CN113651734A - Method for catalytically oxidizing thioether into sulfone - Google Patents
Method for catalytically oxidizing thioether into sulfone Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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Abstract
The invention discloses a method for catalytically oxidizing thioether into sulfone. The method comprises adding thioether and H into ethanol solution2O2Reacting with a boron-nitrogen co-doped graphene catalyst at room temperature to obtain the sulfone. The method has the characteristics of simple and convenient operation, green and environment-friendly reaction process, low production cost, no metal catalyst, no secondary pollution, mild reaction conditions, small catalyst consumption, high oxidation selectivity, high product yield and the like.
Description
Technical Field
The invention belongs to the field of chemical synthesis processes, and particularly relates to a method for catalytically oxidizing thioether into sulfone.
Background
The high-selectivity catalytic oxidation of thioether to sulfone is one of the key reactions in organic synthesis, and sulfone compounds can be used for synthesizing fine chemicals, bioactive compounds and agricultural chemicals, can be used as chiral auxiliary agents, and are recently used as ligands for asymmetric catalysis of transition metals. In addition, sulfide oxidation is also the basis for catalytic oxidative desulfurization of crude oils, under conditions milder than classical industrial catalytic hydrodesulfurization, by selective extraction of sulfur compounds into polar solvents. Therefore, the search for new and efficient catalytic systems for catalyzing the oxidation of organosulfur compounds to the corresponding sulfones compounds has become an important research field today.
The preparation of sulfones usually requires large amounts of oxidizing agents, such as H2O2Potassium hydrogen persulfate, NaClO4、H5IO6NaClO, UHP, m-chloroperbenzoic acid, NaIO4Ketone oxides, and the like. Although there are a myriad of oxidation systems to effect sulfide oxidation, hydrogen peroxide remains the most attractive, clean, and desirable green oxidant because it is cost effective, environmentally friendly, safe and simple to operate. However, hydrogen peroxide-induced oxidation is rather slow and needs to be activated by a suitable catalyst. The traditional catalytic method mostly adopts metal catalysts, and has the defects of expensive solvent, low yield, long reaction time, environmental hazard, high cost, poor recovery and the like. From a green and sustainable chemistry perspective, the search for innovative metal-free heterogeneous catalysts would be highly attractive.
In view of the above, there is a need to develop a method for preparing sulfone by catalytic oxidation of thioether, which is free of metal catalysis, green and environment-friendly, low in production cost, and mild in reaction conditions.
Disclosure of Invention
The invention aims to provide a method for catalytically oxidizing thioether into sulfone, which has the characteristics of mild reaction conditions, environmental protection, low cost, no metal catalyst, high oxidation selectivity, high product yield and the like.
The technical scheme adopted by the invention is as follows:
a process for catalytic oxidizing thioether to sulfone includes adding thioether and H to alcohol solution2O2Reacting with a boron-nitrogen co-doped graphene catalyst at room temperature to obtain the sulfone.
Preferably, in said method for the catalytic oxidation of a thioether to a sulfone, said H2O2The molar ratio of the thioether to the thioether is (1.5-3): 1.
preferably, in the method for catalytically oxidizing thioether into sulfone, the mass of the boron-nitrogen co-doped graphene catalyst is 0.1-15% of that of thioether.
Preferably, in the method for catalytically oxidizing a thioether to a sulfone, the thioether comprises at least one of phenylsulfide, 4-methylthioacetophenone, 4-chloroanisole, 4-aminoanisole, 3, 5-dichloroanisole, ethylphenylsulfide, n-butylsulfide, and carnosol sulfide.
Preferably, in said method for the catalytic oxidation of a thioether to a sulfone, said H2O2Is H with the mass fraction of 30 percent2O2Takes part in the reaction in the form of an aqueous solution, and H2O2H in aqueous solution2O2The mass percentage of (B) is 30-70%.
Preferably, in the method for catalytically oxidizing thioether into sulfone, the catalyst is a metal-free boron-nitrogen co-doped graphene catalyst.
Preferably, in the method for catalytically oxidizing thioether to sulfone, the carbon source and the nitrogen source of the boron-nitrogen co-doped graphene catalyst are both derived from metal-free phthalocyanine or guanine, and the boron source is boric acid, boron oxide, potassium borohydride or sodium borohydride.
