A method for nucleophilic substitution reaction of C-H in the bay area of bisanthene aromatic ring and its application

Abstract

The present invention provides a method for the C-H nucleophilic substitution reaction of the bisanthene aromatic ring bay area and its application, belonging to the field of organic synthesis methodology. This reaction uses bisanthene as the raw material, dichloromethane and acetonitrile as solvents, and is subjected to nitrosylation with hexafluorotellurous acid, and reacts with nucleophilic reagents such as carbanions, oxygen-containing, sulfur-containing, chlorine-containing, nitrogen-containing, phosphorus-containing and cyano groups in one step to synthesize a series of functionalized products modified in the bisanthene bay area; when this reaction method is further applied to the nucleophilic substitution reactions of perylene and N,N'-bis(1,3-diisopropylbenzene)-3,4,9,10-perylene diimide (PDI), it shows good generality. The reaction of the present invention has mild reaction conditions, does not require the introduction of a transition metal as a catalyst, the product is easy to separate and purify, and has the advantages of low cost, high efficiency and greenness; the series of functionalized derivatives constructed by this method can provide important intermediates for the synthesis of larger polycyclic aromatic hydrocarbon molecules in the system; this method has good industrial production prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis methodology, and particularly relates to a C—H nucleophilic substitution reaction method for a bay region of a bisanthene aromatic ring and application thereof. Background Art

[0002] Polycyclic aromatic hydrocarbons (PAHs), which can be viewed as nanographene fragments or building blocks, often exhibit unique properties and have attracted considerable attention in the fields of organic optoelectronics, electronics, and magnetism, showing promising applications. Modifying PAHs with specific functional groups is crucial for their molecular design and synthesis. In particular, the synthesis of novel PAHs often requires the introduction of functional groups at specific positions. Typical methods for functionalizing PAHs include electrophilic substitution reactions of aromatic C-H bonds or coupling reactions involving transition metals. Electrophilic substitution reactions of aromatic C-H bonds are characterized by numerous reactive sites and poor selectivity. For weakly electrophilic reagents, the introduction of electron-donating groups to activate the aromatic rings is often necessary. Transition metal coupling reactions offer a powerful means for expanding PAH molecules, but their synthesis generally requires precursors containing a halogen source and a transition metal catalyst, making large-scale production expensive and potentially polluting. Bisanthene, abbreviated as BA (all abbreviations used below), is an important fused-ring aromatic hydrocarbon building block. Its molecular structure consists of two anthracene molecules connected by three single bonds. It exhibits a classic two-dimensional planar structure with both zigzag edges and a bay region, making it an ideal building block for constructing organic magnetic molecules and near-infrared dyes. It can be chemically modified to synthesize higher-order polycyclic aromatic hydrocarbons. However, directly modifying the bay region of bisanthene to introduce functional groups is extremely difficult, as electrophilic CH substitution preferentially occurs at other positions, such as the peri position. Therefore, achieving highly regioselective CH bond functionalization is a challenge in the synthesis of conjugated fused-ring aromatic hydrocarbons. Summary of the Invention

[0003] Based on the above background technology, the present invention provides a method for C-H nucleophilic substitution reaction with high selectivity in the bisanthene region, synthesizing a series of differently functionalized derivatives modified in the bay region of bisanthene to achieve the regioselectivity of aromatic C-H bond activation, solve the problem of difficult modification in the bay region of bisanthene, and further apply this method to the nucleophilic substitution reaction of C-H in the bay region of molecules such as perylene and N,N'-bis(1,3-diisopropylbenzene)-3,4,9,10-perylene diimide (PDI) to construct their functionalized products, providing a path for the activation and regioselectivity of C-H bonds in conjugated polycyclic aromatic hydrocarbons and enriching the family library of functionalized derivatives of classical polycyclic aromatic hydrocarbons such as bisanthene. The method of the present invention has simple steps, mild, efficient and highly selective reaction conditions, and has the prospect of industrial production. The present invention can be realized through the following scheme:

[0004]

[0005] (1) Reaction with carbanion nucleophiles: Using bisanthene as the starting material, dissolve it in a mixed solution of a certain volume of dichloromethane and acetonitrile at room temperature. Under the protection of an inert gas, add a certain amount of nitrosyl hexafluorotellurate (NOSbF6), and slowly stir for 3 minutes to obtain its cation radical intermediate, and react with carbon anion nucleophiles such as n-butyllithium, phenyllithium, carborane lithium reagent, diethyl malonate, and active methylene carbon anions such as cyanide, and carbon-carbon triple bond carbon anions respectively to synthesize a series of bisanthene derivatives, specifically as follows:

