CN109705002B - Method for synthesizing sulfolane compound through photocatalysis - Google Patents
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Abstract
The invention discloses a method for synthesizing a sulfosulfone compound through photocatalysis, and belongs to the technical field of catalysis. The invention provides a new green and environment-friendly method for efficiently synthesizing sulfolane derivatives, which utilizes cercosporal as a catalyst, and a thioether compound and an oxidant are directly oxidized under illumination to generate the sulfolane compound. The method takes cercospora sporins as a catalyst, has mild catalytic conditions, can be carried out at room temperature under the irradiation of visible light, has high catalytic activity, can catalyze and synthesize the sulfosulfone compound with high selectivity, and can ensure that the yield is higher and can reach more than 90 percent by using a trace catalyst. The photocatalyst and the substrate of the invention have the advantages of simple and easily obtained raw materials, low cost, mass production and good application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a method for synthesizing a sulfosulfone compound through photocatalysis.
Background
The sulfosulfone derivatives are effective building blocks of many organic compounds and drug candidates, and have demonstrated many important biological activities. In view of these importance, their synthesis has attracted considerable attention in the field of synthesis. The most common method of synthesizing sulfones is by oxidation of sulfides. This can be achieved by using stoichiometric amounts of acid or inorganic oxidizing agents, but these methods have poor atom utilization and produce contamination that is difficult to clean. The photocatalysis technology has the advantages of mild reaction conditions, small catalyst consumption, energy conservation and environmental protection, and has attracted extensive attention of people. Therefore, it is very necessary to develop a green catalyst for catalyzing the high-selectivity oxidation of sulfide to prepare the sulfur sulfone compound.
The simplest and most effective method for preparing the sulfolane compound is the direct oxidation of the sulfolane compound. Most of the reported thioether oxidation systems at present have the defects of harsh oxidation conditions, poor reaction selectivity, difficult preparation of catalysts and the like. Particularly, the use of a large amount of transition metal catalysts such as platinum, copper, gold, etc. causes serious environmental problems. Therefore, the development of a green and efficient method for preparing the sulfolane by selectively oxidizing the thioether is of great research value and is an important development direction and focus in the field at present.
Disclosure of Invention
In order to solve the problems, the invention provides a novel green and efficient preparation method for preparing sulfolane by selectively oxidizing thioether. The reaction condition is mild, the efficiency is high and the environment is friendly.
The first purpose of the invention is to provide a preparation method of a sulfosulfone compound, which uses cercosporin as a catalyst, and a thioether compound and an oxidant are directly oxidized under the irradiation of light to generate the sulfosulfone compound.
In one embodiment of the invention, the molar ratio of thioether compound to cercosporin is 1: (0.005-0.2).
In one embodiment of the present invention, the molar ratio of thioether compound and cercosporin is preferably 1: 0.01.
in one embodiment of the present invention, the illumination light source for the illumination light includes any one of white light, blue light and green light.
In one embodiment of the present invention, the irradiation light source is preferably white light.
In one embodiment of the present invention, the oxidant comprises one of oxygen and air.
In one embodiment of the invention, the oxidant is preferably oxygen.
In one embodiment of the invention, the oxidation reaction in the process is carried out in an organic solvent comprising one or more of N, N-dimethylformamide, methanol, tetrahydrofuran, dichloromethane, chloroform.
In one embodiment of the present invention, the solvent is preferably methanol.
In one embodiment of the present invention, the chemical structure of the thioether compound is represented by formula II,
wherein R is1、R2Each independently selected from aliphatic groups, aromatic groups and substituted derivatives thereof.
In one embodiment of the invention, the chemical structural formula of the thioether compound is shown as formula III,
wherein R is3Selected from halogen, nitro, alkyl, alkoxy, substituted alkyl, R4Selected from halogen, alkyl, aryl, substituted alkyl and substituted aryl.
In one embodiment of the invention, the chemical structural formula of cercosporin is shown in formula I,
in an embodiment of the present invention, the method specifically includes:
mixing cercosporin and thioether derivatives in an organic solvent according to a molar ratio, and illuminating for 24 hours at room temperature by taking oxygen as an oxidant to obtain the sulfosulfone compound.
