of about 25.8 mg (BA-OMe) is obtained with a yield of 42%. 1 H NMR (600 MHz, CDCl 3 ): δ 9.16(d, J =6.0 Hz, 1H), 8.31(dd, J = 6.0 Hz, 12.0 Hz, 2H), 7.33-7.38(m, 4H), 7.23(d, J = 6.0Hz, 2H), 7.18(d, J = 6.0 Hz, 2H), 7.11(s, 4H), 4.14(s, 3H), 2.46(s, 6H), 1.87(d, J = 4.8 Hz, 12H); 13 C NMR (150 MHz, CDCl 3): δ155.68, 137.67, 137.20, 137.03,135.04, 134.80, 134.26, 132.68, 132.54, 131.56, 131.17, 130.42, 130.29,128.47, 128.09, 127.50, 127.41, 127.30, 127.05, 126.67, 126.50, 126.31, 126.13, 125.73, 125.50, 125.30, 124.59, 120.30, 119.65, 118.33, 115.91, 56.14,21.21, 19.85; HRMS (APCI) m / z: Calcd for C 53 H 42 O 4 [M+H] + : 617.2766, Found 617.2773.

[0052] Example 7

[0053] Compound BA-SCH 3 The synthetic route:

[0054] Compound BA-SCH 3 Synthesis process: Under inert atmosphere, weigh the raw material BA (60 mg, 0.1 mmol) into a 50 mL double-necked reaction bottle, add NOSbF 6 (26.6 mg, 0.1 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 12 mL (volume ratio of 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, add sodium thiomethoxide solid (35 mg, 1 mmol) at 40°C and react at 40°C for 1 hour. After the reaction is completed, remove the reaction solvent under reduced pressure, extract with 20 mL of dichloromethane and 20 mL of water, repeat the extraction 3 times, separate the organic phase, and then dry with anhydrous sodium sulfate to obtain a crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:4) to obtain about 28.44 mg of a blue solid compound (BA-SCH 3 ), with a yield of 45%. 1 H NMR (600 MHz, CDCl 3 ) δ 8.39(t, J = 6.0 Hz, 2H), 8.08 (d, J= 6.0 Hz, 1H), 7.48-7.51 (m, 2H), 7.44(t, J = 6.0Hz, 2H), 7.33 (t, J = 6.0 Hz, 3H), 7.20 (d, J = 6.0 Hz, 1H), 7.13 (s, 4H), 2.58 (s, 3H), 2.47 (s, 6H), 1.88 (d, J = 6.0 Hz, 12H); HRMS (APCI) m / z: Calcd forC 47 H 36 S[M+H] + : 633.2538, Found: 633.25071.

[0055] Example 8

[0056] Synthesis route of compound BA-SPh:

[0057] Synthesis process of compound BA-SPh: Under an inert atmosphere, weigh the raw material BA (60 mg, 0.1 mmol) into a 50 mL double-necked reaction bottle, add NOSbF 6 (26.6 mg, 0.1 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 12 mL (volume ratio of 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, add sodium thiophenol solid (66 mg, 0.5 mmol) at 40°C and react at 40°C for 2 hours. After the reaction is completed, remove the reaction solvent under reduced pressure, extract with 20 mL of dichloromethane and 20 mL of water, repeat the extraction 3 times, separate the organic phase, and then dry with anhydrous sodium sulfate to obtain a crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:4), and a blue solid compound of about 24.29 mg (BA-SPh) is obtained with a yield of 35%. 1 H NMR (600 MHz, CDCl 3 ) δ8.42 (d, J = 6.0 Hz, 1H), 8.06 (d, J = 6.0 Hz, 1H), 7.61-7.68 (m, 1H), 7.54 (t, J = 6.0 Hz,1H), 7.44-7.48 (m, 3H), 7.37-7.41 (m, 3H), 7.33 (t,J = 6.0 Hz, 3H), 7.15-7.21(m, 5H), 7.09 (s, 1H), 7.06 (d, J = 12.0 Hz ,1H), 2.5 (t, J = 18.0 Hz ,6H), 1.91(t, J = 24.0 Hz, 12H); 13 C NMR (150 MHz, CDCl 3 ): δ137.73, 137.59, 137.27, 135.97,135.13, 135.10, 134.47, 132.92, 132.70, 132.55, 132.42, 131.14, 131.07,130.07, 130.93, 130.75, 129.92, 129.89, 129.33, 129.22, 129.06, 129.01,128.48, 128.45, 127.95, 127.15, 127.05, 126.80, 126.71, 126.29, 125.65,125.49, 124.98, 120.57, 120.34, 21.27, 21.20, 20.01, 19.96; HRMS (APCI) m / z:Calcd for C 52 H 38 S[M+H] + : 695.2694, Found: 695.2664.

