Organic photocatalyst based on isothiatruxene skeleton as well as preparation method and application of organic photocatalyst
By using an organic photocatalyst with an isothiatrimeric indene framework, the problems of complex synthesis and difficult control of redox performance in existing technologies have been solved, enabling simple preparation and efficient visible light photocatalytic applications.
Patent Information
- Application Number
- CN202410775844.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-06-17
- Publication Date
- 2025-12-19
AI Technical Summary
Existing organic photocatalysts suffer from problems such as complex synthesis, lack of sites for molecular structure modification, and difficulty in controlling redox performance. Furthermore, traditional noble metal complex photocatalysts are expensive, have significant toxicity, and are difficult to drive visible light photocatalytic reactions.
Organic photocatalysts with an isothiazolidinium framework structure are prepared through specific reaction raw materials and steps, including the reaction of benzothiophene with dichlorodicyanobenzoquinone, hydrogen peroxide and m-chloroperoxybenzoic acid, to form an isothiazolidinium framework catalyst for catalyzing a variety of photo-redox reactions.
This study demonstrates the efficient application of easily prepared organic photocatalysts in visible light photocatalytic reactions, including carbonyl reduction coupling, alkyne oxidation, and decarboxylation fluorination, exhibiting excellent photocatalytic efficiency.
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Figure QLYQS_2 
Figure QLYQS_3
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of photocatalysis, and particularly relates to an organic photocatalyst based on an isothiatriphenylene skeleton as well as a preparation method and application thereof. BACKGROUND
[0002] Visible light catalytic reactions are one of the research hotspots in the field of organic chemistry in the past ten years. Since most organic compounds do not directly absorb visible light, an additional photocatalyst needs to be added for the reaction. The most commonly used photocatalyst is a noble metal (Ru, Ir, etc.) complex, but it has problems such as high cost, obvious toxicity, and metal residue. In order to solve these problems, chemists have developed various pure organic molecular photocatalysts. These pure organic photocatalysts have the characteristics of simple synthesis, diverse performance, adjustable structure, and relatively low cost, and are fully complementary to traditional noble metal complex photocatalysts. Therefore, the development of organic photocatalysts aims to replace traditional transition metal photocatalysts with "metal-free" pure organic molecular photocatalysts, and is expected to drive traditional reactions that are difficult or impossible to occur and promote the development of new photochemical synthesis methods.
[0003] In recent years, organic molecular photocatalysts have experienced vigorous development. Common pure organic molecular photocatalysts include aromatic ketones, quinones, phenothiazines, acridine salts, and various dye molecules. The above-mentioned organic molecular photocatalysts have few molecular structure modification sites, and their redox properties are difficult to control. We hope to develop a new type of photocatalyst that is simple to synthesize, has an easily modified molecular structure, and has adjustable redox properties. Isothiatriphenylene compounds have a large conjugated molecular skeleton. The large conjugated system makes the maximum absorption wavelength enter the visible light region, and the introduction of multiple sulfur atoms may further cause red shift of the maximum absorption wavelength. Therefore, we believe that isothiatriphenylene compounds have the potential to be used as photocatalysts. Isothiatriphenylene compounds were discovered by Bergman et al. as early as 1986, but the research on this module in the chemical field has been stagnant for a long time. So far, only a few documents have preliminarily studied the photophysical properties of isothiatriphenylene and its derivatives, and there has been no report on its application in the field of organic photocatalysis. SUMMARY
[0004] Based on the above background, the application provides an organic photocatalyst based on an isothiatriphenylene skeleton as well as a preparation method and application thereof.
[0005] To achieve the above-mentioned purpose, the application adopts the following technical solutions.
[0006] An organic photocatalyst based on an isothiatriphenylene skeleton has the general structure as shown in the following formula:
[0007]
[0008] wherein R1 is S, SO, SO2; R2 is S, SO, SO2, C=O; R3 and R4 are H, halogen, substituted or unsubstituted C1-C 30 alkyl, substituted or unsubstituted C3-C 30 alkenyl, substituted or unsubstituted C3-C 30 alkynyl, substituted or unsubstituted C1-C 30 alkoxy, substituted or unsubstituted C3-C 12 cycloalkyl, substituted or unsubstituted C1-C 10 heterocycloalkyl, substituted or unsubstituted C3-C 12 cycloalkenyl, substituted or unsubstituted C1-C 10 heterocycloalkenyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C1-C 30 heteroaryl, acyl or ester group; R5 and R6 are H, halogen, substituted or unsubstituted C1-C 30 alkyl, substituted or unsubstituted C3-C 30 alkenyl, substituted or unsubstituted C3-C 30 alkynyl, substituted or unsubstituted C1-C 30 alkoxy, substituted or unsubstituted C3-C 12 cycloalkyl, substituted or unsubstituted C1-C 10 heterocycloalkyl, substituted or unsubstituted C3-C 12 cycloalkenyl, substituted or unsubstituted C1-C 10 heterocycloalkenyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C1-C 30 heteroaryl, acyl or ester group. Further, the specific structural formula of the organic photocatalyst is as follows:
[0009]
[0010]
[0011]
[0012] The preparation of the organic catalyst based on the isothianaphthene skeleton is to use substituted or unsubstituted benzothiophene as the reaction raw material; specifically, when benzothiophene is used as the reaction raw material, the reaction flow is as follows:
[0013]
[0014] (1) The reaction raw materials benzothiophene 1 and dichlorodicyanoquinone were added to dichloromethane to make benzothiophene completely dissolved, and then trifluoromethanesulfonic acid was added dropwise under ice bath, and stirred during the dropwise process. The reaction was carried out at room temperature for 3-12 h. After the reaction was completed, compound 2a was obtained by separation and purification.
[0015] (2) The obtained compound 2a was dissolved in dichloromethane, and then hydrogen peroxide was added to the system. After the reaction was completed, compound 6a was obtained by separation and purification.
[0016] (3) The obtained compound 2a was dissolved in dichloromethane, and then m-chloroperbenzoic acid was added to the system. After the reaction was completed, compound 10a was obtained by separation and purification.
[0017] When substituted or unsubstituted benzothiophene and substituted or unsubstituted indantrione are used as reaction raw materials, the reaction flow is as follows:
[0018]
[0019] (1) The reaction raw materials benzothiophene 1 and dichlorodicyanoquinone were added to dichloromethane to make benzothiophene completely dissolved, and then trifluoromethanesulfonic acid was added dropwise under ice bath, and stirred during the dropwise process. The reaction was carried out at room temperature for 3-12 h. After the reaction was completed, compound 2a was obtained by separation and purification.
[0020] (2) After the dropwise addition was completed, the reaction was carried out at 90°C for 3-12 h.
[0021] (3) After the reaction was completed, it was cooled to room temperature, and then filtered, washed with water, dichloromethane, methanol and acetone, and then dried in a vacuum drying box at 60°C overnight to obtain compounds 5a-5d.