Preferably, in the method for catalytically oxidizing thioether into sulfone, the preparation method of the boron-nitrogen co-doped graphene catalyst comprises the following steps: ultrasonically dispersing 1-5 g of nitrogen source and 1-50 g of boron source uniformly in a water bath condition at 40-100 ℃ for 0.5-2 h, placing dried solid matters in a quartz tube furnace, and carrying out temperature programming at the temperature rising rate of 3-40 ℃/min; and (3) preserving heat at 300-1000 ℃ for 1-10 h, naturally cooling to obtain a black solid crude product, washing to remove residual impurities, and drying to obtain the boron-nitrogen co-doped graphene catalyst.
Preferably, in the method for catalytically oxidizing thioether into sulfone, the reaction temperature is 0-100 ℃, and the reaction time is 12-36 h.
The crude product obtained by the invention is further separated and purified to prepare a refined product, and the specific method comprises the following steps: separating the catalyst to quench the reaction, washing with an organic solvent, collecting the reaction solution, drying with anhydrous magnesium sulfate, concentrating under reduced pressure, and separating by column chromatography to obtain the purified sulfone compound.
The invention has the beneficial effects that: the method for catalytically oxidizing the thioether into the sulfone has the advantages of high product yield, mild reaction conditions, simple operation, low cost, clean solvent and oxidant used in the reaction, environmental friendliness and no pollution.
Drawings
Fig. 1 is a full X-ray spectrum (XPS) diagram of a boron-nitrogen co-doped graphene catalyst.
Detailed Description
The technical solution of the present invention will be described in detail with reference to the following embodiments of the present invention and the accompanying drawings.
In the following examples, the preparation method of the metal-free catalyst, i.e., the boron-nitrogen co-doped graphene catalyst, is as follows:
after 1g of metal-free phthalocyanine was dispersed in 50mL of deionized water, 8g H was added under 40 ℃ water bath conditions3BO3And carrying out ultrasonic treatment for 1h under the condition of heating to 80 ℃. And after the ultrasonic treatment is finished, placing the mixture in an electrothermal blowing oven at the temperature of 60 ℃ for baking for 48 hours to obtain a dark green solid. Placing the obtained dark green solid in a quartz tube furnace, and carrying out temperature programming at the temperature rising rate of 3-10 ℃/min; preserving the heat at 350 ℃, 400 ℃, 450 ℃, 500 ℃ and 800 ℃ for 1h, 2h and 6h respectively, and naturally cooling to obtain black solids. Washing the black solid to be neutral by using a 10% hydrochloric acid solution and a large amount of deionized water; and (5) drying the graphene in an electric heating blast oven at 60 ℃ for 24h to obtain the boron-nitrogen co-doped graphene.
XPS full spectrum scanning is carried out on the prepared boron-nitrogen co-doped graphene catalyst, the scanning result is shown in figure 1, absorption peaks of N1s and B1s and an absorption peak of O1s can be obviously seen from the scanning result, and it can be inferred that the boron-nitrogen co-doped graphene contains rich N, B, O elements.
Example 1
This example is the preparation of methyl phenyl sulfone by catalytic oxidation of methyl phenyl sulfide:
10mg of the catalyst, 0.5mmol of methyl phenyl sulfide, 300. mu.L of 30% hydrogen peroxide and 0.5mL of ethanol were mixed and stirred at room temperature, followed by reaction for 24 hours. After completion of the reaction, the catalyst was filtered off with a silica gel column, washed with dichloromethane (3X2mL), the reaction solution was collected and dried, concentrated under reduced pressure, and subjected to column chromatography (developer: n-hexane: ethyl acetate 1:1) to obtain a white target product in a yield of 93% (72.8 mg).
Example 2
This example is a 4-methylsulfonylacetophenone preparation by catalytic oxidation of 4-methylthioacetophenone:
the catalyst 10mg, 4-methylthioacetophenone 0.5mmol, 30% hydrogen peroxide 300. mu.L, ethanol 0.5mL, were mixed and stirred at room temperature and reacted for 24 hours. After the completion of the reaction, the catalyst was filtered off with a silica gel column, washed with dichloromethane (3X2mL), the reaction solution was collected and dried, concentrated under reduced pressure, and subjected to column chromatography (developer: n-hexane: ethyl acetate 1:1) to obtain a white target product with a yield of 96% (94.8 mg).