[0058] Example 9

[0059] Synthesis route of compound BA-2Cl:

[0060] Synthesis process of compound BA-2Cl: Under an inert atmosphere, weigh 1-butyl-3-methylimidazolium chloride, abbreviated as [Bmin][Cl] (1.72 g, 10 mmol), liquid Br 2 (0.16 g, 1 mmol) was placed in a 100 mL double-necked reaction bottle, 3 mL of ultra-dry THF was added, and the liquid nitrogen was used for freezing-evacuation / ventilation-thawing to deoxygenate. This operation was repeated 3 times, and the temperature was slowly raised to 100 °C. The reaction was carried out at this temperature for 30 minutes to obtain a chloride ion nucleophile (Br 2 Cl - ). Will be NOSbF 6The oxidized raw material BA (120 mg, 0.2 mmol) was added to the above prepared chloride ion nucleophile system and reacted at 100 ° C for 30 minutes. After the reaction was completed, the reaction solvent was removed under reduced pressure, and 10 mL of diethyl ether was used for extraction. The extraction was repeated 3 times, and the organic phase was separated and then dried over anhydrous sodium sulfate to obtain a crude product. The crude product solid was separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:6) to obtain about 82.3 mg of a blue solid compound (BA-2Cl) with a yield of 63%. 1 H NMR (600 MHz, CDCl 3 ): δ9.34 (t, J = 6.0 Hz, 2H), 7.49 (t, J = 6.0 Hz, 2H), 7.42-7.46 (m, 3H), 7.38 (d, J =12.0 Hz, 1H), 7.23 (d, J = 12.0 Hz, 1H ), 7.19 (d, J = 12.0 Hz, 1H), 7.14 (s, 4H), 2.48 (s, 6H), 1.87 (t, J = 6.0 Hz,12H); 13 C NMR (150 MHz, CDCl 3 ): δ137.73,137.66, 137.54, 135.63, 135.59, 134.27, 131.86, 131.69, 130.41, 130.12,129.64, 129.48, 129.27, 129.06, 128.76, 128.67, 128.59, 128.11, 127.47,126.83, 126.76, 126.44, 126.29, 126.25, 125.94, 125.62, 124.63, 21.31, 20.09,20.01, 19.93. HRMS (APCI) m / z: Calcd for C 46 H 32 Cl 2 [M+H] + :655.1881, Found:655.1949.

[0061] Example 10

[0062] Synthesis route of compounds BA-CN and BA-2CN:

[0063] Synthesis process of compounds BA-CN and BA-2CN: Under an inert atmosphere, weigh the raw material BA (60 mg, 0.1 mmol) into a 50 mL double-necked reaction bottle, add NOSbF 6 (26.6 mg, 0.1 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 12 mL (volume ratio of 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, add TMSCN (66 mg, 0.6 mmol) at room temperature and react at room temperature for 1 hour. After the reaction is completed, remove the reaction solvent under reduced pressure, extract with 20 mL of dichloromethane and 20 mL of water, repeat the extraction 3 times, separate the organic phase, and then dry with anhydrous sodium sulfate to obtain a crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:3), and a blue solid compound (BA-CN) of about 30.5 mg is obtained with a yield of 45%, and a blue-green solid compound (BA-2CN) of about 15.3 mg is obtained with a yield of 24%. Among them, the basic characterization data of BA-CN 1 H NMR (600 MHz, CDCl 3 ): δ9.42 (d, J = 12.0Hz, 1H), 8.41 (dd, J = 6.0 Hz, 12.0 Hz, 2H), 7.44-7.55 (m, 5H), 7.36 (d, J = 12.0Hz, 1H), 7.29 (d, J = 12.0 Hz, 1H ), 7.22 (d, J = 12.0 Hz, 1H), 7.13 (s, 4H), 2.47 (d, J = 6.0 Hz, 6H), 1.87(s, 12H); 13 C NMR (150 MHz, CDCl 3): δ155.70,137.76, 137.29, 137.11, 135.15, 134.94, 134.37, 132.77,132.63, 131.65,131.26, 130.50, 130.29, 128.56, 128.18, 127.58, 127.50, 127.38, 127.14,126.75, 126.59, 126.39, 126.22, 125.82, 125.59, 125.39, 124.68, 120.38,119.74, 118.42, 116.00, 56.23, 21.30, 19.94; HRMS (APCI) m / z: Calcd forC 47 H 37 N[M+H] + : 612.2613, Found: 612.2685.BA-2CN Basic Characterization Data 1 H NMR (600 MHz, CDCl 3 ): δ9.48 (dd, J = 6.0 Hz, 24 Hz, 2H), 7.58-7.68 (m, 6H), 7.40 (dd, J = 6.0Hz, 24 Hz, 2H), 7.17 (s, 4H), 2.5 (s, 6H), 1.87 (s, 12H); 13 C NMR (150 MHz, CDCl 3 ): δ138.17, 137.42, 137.37, 137.12, 136.71, 133.25, 132.06, 132.02,131.81, 131.35, 130.71, 130.03, 129.85, 128.80, 128.65, 128.59, 128.06,127.76, 127.44, 126.30, 126.14, 126.10, 125.98, 125.72, 125.45, 125.20,122.41, 104.28, 103.57, 21.23, 21.95; HRMS (APCI) m / z: Calcd for C 48 H 32 N 2 [M+H] + : 637.2565, Found: 637.2636.

[0064] Embodiment 11

[0065] Synthesis route of compound BA-6-CNCOOR:

[0066] The synthesis process of compound BA-6-CNOOR: Under an inert atmosphere, ethyl cyanoacetate (56.5 mg, 0.5 mmol) was weighed, and 0.5 mL of 2 mol / L LDA solution was slowly added and reacted at 0°C for 2 hours; the raw material BA (60 mg, 0.1 mmol) was weighed and placed in a 50 mL double-necked reaction bottle, and NOSbF 6 (26.6 mg, 0.1 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 12 mL (volume ratio of 5:1), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple; at 0°C, add the above ethyl cyanoacetate solution after LDA reaction to nitrosohexafluorotelluride (NOSbF 6 ) was added to the oxidized raw material solution and reacted for 5 hours. After the reaction was completed, the reaction solution was quenched with 1 mL of saturated ammonium chloride solution; the reaction solvent was removed under reduced pressure, and the mixture was extracted with 20 mL of dichloromethane and 20 mL of water, and the extraction was repeated 3 times. The organic phase was separated and then dried with anhydrous sodium sulfate to obtain a crude product. The crude product solid was separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:3) to obtain 31.8 mg of purple solid, which was compound BA-6-CNCOOR, with a yield of 45%. 1 H NMR (600 MHz, CDCl 3 ): δ9.25(t, J = 6.0 Hz, 2H), 8.53 (d, J = 6.0 Hz, 1H), 8.33 (d, J = 6.0 Hz, 1H), 8.01-8.10(m, 4H), 7.96 (d, J = 6.0 Hz, 1H), 7.83 (d, J = 12.0 Hz, 1H), 7.25 (d, J = 6.0 Hz,4H), 4.73 (q, J = 6.0 Hz, 2H), 2.57 (d, J = 6.0 Hz, 6H), 1.91 (d, J = 6.0 Hz, 12H),1.63 (t, J = 6.0 Hz, 3H). 13C NMR (150 MHz, CDCl 3 ): δ137.97, 137.87, 137.67,137.64, 137.58, 136.72, 134.09, 133.98, 131.89, 131.82, 131.35, 131.20,131.14, 130.38, 129.54, 128.74, 128.68, 128.60, 128.56, 128.51, 127.55,127.48, 127.28, 126.19, 125.96, 125.49, 125.47, 125.14, 125.01, 124.66,121.96, 121.90, 121.62, 117.15, 62.95, 21.35, 20.16, 20.12, 14.12; HRMS(APCI) m / z: Calcd forC 52 H 37 NO 2 [M+H] + : 708.2824, Found: 708.2804.