The second object of the present invention is to apply the above method to the field of agricultural chemicals or pharmaceutical synthesis.
The invention has the beneficial effects that:
1. the invention provides a novel green and environment-friendly method for efficiently synthesizing the sulfolane derivative. The cercosporal bacteriocin is used as a photocatalyst, the substrate raw material is simple and easy to obtain, the cost is low, the cercosporal bacteriocin can be produced in a large scale, and the process application prospect is very good.
2. The method takes cercospora mycin as a catalyst, has mild catalytic conditions, and can be carried out at room temperature under the irradiation of visible light.
3. The cercosporal bacteriocin catalyst has good catalytic activity, can catalyze and synthesize the sulfosulfone compound with high selectivity, and has the advantages of small catalyst dosage in a reaction system, mild condition, high reaction efficiency and high yield which can reach more than 90 percent.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
EXAMPLE 1 catalytic Synthesis of benzylphenylsulfone with Cercosporin catalyst
Cercosporin (0.005mmol), benzyl phenyl sulfide (0.5mmol) and 2mL of methanol are sequentially added into a 10mL reaction tube, and then the mixture is subjected to oxygen protection, 15W white light irradiation and reaction at room temperature of 25 ℃ for 24 hours. The reaction solution is evaporated by rotary evaporation to dryness, and then is quickly separated by a thin-layer silica gel plate with 300-500 meshes, and the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that the benzyl phenyl sulfone is obtained with the yield of 90%.
Example 2 catalytic Synthesis of benzyl sulfone with Cercospora Ensulosin catalyst
Cercosporin (0.005mmol), benzyl sulfide (0.5mmol) and 2mL of methanol are sequentially added into a 10mL reaction tube, and then the mixture is subjected to oxygen protection, 15W white light irradiation and reaction at room temperature of 25 ℃ for 24 hours. The reaction solution is evaporated by rotary evaporation to dryness, and then is quickly separated by a thin-layer silica gel plate with 300-500 meshes, and the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that the benzyl sulfone is obtained with the yield of 95%.
Example 3 catalytic Synthesis of phenyl methyl sulfone with Cercospora Ensulodin catalyst
Cercosporin (0.005mmol), phenyl methyl sulfide (0.5mmol) and 2mL of methanol are sequentially added into a 10mL reaction tube, and then the mixture is subjected to oxygen protection, 15W white light irradiation and reaction at room temperature of 25 ℃ for 24 hours. The reaction solution is evaporated by rotary evaporation to dryness, and then is quickly separated by a thin-layer silica gel plate with 300-500 meshes, and the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that the phenyl methyl sulfone is obtained with the yield of 90%.
Example 4 catalytic Synthesis of 4-chloro-4' -methyldiphenylsulfide sulfone with Cercosporastatin catalyst
Cercosporin (0.005mmol), 4-chloro-4' -methyl diphenyl sulfide (0.5mmol) and 2mL of methanol are sequentially added into a 10mL reaction tube, and then the mixture is subjected to oxygen protection, 15W white light irradiation and reaction at room temperature of 25 ℃ for 24 hours. The reaction solution is evaporated by rotary evaporation to dryness, and then is quickly separated by a thin-layer silica gel plate with 300-500 meshes, and the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that 4-chloro-4' -methyl diphenyl sulfide sulfone is obtained with the yield of 86%.
Example 5 catalytic Synthesis of 4-bromo-phenylmethylsulfone with Cercosporin catalyst
Cercosporin (0.005mmol), 4-bromo-phenyl methyl sulfide (0.5mmol) and 2mL of methanol are sequentially added into a 10mL reaction tube, and then the mixture is subjected to oxygen protection, 15W white light irradiation and reaction at room temperature of 25 ℃ for 24 hours. The reaction solution is evaporated by rotary evaporation to dryness, and then is quickly separated by a thin-layer silica gel plate with 300-500 meshes, and the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that the 4-bromo-phenylmethylsulfone is obtained with the yield of 95%.