[0022] (4) The synthesized compounds 5a-5d were added to a flask, dichloromethane was added, and then hydrogen peroxide was slowly added to the flask. The reaction was carried out at room temperature for 6-48 h. After the reaction was completed, saturated sodium sulfite was added to quench the reaction, stirred for 20 min, and then filtered. Then, the filter was washed with water, dichloromethane, methanol and acetone, and then dried in a vacuum drying box at 60°C overnight to obtain compounds 9a-9d.
[0023] The obtained organic photocatalyst based on isothiatriphenylene skeleton can be used to catalyze various photo-oxidation and reduction reactions, including but not limited to carbonyl reductive coupling, oxidation of alkyne, decarboxylative fluorination, toluene oxidation, amino heteroarylization of non-activated olefin, reductive deoxygenation of N-heteroaryl carbonyl compound, styrene hydroformylation, styrene alkoxyacylation, and dehalogenation of halogenated aromatic hydrocarbon.
[0024] The present application provides an organic photocatalyst based on isothiatriphenylene skeleton and a preparation method thereof. The preparation process of the organic photocatalyst is simple, and the organic photocatalyst exhibits excellent photocatalytic efficiency in visible light catalyzed organic reactions such as carbonyl reductive coupling, oxidation of alkyne, decarboxylative fluorination, toluene oxidation, amino heteroarylization of non-activated olefin, reductive deoxygenation of N-heteroaryl carbonyl compound, styrene hydroformylation, styrene alkoxyacylation, and dehalogenation of halogenated aromatic hydrocarbon, thus having practical application value. DETAILED DESCRIPTION
[0025] In order to make the content of the present application more convenient to understand, the technical solutions of the present application will be further described below in combination with specific embodiments, but the present application is not limited thereto.
[0026] Example 1
[0027] An organic photocatalyst based on isothiatriphenylene skeleton, the synthesis process and specific preparation method thereof are as follows:
[0028]
[0029] (1) Synthesis of compound 2a:
[0030] The reactants benzothiophene 1 (30 mmol) and dichlorodicyanoquinone (30 mmol) were weighed and added to a 500 mL flask, then dichloromethane (50 mL) was added to completely dissolve the benzothiophene. Then trifluoromethanesulfonic acid (90 mmol) was added dropwise to the flask containing benzothiophene under ice bath conditions, and stirring was continuously performed during the dropwise addition. After the dropwise addition was completed, the reaction was carried out at room temperature for 6 h. After the reaction was completed, methanol was added for quenching, stirring was performed for 30 min, and concentration was performed under reduced pressure. Column chromatography purification was performed with dichloromethane and petroleum ether mixed solvent (DCM: PE = 1:8, v / v) as eluent to obtain light yellow solid 2a (yield 43%). 1 HNMR (400 MHz, Chloroform-d) δ 8.77 (dd, J = 8.2, 8.0 Hz, 2H), 8.64 (d, J = 7.9 Hz, 1H), 8.15-8.10 (m, 1H), 8.05 (t, J = 7.9 Hz, 1H), 7.73-7.68 (m, 1H), 7.59-7.45 (m, 6H).
[0031] (2) Synthesis of compound 6a:
[0032] Compound 2a (2 mmol) was taken in a 100 mL flask, then 30 mL of dichloromethane was added, 2a was completely dissolved, then m-chloroperbenzoic acid (20 mmol) was slowly added to the flask, and the reaction was carried out at room temperature for 48 h. After the reaction was completed, saturated sodium bicarbonate and saturated sodium sulfite were added to quench the reaction, stirred for 20 min, concentrated under reduced pressure, and column chromatography was carried out with dichloromethane and petroleum ether and ethyl acetate mixed solvent (DCM: PE: EA = 2:2:1, v / v / v) as eluent to obtain yellow solid 6a (yield 95%). 1 HNMR (400 MHz, Chloroform-d) δ 8.67 (d, J = 7.9 Hz, 1H), 8.44 (dd, J = 5.9, 3.2 Hz, 1H), 8.35-8.31 (m, 1H), 8.04 (td, J = 7.0, 6.6, 3.1 Hz, 2H), 8.01-7.95 (m, 1H), 7.84 (td, J = 7.8, 1.3 Hz, 1H), 7.81-7.69 (m, 5H).
[0033] (3) Synthesis of compound 10a:
[0034] Compound 2a (2 mmol) was taken in a 100 mL flask, then 30 mL of dichloromethane was added, 2a was completely dissolved, then m-chloroperbenzoic acid (20 mmol) was slowly added to the flask, and the reaction was carried out at room temperature for 48 h. After the reaction was completed, saturated sodium bicarbonate and saturated sodium sulfite were added to quench the reaction, stirred for 20 min, concentrated under reduced pressure, and column chromatography was carried out with dichloromethane and petroleum ether and ethyl acetate mixed solvent (DCM: PE: EA = 2:2:1, v / v / v) as eluent to obtain yellow solid 10a (yield 95%). 1 HNMR (400 MHz, Chloroform-d) δ 8.67 (d, J = 7.9 Hz, 1H), 8.44 (dd, J = 5.9, 3.2 Hz, 1H), 8.35-8.31 (m, 1H), 8.04 (td, J = 7.0, 6.6, 3.1 Hz, 2H), 8.01-7.95 (m, 1H), 7.84 (td, J = 7.8, 1.3 Hz, 1H), 7.81-7.69 (m, 5H).
[0035] Example 2
[0036] An organic photocatalyst based on an isothianaphthene skeleton, its synthesis process and specific preparation method are as follows:
[0037]
[0038] (1) Synthesis of compounds 2b-2e:
[0039] The reactants p-substituted benzothiophene 1 (30 mmol) and dichlorodicyanoquinone (30 mmol) were weighed into a 500 mL flask, then dichloromethane (50 mL) was added and it was completely dissolved. Then trifluoromethanesulfonic acid (90 mmol) was added dropwise to the flask under ice bath conditions, and stirred during the dropwise addition. After the dropwise addition was completed, it was placed at room temperature for 3-12 h, after the reaction was completed, 50 mL of methanol was added to quench, stirred for 30 min, concentrated under reduced pressure, and purified by column chromatography with dichloromethane and petroleum ether mixed solvent (DCM: PE = 1:8, v / v) as eluent to obtain compounds 2b-2e.
[0040] 2b, yellow solid, yield 44%, 1 H NMR (500 MHz, Chloroform-d) δ 8.52 (d, J = 2.4 Hz, 1H), 8.12-8.01 (m, 3H), 7.97 (d, J = 2.0 Hz, 1H), 7.92 (d, J = 2.5 Hz, 1H), 7.45-7.37 (m, 3H).
[0041] 2c, yellow solid, yield 47%, 1 H NMR (500 MHz, Chloroform-d) δ 8.06 (d, J = 2.1 Hz, 1H), 8.03-7.87 (m, 5H), 7.35-7.19 (m, 3H), 2.44-2.40 (m, 9H).
