阅读说明：本技术 一种硫代磺酸酯化合物的制备方法 (Preparation method of thiosulfonate compound ) 是由 吕玉芬 魏伟 岳会兰 何林 于 2020-12-29 设计创作，主要内容包括：本发明属于有机合成化学领域,具体公开了一种硫代磺酸酯化合物的制备方法。具体制备过程为：以芳基重氮盐,焦亚硫酸钠和硫酚/硫醇为原料,有机染料为光催化剂,加入有机溶剂,LED可见光灯照射下,氮气保护,室温反应12小时即可生成硫代磺酸酯。反应完毕后,往反应体系中加入蒸馏水,然后用乙酸乙酯萃取反应液,浓缩萃取液得粗产物,粗产物经硅胶柱层析分离得到硫代磺酸酯。本发明所述方法采用简单易得的焦亚硫酸钠为砜源,便宜的有机染料为光催化剂和清洁的光能为反应能源,避免了使用高能耗的加热装置及金属催化剂或强酸,反应条件温和,操作简便,为硫代磺酸酯提供了一种绿色的合成策略。(The invention belongs to the field of organic synthetic chemistry, and particularly discloses a preparation method of a thiosulfonate compound. The preparation process comprises the following steps: aryl diazonium salt, sodium pyrosulfite and thiophenol/mercaptan are used as raw materials, organic dye is used as a photocatalyst, an organic solvent is added, and the raw materials react for 12 hours at room temperature under the protection of nitrogen under the irradiation of an LED visible light lamp to generate the thiosulfonate. And after the reaction is finished, adding distilled water into the reaction system, extracting the reaction solution by using ethyl acetate, concentrating the extract liquor to obtain a crude product, and carrying out chromatographic separation on the crude product by using a silica gel column to obtain the thiosulfonate. The method adopts simple and easily obtained sodium metabisulfite as a sulfone source, cheap organic dye as a photocatalyst and clean light energy as reaction energy, avoids using a heating device with high energy consumption and a metal catalyst or strong acid, has mild reaction conditions and simple and convenient operation, and provides a green synthesis strategy for thiosulfonate.)

1. A preparation method of a thiosulfonate compound is characterized in that a compound aryl diazonium salt shown in a structural formula I, a compound sodium pyrosulfite shown in a structural formula II, a compound thiophenol/mercaptan shown in a structural formula III and a catalyst are mixed, then an organic solvent is added and fully mixed, under the irradiation of an LED visible light lamp, nitrogen protection is carried out, the reaction is carried out for 12 hours at room temperature, after the monitoring reaction of a thin-layer chromatographic plate is finished, distilled water is added, then ethyl acetate is used for extraction, the extract liquid is subjected to reduced pressure concentration treatment to obtain a crude product, and the crude product is subjected to column chromatography separation and purification to obtain the thiosulfonate shown in a general formula IV;

R¹is optionally substituted alkoxy, alkyl, halogen, nitro, acyl, cyano or aryl; r²Is optionally substituted 1-8 carbon alkyl, benzyl, cycloalkyl, aryl or heteroaryl.

2. The method according to claim 1, wherein the photocatalyst is acridine red, rhodamine B, rhodamine 6G, 2,4,5, 6-tetrakis (9-carbazolyl) -isophthalonitrile, water-soluble eosin, 9-fluorenone, methylene blue, eosin B, alcohol-soluble eosin, or rose bengal B.

3. The preparation method according to claim 1 or 2, wherein the molar ratio of the compound of formula I, the compound of formula II and the compound of formula III is 4:4: 1-1: 1: 1.

4. The method according to any one of claims 1 to 3, wherein the molar ratio of the compound of formula III to the photocatalyst is 1:0.01 to 1: 0.1.

5. The method according to claim 1, wherein the organic solvent is ethyl acetate, 1, 4-dioxane, toluene, benzene, acetonitrile, tetrahydrofuran, 1, 2-dichloroethane, chloroform, dichloromethane, dimethyl sulfoxide, ethanol, methanol, or propanol.

6. The method for preparing a LED lamp according to claim 1, wherein the visible light lamp light source is a blue LED lamp with power of 3w-50w, a white LED lamp with power of 3w-50w, or a green LED lamp with power of 3w-50 w.