Example 6 catalytic Synthesis of 4-Nitro-phenylmethylsulfone with Cercosporin catalyst
Cercosporin (0.005mmol), 4-nitro-phenyl methyl sulfide (0.5mmol) and 2mL of methanol are sequentially added into a 10mL reaction tube, and then the mixture is subjected to oxygen protection, 15W white light irradiation and reaction at room temperature of 25 ℃ for 24 hours. The reaction solution is evaporated by rotary evaporation to dryness, and then is quickly separated by a thin-layer silica gel plate with 300-500 meshes, and the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that the 4-nitro-phenyl methyl sulfone is obtained with the yield of 92%.
Example 7 catalytic Synthesis of Diphenylsulfone with Cercosporanin catalyst
Cercosporin (0.005mmol), diphenyl sulfide (0.5mmol) and 2mL of methanol are sequentially added into a 10mL reaction tube, and then the mixture is subjected to oxygen protection, 15W white light irradiation and reaction at room temperature of 25 ℃ for 24 hours. The reaction solution is evaporated by rotary evaporation to dryness, and then is quickly separated by a thin-layer silica gel plate with 300-500 meshes, and the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that the diphenyl sulfone is obtained with the yield of 90%.
Example 8 catalytic Synthesis of 4-methoxy-4' -methyldiphenylsulfide sulfone with Cercosporastatin catalyst
Cercosporin (0.005mmol), 4-methoxy-4' -methyl diphenyl sulfide (0.5mmol) and 2mL of methanol are sequentially added into a 10mL reaction tube, and then the mixture is subjected to oxygen protection, 15W white light irradiation and room temperature 25 ℃ reaction for 24 hours. The reaction solution is evaporated by rotary evaporation to dryness, and then is quickly separated by a thin-layer silica gel plate with 300-500 meshes, and the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that the 4-methoxy-4' -methyl diphenyl sulfide sulfone is obtained with the yield of 95%.
Example 9 catalytic Synthesis of 4-Chlorodiphenylsulfone with Cercosporin catalyst
Cercosporin (0.005mmol), 4-chlorobenzenethioether (0.5mmol) and 2mL methanol are sequentially added into a 10mL reaction tube, and then the mixture is subjected to oxygen protection, 15W white light irradiation and reaction at room temperature of 25 ℃ for 24 hours. The reaction solution is evaporated by rotary evaporation to dryness, and then is quickly separated by a thin-layer silica gel plate with 300-500 meshes, and the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that the 4-chlorodiphenyl sulfide sulfone is obtained with the yield of 95%.
Example 10 catalytic Synthesis of 1, 3-dimethyl-4' -methyldiphenylsulfide sulfone with Cercospora Citroboide catalyst
Cercosporin (0.005mmol), 1, 3-dimethyl-4' -methyl diphenyl sulfide (0.5mmol) and 2mL of methanol are sequentially added into a 10mL reaction tube, and then the mixture is subjected to oxygen protection, 15W white light irradiation and reaction at room temperature of 25 ℃ for 24 hours. The reaction solution is evaporated by rotary evaporation to dryness, and then is quickly separated by a thin-layer silica gel plate with 300-500 meshes, and the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that the 1, 3-dimethyl-4' -methyl diphenyl sulfide sulfone is obtained with the yield of 86%.
Example 11 catalytic Synthesis of 4-tert-butyl diphenyl sulfide sulfone with Cercosporin catalyst
Cercosporin (0.005mmol), 4-tert-butyl diphenyl sulfide (0.5mmol) and 2mL of methanol are sequentially added into a 10mL reaction tube, and then the mixture is subjected to oxygen protection, 15W white light irradiation and reaction at room temperature of 25 ℃ for 24 hours. The reaction solution is evaporated by rotary evaporation to dryness, and then is quickly separated by a thin-layer silica gel plate with 300-500 meshes, and the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that the 4-tert-butyl diphenyl sulfide sulfone is obtained with the yield of 82%.
Example 12 catalytic Synthesis of 4-Bromodiphenyl sulfide sulfone with Cercosporin catalyst
Cercosporin (0.005mmol), 4-bromo diphenyl sulfide (0.5mmol) and 2mL of methanol are sequentially added into a 10mL reaction tube, and then the mixture is subjected to oxygen protection, 15W white light irradiation and reaction at room temperature of 25 ℃ for 24 hours. And (3) evaporating the solvent by rotary evaporation, and quickly separating the reaction solution by using a 300-500-mesh thin-layer silica gel plate, wherein the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that the 4-bromodiphenyl sulfide sulfone is obtained with the yield of 92%.