Example 3
This example is the preparation of 4-chloroanisole sulfone by catalytic oxidation of 4-chloroanisole sulfide.
10mg of catalyst, 0.5mmol of 4-chloroanisole, 300. mu.L of 30% hydrogen peroxide and 0.5mL of ethanol were mixed and stirred at room temperature, and reacted for 24 hours. After the completion of the reaction, the catalyst was filtered off with a silica gel column, washed with dichloromethane (3X2mL), the reaction solution was collected and dried, concentrated under reduced pressure, and subjected to column chromatography (developer: n-hexane: ethyl acetate 1:1) to obtain a white target product with a yield of 97% (92.8 mg).
Example 4
This example is the preparation of 4-aminoanisole sulfone by catalytic oxidation of 4-aminoanisole thioether.
10mg of catalyst, 0.5mmol of 4-aminothioanisole, 300. mu.L of 30% hydrogen peroxide and 0.5mL of ethanol were mixed and stirred at room temperature, and reacted for 24 hours. After the completion of the reaction, the catalyst was filtered off with a silica gel column, washed with dichloromethane (3X2mL), the reaction solution was collected and dried, concentrated under reduced pressure, and subjected to column chromatography (developer: n-hexane: ethyl acetate 1:1) to obtain a yellow target product with a yield of 90% (76.7 mg).
Example 5
This example is the preparation of 3, 5-dichloroanisole sulfone by catalytic oxidation of 3, 5-dichloroanisole sulfide.
10mg of catalyst, 0.5mmol of 3, 5-dichlorothioanisole, 300. mu.L of 30% hydrogen peroxide and 0.5mL of ethanol were mixed and stirred at room temperature, and reacted for 24 hours. After completion of the reaction, the catalyst was filtered off with a silica gel column, washed with dichloromethane (3X2mL), the reaction solution was collected and dried, concentrated under reduced pressure, and subjected to column chromatography (developer: n-hexane: ethyl acetate 1:1) to obtain a white target product in a yield of 92% (103.6 mg).
Example 6
This example is the catalytic oxidation of ethylphenylthio to ethylphenylsulfone.
10mg of the catalyst, 0.5mmol of ethylphenylthio, 300. mu.L of 30% hydrogen peroxide and 0.5mL of ethanol were mixed and stirred at room temperature, followed by reaction for 24 hours. After the completion of the reaction, the catalyst was filtered off with a silica gel column, washed with dichloromethane (3X2mL), the reaction solution was collected and dried, concentrated under reduced pressure, and subjected to column chromatography (developer: n-hexane: ethyl acetate 1:1) to obtain a white target product with a yield of 96% (82.0 mg).
Example 7
This example is the preparation of n-butyl sulfone by catalytic oxidation of n-butyl sulfide.
10mg of the catalyst, 0.5mmol of n-butyl sulfide, 300. mu.L of 30% hydrogen peroxide and 0.5mL of ethanol were mixed and stirred at room temperature, followed by reaction for 24 hours. After the completion of the reaction, the catalyst was filtered off with a silica gel column, washed with dichloromethane (3X2mL), the reaction solution was collected and dried, concentrated under reduced pressure, and subjected to column chromatography (developer: n-hexane: ethyl acetate 1:1) to obtain a white target product with a yield of 97% (86.9 mg).
Example 8
This example is the preparation of shoyu suyu sulfone by catalytic oxidation of shoyu suyu thioether.
10mg of the catalyst, 0.5mmol of harpagophytum procumbens thioether, 300. mu.L of 30% hydrogen peroxide and 0.5mL of ethanol were mixed and stirred at room temperature, and reacted for 24 hours. After the completion of the reaction, the catalyst was filtered off with a silica gel column, washed with dichloromethane (3X2mL), the reaction solution was collected and dried, concentrated under reduced pressure, and subjected to column chromatography (developer: n-hexane: ethyl acetate 1:1) to obtain a white target product in a yield of 96% (118.9 mg).
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples. Other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A process for the catalytic oxidation of a thioether to a sulfone, comprising: adding thioether and H into ethanol solution2O2And boron-nitrogen co-doped graphene catalyst in chamberThe reaction is carried out at a mild condition to obtain the sulfone.