[0042] 2d, yellow solid, yield 40%, 1 H NMR (500 MHz, DMSO-d6) δ 9.03 (d, J = 1.4 Hz, 1H), 8.99 (d, J = 1.8 Hz, 1H), 8.88 (d, J = 1.6 Hz, 1H), 8.22-8.14 (m, 3H), 8.10 (d, J = 8.4 Hz, 1H), 8.08-8.01 (m, 2H).
[0043] 2e, brown solid, yield 48%, 1H NMR (500 MHz, Chloroform-d) δ 8.71 (d, J = 2.4 Hz, 1H), 8.68 (d, J = 1.9 Hz, 1H), 8.62 (d, J = 2.4 Hz, 1H), 8.23-8.17 (m, 3H), 7.96 (ddd, J = 16.6, 8.4, 2.3 Hz, 3H), 7.58 (dt, J = 8.0, 1.3 Hz, 6H), 7.44 (dd, J = 8.2, 7.2 Hz, 6H), 7.37-7.33 (m, 3H).
[0044] (2) Synthesis of compounds 6b-6e:
[0045] To the synthesized compound 2b-2e (2 mmol) was added to a 100 mL tomato bottle, then 30 mL of dichloromethane was added, and it was completely dissolved, and then hydrogen peroxide (10 mmol) was slowly added to the tomato bottle, and the reaction was carried out at room temperature for 6-48 h. After the reaction was completed, saturated sodium sulfite was added to quench the reaction, stirred for 20 min, concentrated under reduced pressure, and column chromatography was performed with dichloromethane, petroleum ether, ethyl acetate mixed solvent (DCM: PE: EA = 2:2:1, v / v / v) as eluent to obtain compounds 6b-6e.
[0046] 6b, yellow solid, yield 87%, 1 HNMR (500 MHz, Chloroform-d) δ 8.52 (d, J = 2.4 Hz, 1H), 8.38 (d, J = 2.4 Hz, 1H), 8.31 (d, J = 8.4 Hz, 1H), 8.15 (d, J = 2.1 Hz, 1H), 8.08 (d, J = 8.4 Hz, 1H), 7.82 (d, J = 8.4 Hz, 1H), 7.64 (dt, J = 8.4, 2.1 Hz, 2H), 7.57 (dd, J = 8.4, 1.8 Hz, 1H).
[0047] 6c, yellow solid, yield 91%, 1 HNMR (500 MHz, Chloroform-d) δ 8.14-8.10 (m, 2H), 8.06 (d, J = 8.4 Hz, 1H), 8.01 (d, J = 2.4 Hz, 1H), 7.91 (d, J = 8.4 Hz, 1H), 7.83 (d, J = 1.8 Hz, 1H), 7.52 (dd, J = 8.4, 2.4 Hz, 1H), 7.44 (dd, J = 8.5, 1.9 Hz, 2H), 2.76-2.23 (m, 9H).
[0048] 6d, yellow solid, yield 89%, 1 HNMR (500 MHz, Chloroform-d) δ 9.01 (d, J = 1.6 Hz, 1H), 8.95 (d, J = 1.6 Hz, 1H), 8.91 (d, J = 2.0 Hz, 1H), 8.44 (d, J = 8.4 Hz, 1H), 8.24 (dd, J = 8.4, 1.5 Hz, 2H), 8.15 (dd, J = 8.4, 1.8 Hz, 1H), 8.12 (dd, J = 8.5, 1.4 Hz, 2H).
[0049] 6e, brown solid, yield 88%, 1HNMR (500 MHz, Chloroform-d) δ 9.09 (d, J = 2.5 Hz, 1H), 9.04 (d, J = 2.4 Hz, 1H), 8.42 (d, J = 8.4 Hz, 1H), 8.25 (d, J = 8.4 Hz, 1H), 8.21 (d, J = 1.9 Hz, 1H), 8.12 (d, J = 8.4 Hz, 1H), 7.90 (dd, J = 8.4, 2.4 Hz, 1H), 7.81 (dd, J = 8.4, 2.4 Hz, 1H), 7.75 (dd, J = 8.4, 1.8 Hz, 1H), 7.57 (ddd, J = 8.3, 2.5, 1.4 Hz, 6H), 7.41 (td, J = 7.7, 1.2 Hz, 6H), 7.36 - 7.29 (m, 3H).
[0050] (3) Synthesis of compounds 10b-10e:
[0051] To the synthesized compound 2b-2e (2 mmol) was added to a 100 mL tomato bottle, then 30 mL of dichloromethane was added, and it was completely dissolved, and then m-chloroperbenzoic acid (20 mmol) was slowly added to the tomato bottle, and the reaction was carried out at room temperature for 6-48 h. After the reaction was completed, saturated sodium bicarbonate and saturated sodium sulfite were added to quench the reaction, stirred for 20 min, concentrated under reduced pressure, and purified by column chromatography with dichloromethane, petroleum ether, ethyl acetate mixed solvent (DCM: PE: EA = 2:2:1, v / v / v) as eluent to obtain compounds 10b-10e.
[0052] 10b, yellow solid, yield 95%, 1 H NMR (500 MHz, Chloroform-d) δ 8.54 (d, J = 2.4 Hz, 1H), 8.41 (d, J = 2.4 Hz, 1H), 8.34 (d, J = 8.4 Hz, 1H), 8.18 (d, J = 2.1 Hz, 1H), 8.11 (d, J = 8.4 Hz, 1H), 7.86 (d, J = 8.4 Hz, 1H), 7.68 (dt, J = 8.4, 2.1 Hz, 2H), 7.60 (dd, J = 8.4, 1.8 Hz, 1H).
[0053] 10c, yellow solid, yield 93%, 1HNMR (500 MHz, Chloroform-d) δ 8.16-8.12 (m, 2H), 8.10 (d, J = 8.4 Hz, 1H), 8.05 (d, J = 2.4 Hz, 1H), 7.95 (d, J = 8.4 Hz, 1H), 7.87 (d, J = 1.8 Hz, 1H), 7.54 (dd, J = 8.4, 2.4 Hz, 1H), 7.47 (dd, J = 8.5, 1.9 Hz, 2H), 2.76-2.23 (m, 9H).
[0054] 10d, yellow solid, yield 88%, 1 H NMR (500 MHz, Chloroform-d) δ 9.01 (d, J = 1.6 Hz, 1H), 8.99 (d, J = 1.6 Hz, 1H), 8.94 (d, J = 2.0 Hz, 1H), 8.47 (d, J = 8.4 Hz, 1H), 8.28 (dd, J = 8.4, 1.5 Hz, 2H), 8.19 (dd, J = 8.4, 1.8 Hz, 1H), 8.14 (dd, J = 8.5, 1.4 Hz, 2H).