[0067] Example 12

[0068] Synthesis route of compound BA-6-Me-EA:

[0069] Synthesis process of compound BA-6-Me-EA: Under an inert atmosphere, ethyl acetoacetate (65 mg, 0.5 mmol) was weighed, and 0.5 mL of 2 mol / L LDA solution was slowly added to react at 0°C for 2 hours; original BA (60 mg, 0.1 mmol) was weighed in a 50 mL double-necked reaction bottle, and NOSbF 6 (26.6 mg, 0.1 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 12 mL (volume ratio of 5:1), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple; at 0°C, add the ethyl cyanoacetate solution reacted with lithium diisopropylamide (LDA) to nitrosohexafluorotellurate (NOSbF 6) was added to the oxidized solution and reacted for 5 hours. After the reaction was completed, the reaction solution was quenched with 1 mL of saturated ammonium chloride solution; the reaction solvent was removed under reduced pressure, and the mixture was extracted with 20 mL of dichloromethane and 20 mL of water, and the extraction was repeated 3 times. The organic phase was separated and then dried with anhydrous sodium sulfate to obtain a crude product. The crude product solid was separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:4) to obtain 29.2 mg of purple solid, which was compound BA-6-Me-EA, with a yield of 42%. 1 H NMR (600 MHz, (CD 3 ) 2 CO): δ9.35 (d, J = 6.0 Hz, 2H), 8.45 (d, J = 6.0 Hz, 1H), 8.06-8.11 (m, 3H), 7.91 (d, J = 12.0 Hz, 2H), 7.76 (d, J = 6.0 Hz, 1H), 7.70 (d, J = 6.0 Hz, 1H), 7.29(d, J = 6.0 Hz, 4H), 4.70 (q, J = 6.0 Hz, 2H), 3.10 (s, 3H), 2.53 (d, J = 6.0 Hz,6H), 1.91 (d, J = 6.0 Hz, 12H), 1.53 (t, J = 6.0 Hz ,3H); 13 C NMR (150 MHz, CDCl 3): δ171.26, 138.32, 137.47, 135.31, 134.93, 134.79, 134.71, 132.02, 131.86,130.87, 130.66, 130.17, 130.02, 129.73, 128.57, 128.54, 128.42, 128.28,128.20, 127.06, 126.75, 126.63, 126.41, 125.50, 125.32, 125.24, 124.76,124.19, 124.02, 123.33, 122.36, 122.29, 120.78, 120.65, 61.78, 21.35, 20.13,17.18, 14.48; HRMS (APCI) m / z: Calcd for C 52 H 40 O 2 [M+H] + :697.3028, Found:697.3093.

[0070] Embodiment 13

[0071] Synthesis route of compound BA-Pyo-1:

[0072] Synthesis process of compound BA-Pyo-1: Under an inert atmosphere, weigh the raw material BA (60 mg, 0.1 mmol) into a 50 mL double-necked reaction bottle, add NOSbF 6 (26.6 mg, 0.1 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 12 mL (volume ratio of 5:1), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, add n-butylamine (73 mg, 0.5 mmol) at room temperature and react at room temperature for 1 hour. After the reaction is completed, remove the reaction solvent under reduced pressure, extract with 20 mL of dichloromethane and 20 mL of water, repeat the extraction 3 times, separate the organic phase, and then dry with anhydrous sodium sulfate to obtain a crude product. The crude solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:3), and a blue solid compound of about 24.49 mg (BA-Pyo-1) is obtained with a yield of 45%. 1 H NMR (600 MHz, CDCl 3 ): δ9.05 (s,2H), 8.09 (d, J = 12.0 Hz, 2H), 7.89 (t, J= 6.0 Hz, 2H), 7.81 (s, 2H ), 7.41 (s,2H), 7.24 (s, 4H), 5.04 (t, J = 6.0 Hz, 2H), 2.50 (s, 6H), 2.21-2.25 (m, 2H), 1.92 (s, 12H), 1.49-1.54 (m, 2H), 1.00 (t, J = 6.0 Hz,3H); 13 C NMR (150 MHz, CDCl 3 ): δ137.41, 137.15, 134.43, 132.58, 131.46, 130.92, 130.68, 129.52,128.62, 128.42, 127.30, 126.63, 126.32, 126.11, HRMS (APCI) m / z: Calcd for C 50 H 41 N[M+H] + : 656.3239, Found:697.3206.