[0006]

[0007] (2) Reaction with heteroatom nucleophiles: Using bisanthene as the starting material, dissolve it in a mixed solution of a certain volume of dichloromethane and acetonitrile at room temperature. Under the protection of an inert gas, add a certain amount of nitrosyl hexafluorotellurate (NOSbF6), and slowly stir for 3 minutes to obtain its cation radical intermediate, and react with sodium methoxide respectively to obtain a functionalized derivative of BA containing a methoxy group; react with sodium methanethiolate and sodium benzenethiolate to obtain a functionalized derivative of BA containing a sulfur atom; react with the lithium reagent of diphenylphosphine to obtain a functionalized derivative of BA containing a phosphine group; react with a chlorine source to produce a functionalized product of BA containing chlorine; react with nitrogen nucleophiles such as n-butylamine, aniline and benzylamine to synthesize nitrogen-doped BA derivatives, specifically as follows:

[0008]

[0009] (3)Application of this reaction method: By using this nucleophilic substitution reaction method, the reaction substrates were extended to molecules such as perylene and N,N′-bis(1,3-diisopropylbenzene)-3,4,9,10-perylenediimide (PDI). Using perylene and N,N′-bis(1,3-diisopropylbenzene)-3,4,9,10-perylenediimide (PDI) as the starting materials, they were dissolved in a mixed solution of a certain volume of dichloromethane and acetonitrile at room temperature. Under the protection of an inert gas, a certain amount of nitronium hexafluorotellurate (NO2SbF6) was added, and it was slowly stirred for 3 minutes to obtain its cation radical intermediate. Then, a certain amount of methoxy and cyano nucleophiles were added to synthesize the corresponding functionalized derivatives, specifically as follows:

[0010]

[0011] Compared with the prior art, the present invention has the following advantages and technical effects:

[0012] (1)The present invention discloses for the first time a method for the C-H nucleophilic substitution reaction in the bay region of the bisanthene aromatic ring, and at the same time applies this method to the nucleophilic substitution reactions of molecules such as perylene and N,N′-bis(1,3-diisopropylbenzene)-3,4,9,10-perylenediimide (PDI), providing an effective route for the synthesis of functionalized products of such compounds, showing good generality and strong applicability;

[0013] (2)The present invention realizes the modification of the C-H bond in the bay region of bisanthene without introducing expensive transition metal catalysts, overcomes the problems of poor reactivity and poor regioselectivity of the C-H bond modification reaction of traditional aromatic compounds, and has the advantages of greenness, low cost and specific regioselectivity of the reaction site;

[0014] (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 be industrially produced. Description of the Drawings

[0015] Figure 1 is the basic technical route diagram of the reaction of the present invention.

[0016] Figure 2 is the 1H NMR spectrum of compound BA-Bu.

[0017] Figure 3 is the 1H NMR spectrum of compound BA-CCPh.

[0018] Figure 4 is the 1H NMR spectrum of compound BA-THF.

[0019] Figure 5It is the 1H NMR spectrum of the compound BA-Carborane.

[0020] Figure 6 It is the 1H NMR spectrum of the compound BA-BESEYZ.

[0021] Figure 7 It is the 1H NMR spectrum of the compound BA-OMe.

[0022] Figure 8 It is the 1H NMR spectrum of the compound BA-SCH3.

[0023] Figure 9 It is the 1H NMR spectrum of the compound BA-SPh.

[0024] Figure 10 It is the 1H NMR spectrum of the compound BA-imide.

[0025] Figure 11 It is the 1H NMR spectrum of the compound BA-2Cl.

[0026] Figure 12 It is the 1H NMR spectrum of the compound BA-CN.

[0027] Figure 13 It is the 1H NMR spectrum of the compound BA-2CN.

[0028] Figure 14 It is the 1H NMR spectrum of the compound BA-5-2CN.

[0029] Figure 15 It is the 1H NMR spectrum of the compound BA-6-2CN.

[0030] Figure 16 It is the 1H NMR spectrum of the compound BA-6-CNCOOR.

[0031] Figure 17 It is the 1H NMR spectrum of the compound BA-6-Me-EA.

[0032] Figure 18 It is the 1H NMR spectrum of the compound BA-Pyo-1.

[0033] Figure 19 It is the 1H NMR spectrum of the compound BA-Pyo-2.