[0055] 10e, brown solid, yield 92%, 1 H NMR (500 MHz, Chloroform-d) δ 9.11 (d, J = 2.5 Hz, 1H), 9.07 (d, J = 2.4 Hz, 1H), 8.44 (d, J = 8.4 Hz, 1H), 8.29 (d, J = 8.4 Hz, 1H), 8.25 (d, J = 1.9 Hz, 1H), 8.14 (d, J = 8.4 Hz, 1H), 7.92 (dd, J = 8.4, 2.4 Hz, 1H), 7.85 (dd, J = 8.4, 2.4 Hz, 1H), 7.79 (dd, J = 8.4, 1.8 Hz, 1H), 7.59 (ddd, J = 8.3, 2.5, 1.4 Hz, 6H), 7.43 (td, J = 7.7, 1.2 Hz, 6H), 7.36 - 7.29 (m, 3H).
[0056] Example 3
[0057] An organic photocatalyst based on isothianaphthindene skeleton, its synthesis process and specific preparation method are as follows:
[0058]
[0059] (1) Synthesis of compounds 3a-3d:
[0060] The reactants 6-substituted benzothiophene 1 (30 mmol) and dichlorodicyanoquinone (30 mmol) were weighed into a 500 mL flask, then dichloromethane (50 mL) was added and it was completely dissolved. Then trifluoromethanesulfonic acid (90 mmol) was added dropwise to the flask under ice bath conditions, and stirred constantly during the dropwise addition. After the dropwise addition was completed, it was allowed to react at room temperature for 3-12 h. After the reaction was completed, methanol was added to quench, stirred for 30 min, concentrated under reduced pressure, and purified by column chromatography with dichloromethane and petroleum ether mixed solvent (DCM: PE = 1:8, v / v) as eluent to obtain compounds 3a-3d.
[0061] 3a, yellow solid, yield 45%, 1 H NMR (500 MHz, Chloroform-d) δ 8.21-8.12 (m, 3H), 7.74 (d, J = 1.9 Hz, 1H), 7.65 (dd, J = 8.9, 2.0 Hz, 2H), 7.15-7.03 (m, 3H), 3.83-3.81 (m, 9H).
[0062] 3b, yellow solid, yield 37%, 1 H NMR (500 MHz, Chloroform-d) δ 8.14-8.07 (m, 3H), 7.46 (d, J = 2.0 Hz, 1H), 7.38 (d, J = 2.0 Hz, 1H), 7.36 (d, J = 2.2 Hz, 1H), 6.99 (td, J = 8.2, 2.0 Hz, 2H), 6.94-6.91 (m, 2H), 6.61 (s, 2H).
[0063] 3c, yellow solid, yield 44%, 1 H NMR (500 MHz, Chloroform-d) δ 8.76 (d, J = 1.9 Hz, 1H), 8.72 (d, J = 2.3 Hz, 1H), 8.67 (d, J = 2.0 Hz, 1H), 8.45 (d, J = 8.4 Hz, 1H), 8.38 (dd, J = 8.4, 2.2 Hz, 2H), 8.01-7.93 (m, 3H), 2.61-2.60 (m, 9H).
[0064] 3d, yellow solid, yield 40%, 1H NMR (500 MHz, Chloroform-d) δ 10.08 (s, 1H), 10.04 (s, 2H), δ 8.71 (d, J = 2.1 Hz, 1H), 8.63 (d, J = 2.3 Hz, 1H), 8.61 (d, J = 2.1 Hz, 1H), 8.41 - 8.34 (m, 3H), 7.96 (dd, J = 8.4, 2.0 Hz, 2H), 7.87 (dd, J = 8.4, 2.0 Hz, 1H).
[0065] (2) Synthesis of compounds 7a-7d:
[0066] To the synthesized compounds 3a-3d (2 mmol) were added to 100 mL of a tomato-shaped bottle, then 30 mL of dichloromethane was added, and it was completely dissolved, and then hydrogen peroxide (10 mmol) was slowly added to the tomato-shaped bottle, and the reaction was carried out at room temperature for 6-48 h. After the reaction was completed, saturated sodium sulfite was added to quench the reaction, stirred for 20 min, concentrated under reduced pressure, and purified by column chromatography with dichloromethane, petroleum ether, and ethyl acetate mixed solvents (DCM: PE: EA = 2:2:1, v / v / v) as eluent to obtain compounds 7a-7d.
[0067] 7a, yellow solid, yield 89%, 1 H NMR (500 MHz, Chloroform-d) δ 8.42 (d, J = 8.5 Hz, 1H), 8.23 (d, J = 8.5 Hz, 1H), 8.01 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 1.8 Hz, 1H), 7.56 (dd, J = 8.6, 2.1 Hz, 2H), 7.37 - 7.15 (m, 3H), 3.81 (s, 6H), 3.81 (s, 3H).
[0068] 7b, yellow solid, yield 89%, 1 H NMR (500 MHz, Chloroform-d) δ 8.41 (d, J = 8.4 Hz, 1H), 8.21 (d, J = 8.4 Hz, 1H), 8.06 (d, J = 8.5 Hz, 1H), 7.93 (s, 1H), 7.81 (d, J = 8.4 Hz, 2H), 7.75 (d, J = 1.9 Hz, 1H), 7.52 (d, J = 1.8 Hz, 1H), 7.42 (d, J = 2.2 Hz, 1H), 7.23 - 7.17 (m, 3H).
[0069] 7c, yellow solid, yield 96%, 1H NMR (500 MHz, Chloroform-d) δ 9.01 (d, J = 1.8 Hz, 1H), 8.93 (d, J = 1.9 Hz, 1H), 8.85 (d, J = 2.2 Hz, 1H), 8.63 (d, J = 8.4 Hz, 1H), 8.45 (d, J = 8.5 Hz, 1H), 8.36 (dd, J = 8.4, 1.8 Hz, 2H), 8.34 (d, J = 8.4 Hz, 1H), 8.22 (dd, J = 8.4, 2.2 Hz, 1H), 2.56 (s, 6H), 2.54 (s, 3H).
[0070] 7d, yellow solid, yield 86%, 1 H NMR (500 MHz, Chloroform-d) δ 10.08 (s, 1H), 10.06 (s, 2H), 9.02 (d, J = 1.8 Hz, 1H), 8.78 (dd, J = 8.4, 2.2 Hz, 2H), 8.62 (d, J = 8.4 Hz, 1H), 8.41 (d, J = 8.4 Hz, 1H), 8.26 (d, J = 8.4 Hz, 1H), 8.21 - 8.14 (m, 2H), 8.04 (dd, J = 8.4, 2.0 Hz, 1H).
[0071] (3) Synthesis of compounds 11a-11d:
[0072] The synthesized compound 3a-3d (2 mmol) was added to a 100 mL tomato bottle, then 30 mL of dichloromethane was added, and it was completely dissolved, then m-chloroperbenzoic acid (20 mmol) was slowly added to the tomato bottle, and the reaction was carried out at room temperature for 6-48 h. After the reaction was completed, saturated sodium bicarbonate and saturated sodium sulfite were added to quench the reaction, stirred for 20 min, concentrated under reduced pressure, and purified by column chromatography with dichloromethane, petroleum ether, ethyl acetate mixed solvent (DCM: PE: EA = 2:2:1, v / v / v) as eluent to obtain compounds 11a-11d.