7. The method of claim 1, wherein the reaction is carried out under nitrogen and the reaction is carried out at 25 ℃.

8. The method of claim 1, wherein the purifying step is: after the reaction is finished, adding distilled water, extracting the reaction solution by ethyl acetate, and carrying out reduced pressure concentration treatment on the extract under the pressure of 0.07-0.10Mpa to obtain a crude product without containing an organic solvent; and (3) performing column chromatography treatment on the crude product through a silica gel column, washing the crude product by using an eluent of petroleum ether and ethyl acetate according to the volume ratio of 5:1, and collecting the product to obtain the thiosulfonic acid ester shown in the general formula IV.

Technical Field

The invention belongs to the field of organic synthetic chemistry, and particularly relates to a preparation method of a photocatalytic thiosulfonate compound.

Background

The thiosulfonic acid ester has important application value in the field of medicine as an organic sulfide with great value. The compound containing the thiosulfonate structural unit has wide biological activity, such as insecticidal activity, antisepsis activity, antibacterial activity, antipyretic activity, anti-inflammatory activity, analgesic activity, hypoglycemic activity and the like. Therefore, the synthesis method of the thiosulfonate compound draws great attention of chemical researchers, and various synthesis strategies are developed by synthetic chemists. As shown in the reaction formula 1, the synthesis method mainly comprises the following steps: strategy (1) symmetric thiosulfonates were obtained by oxidation of symmetric disulfides; strategy (2) obtaining symmetric thiosulfonate by oxidizing mercaptan in one step; strategy (3) sulfurization of sulfinates with compounds containing-SR groups to prepare symmetrical and asymmetrical thiosulfonates; strategy (4) the substitution reaction of sodium (potassium) thiosulfonate and alkyl halohydrocarbon to obtain symmetrical or asymmetrical thiosulfonate; strategy (5) decomposing sulfonyl hydrazide or sulfonyl hydrazide and thiol for condensation reaction to obtain thiosulfonate; strategy (6) reduction of sulfonyl chloride gives a symmetrical thiosulfonate.

Most of these strategies have some limitations: (1) the synthesis of asymmetric thiosulfonates requires metal catalysis conditions; (2) the application range of the substrate is narrow; (3) the oxidation reaction needs to use equivalent inorganic oxidant, and the waste causes pollution to the environment; (4) the system is complex, the byproducts are many, and the post-treatment is not facilitated.

The aryl diazonium salt is widely applied in the field of organic synthesis due to the characteristics of low price, easy obtaining, high reaction activity and the like. Recently, two synthetic methods have been developed for the reaction of arylating reagents, a "sulfur dioxide" source and thiophenol, to construct thiosulfonates. The method 1 comprises the following steps: the Yang group developed in 2019 as a strategy for the construction of thiosulfonates (adv. synth. cat., 2019,361, 1808-substituted 1814) using a three-component reaction of 1 equivalent of trifluoroacetic acid mediated aryl diazonium salt, 1, 4-diazabicyclo [2.2.2] octane-1, 4-diimmonium-1, 4-Disulfinic Acid (DABSO) and thiol (equation 2).

The method 2 comprises the following steps: ji and Wang subject group reported in 2020 using 1 equivalent trifluoroacetic acid mediated aryl diazonium salt, sodium metabisulfite (Na)₂S₂O₅) And thiophenol three-component reaction strategy for the construction of thiosulfonates (Chinese Chemical Letters 2020,31, 1923-1926) (equation 3). The method ingeniously uses the cheap sodium pyrosulfite to replace the 1, 4-diazabicyclo [2.2.2]Octane-1, 4-diimmonium-1, 4-disulfonic acid as a sulfone source to construct a thiosulfonate.

However, both methods require the use of a large amount of trifluoroacetic acid and heating conditions, and are highly corrosive to reaction equipment and generate high energy consumption in actual production. Therefore, there is still a need to develop a mild, green aryl diazonium salt to participate in a multi-component reaction to construct thiosulfonates.