[0034] Figure 20 It is the 1H NMR spectrum of the compound BA-Pyo-3.

[0035] Figure 21 It is the 1H NMR spectrum of the compound BA-Pyd-2.

[0036] Figure 22 It is the 1H NMR spectrum of the compound BA-PO.

[0037] Figure 23 It is the 1H NMR spectrum of the compound Per-OMe.

[0038] Figure 24 It is the 1H NMR spectrum of the compound Per-CN.

[0039] Figure 25 It is the 1H NMR spectrum of the compound PDI-SCH3. Detailed implementation manners

[0040] For the convenience of understanding the present invention, the present invention will be described in more detail below. However, it should be understood that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0041] Example 1

[0042] Synthesis route of the compound BA:

[0043]

[0044] Synthesis Process of Compound BA: BA is the raw material used in this invention. The synthesis process refers to the reported literature (Konishi A et al., Chemistry Letters, 2013, 42(6): 592 - 594). The synthesis process is as follows: Under an air environment, anthrone, i.e., compound 1 (3 g, 15.6 mmol) and potassium carbonate (14.28 g, 100 mmol) are added into a 250 mL two-neck reaction flask, and 180 mL of acetone is added. The temperature is slowly raised to 50 °C and the reaction is carried out for 18 hours. After the reaction is completed, the solvent of the reaction solution is removed by vacuum distillation. 50 mL of deionized water is added to dissolve it, and 80 mL of dichloromethane is added for extraction. The extraction is repeated 3 times. The extraction liquids are combined, and dichloromethane is removed by vacuum distillation to obtain a solid crude product. The crude product is separated and purified by silica gel chromatography (the eluent is dichloromethane: petroleum ether = 1:1) to obtain about 2.4 g of a light yellow solid (compound 2) with a yield of 40%; Under an inert atmosphere, compound 2 (1 g, 2.58 mmol) is added into a 150 mL two-neck reaction flask. 50 mL of dry tetrahydrofuran solution (which needs to be redistilled) is added to the reaction flask. Liquid nitrogen is used for freezing - evacuation / ventilation - thawing to remove water and oxygen. This operation is repeated 3 times. After the system temperature returns to room temperature, the reaction solution is placed in an ice-water bath, and 2-mesitylmagnesium bromide (1 mol / L, 16 mL) is slowly added dropwise. The reaction is carried out at 0 °C for 36 hours. The reaction solution is quenched with glacial acetic acid, and the reaction solvent is removed under reduced pressure using a rotary evaporator; Sodium iodide (2.6 g, 17.0 mmol) and sodium hypophosphite monohydrate (2.3 g, 21.7 mmol) are added to the reaction flask from which the solvent has been removed. 80 mL of glacial acetic acid solution is added, and the temperature is slowly raised to 118 °C and the reaction is carried out for 2 hours. After the reaction is completed, the solvent glacial acetic acid is removed by vacuum distillation method. Extraction is carried out with 50 mL of dichloromethane and 30 mL of water. The extraction is repeated 3 times. The organic phase is separated, and then dried with anhydrous sodium sulfate to obtain the crude product.The crude product solid was separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:5), obtaining 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 into a 150 mL two-neck reaction flask. Then 50 mL of dry chlorobenzene solution (which needed to be redistilled) was added to the reaction flask. The reaction flask was frozen with liquid nitrogen - evacuated / ventilated - thawed to remove water and oxygen, and this operation was repeated 3 times. After the system temperature returned to room temperature, the temperature of the reaction solution was slowly raised to 132 °C and stirred for 36 hours. After the reaction ended, the reaction solution was quenched with 5 mL of hydrazine hydrate, and the reaction solvent was removed under reduced pressure using a rotary evaporator to obtain the crude product. The crude product solid was separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:3), obtaining about 0.128 g of a blue solid compound (BA) with a yield of 55%.