[0073] 11a, yellow solid, yield 85%, 1 H NMR (500 MHz, Chloroform-d) δ 8.45 (d, J = 8.5 Hz, 1H), 8.25 (d, J = 8.5 Hz, 1H), 8.02 (d, J = 8.5 Hz, 1H), 7.87 (d, J = 1.8 Hz, 1H), 7.60 (dd, J = 8.6, 2.1 Hz, 2H), 7.37 - 7.15 (m, 3H), 3.82 (s, 6H), 3.81 (s, 3H).
[0074] 11b, yellow solid, yield 87%, 1H NMR (500 MHz, Chloroform-d) δ 8.42 (d, J = 8.4 Hz, 1H), 8.24 (d, J = 8.4 Hz, 1H), 8.08 (d, J = 8.5 Hz, 1H), 7.93 (s, 1H), 7.82 (d, J = 8.4 Hz, 2H), 7.77 (d, J = 1.9 Hz, 1H), 7.52 (d, J = 1.8 Hz, 1H), 7.45 (d, J = 2.2 Hz, 1H), 7.23 - 7.17 (m, 3H).
[0075] 11c, yellow solid, yield 94%, 1 H NMR (500 MHz, Chloroform-d) δ 9.01 (d, J = 1.8 Hz, 1H), 8.95 (d, J = 1.9 Hz, 1H), 8.90 (d, J = 2.2 Hz, 1H), 8.66 (d, J = 8.4 Hz, 1H), 8.47 (d, J = 8.5 Hz, 1H), 8.40 (dd, J = 8.4, 1.8 Hz, 2H), 8.36 (d, J = 8.4 Hz, 1H), 8.24 (dd, J = 8.4, 2.2 Hz, 1H), 2.56 (s, 6H), 2.54 (s, 3H).
[0076] 11d, yellow solid, yield 90%, 1 H NMR (500 MHz, Chloroform-d) δ 10.08 (s, 1H), 10.06 (s, 2H), 9.02 (d, J = 1.8 Hz, 1H), 8.81 (dd, J = 8.4, 2.2 Hz, 2H), 8.65 (d, J = 8.4 Hz, 1H), 8.44 (d, J = 8.4 Hz, 1H), 8.29 (d, J = 8.4 Hz, 1H), 8.23 - 8.16 (m, 2H), 8.08 (dd, J = 8.4, 2.0 Hz, 1H).
[0077] Example 4
[0078] An organic photocatalyst based on isothianaphthindene skeleton, its synthesis process and specific preparation method are as follows:
[0079]
[0080] (1) Synthesis of compounds 4a-4b:
[0081] The reactants 5,6-substituted benzothiophene 1 (30 mmol) and dichlorodicyanoquinone (30 mmol) were weighed into a 500 mL flask, then dichloromethane (50 mL) was added, and the 5,6-substituted benzothiophene was completely dissolved. Then trifluoromethanesulfonic acid (90 mmol) was added dropwise into the flask under ice bath conditions, and stirred during the dropwise addition. After the dropwise addition was completed, it was placed at room temperature for 3-12 h of reaction. After the reaction was completed, methanol was added to quench, stirred for 30 min, concentrated under reduced pressure, and purified by column chromatography with dichloromethane and petroleum ether mixed solvent (DCM:PE = 1:8, v / v) as eluent to obtain compounds 4a-4b.
[0082] 4a, yellow solid, yield 30%, 1 H NMR (500 MHz, Chloroform-d) δ 8.78 (s, 1H), 8.75-8.73 (m, 2H), 8.66 (s, 1H), 8.61 (s, 1H), 8.56 (s, 1H).
[0083] 4b, yellow solid, yield 37%, 1 H NMR (500 MHz, Chloroform-d) δ 8.93 (s, 1H), 8.91 (d, J = 1.6 Hz, 2H), 8.81 (s, 1H), 8.71 (s, 1H), 8.64 (s, 1H), 3.90 (s, 12H), 3.88 (s, 6H).
[0084] (2) Synthesis of compounds 8a-8b
[0085] The synthesized compounds 4a-4b (2 mmol) were added to a 100 mL flask, then 30 mL of dichloromethane was added, and it was completely dissolved. Then hydrogen peroxide (10 mmol) was slowly added to the flask, and the reaction was carried out at room temperature for 6-48 h. After the reaction was completed, saturated sodium sulfite was added to quench the reaction, stirred for 20 min, concentrated under reduced pressure, and purified by column chromatography with dichloromethane, petroleum ether, ethyl acetate mixed solvent (DCM:PE:EA = 2:2:1, v / v / v) as eluent to obtain compounds 8a-8b.
[0086] 8a, yellow solid, yield 84%, 1 H NMR (500 MHz, Chloroform-d) δ 8.91 (s, 1H), 8.82 (s, 1H), 8.75-8.71 (m, 3H), 8.57 (s, 1H).
[0087] 8b, yellow solid, yield 89%, 1H NMR (500 MHz, Chloroform-d) δ 9.16 (s, 1H), 9.03 (s, 1H), 8.91 (s, 1H), 8.88 (s, 1H), 8.80 (d, J = 1.9 Hz, 2H), 3.90-3.88 (m, 18H).
[0088] (3) Synthesis of compounds 12a-12b
[0089] To the synthesized compound 4a-4b (2 mmol) was added to a 100 mL tomato bottle, then 30 mL of dichloromethane was added, and it was completely dissolved, and then m-chloroperbenzoic acid (20 mmol) was slowly added to the tomato bottle, and the reaction was carried out at room temperature for 6-48 h. After the reaction was completed, saturated sodium bicarbonate and saturated sodium sulfite were added to quench the reaction, stirred for 20 min, concentrated under reduced pressure, and purified by column chromatography with dichloromethane, petroleum ether, ethyl acetate mixed solvent (DCM: PE: EA = 2:2:1, v / v / v) as eluent to obtain compounds 12a-12b.
[0090] 12a, yellow solid, yield 80%, 1 H NMR (500 MHz, Chloroform-d) δ 8.94 (s, 1H), 8.84 (s, 1H), 8.78-8.73 (m, 3H), 8.60 (s, 1H).
[0091] 12b, yellow solid, yield 87%, 1 H NMR (500 MHz, Chloroform-d) δ 9.20 (s, 1H), 9.07 (s, 1H), 8.93 (s, 1H), 8.90 (s, 1H), 8.83 (d, J = 1.9 Hz, 2H), 3.90-3.88 (m, 18H).