Disclosure of Invention

In order to break through the limitation of the existing synthesis technology, the invention aims to provide a method for constructing thiosulfonate on the basis of a visible light technology by using simple and easily-obtained aryl diazonium salt, sodium metabisulfite and thiophenol as raw materials and using an organic dye as a photocatalyst under mild conditions.

In order to achieve the purpose, the invention adopts the technical scheme that:

(1) adding a compound aryl diazonium salt shown in a structural formula I, a compound sodium pyrosulfite shown in a structural formula II, a compound thiophenol/mercaptan shown in a structural formula III and an organic photocatalyst into a reaction bottle, then adding an organic solvent for fully mixing, placing the reaction bottle into a reactor, and reacting at room temperature under the irradiation of an LED visible light lamp and under the protection of nitrogen;

(2) after the thin-layer chromatography plate monitoring reaction is finished, adding distilled water, extracting with ethyl acetate, carrying out reduced pressure concentration treatment on the extract liquid to obtain a crude product, and finally carrying out column chromatography separation and purification on the crude product to obtain the thiosulfonate shown in the general formula IV;

in the general formula I, R¹Is optionally substituted alkoxy, alkyl, halogen, nitro, acyl, cyano or aryl, etc.; in the general formula II, R²Is optionally substituted 1-8 carbon alkyl, benzyl, cycloalkyl, aryl or heteroaryl, etc.

Further, the reaction in the step (1) is carried out in the air at room temperature of 25 ℃ for 12 hours.

Further, the purification step in the step (2) is: after the reaction is finished, adding distilled water, extracting the reaction solution by ethyl acetate, and carrying out reduced pressure concentration treatment on the extract under the pressure of 0.07-0.10Mpa to obtain a crude product without containing an organic solvent; and (3) performing column chromatography treatment on the crude product through a silica gel column, washing the crude product by using an eluent of petroleum ether and ethyl acetate according to the volume ratio of 5:1, and collecting the product to obtain the thiosulfonic acid ester shown in the general formula IV.

Further, the organic photocatalyst is acridine red, rhodamine B, rhodamine 6G, 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile, water-soluble eosin, 9-fluorenone, methylene blue, eosin B, alcohol-soluble eosin or rose bengal B; preferably, the rhodamine 6G.

Further, the molar ratio of the compound of formula III to the photocatalyst is: 1: 0.01-1: 0.1; preferably: 1:0.01.

Further, the organic solvent is 1, 4-dioxane, toluene, benzene, acetonitrile, tetrahydrofuran, 1, 2-dichloroethane, chloroform, ethyl acetate, dichloromethane, dimethyl sulfoxide, methanol, ethanol or propanol; preferably, acetonitrile.

Further, the visible light LED lamp light source is a white LED lamp with power of 3W-50W, a green LED lamp with power of 3W-50W or a blue LED lamp with power of 3W-50W. A white LED lamp with a power of 3W is preferred.

The invention has the advantages of

1. The method has the advantages of simple and easily obtained raw materials and simple and convenient reaction operation.

2. The method uses clean visible light as reaction energy, and the reaction is carried out at room temperature, so that the energy consumption is low.

3. The method uses cheap non-metal organic dye as the photocatalyst, avoids the use of metal and strong acid reagent, has less waste and is environment-friendly.

Detailed Description

The invention is further illustrated by the following specific examples, it being understood that the preparation of the examples is illustrative only and is not intended to be limiting; on the premise of the conception of the invention, simple modification of the preparation method of the invention belongs to the protection scope of the invention.

It should also be noted that various preferred features of the method of the present invention mentioned above and various specific features in the embodiments specifically described below may be combined, and all combinations of these features, all numerical ranges bounded by upper and lower numerical values specifically disclosed herein, and the like, fall within the scope of the present invention.

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.

The materials and reagents used in the following examples are commercially available or synthesized from commercially available starting materials, unless otherwise specified.

Specific examples of the present invention will be described in detail below with reference to the technical solutions, but the process conditions are not limited to these examples.