Example 13 catalytic Synthesis of 4, 4' -Dibromophenylsulfone with Cercospora Citroboide catalyst
Cercosporin (0.005mmol), 4' -dibromodiphenyl sulfide (0.5mmol) and 2mL methanol are added into a 10mL reaction tube in sequence, and then the mixture is subjected to oxygen protection, 15W white light irradiation and reaction at room temperature of 25 ℃ for 24 hours. The reaction solution is evaporated by rotary evaporation to dryness, and then is quickly separated by a thin-layer silica gel plate with 300-500 meshes, and the eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), so that the 4, 4' -dibromophenylthiosulfone is obtained with the yield of 86%.
Example 14 examination of solvent
Referring to example 1, the sulfosulfone product was prepared with varying solvent selection (as shown in table 1) and other conditions. The yields of the obtained products are shown in table 1.
TABLE 1 preparation of sulfolane products with different solvents
| Kind of solvent | CH3OH | CHCl3 | CH3CN | THF | DMF |
| Yield (%) | 90 | 54 | 62 | 21 | 25 |
Comparative example 1
Referring to example 1, the solvent was replaced with DMSO without changing other conditions to prepare a sulfolane product; the yield of the product obtained was < 5%, essentially negligible.
Comparative example 2 preparation of Sulfur sulfone Compound without illumination
Referring to example 1, the sulfolane product was prepared without light and other conditions; the yield of the product obtained is less than 10%.
Comparative example 3 preparation of Sulfur sulfone Compound with different catalysts
Referring to example 1, cercosporin was replaced with the catalysts shown in table 2, respectively, and under otherwise unchanged conditions, a sulfolane product was prepared; the yield of the obtained yields are shown in table 2.
TABLE 2 preparation of Sulfur sulfone Compounds with different catalysts
| Kind of catalyst | Yield (%) |
| Acr+-Mes | 12 |
| Ru(bpy)3Cl2 | 15 |
| Eosin Y | 8 |
| Ir(ppy)2bpy | 10 |
| Without catalyst | No reaction |
Wherein, Acr+-Mes is a photocatalyst, 9-mesityl-10-methylacridine ion.
Claims (10)
1. A preparation method of a sulfur-sulfone compound is characterized in that cercosporin is used as a catalyst, and a sulfur-sulfide compound and an oxidant are directly oxidized under the irradiation of light to generate the sulfur-sulfone compound.
2. The method of claim 1, wherein the molar ratio of thioether compound to cercosporin is 1: (0.005-0.2).
3. The method of claim 1, wherein the illumination source comprises any one of white light, blue light and green light.
4. The method of claim 2, wherein the illumination source comprises any one of white light, blue light and green light.
5. The method of claim 1, wherein the oxidant comprises one of oxygen, air.
6. The method according to claim 1, wherein the oxidation reaction in the method is carried out in an organic solvent comprising one or more of N, N-dimethylformamide, methanol, tetrahydrofuran, dichloromethane, chloroform.
7. The method of claim 1, wherein the thioether compound has a chemical formula as shown in formula (II),
wherein R is1、R2Each independently selected from aliphatic groups, aromatic groups and substituted derivatives thereof.
8. The method of claim 1, wherein the thioether compound has a chemical formula as shown in formula (III),
wherein R is3Selected from halogen, nitro, alkyl, alkoxy, substituted alkyl, R4Selected from alkyl, aryl, substituted alkyl and substituted aryl.
9. The method of claim 1, wherein the molar ratio of thioether compound to cercosporin is 1: 0.01.
10. the method according to any one of claims 1 to 9, characterized in that it comprises in particular:
mixing cercosporin and a thioether compound in an organic solvent according to a molar ratio, and illuminating for 24 hours at room temperature by taking oxygen as an oxidant to obtain the sulfosulfone compound.
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| CN112375021A (en) * | 2020-11-20 | 2021-02-19 | 湖南生物机电职业技术学院 | Method for synthesizing diaryl sulfone compound by photocatalytic oxidation of diaryl sulfide |
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