[0092] Example 5
[0093] An organic photocatalyst based on an isothianaphthindene skeleton, its synthesis process and specific preparation method are as follows:
[0094]
[0095] (1) Synthesis of compounds 5a-5d:
[0096] The reactants 5 / 6-substituted benzothiophene 1 (10 mmol) and 5 / 6-substituted indantrione 2 (5 mmol) were weighed into a 250 mL tomato flask, then 120 mL of glacial acetic acid (98%) was added, and finally 0.4 mL of concentrated sulfuric acid (98%) was slowly added dropwise. After the dropwise addition was completed, the reaction was refluxed at 90°C for 3-12 h. After the reaction was completed, it was cooled to room temperature, filtered, washed with water, dichloromethane, methanol, acetone, and then placed in a vacuum drying oven at 60°C overnight to obtain compounds 5a-5d.
[0097] 5a, red solid, yield 45%, 1 HNMR (500 MHz, Chloroform-d) δ 8.71-8.68 (m, 1H), 8.33 (dd, J = 7.7, 1.2 Hz, 1H), 8.28 (dd, J = 7.9, 1.2 Hz, 1H), 8.01 (ddd, J = 8.0, 6.4, 1.5 Hz, 2H), 7.89 (dd, J = 7.8, 1.7 Hz, 1H), 7.66 (td, J = 7.7, 1.6 Hz, 1H), 7.54 (tdd, J = 7.7, 4.1, 1.5 Hz, 2H), 7.49 (td, J = 7.6, 1.3 Hz, 1H), 7.28 (ddt, J = 7.7, 1.9, 1.2 Hz, 2H).
[0098] 5b, red solid, yield 37%, 1H NMR (500 MHz, Chloroform-d) δ 8.78 (d, J = 2.7 Hz, 1H), 8.58 (d, J = 1.7 Hz, 1H), 8.27 (dd, J = 7.8, 1.4 Hz, 1H), 8.02 (dd, J = 8.4, 6.0 Hz, 2H), 7.91 (dd, J = 7.8, 1.7 Hz, 1H), 7.66 (td, J = 7.7, 1.7 Hz, 1H), 7.50-7.43 (m, 3H).
[0099] 5c, red solid, yield 44%, 1 HNMR (500 MHz, Chloroform-d) δ 8.19 (dd, J = 10.1, 8.4 Hz, 2H), 8.14 (d, J = 2.7 Hz, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.93 (d, J = 2.0 Hz, 1H), 7.80 (d, J = 2.7 Hz, 1H), 7.15 (dd, J = 8.4, 2.7 Hz, 1H), 7.08 (dd, J = 8.4, 2.4 Hz, 2H), 3.86-3.80 (m, 9H).
[0100] 5d, red solid, yield 40%, 1H NMR (500 MHz, Chloroform-d) δ 8.42 (dd, J = 8.5, 2.0 Hz, 1H), 8.24 (dd, J = 8.4, 2.0 Hz, 1H), 8.10 (dd, J = 8.4, 1.9 Hz, 1H), 7.90-7.82 (m, 3H), 7.44 (td, J = 8.3, 1.9 Hz, 1H), 7.31 (dd, J = 8.3, 2.1 Hz, 2H).
[0101] (2) Synthesis of compounds 9a-9d
[0102] To the synthesized compound 5a-5b (2 mmol) was added to a 100 mL tomato bottle, then 30 mL of dichloromethane was added, and then hydrogen peroxide (8 mmol) was slowly added to the tomato bottle, and the reaction was carried out at room temperature for 6-48 h. After the reaction was completed, saturated sodium sulfite was added to quench the reaction, and after stirring for 20 min, it was filtered, washed with water, dichloromethane, methanol, acetone, and then placed in a vacuum drying oven at 60°C overnight to obtain compounds 9a-9d.
[0103] 9a, red solid, yield 88%, 1 H NMR (500 MHz, Chloroform-d) δ 8.42 (dd, J = 8.5, 2.0 Hz, 1H), 8.24 (dd, J = 8.4, 2.0 Hz, 1H), 8.10 (dd, J = 8.4, 1.9 Hz, 1H), 7.90-7.82 (m, 3H), 7.44 (td, J = 8.3, 1.9 Hz, 1H), 7.31 (dd, J = 8.3, 2.1 Hz, 2H).
[0104] 9b, red solid, yield 89%, 1 H NMR (500 MHz, Chloroform-d) δ 8.42 (dd, J = 8.5, 2.0 Hz, 1H), 8.24 (dd, J = 8.4, 2.0 Hz, 1H), 8.10 (dd, J = 8.4, 1.9 Hz, 1H), 7.90-7.82 (m, 3H), 7.44 (td, J = 8.3, 1.9 Hz, 1H), 7.31 (dd, J = 8.3, 2.1 Hz, 2H).
[0105] 9c, red solid, yield 86%, 1H NMR (500 MHz, Chloroform-d) δ 8.14 (d, J = 8.4 Hz, 1H), 8.05 (d, J = 2.7 Hz, 1H), 8.01 (dd, J = 8.4, 2.3 Hz, 2H), 7.88 (d, J = 2.7 Hz, 1H), 7.66 (d, J = 2.1 Hz, 1H), 7.23 (dd, J = 8.4, 2.7 Hz, 1H), 7.18 - 7.12 (m, 2H), 3.86 - 3.83 (m, 9H).
[0106] 9d, red solid, yield 95%, 1 H NMR (500 MHz, Chloroform-d) δ 8.47 (dd, J = 8.4, 5.0 Hz, 1H), 8.16 (dd, J = 8.4, 5.0 Hz, 1H), 8.11 (dd, J = 8.4, 5.0 Hz, 1H), 7.94 (dd, J = 7.9, 1.9 Hz, 1H), 7.83 (ddd, J = 8.2, 8.0, 2.0 Hz, 2H), 7.44 (dd, J = 8.3, 1.9 Hz, 2H), 7.38 (td, J = 8.3, 2.2 Hz, 1H).
[0107] (3) Synthesis of compounds 13a-13d
[0108] To the synthesized compound 5a-5b (2 mmol) was added to a 100 mL tomato bottle, then 30 mL of dichloromethane was added, and then m-chloroperbenzoic acid (15 mmol) was slowly added to the tomato bottle, and the reaction was carried out at room temperature for 6-48 h. After the reaction was completed, saturated sodium bicarbonate and saturated sodium sulfite were added to quench the reaction, and after stirring for 20 min, filtration was performed, and then washing was performed with water, dichloromethane, methanol, and acetone, and then drying was performed in a vacuum drying oven at 60°C overnight to obtain compounds 13a-13d.
[0109] 13a, red solid, yield 85%, 1 H NMR (500 MHz, Chloroform-d) δ 8.51 (dd, J = 7.7, 1.5 Hz, 1H), 8.30 (dd, J = 7.9, 1.2 Hz, 1H), 8.18 - 8.14 (m, 1H), 8.04 (ddd, J = 7.5, 2.6, 1.6 Hz, 2H), 7.91 (dd, J = 7.9, 1.6 Hz, 1H), 7.66 (dd, J = 7.7, 1.6 Hz, 1H), 7.56 - 7.47 (m, 5H).