[0045] Example 2

[0046] Synthetic route of compound BA - Bu:

[0047]

[0048] Synthetic process of compound BA - Bu: Under an inert atmosphere, 60 mg (0.09 mmol) of raw material BA was weighed into a 50 mL two-neck reaction flask, NOSbF6 (26.6 mg, 0.1 mmol) was added, and 12 mL of ultradry dichloromethane (redistilled) and ultradry acetonitrile (volume ratio 1:5) were added. The mixture was stirred at room temperature for 3 minutes, and the color of the reaction system changed from blue to purple. At -78 °C, a solution of n-butyllithium (2.5 mol / L in hexane, 210 μL) was slowly added dropwise, and the reaction was carried out at -78 °C for 10 minutes. After the reaction ended, the reaction solution was quenched with 1 mL of saturated ammonium chloride solution; under an inert atmosphere, the reaction solvent was removed under reduced pressure to obtain the crude product. The crude product solid was separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:5), obtaining about 40.4 mg of a blue solid compound (BA - Bu) with a yield of 70%. 1 H NMR (600 MHz, (CD3)2CO) 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, CDCl3) 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。

[0049] Example 3

[0050] Synthetic route of compound BA - CCPh:

[0051]

[0052] Synthesis Process of Compound BA-CCPh: Under an inert atmosphere, weigh raw material BA (60 mg, 0.1 mmol) into a 50 mL two-neck reaction flask, add NOSbF6 (26.6 mg, 0.1 mmol), add 12 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 1:5), stir at room temperature for 3 minutes. The color of the reaction system changes from blue to purple. Slowly add the prepared phenylacetylene lithium solution (0.85 mol / L in THF, 400 μL) dropwise at 0 °C and react at 0 °C for 1 hour. After the reaction is completed, quench the reaction solution with 1 mL of 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 the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:4) to obtain about 27.44 mg of blue solid compound (BA-CCPh), with a yield of 40%. 1 H NMR (600MHz, CDCl3): 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). 1313C NMR (150 MHz, CDCl3): 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。

[0053] Example 4

[0054] Synthetic route of compound BA-THF:

[0055]

[0056] Synthesis process of compound BA-THF: Under an air atmosphere, weigh the raw materials BA (60 mg, 0.1 mmol) and potassium tert-butoxide (44.8 mg, 0.4 mmol) into a 50 mL two-neck reaction flask, add 10 mL of ultra-dry tetrahydrofuran, and react at 66 °C for 12 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 it with anhydrous sodium sulfate to obtain the crude product. The crude product solid is separated and purified by silica gel column chromatography (the eluent is dichloromethane: petroleum ether = 1:3) to obtain about 23.1 mg of a blue solid compound, and the yield is 35% (BA-THF). The process experienced by this reaction is that under a strong alkaline environment, the hydrogen at the α-position of tetrahydrofuran is removed to form a carbanion, and this carbanion attacks the BA bay area to form the final product. 1 1H NMR (600 MHz, CDCl3): δ8.37 (d, J 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, CDCl3): 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).

[0057] Example 5

[0058] Synthetic route of compound BA - BESEYZ:

[0059]

[0060] Synthesis Process of Compound BA - BESEYZ: Under an inert atmosphere, weigh diethyl malonate (80 mg, 0.5 mmol), slowly add dropwise 0.5 mL of lithium diisopropylamide (LDA) (2.0 M in THF), and react at 0 °C for 2 hours; weigh raw material BA (60 mg, 0.1 mmol) into a 50 mL two-neck reaction flask, add NOSbF6 (26.6 mg, 0.1 mmol), add 12 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 1:5), stir at room temperature for 3 minutes, and the color of the reaction system changes from blue to purple; at 0 °C, add the above diethyl malonate solution reacted with LDA to the BA solution oxidized by telluric acid hexafluoride and react for 5 hours. After the reaction is completed, quench the reaction solution with 1 mL of 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 the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:3) to obtain about 30.1 mg of blue solid compound (BA - BESEYZ), and the yield is 41%. 1 H NMR (600 MHz, (CD3)2CO): 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); 1313C NMR (150 MHz, CDCl3): 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 O4[M+H] + : 743.3083, Found: 743.3154。

[0061] Example 6

[0062] Synthetic route of compound BA-OMe:

[0063]

[0064] Synthetic process of compound BA-OMe: Under an inert atmosphere, weigh the raw material BA (60 mg, 0.1 mmol) into a 50 mL two-neck reaction flask, add NOSbF6 (26.6 mg, 0.1 mmol), add 12 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, add solid sodium methoxide (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 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 the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:4) to obtain about 25.8 mg of blue solid compound (BA-OMe), and the yield is 42%. 1 1H NMR (600 MHz, CDCl3): 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, CDCl3): 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 O4[M+H] + : 617.2766, Found 617.2773。

[0065] Example 7

[0066] Synthetic route of compound BA-SCH3:

[0067]