Example 1

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4aa of the embodiment with the yield of 75%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.58-7.56(m,3H),7.42(dd,2H,J＝7.9,7.8Hz),7.23(d,2H,J＝8.1Hz),7.13(d,2H,J＝8.0Hz),2.37(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ143.1,142.2,136.5,133.6,130.23,128.78,127.6,124.34,21.5。

example 2

At room temperature, photocatalyst water-soluble eosin (0.002mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4aa of the embodiment with the yield of 56%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.58-7.56(m,3H),7.42(dd,2H,J＝7.9,7.8Hz),7.23(d,2H,J＝8.1Hz),7.13(d,2H,J＝8.0Hz),2.37(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ143.1,142.2,136.5,133.6,130.23,128.78,127.6,124.34,21.5。

example 3

At room temperature, the photocatalyst rose bengal B (0.002mmol), the aryl diazonium salt 1a (0.4mmol), the sodium metabisulfite 2(0.4mmol), the p-toluene thiophenol 3a (0.2mmol) and the acetonitrile are added in sequence into a 20mL reaction tube and mixed uniformly. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4aa of the embodiment with the yield of 70%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.58-7.56(m,3H),7.42(dd,2H,J＝7.9,7.8Hz),7.23(d,2H,J＝8.1Hz),7.13(d,2H,J＝8.0Hz),2.37(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ143.1,142.2,136.5,133.6,130.23,128.78,127.6,124.34,21.5。

example 4

Photocatalyst 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile (0.002mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.2mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube at room temperature and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4aa of the embodiment with the yield of 38%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.58-7.56(m,3H),7.42(dd,2H,J＝7.9,7.8Hz),7.23(d,2H,J＝8.1Hz),7.13(d,2H,J＝8.0Hz),2.37(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ143.1,142.2,136.5,133.6,130.23,128.78,127.6,124.34,21.5。

example 5

At room temperature, photocatalyst yellow B (0.002mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are added in sequence into a 20mL reaction tube and mixed uniformly. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4aa of the embodiment with the yield of 58%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.58-7.56(m,3H),7.42(dd,2H,J＝7.9,7.8Hz),7.23(d,2H,J＝8.1Hz),7.13(d,2H,J＝8.0Hz),2.37(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ143.1,142.2,136.5,133.6,130.23,128.78,127.6,124.34,21.5。

example 6

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 10W blue LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4aa of the embodiment with the yield of 56%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.58-7.56(m,3H),7.42(dd,2H,J＝7.9,7.8Hz),7.23(d,2H,J＝8.1Hz),7.13(d,2H,J＝8.0Hz),2.37(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ143.1,142.2,136.5,133.6,130.23,128.78,127.6,124.34,21.5。

example 7

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1a (0.8mmol), sodium metabisulfite 2(0.8mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a green LED lamp with the power of 50W and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4aa of the embodiment with the yield of 42%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.58-7.56(m,3H),7.42(dd,2H,J＝7.9,7.8Hz),7.23(d,2H,J＝8.1Hz),7.13(d,2H,J＝8.0Hz),2.37(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ143.1,142.2,136.5,133.6,130.23,128.78,127.6,124.34,21.5。

example 8

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3a (0.2mmol) and dimethyl sulfoxide 2mL are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4aa of the embodiment with the yield of 10%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.58-7.56(m,3H),7.42(dd,2H,J＝7.9,7.8Hz),7.23(d,2H,J＝8.1Hz),7.13(d,2H,J＝8.0Hz),2.37(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ143.1,142.2,136.5,133.6,130.23,128.78,127.6,124.34,21.5。

example 9

At room temperature, photocatalyst rhodamine 6G (0.004mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.2mmol), p-toluene thiophenol 3a (0.2mmol) and toluene 2mL are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4aa of the embodiment with the yield of 36%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.58-7.56(m,3H),7.42(dd,2H,J＝7.9,7.8Hz),7.23(d,2H,J＝8.1Hz),7.13(d,2H,J＝8.0Hz),2.37(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ143.1,142.2,136.5,133.6,130.23,128.78,127.6,124.34,21.5。

example 10

At room temperature, photocatalyst rhodamine 6G (0.02mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4aa of the embodiment with the yield of 68%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.58-7.56(m,3H),7.42(dd,2H,J＝7.9,7.8Hz),7.23(d,2H,J＝8.1Hz),7.13(d,2H,J＝8.0Hz),2.37(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ143.1,142.2,136.5,133.6,130.23,128.78,127.6,124.34,21.5。