[0073] Embodiment 14

[0074] Synthesis route of compound BA-Carborane:

[0075] Synthesis process of compound BA-Carborane: Under an inert atmosphere, weigh BA (30 mg, 0.05 mmol) into a 50 mL double-necked reaction bottle, add NOSbF 6(13.3 mg, 0.05 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 6 mL (volume ratio of 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, and add the above-prepared 0.35 mol / L lithium orthocarborane reagent (1 mL, 0.35 mmol) at 0°C. After the reaction is completed, quench the reaction solution with saturated ammonium chloride solution. Remove the reaction solvent under reduced pressure, extract with 20 mL dichloromethane and 20 mL water, repeat the extraction 3 times, separate the organic phase, and then dry with anhydrous sodium sulfate to obtain a crude product. The crude solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:5), and a blue solid compound of about 10.9 mg (BA-Carborane) is obtained with a yield of 30%. 1 H NMR (600 MHz, CDCl 3 ): δ8.50 (d, J = 12.0 Hz, 2H), 7.75 (d, J = 6.0Hz, 2H), 7.53 (t, J = 6.0 Hz, 2H), 7.48 (d, J = 6.0 Hz, 2H), 7.41 (d, J = 12.0 Hz, 2H), 7.14 (s, 4H), 2.48 (s, 6H), 1.87 (s, 12H). 13 C NMR (150 MHz, CDCl 3 ): δ137.76, 137.49, 136.36, 133.82, 132.36, 131.88, 130.64, 129.76, 128.66,128.35, 127.87, 127.56, 126.86, 126.51, 126.06, 125.84, 124.11, 122.89,121.27, 73.17, 21.19, 19.15; 11 B{1H} NMR (600MHz, CDCl 3 ): δ -2.78, -9.50, -13.75, -14.72. (MALDI) m / z: Calcd for C 48 H 42 B 10 : 726.5132, Found: 726.5010.

[0076] Embodiment 15

[0077] Synthesis route of compound BA-PO:

[0078] Synthesis process of compound BA-PO: Under an inert atmosphere, weigh BA (60 mg, 0.1 mmol) into a 50 mL double-necked reaction bottle, add NOSbF 6 (55.9 mg, 0.2 mmol), add ultra-dry dichloromethane (re-evaporated) and ultra-dry acetonitrile 6 mL (volume ratio of 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, and add the above-prepared 0.15 mol / L lithium diphenylphosphine reagent (0.2 mL, 0.3 mmol) at 0°C. After the reaction is completed, quench the reaction solution with saturated ammonium chloride solution. Remove the reaction solvent under reduced pressure, extract with 20 mL of dichloromethane and 20 mL of water, repeat the extraction 3 times, separate the organic phase, and then dry it with anhydrous sodium sulfate to obtain a crude product. The crude solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:5), and a blue solid compound of about 24.49 mg (BA-PO) is obtained with a yield of 31%. 1 HNMR (600 MHz, (CD 3 ) 2 CO) δ 8.81 (d, J = 6.9 Hz, 1H), 8.57 (t, J = 7.9 Hz, 2H),7.59–7.54 (m, 4H), 7.54–7.48 (m, 2H), 7.29–7.24 (m, 3H), 7.23–7.19 (m, 2H),7.12–7.03 (m, 9H), 6.99 (dd, J = 8.6, 6.9 Hz, 1H), 6.95 (d, J = 8.5 Hz, 1H),2.32 (d, J = 12.1 Hz, 6H), 1.77 (s, 6H), 1.67 (s, 6H); 13 C NMR (126 MHz, (CD 3 ) 2CO) δ 138.49, 138.02, 135.08, 132.25, 132.18, 131.90, 130.57, 129.52,129.38, 129.04, 128.95, 128.77, 128.33, 127.91, 126.11, 122.22, 110.91,23.33, 20.14, 20.07; 31 P NMR (243 MHz, (CD 3 ) 2 CO) δ 29.13; (MALDI) m / z: Calcdfor C 58 H 43 OP: 786.3052, Found: 786.4887.