[0068] Synthetic process of compound BA-SCH3: Under an inert atmosphere, weigh raw material BA (60 mg, 0.1 mmol) into a 50 mL two-neck reaction flask, add NOSbF6 (26.6 mg, 0.1 mmol), add 12 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 1:5), stir at room temperature for 3 minutes. The color of the reaction system changes from blue to purple. Add sodium methanethiolate 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 the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:4) to obtain about 28.44 mg of blue solid compound (BA-SCH3), and the yield is 45%. 1 H NMR (600 MHz, CDCl3) 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。

[0069] Example 8

[0070] Synthetic route of compound BA - SPh:

[0071]

[0072] Synthesis process of compound BA - SPh: Under an inert atmosphere, weigh raw material BA (60 mg, 0.1 mmol) into a 50 - mL two - neck reaction flask, add NOSbF6 (26.6 mg, 0.1 mmol), add 12 mL of super - dry dichloromethane (re - distilled) and super - dry acetonitrile (volume ratio 1:5), stir at room temperature for 3 minutes. The color of the reaction system changes from blue to purple. Add sodium phenylthiolate 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 it with anhydrous sodium sulfate to obtain the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:4) to obtain about 24.29 mg of blue solid compound (BA - SPh), and the yield is 35%. 1 H NMR (600 MHz, CDCl3) 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, CDCl3): 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。

[0073] Example 9

[0074] Synthetic route of compound BA - 2Cl:

[0075]

[0076] Synthetic process of compound BA - 2Cl: Under an inert atmosphere, weigh 1 - butyl - 3 - methylimidazolium chloride, abbreviated as [Bmin][Cl] (1.72 g, 10 mmol), and liquid Br2 (0.16 g, 1 mmol) into a 100 mL two - neck reaction flask. Add 3 mL of ultradry THF, freeze with liquid nitrogen - evacuate / exchange gas - thaw to remove oxygen, and repeat this operation 3 times. Slowly raise the temperature to 100 °C and react at this temperature for 30 minutes to obtain the chloride ion nucleophile (Br2Cl -). The raw material BA (120 mg, 0.2 mmol) oxidized by NOSbF6 was added to the above-prepared chloride ion nucleophile system, and the reaction was carried out at 100 °C for 30 minutes. After the reaction was completed, the reaction solvent was removed under reduced pressure, extracted with 10 mL of diethyl ether, and the extraction was repeated 3 times. The organic phase was separated, and then dried over anhydrous sodium sulfate to obtain the crude product. The crude product solid was separated and purified by silica gel column chromatography (the eluent was dichloromethane:petroleum ether = 1:6) to obtain about 82.3 mg of a blue solid compound (BA-2Cl), and the yield was 63%. 1 H NMR (600 MHz, CDCl3): 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, CDCl3): 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 Cl2[M+H] + : 655.1881, Found:655.1949 。

[0077] Example 10

[0078] Synthetic routes of compounds BA-CN and BA-2CN:

[0079]

[0080] 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 two-neck reaction flask, add NOSbF6 (26.6 mg, 0.1 mmol), add 12 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 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 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 the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:3) to obtain about 30.5 mg of blue solid compound (BA-CN) with a yield of 45%, and about 15.3 mg of blue-green solid compound (BA-2CN) with a yield of 24%. Among them, the basic characterization data of BA-CN 1 H NMR (600 MHz, CDCl3): 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); 1313C NMR (150 MHz, CDCl3): 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 for C 47 H 37 N [M+H] + : 612.2613, Found: 612.2685. BA-2CN Basic Characterization Data 1 1H NMR (600 MHz, CDCl3): δ9.48 (dd, J J = 6.0 Hz, 24 Hz, 2H), 7.58 - 7.68 (m, 6H), 7.40 (dd, J J = 6.0 Hz, 24 Hz, 2H), 7.17 (s, 4H), 2.5 (s, 6H), 1.87 (s, 12H); 13 13C NMR (150 MHz, CDCl3): 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 N2 [M+H] + : 637.2565, Found: 637.2636。

[0081] Example 11

[0082] Synthesis route of compound BA-6-CNCOOR:

[0083]