example 11

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1b (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing flash column chromatography on a silica gel column to obtain the thiosulfonic acid ester 4ba of the embodiment with the yield of 75%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.45(d,J＝8.2Hz,2H),7.25(t,J＝7.3Hz,4H),7.21(d,J＝8.2Hz,2H),2.41(s,3H),2.36(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ144.7,142.1,140.4,136.5,130.3,129.4,127.6,124.6,21.7,21.5。

example 12

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1c (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4ca of the embodiment with yield of 80%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.50(d,J＝9.0Hz,2H),7.25(d,J＝8.0Hz,2H),7.14(d,J＝8.0Hz,2H),6.86(d,J＝9.0Hz,2H),3.87(s,3H),2.37(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ163.5,142.0,136.5,135.1,130.2,129.9,124.7,113.8,55.7,21.5.

example 13

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1d (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and then washed with a mixed eluent of petroleum ether and ethyl acetate, and subjected to flash column chromatography on a silica gel column to obtain the thiosulfonate 4da of the example with a yield of 72%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δδ7.49(d,J＝8.7Hz,2H),7.39(d,J＝8.7Hz,2H),7.24(d,J＝8.2Hz,2H),7.16(d,J＝8.0Hz,2H),2.39(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ142.5,141.5,140.2,136.5,130.4,129.1,129.0,124.2,21.6。

example 14

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1e (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and then washed with a mixed eluent of petroleum ether and ethyl acetate, and subjected to silica gel column flash column chromatography to obtain thiosulfonate 4ea of the example with a yield of 68%.

The product profile data obtained were:

¹H NMR(400MHz,CDCl₃):δ7.60–7.56(m,2H),7.23(d,J＝8.2Hz,2H),7.15(d,J＝8.2Hz,2H),7.09(t,J＝8.2Hz,2H),2.38(s,3H).¹³C NMR(CDCl₃,125MHz,ppm)δ165.6(d,JC-F＝255.1Hz),142.5,139.1(d,JC-F＝3.0Hz),136.5,130.4(d,JC-F＝9.6Hz),130.3,124.3,116.2(d,JC-F＝22.7Hz),21.5。

example 15

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1f (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and then washed with a mixed eluent of petroleum ether and ethyl acetate, and subjected to silica gel column flash column chromatography to obtain the thiosulfonate 4fa of the example with a yield of 57%.

The product profile data obtained were:

¹H NMR(400MHz,CDCl₃):δ7.72(d,J＝8.6Hz,2H),7.66(d,J＝8.6Hz,2H),7.23(d,J＝8.2Hz,2H),7.17(d,J＝8.2Hz,2H),2.39(s,3H).¹³C NMR(CDCl₃,100MHz,ppm)δ146.6,142.9,136.4,132.7,130.6,128.1,123.5,117.1,117.1,21.6。

example 16

At room temperature, a photocatalyst rhodamine 6G (0.002mmol), 1G (0.4mmol) of aryl diazonium salt, 2(0.4mmol) of sodium metabisulfite, 3a (0.2mmol) of p-toluene thiophenol and 2mL of acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain thiosulfonate 4ga of the embodiment with the yield of 70%.

The product profile data obtained were:

¹H NMR(400MHz,CDCl₃):δ7.97(d,J＝8.5Hz,2H),7.65(d,J＝8.5Hz,2H),7.23(d,J＝8.1Hz,2H),7.15(d,J＝8.1Hz,2H),2.64(s,3H),2.38(s,3H).¹³C NMR(CDCl₃,100MHz,ppm)δ196.7,146.5,142.6,140.4,136.4,130.5,128.7,127.8,123.9,27.0,21.5。

example 17

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt for 1h (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3a (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and carrying out flash column chromatography on a silica gel column to obtain the thiosulfonate 4ha of the embodiment with the yield of 62%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ8.27(d,J＝8.8Hz,2H),7.74(d,J＝8.8Hz,2H),7.25(d,J＝8.0Hz,2H),7.19(d,J＝7.9Hz,2H),2.40(s,3H)；¹³C NMR(125MHz,CDCl₃):δδ150.3,148.0,143.0,136.4,130.7,128.8,124.1,123.4,21.6。