[0079] Example 16

[0080] The synthetic route of compound Perylene-OMe:

[0081] Synthesis process of compound Perylene-OMe: Under an inert atmosphere, perylene (50 mg, 0.2 mmol) was weighed into a 50 mL double-necked reaction bottle, and NO 2 Sb 6 (83.9 mg, 0.3 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 12 mL (volume ratio of 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, and add sodium methoxide (54 mg, 1mmol). After the reaction is completed, quench the reaction solution with saturated ammonium chloride solution. Remove the reaction solvent under reduced pressure, extract with 20 mL of dichloromethane and 20 mL of water, repeat the extraction 3 times, separate the organic phase, and then dry it with anhydrous sodium sulfate to obtain a crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:4), and a yellow solid compound of about 10.2 mg (Perylene-OMe) is obtained with a yield of 20%. 1 H NMR (600 MHz, CDCl 3 ) δ 8.23 ​​(d, J = 7.5 Hz, 1H), 8.16 (d, J = 7.4 Hz, 1H), 8.12 (t, J = 8.5 Hz,2H), 8.07 (d, J = 7.5 Hz, 1H), 7.65 (d,J = 8.0 Hz, 1H), 7.60 (d, J = 8.2 Hz, 1H),7.51 – 7.41 (m, 3H), 6.88 (d, J = 8.2 Hz, 1H), 4.05 (s, 3H); 13 C NMR (151 MHz, CDCl 3 ) δ 155.51, 135.07, 131.84, 131.65, 131.25, 129.79, 128.70, 127.84,126.78, 126.66, 126.63, 126.60, 126.13, 124.18, 122.04, 121.15, 120.88,120.03, 118.97, 105.18, 55.80, 32.11, 29.88, 22.87, 14.28; HRMS (APCI) m / z:Calcd for C 21 H 14 O [M+H] + :283.1118, Found: 283.1353.

[0082] Embodiment 17

[0083] The synthetic route of compound Perylene-CN:

[0084] Synthesis process of compound Perylene-CN: Under an inert atmosphere, perylene (50 mg, 0.2 mmol) was weighed into a 50 mL double-necked reaction bottle, and NO 2 Sb 6 (83.9 mg, 0.3 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 12 mL (volume ratio of 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, and add TMSCN (66 mg, 0.6 mmol). After the reaction is completed, quench the reaction solution with saturated ammonium chloride solution. Remove the reaction solvent under reduced pressure, extract with 20 mL of dichloromethane and 20 mL of water, repeat the extraction 3 times, separate the organic phase, and then dry it with anhydrous sodium sulfate to obtain a crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:5), and a yellow-green solid compound of about 16.6 mg (Perylene-CN) is obtained with a yield of 30%. 1 H NMR (600 MHz, CDCl3 ) δ 9.27 (d, J = 7.7 Hz, 1H), 8.29 (dd, J = 12.0, 7.5 Hz, 2H), 7.88 (d, J =8.1 Hz, 1H), 7.82 (d, J = 7.9 Hz, 1H), 7.72 (dd, J = 11.8, 8.2 Hz, 2H), 7.69-7.60(m, 3H), 7.58 (t, J = 7.8 Hz, 1H); 13 C NMR (151 MHz, CDCl 3 ) δ 136.31, 135.83,134.16, 131.97, 131.16, 130.67, 129.92, 129.89, 129.77, 129.01, 128.83,128.44, 127.69, 127.50, 126.74, 126.67, 125.85, 124.75, 124.46, 124.37,123.96, 123.47, 122.05, 121.69, 121.62, 119.14, 118.90, 114.05, 103.75; HRMS(APCI) m / z: Calcd for C 21 H 11 N [M+H] + : 278.0965, Found: 283.1233.