[0084] Synthesis process of compound BA-6-CNOOR: Under an inert atmosphere, weigh ethyl cyanoacetate (56.5 mg, 0.5 mmol), slowly drop 0.5 mL of 2 mol / L LDA solution and react at 0 °C for 2 hours; weigh raw material BA (60 mg, 0.1 mmol) into a 50 mL two-neck reaction flask, add NOSbF6 (26.6 mg, 0.1 mmol), add 12 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 5:1), stir at room temperature for 3 minutes, and the color of the reaction system changes from blue to purple; at 0 °C, add the above-mentioned ethyl cyanoacetate solution after the LDA reaction to the raw material solution oxidized by nitrosyl hexafluorotellurate (NOSbF6) and react for 5 hours. After the reaction is completed, quench the reaction solution with 1 mL of 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 with anhydrous sodium sulfate to obtain the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:3) to obtain 31.8 mg of purple solid, which is compound BA-6-CNCOOR, and the yield is 45%. 1 H NMR (600 MHz, CDCl3): 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). 1313C NMR (150 MHz, CDCl3): δ 137.97, 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 for C 52 H 37 NO2 [M + H] + : 708.2824, Found: 708.2804。

[0085] Example 12

[0086] Synthetic route of compound BA-6-Me-EA:

[0087]

[0088] Synthesis process of compound BA-6-Me-EA: Under an inert atmosphere, weigh ethyl acetoacetate (65 mg, 0.5 mmol), slowly drop 0.5 mL of 2 mol / L LDA solution and react at 0 °C for 2 hours; weigh original BA (60 mg, 0.1 mmol) into a 50 mL two-neck reaction flask, add NOSbF6 (26.6 mg, 0.1 mmol), add 12 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 5:1), stir at room temperature for 3 minutes, and the color of the reaction system changes from blue to purple; at 0 °C, add the above-mentioned ethyl cyanoacetate solution reacted with lithium diisopropylamide (LDA) to the solution oxidized by nitrosyl hexafluorotellurate (NOSbF6) and react for 5 hours. After the reaction is completed, quench the reaction solution with 1 mL of 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 with anhydrous sodium sulfate to obtain the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:4) to obtain 29.2 mg of purple solid, which is compound BA-6-Me-EA, and the yield is 42%. 11H NMR (600 MHz, (CD3)2CO): δ 9.35 (d, J J = 6.0 Hz, 2H), 8.45 (d, J J = 6.0 Hz, 1H), 8.06 - 8.11 (m, 3H), 7.91 (d, J J = 12.0 Hz, 2H), 7.76 (d, J J = 6.0 Hz, 1H), 7.70 (d, J J = 6.0 Hz, 1H), 7.29 (d, J J = 6.0 Hz, 4H), 4.70 (q, J J = 6.0 Hz, 2H), 3.10 (s, 3H), 2.53 (d, J J = 6.0 Hz, 6H), 1.91 (d, J J = 6.0 Hz, 12H), 1.53 (t, J J = 6.0 Hz, 3H); 13 13C NMR (150 MHz, CDCl3): δ 171.26, 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 O2 [M + H] + : 697.3028, Found: 697.3093 。

[0089] Example 13

[0090] Synthetic route of compound BA - Pyo - 1:

[0091]

[0092] Synthesis Process of Compound BA-Pyo-1: Under an inert atmosphere, weigh raw material BA (60 mg, 0.1 mmol) into a 50 mL two-neck reaction flask, add NOSbF6 (26.6 mg, 0.1 mmol), add 12 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 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 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 the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:3) to obtain about 24.49 mg of blue solid compound (BA-Pyo-1), with a yield of 45%. 1 H NMR (600 MHz, CDCl3): 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,CDCl3): 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, 125.72, 125.36, 125.23,122.06, 121.70, 120.44, 120.04, 118.01, 117.08, 46.13, 33.90, 20.44, 20.07,19.24, 13.07. HRMS (APCI) m / z: Calcd for C 50 H 41 N[M+H] + : 656.3239, Found:697.3206。

[0093] Example 14

[0094] Synthetic route of compound BA-Carborane:

[0095]

[0096] Synthesis process of compound BA-Carborane: Under an inert atmosphere, weigh BA (30 mg, 0.05 mmol) into a 50 mL two-neck reaction flask, add NOSbF6 (13.3 mg, 0.05 mmol), add 6 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 1:5), stir at room temperature for 3 minutes, the color of the reaction system changes from blue to purple, and add the prepared 0.35 mol / L lithium o-carborane 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 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 the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:5) to obtain about 10.9 mg of blue solid compound (BA-Carborane), and the yield is 30%. 1 H NMR (600 MHz, CDCl3): 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, CDCl3):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; 11B{1H} NMR (600 MHz, CDCl3): 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。

[0097] Example 15

[0098] Synthetic route of compound BA-PO:

[0099]