example 18

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3b (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4ab of the embodiment with the yield of 83%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.59-7.56(m,3H),7.43(t,J＝7.4Hz,2H),7.24(d,J＝8.6Hz,2H),6.83(d,J＝8.6Hz,2H),3.82(s,3H)；¹³C NMR(125MHz,CDCl₃):δ162.4,143.0,138.4,133.6,128.8,127.6,118.5,115.0,55.5。

example 19

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3c (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and carrying out silica gel column flash column chromatography to obtain the thiosulfonate 4ac of the embodiment with the yield of 77%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.62-7.57(m,3H),7.47-7.42(m,2H),7.36-7.32(m,2H),7.03(t,J＝8.6Hz,2H),3.98(s,3H)；¹³C NMR(125MHz,CDCl₃):δ164.8(t,J＝252.5Hz),142.7,138.9(d,J＝9.1Hz),133.8,128.9,127.6,123.4(d,J＝3.3Hz),116.8(d,J＝22.1Hz)。

example 20

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3d (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and carrying out silica gel column flash column chromatography to obtain the thiosulfonate 4ad of the embodiment with the yield of 69%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.64-7.60(m,2H),7.50-7.46(m,3H),7.32-7.29(m,3H)；¹³C NMR(125MHz,CDCl₃):δ142.7,136.1,134.9,134.7,134.0,131.6,130.5,129.5,129.0,127.6。

example 21

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1a (0.2mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3e (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and carrying out flash column chromatography on a silica gel column to obtain the thiosulfonate 4ae of the embodiment with the yield of 73%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.62-7.58(m,3H),7.49-7.44(m,4H),7.20(d,J＝8.4Hz,2H).¹³C NMR(CDCl₃,125MHz,ppm)δ142.8,137.9,133.9,132.8,129.0,127.6,126.9,126.8.

example 22

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3f (0.2mmol) and acetonitrile are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4af of the embodiment with the yield of 65%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ7.62-7.58(m,3H),7.49-7.44(m,4H),7.20(d,J＝8.4Hz,2H).¹³C NMR(CDCl₃,125MHz,ppm)δ142.8,137.9,133.9,132.8,129.0,127.6,126.9,126.8.

example 24

At room temperature, photocatalyst rhodamine 6G (0.002mmol), aryl diazonium salt 1a (0.4mmol), sodium metabisulfite 2(0.4mmol), p-toluene thiophenol 3h (0.2mmol) and acetonitrile 2mL are sequentially added into a 20mL reaction tube and uniformly mixed. Then, the mixture is irradiated by a 3W white LED lamp and reacted for 12 hours at room temperature under the protection of nitrogen. After TLC detection to the completion of the reaction, distilled water was added, the reaction solution was extracted with ethyl acetate, and the extract was concentrated under reduced pressure in vacuo (0.08MPa) to be solvent-free to obtain a crude product, which was then purified by column chromatography using a solvent in a volume ratio of 5:1 and washing with mixed eluent of petroleum ether and ethyl acetate, and performing silica gel column flash column chromatography to obtain the thiosulfonate 4ah of the embodiment with the yield of 60%.

The product profile data obtained were:

¹H NMR(500MHz,CDCl₃):δ8.05(d,J＝7.4Hz,2H),7.74(d,J＝7.4Hz,1H),7.66(t,J＝7.9Hz,2H),7.40-7.30(m,3H),7.19(d,J＝7.0Hz,2H),3.34(d,J＝7.4Hz,2H),3.00(d,J＝7.4Hz,2H)；¹³C NMR(125MHz,CDCl₃):δ144.9,138.7,133.8,129.4,128.7,128.6,127.0,126.9,37.2,35.2。

the above embodiment is only one implementation form of the method for preparing thiosulfonate ester based on visible light catalysis provided by the invention, and other modifications, additions, subtractions or steps of the method, or applications of the method in other technical fields similar to the invention, are also within the protection scope of the invention.