[0110] 13b, red solid, yield 87%, 1H NMR (500 MHz, Chloroform-d) δ 8.70 (d, J = 2.4 Hz, 1H), 8.35 (dd, J = 7.9, 1.3 Hz, 1H), 8.32 (d, J = 1.9 Hz, 1H), 8.13 (d, J = 8.4 Hz, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.90 (dd, J = 7.8, 1.7 Hz, 1H), 7.83 (dd, J = 8.4, 2.6 Hz, 1H), 7.77 (dd, J = 8.4, 2.0 Hz, 1H), 7.67 (td, J = 7.7, 1.7 Hz, 1H), 7.50 (td, J = 7.6, 1.3 Hz, 1H).
[0111] 13c, red solid, yield 84%, 1 H NMR (500 MHz, Chloroform-d) δ 8.16 (d, J = 8.4 Hz, 1H), 8.09 (d, J = 2.7 Hz, 1H), 8.02 (dd, J = 8.4, 2.3 Hz, 2H), 7.91 (d, J = 2.7 Hz, 1H), 7.69 (d, J = 2.1 Hz, 1H), 7.25 (dd, J = 8.4, 2.7 Hz, 1H), 7.18 - 7.12 (m, 2H), 3.86 - 3.83 (m, 9H).
[0112] 13d, red solid, yield 90%, 1 H NMR (500 MHz, Chloroform-d) δ 8.51 (dd, J = 8.4, 5.0 Hz, 1H), 8.18 (dd, J = 8.4, 5.0 Hz, 1H), 8.13 (dd, J = 8.4, 5.0 Hz, 1H), 7.97 (dd, J = 7.9, 1.9 Hz, 1H), 7.86 (ddd, J = 8.2, 8.0, 2.0 Hz, 2H), 7.46 (dd, J = 8.3, 1.9 Hz, 2H), 7.41 (td, J = 8.3, 2.2 Hz, 1H).
[0113] Application Example 1: Visible light catalyzed carbonyl reductive coupling reaction
[0114]
[0115] The different isothiatriphenylene compounds prepared by the examples were used as photocatalysts (5 mol%) with phenylacetone (0.1 mmol), DIPEA (0.3 mmol), methanol (1 mL) added to a 10 mL sealed tube, after three freeze-thaw cycles degassing, stirring under 427 nm Kessil lamp irradiation for 36 h, the reaction was monitored by thin layer chromatography, after the reaction was completed, triphenylmethane (0.1 mmol) was added, the yield was calculated by crude nuclear magnetic resonance of the reaction mixture, and the results are shown in Table 1.
[0116] Table 1
[0117]
[0118]
[0119]
[0120] As can be seen from Table 1, the different isothiatriphenylene compounds obtained were used as organic photocatalysts, and the reaction proceeded smoothly, with a yield of 15-95%.
[0121] Application Example 2: Visible light catalytic oxidation of alkynes
[0122]
[0123] The different isothiatriphenylene compounds prepared by the examples were used as photocatalysts (5 mol%) with diphenylacetylene (0.1 mmol), LiNO3 (0.2 mmol), acetonitrile (1 mL) added to a 10 mL reaction tube, a balloon filled with oxygen was installed on the mouth of the reaction tube, stirring under 427 nm Kessil lamp irradiation for 36 h, the reaction was monitored by thin layer chromatography, after the reaction was completed, triphenylmethane (0.1 mmol) was added, the yield was calculated by crude nuclear magnetic resonance of the reaction mixture, and the results are shown in Table 2.
[0124] Table 2
[0125]
[0126]
[0127]
[0128] As can be seen from Table 2, the different compounds obtained were used as organic photocatalysts, with a yield of 12-94%.
[0129] Application Example 3: Visible light catalytic decarboxylative fluorination
[0130]
[0131] The different isothiatriphenylene compounds prepared in the examples were used as photocatalysts (5 mol%) with 2,2-diphenylacetic acid (0.1 mmol), Selectfluor (0.2 mmol), Cs2CO3(0.1 mmol), MeCN (0.5 mL) and H2O (0.5 mL) added to a 10 mL sealed tube, which was stirred under irradiation of a 427 nm Kessil lamp for 36 h, the reaction was monitored by thin layer chromatography, after the reaction was completed, triphenylmethane (0.1 mmol) was added to the reaction mixture, the yield was calculated by crude NMR, the results are shown in Table 3.
[0132] Table 3
[0133]
[0134]
[0135]
[0136] As can be seen from Table 3, the yield of the different compounds obtained as organic photocatalysts is between 14 and 89%.
[0137] Application Example 4: Visible light catalysis of toluene oxidation
[0138]
[0139] The different isothiatriphenylene compounds prepared in the examples were used as photocatalysts (5 mol%) with toluene (0.1 mmol), HCl (0.3 mmol), acetonitrile (0.5 mL) and H2O (0.5 mL) added to a 10 mL sealed tube, a balloon filled with oxygen was installed on the mouth of the reaction tube, which was stirred under irradiation of a 427 nm Kessil lamp for 36 h, the reaction was monitored by thin layer chromatography, after the reaction was completed, triphenylmethane (0.1 mmol) was added to the reaction mixture, the yield was calculated by crude NMR, the results are shown in Table 4.
[0140] Table 4
[0141]
[0142]
[0143]
[0144] As can be seen from Table 4, the yield of the different compounds obtained as organic photocatalysts is between 15 and 92%.
[0145] Application Example 5: Visible light catalyzed amination of unactivated olefins with heteroaryl groups
[0146]
[0147] The different isothiatriphenylene compounds prepared in the examples were used as photocatalysts (5 mol%) with heteroaryl substituted tertiary alcohols (0.1 mmol), N-protected 1-aminopyridine salts (0.3 mmol), dichloromethane (1 mL) were added to a 10 mL sealed tube, after three freeze-thaw cycles degassing, under 427 nm Kessil lamp irradiation stirring for 36 h, the reaction was monitored by thin layer chromatography, after the reaction was completed, triphenylmethane (0.1 mmol) was added to it, the nuclear magnetic yield was calculated by crude nuclear magnetic resonance of the reaction mixture, the results are shown in Table 5.
[0148] Table 5
[0149]
[0150]
[0151]
[0152] As can be seen from Table 5, the yield of different compounds obtained as organic photocatalysts is between 14-87%.
[0153] Application Example 6: Visible light catalyzed reductive decarboxylation of N-heteroaryl ketones
[0154]
[0155] The different isothiatriphenylene compounds prepared in the examples were used as photocatalysts (5 mol%) with (4-methyl-2-quinolinyl)(phenyl)methanone (0.1 mmol), LiBr (0.05 mmol), acetonitrile (1 mL), trifluoromethanesulfonic acid (0.1 mmol), benzaldehyde (0.2 mmol) were added to a 10 mL sealed tube, after three freeze-thaw cycles degassing, under 427 nm Kessil lamp irradiation stirring for 36 h, the reaction was monitored by thin layer chromatography, after the reaction was completed, triphenylmethane (0.1 mmol) was added to it, the nuclear magnetic yield was calculated by crude nuclear magnetic resonance of the reaction mixture, the results are shown in Table 6.