[0100] Synthetic process of compound BA-PO: Under an inert atmosphere, weigh BA (60 mg, 0.1 mmol) into a 50 mL two-necked reaction flask, add NOSbF6 (55.9 mg, 0.2 mmol), add 6 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 1:5), stir at room temperature for 3 minutes. The color of the reaction system changes from blue to purple. Add the prepared 0.15 mol / L lithium diphenylphosphide 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 the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:5) to obtain about 24.49 mg of blue solid compound (BA-PO), and the yield is 31%. 1 1H NMR (600 MHz, (CD3)2CO) δ 8.81 (d, J J J = 6.9 Hz, 1H), 8.57 (t, J J 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 J 1313C NMR (126 MHz, (CD3)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 31P NMR (243 MHz, (CD3)2CO) δ 29.13; (MALDI) m / z: Calcd for C 58 H 43 OP: 786.3052, Found: 786.4887。

[0101] Example 16

[0102] Synthetic route of compound Perylene-OMe:

[0103]

[0104] Synthesis process of compound Perylene-OMe: Under an inert atmosphere, weigh perylene (50 mg, 0.2 mmol) into a 50 mL two-neck reaction flask, add NO2SbF6 (83.9 mg, 0.3 mmol), add 12 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 1:5), stir at room temperature for 3 minutes. The color of the reaction system changes from blue to purple, then add sodium methoxide (54 mg, 1 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 the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:4) to obtain about 10.2 mg of yellow solid compound (Perylene-OMe), and the yield is 20%. 1 1H NMR (600 MHz, CDCl3) δ 8.23 (d, J J = 7.5 Hz, 1H), 8.16 (d, J J = 7.4 Hz, 1H), 8.12 (t, J J = 8.5 Hz, 2H), 8.07 (d, J 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,CDCl3) 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。

[0105] Example 17

[0106] Synthetic route of compound Perylene-CN:

[0107]

[0108] Synthesis process of compound Perylene-CN: Under an inert atmosphere, weigh perylene (50 mg, 0.2 mmol) into a 50 mL two-neck reaction flask, add NO2SbF6 (83.9 mg, 0.3 mmol), add 12 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 1:5), stir at room temperature for 3 minutes. The color of the reaction system changes from blue to purple, then 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 the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:5) to obtain about 16.6 mg of a yellow-green solid compound (Perylene-CN), 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, CDCl3) 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。

[0109] Example 18

[0110] Synthetic route of compound PDI - SCH3:

[0111]

[0112] Synthesis Process of Compound PDI-SCH3: Under an inert atmosphere, weigh PDI (28.2 mg, 0.04 mmol) into a 50 mL two-neck reaction flask, add NO2SbF6 (33.6 mg, 0.12 mmol), add 12 mL of super-dry dichloromethane (re-distilled) and super-dry acetonitrile (volume ratio 1:5), stir at room temperature for 3 minutes. The color of the reaction system changes from blue to purple. Then add sodium methanethiolate (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 the crude product. The crude product solid is separated and purified by silica gel column chromatography (eluent: dichloromethane: petroleum ether = 1:3) to obtain about 12.09 mg of blue solid compound (PDI-SCH3), and the yield is 40%. 1 H NMR (600 MHz, CDCl3) 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); 1313C NMR (151 MHz, CDCl3) 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 N2O4S [M] -: 756.3027, Found: 756.3025。

[0113] Example 19

[0114] Basic optoelectronic properties of the synthesized series of target compounds: By using the method of C-H nucleophilic substitution reaction in the BA bay area, a series of BA functionalized products are synthesized by modifying the C-H bond in the BA bay area. These products exhibit a relatively wide absorption band and strong luminescence performance, with a small optical band gap and energy band gap, showing good application prospects in the field of organic optoelectronic materials. There are certain changes in both their absorption and emission spectra. According to the change rules of the chemical shift values of the maximum absorption peak and emission peak in the absorption spectrum, they can be roughly divided into two categories. That is, compared with BA, compounds such as BA-Bu, BA-THF, 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. show a blue shift phenomenon. Among them, 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 more than 50 nm; while compounds such as BA-CCPh, BA-CN, and BA-2CN show a relatively large red shift, with an average red shift of more than 20 nm, showing strong absorption and emission characteristics in the near-infrared region. The series of BA functionalized derivatives exhibit good luminescence characteristics and have a high fluorescence quantum yield. Among them, the fluorescence quantum yields of BA-6-2CN, BA-6-CNCOOR, BA-6-Me-EA, and BA-Pyd-2 in organic solvents reach more than 70%. The series of target products have potential application values in the fields of organic light-emitting materials and biological imaging.