2. The process of claim 1, wherein the catalytic oxidation of a thioether to a sulfone comprises: said H2O2The molar ratio of the thioether to the thioether is (1.5-3): 1.
3. the process of claim 1, wherein the catalytic oxidation of a thioether to a sulfone comprises: the mass of the boron-nitrogen co-doped graphene catalyst is 0.1-15% of that of thioether.
4. A process for the catalytic oxidation of a thioether to a sulfone, according to anyone of claims 1 to 3, characterized in that: the thioether comprises at least one of phenylsulfide, 4-methylthioacetophenone, 4-chloroanisole, 4-aminoanisole, 3, 5-dichloroanisole, ethyl phenyl sulfide, n-butyl sulfide and turpentine sulfide.
5. A process for the catalytic oxidation of a thioether to a sulfone, according to claim 1 or 2, characterized in that: said H2O2Is H2O2Takes part in the reaction in the form of an aqueous solution, and H2O2H in aqueous solution2O2The mass percentage of (B) is 30-70%.
6. The process of claim 1, wherein the catalytic oxidation of a thioether to a sulfone comprises: the catalyst is a metal-free boron-nitrogen co-doped graphene catalyst.
7. The process of claim 6, wherein the catalytic oxidation of the thioether to the sulfone comprises: the carbon source and the nitrogen source of the boron-nitrogen co-doped graphene catalyst are both from metal-free phthalocyanine or guanine, and the boron source is boric acid, boron oxide, potassium borohydride or sodium borohydride.
8. A process for the catalytic oxidation of a thioether to a sulfone, according to claims 6 and 7, wherein: the preparation method of the boron-nitrogen co-doped graphene catalyst comprises the following steps: ultrasonically dispersing 1-5 g of nitrogen source and 1-50 g of boron source uniformly in a water bath condition at 40-100 ℃ for 0.5-2 h, placing dried solid matters in a quartz tube furnace, and carrying out temperature programming at the temperature rising rate of 3-40 ℃/min; and (3) preserving heat at 300-1000 ℃ for 1-10 h, naturally cooling to obtain a black solid crude product, washing to remove residual impurities, and drying to obtain the boron-nitrogen co-doped graphene catalyst. And naturally cooling to obtain a black solid crude product, washing to remove residual impurities, and drying to obtain the boron-nitrogen co-doped graphene catalyst.
9. The process of claim 1, wherein the catalytic oxidation of a thioether to a sulfone comprises: the reaction temperature is 0-100 ℃, and the reaction time is 12-36 h.
10. The process of claim 1, wherein the catalytic oxidation of a thioether to a sulfone comprises: separating the catalyst to quench the reaction, washing with an organic solvent, collecting the reaction solution, drying with anhydrous magnesium sulfate, concentrating under reduced pressure, and separating by column chromatography to obtain the purified sulfone compound.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130149211A1 (en) * | 2010-05-28 | 2013-06-13 | Graphea, Inc. | Graphene oxide and graphite oxide catalysts and systems |
| CN111450818A (en) * | 2020-03-10 | 2020-07-28 | 广东省石油与精细化工研究院 | Niobium pentoxide @ reduced graphene oxide catalyst and preparation method and application thereof |
| CN112093796A (en) * | 2020-09-24 | 2020-12-18 | 江苏江南烯元石墨烯科技有限公司 | Preparation method of sulfur-nitrogen doped graphene material |
| CN112592300A (en) * | 2020-12-02 | 2021-04-02 | 广东省科学院化工研究所 | Method for preparing sulfone by catalytic oxidation of thioether |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130149211A1 (en) * | 2010-05-28 | 2013-06-13 | Graphea, Inc. | Graphene oxide and graphite oxide catalysts and systems |
| CN111450818A (en) * | 2020-03-10 | 2020-07-28 | 广东省石油与精细化工研究院 | Niobium pentoxide @ reduced graphene oxide catalyst and preparation method and application thereof |
| CN112093796A (en) * | 2020-09-24 | 2020-12-18 | 江苏江南烯元石墨烯科技有限公司 | Preparation method of sulfur-nitrogen doped graphene material |
| CN112592300A (en) * | 2020-12-02 | 2021-04-02 | 广东省科学院化工研究所 | Method for preparing sulfone by catalytic oxidation of thioether |
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