[0085] Embodiment 18

[0086] Compound PDI-SCH 3 The synthetic route:

[0087] Compound PDI-SCH 3 Synthesis process: Under inert atmosphere, weigh PDI (28.2 mg, 0.04 mmol) into a 50 mL double-necked reaction bottle, add NO 2 Sb 6(33.6 mg, 0.12 mmol), add ultra-dry dichloromethane (re-distilled) and ultra-dry acetonitrile 12 mL (volume ratio of 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, and add sodium methyl mercaptan (70 mg, 2 mmol). After the reaction is completed, quench the reaction solution with saturated ammonium chloride solution. Remove the reaction solvent under reduced pressure, extract with 20 mL of dichloromethane and 20 mL of water, repeat the extraction 3 times, separate the organic phase, and then dry it with anhydrous sodium sulfate to obtain a crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent is dichloromethane: petroleum ether = 1:3) to obtain about 12.09 mg of a blue solid compound (PDI-SCH 3 ), with a yield of 40%. 1 H NMR (600 MHz, CDCl 3 ) δ 9.03(d, J = 8.1 Hz, 1H), 8.88-8.82 (m, 3H), 8.78-8.74 (m, 3H), 7.52 (td, J = 7.8,3.7 Hz, 2H), 7.38 (d, J = 7.8 Hz, 4H), 2.83 (s, 3H), 2.78 (dd, J = 10.9, 6.5 Hz,4H), 1.21-1.19 (m, 24H); 13 C NMR (151 MHz, CDCl 3) δ 163.89, 163.71, 163.57,163.46, 149.34, 149.31, 147.82, 147.78, 147.22, 145.82, 145.80, 145.61,141.16, 139.10, 138.68, 138.62, 134.97, 134.73, 134.06, 133.11, 131.63,131.56, 131.07, 130.75, 130.60, 130.53, 129.88, 129.83, 129.68, 129.24,128.25, 127.66, 127.12, 124.86, 124.61, 124.52, 124.26, 124.13, 124.10,123.62, 123.12, 122.90, 122.73, 122.40, 119.26, 119.15, 119.03, 31.66, 31.59,30.35, 30.29, 24.17; HRMS (APCI) m / z: Calcd for C 49 H 44 N 2 O 4 S [M] -: 756.3027,Found: 756.3025.

[0088] Embodiment 19

[0089] Basic photoelectric properties of the synthesized series of target compounds: The present invention utilizes the CH nucleophilic substitution reaction method of the BA bay region to modify the CH bond of the BA bay region to synthesize a series of BA functionalized products, which exhibit a wider absorption band and stronger luminescence performance, have a smaller optical band gap and energy band gap, and show good application prospects in the field of organic photoelectric materials. Both the absorption and emission spectra show a certain degree of change. According to the change law of the chemical shift value of the maximum absorption peak and emission peak of the absorption spectrum, they can be roughly divided into two categories, namely, compared with BA, BA-Bu, BA-THF, and BA- SMe, BA-2Cl, BA-Carborane, BA-PO, BA-6-2CN, BA-6-CNCOOR, BA-6-Me-EA, BA-Pyo-1, BA-Pyo-2, BA-Pyo-3, BA-Pyd-2, etc. The compound exhibits a blue shift phenomenon, in which the characteristic absorption peaks of BA-6-2CN, BA-6-CNCOOR, BA-6-CNCOOR, BA-6-Me-EA, BA-Pyo-1, BA-Pyo-2, BA-Pyo-3 and BA-Pyd-2 are blue-shifted by 50 nm or more; while compounds such as BA-CCPh, BA-CN and BA-2CN show a large degree of red shift, with an average red shift of more than 20 nm, showing strong near-infrared absorption and emission characteristics; a series of BA functionalized derivatives show good luminescence properties and high fluorescence quantum yields, among which BA-6-2CN, BA-6-CNCOOR, BA-6-Me-EA and BA-Pyd-2 have a fluorescence quantum yield of more than 70% in organic solvents. The series of target products have potential application value in the fields of organic luminescent materials and bioimaging.