[0115] Table 1. Basic optoelectronic properties of the series of compounds

[0116]

Claims

1. A method for the nucleophilic substitution reaction of C-H in the bay region of the bisanthene aromatic ring, characterized in that Bisanthene is oxidized by nitrous hexafluorotellurate to form a cationic free intermediate, and then it is directly synthesized with carbanions, oxygen-containing, sulfur-containing, chlorine-containing, nitrogen-containing, and phosphorus-containing nucleophiles to obtain bisanthene bay-region modified functionalized products. The carbanion nucleophiles include n-butyllithium, carborane lithium reagent, phenylacetylene lithium reagent, and active methylene type carbanions such as diethyl malonate, ethyl cyanoacetate, and ethyl acetoacetate; the oxygen nucleophile is sodium methoxide; the sulfur nucleophiles are sodium methanethiolate and sodium benzenethiolate; the phosphorus nucleophile is the lithium reagent of diphenylphosphine; the chlorine nucleophile is 1-butyl-3-methylimidazolium chloride ionic liquid; the nitrogen nucleophiles include n-butylamine, benzylamine, aniline, and N-iodosuccinimide.

2. The method for the C-H nucleophilic substitution reaction in the bay region of the bisanthene aromatic ring according to claim 1, wherein The reaction method includes the following steps: Under nitrogen protection, at room temperature, bisanthene as the raw material is dissolved in a mixed solution of dichloromethane and acetonitrile with a volume ratio of 3:1, and then nitrous hexafluorotellurate is added for oxidation for 3 minutes. The temperature system is controlled at -78°C to 30°C, the above-mentioned nucleophile is added, and it is slowly stirred for 10 to 60 minutes. The reaction mixture is quenched with water, concentrated, and the solvent is removed to obtain a crude product. The obtained crude product is separated and purified to obtain a series of bisanthene functionalized products.

3. A method for the C-H nucleophilic substitution reaction in the bay region of the bisanthene aromatic ring according to claim 2, characterized in that The molar ratios of bisanthene, nitrous hexafluorotellurate, and the nucleophile are 1:(1 - 5):(1 - 15) respectively.

4. Application of a method for nucleophilic substitution reaction of C-H in the bay region of a bisanthene aromatic ring, characterized in that This reaction method is applied to the functionalized construction of perylene molecules. The oxidant is nitrous hexafluoronitrate, and the nucleophiles are sodium methanethiolate and trimethylsilyl cyanide. The reaction process is as follows: Under nitrogen protection, perylene is dissolved in a mixed solution of dichloromethane and acetonitrile with a volume ratio of 5:1, and then nitrous hexafluoronitrate is added for oxidation for 3 minutes; sodium methanethiolate and trimethylsilyl cyanide are added respectively and slowly stirred for 30 minutes. The reaction mixture is quenched with water, concentrated, and the solvent is removed to obtain a crude product. The obtained crude product is separated and purified to obtain the target compound.

5. Use of the method for nucleophilic substitution reaction of C-H in the bay region of bisanthene aromatic ring according to claim 4, characterized in that The molar ratios of perylene, nitrous hexafluoronitrate, and the nucleophile are 1:(4 - 8):(5 - 10) respectively.

6. Use of the method for C-H nucleophilic substitution reaction in the bay region of the bisanthene aromatic ring according to claim 5, characterized in that This method is applied to the functionalized construction of N,N'-bis(1,3-diisopropylbenzene)-3,4,9,10-perylenedicarboximide molecules. The reaction process is as follows: Under nitrogen protection, N,N'-bis(1,3-diisopropylbenzene)-3,4,9,0-perylenedicarboximide is dissolved in a mixed solution of dichloromethane and acetonitrile with a volume ratio of 5:1, and then nitrous hexafluoronitrate is added for oxidation for 3 minutes; sodium methanethiolate is added and slowly stirred at room temperature for 30 minutes. The reaction mixture is quenched with water, concentrated, and the solvent is removed to obtain a crude product. The obtained crude product is separated and purified to obtain the target compound.

7. Use of the method for the C-H nucleophilic substitution reaction in the bay region of the bisanthene aromatic ring according to claim 6, characterized in that The molar ratios of N,N'-bis(1,3-diisopropylbenzene)-3,4,9,10-perylenedicarboximide, nitrous hexafluoronitrate, and sodium methanethiolate are 1:4:10 respectively.

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