[0156] Table 6
[0157]
[0158]
[0159]
[0160] As can be seen from Table 6, the yield of the different compounds obtained as organic photocatalysts is between 14-95%.
[0161] Application Example 7: Visible light catalyzed styrene hydroformylation
[0162]
[0163] The different isothiatriphenylene compounds prepared in the examples were used as photocatalysts (5 mol%) with p-trifluoromethylstyrene (0.1 mmol), 2,2-diethoxyacetic acid (0.3 mmol), cesium carbonate (0.05 mmol), acetonitrile (1 mL) added to a 10 mL sealed tube, after three freeze-thaw cycles degassing, stirring under 427 nm Kessil lamp irradiation for 48 h, the reaction was monitored by thin layer chromatography, after the reaction was completed, HCl (0.3 mmol) was added, stirring was continued for 30 min, then triphenylmethane (0.1 mmol) was added, the yield was calculated by crude NMR, the results are shown in Table 7.
[0164] Table 7
[0165]
[0166]
[0167]
[0168] As can be seen from Table 7, the yield of the different compounds obtained as organic photocatalysts is between 14-92%.
[0169] Application Example 8: Visible light catalyzed styrene alkoxyacylation reaction
[0170]
[0171] The different isothiatriphenylene compounds prepared in the examples were used as photocatalysts (5 mol%) with styrene (0.1 mmol), benzoyl chloride (0.3 mmol), cesium carbonate (0.4 mmol), methanol (1 mL) added to a 10 mL sealed tube, after three freeze-thaw cycles degassing, stirring under 427 nm Kessil lamp irradiation for 36 h, the reaction was monitored by thin layer chromatography, after the reaction was completed, triphenylmethane (0.1 mmol) was added, the yield was calculated by crude NMR, the results are shown in Table 8.
[0172] Table 8
[0173]
[0174]
[0175]
[0176] As can be seen from Table 8, the yield of different compounds obtained as organic photocatalysts is between 15-95%.
[0177] Application Example 9: Visible light catalytic reduction dehalogenation reaction of halogenated aromatic hydrocarbons
[0178]
[0179] The different isothiatriphenylene compounds prepared in the examples were used as photocatalysts (5 mol%) and 4-bromobenzonitrile (0.1 mmol), DIPEA (0.1 mmol), methanol (1 mL) were added to a 10 mL sealed tube, after three freeze-thaw cycles degassing, under the irradiation of a 427 nm Kessil lamp for 36 h, the reaction was monitored by thin layer chromatography, after the reaction was completed, triphenylmethane (0.1 mmol) was added, the yield was calculated by crude NMR, and the results are shown in Table 9.
[0180] Table 9
[0181]
[0182]
[0183]
[0184] As can be seen from Table 9, the yield of different compounds obtained as organic photocatalysts is between 17-91%.
[0185] In summary, among the organic photocatalysts based on isothiatriphenylene skeleton, the photocatalysts with sulfoxide hetero-isotriphenylene skeleton show strong oxidation performance, the isothiatriphenylene photocatalysts show strong reduction performance, and the photocatalysts with sulfoxide hetero-isotriphenylene skeleton show oxidation and reduction performance between the two.
[0186] The above is merely an example and description of the present application, and those skilled in the art can make modifications or supplements to the described specific embodiments or adopt similar ways to replace without creative labor, which is still within the protection scope of the present patent.
Claims
1. An organic photocatalyst based on an isothiazolidinium trimeric framework, characterized in that, The general structural formula of the organic photocatalyst is shown below: ， Wherein, R1 is S, SO, or SO2; R2 is S, SO, SO2, or C=O; and R3 and R4 are H, halogens, or substituted or unsubstituted Cl-C atoms. 30 Alkyl, substituted or unsubstituted C3-C 30 alkenyl, substituted or unsubstituted C3-C 30 Alkyne, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C3-C 12 cycloalkyl, substituted or unsubstituted C1-C 10 Heterocyclic alkyl, substituted or unsubstituted C3-C 12 Cycloalkenyl, substituted or unsubstituted C1-C 10 Heterocyclic alkenyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C1-C 30 Heteroaryl, acyl, or ester group; R5 and R6 are H, halogen, substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C3-C 30 alkenyl, substituted or unsubstituted C3-C 30 Alkyne, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C3-C 12 cycloalkyl, substituted or unsubstituted C1-C 10 Heterocyclic alkyl, substituted or unsubstituted C3-C 12 Cycloalkenyl, substituted or unsubstituted C1-C 10 Heterocyclic alkenyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C1-C 30 heteroaryl, acyl, or ester group.
2. The organic photocatalyst based on the isothiazotriazine framework as described in claim 1, characterized in that, The specific structural formula of the organic photocatalyst includes: ， ， 。 3. The method for preparing the organic photocatalyst based on the isothiazotriazine framework as described in claim 1, characterized in that: Using substituted or unsubstituted benzothiophene as a raw material, it and dichlorocyanobenzoquinone are added to dichloromethane solvent to completely dissolve the benzothiophene. Then, trifluoromethanesulfonic acid is added dropwise under ice bath conditions with continuous stirring during the addition. The mixture is stirred at room temperature for 3-12 hours to obtain an organic photocatalyst based on the isothiazolyl indene framework. The obtained catalyst is then dissolved in dichloromethane, followed by the addition of hydrogen peroxide or m-chloroperoxybenzoic acid. The mixture is stirred at room temperature for 6-48 hours to obtain an organic photocatalyst based on the sulfoxide or sulfone isothiazolyl indene framework.
4. The method for preparing the organic photocatalyst based on the isothiazotriazine framework as described in claim 1, characterized in that: Using substituted or unsubstituted benzothiophene and substituted or unsubstituted ninhydrin as raw materials, they were added to a reaction vessel, followed by the addition of acetic acid solution, and finally the slow addition of concentrated sulfuric acid. After the addition was complete, the mixture was refluxed at 90°C for 3-12 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed sequentially with water, dichloromethane, methanol, and acetone. Then, it was dried overnight in a vacuum drying oven at 60°C to obtain an organic photocatalyst based on an isothiazolyl indene framework. The obtained catalyst was then dissolved in dichloromethane, followed by the addition of hydrogen peroxide or m-chloroperoxybenzoic acid. The mixture was stirred at room temperature for 6-48 hours to obtain an organic photocatalyst based on a sulfoxide or sulfone isothiazolyl indene framework.
5. The application of an organic photocatalyst based on an isothiazolidinium framework as described in claim 1 in visible light-catalyzed organic reactions.
6. The application according to claim 5, characterized in that: The visible light catalytic organic reactions include: carbonyl reduction coupling, alkyne oxidation, decarboxylation and fluorination, toluene oxidation, aminoheteroarylation of non-activated alkenes, reductive deoxygenation of N-heteroaryl carbonyl compounds, styrene hydroformylation, styrene alkoxylation, and dehalogenation and hydrogenation of halogenated aromatics.