[0090] Table 1. Basic photoelectric properties of the series of compounds

Claims

1. A method for the nucleophilic substitution reaction of CH in the bay region of a bisanthene aromatic ring and its application, characterized in that Bisanthene is oxidized by nitrite hexafluorotellurate to form a cationic free intermediate, which is then reacted with carbon anions, oxygen-containing, sulfur-containing, chlorine-containing, nitrogen-containing and phosphorus-containing nucleophiles to synthesize bisanthene bay region modified functionalized products in one step. The carbon anion nucleophiles include n-butyl lithium, carborane lithium reagent, phenylacetylene lithium reagent, cyano and diethyl malonate, ethyl nitrile acetate, and ethyl acetoacetate type active methylene carbon anions; the oxygen nucleophile is sodium methoxide; the sulfur nucleophile is sodium methyl mercaptan and sodium thiophenol; the phosphine nucleophile is the lithium reagent of diphenylphosphine; the chlorine nucleophile is 1-butyl-3-methylimidazolium chloride ion liquid; the nitrogen nucleophiles include n-butylamine, benzylamine, aniline and N-iodosuccinimide.

2. A bisanthene aromatic ring bay region CH nucleophilic substitution reaction method and its application according to claim 1, characterized in that The reaction method comprises the following steps: under nitrogen protection, dissolving the raw material bisanthene in a mixed solution of dichloromethane and acetonitrile in a volume ratio of 3:1 at room temperature, adding hexafluorotelluric acid nitrite for oxidation for 3 minutes; controlling the temperature system to -78°C to 30°C, adding the above nucleophilic reagent, slowly stirring for 10 to 60 minutes, quenching the reaction mixture with water, concentrating, removing the solvent to obtain a crude product, and separating and purifying the obtained crude product to obtain a series of bisanthene functionalized products.

3. A bisanthene aromatic ring bay region CH nucleophilic substitution reaction method and its application according to claim 2, characterized in that The molar ratios of bisanthene, nitrosohexafluorotellurate, and nucleophile are 1:(1-5):(1-15) respectively.

4. A bisanthene aromatic ring bay region CH nucleophilic substitution reaction method and its application according to claim 3, characterized in that The reaction method was applied to the functionalization construction of perylene molecules. The oxidant was nitro hexafluorotelluride, and the nucleophiles were sodium methyl mercaptan and trimethylsilyl cyanide. The reaction process was as follows: under nitrogen protection, perylene was dissolved in a mixed solution of dichloromethane and acetonitrile with a volume ratio of 5:1, and nitro hexafluorotelluride was added for oxidation for 3 minutes; sodium methyl mercaptan and trimethylsilyl cyanide were added separately and slowly stirred for 30 minutes, the reaction mixture was quenched with water, concentrated, and desolvated to obtain a crude product, and the crude product was separated and purified to obtain the target compound.

5. A bisanthene aromatic ring bay region CH nucleophilic substitution reaction method and its application according to claim 4, characterized in that The molar ratios of perylene, hexafluorotelluric acid nitro and nucleophilic agent are 1:(4-8):(5-10) respectively.

6. A bisanthene aromatic ring bay region CH nucleophilic substitution reaction method and its application according to claim 5, characterized in that This method was applied to the functionalization construction of N, N'-bis(1,3-diisopropylbenzene)-3,4,9,10-perylene dicarboximide molecules. The reaction process was as follows: under nitrogen protection, N, N'-bis(1,3-diisopropylbenzene)-3,4,9,0-perylene dicarboximide was dissolved in a mixed solution of dichloromethane and acetonitrile with a volume ratio of 5:1, and hexafluorotelluric acid nitrate was added for oxidation for 3 minutes; sodium methyl mercaptan was added and slowly stirred at room temperature for 30 minutes, the reaction mixture was quenched with water, and a crude product was obtained after concentration and desolvation. The crude product was separated and purified to obtain the target compound.

7. A bisanthene aromatic ring bay region CH nucleophilic substitution reaction method and its application according to claim 6, characterized in that The molar ratios of N,N′-bis(1,3-diisopropylbenzene)-3,4,9,10-perylene dicarboximide, nitrohexafluorotellurate and sodium methyl mercaptan are 1:4:10 respectively.

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