CN110590617B - Method for preparing sulfone by catalytic oxidation of thioether - Google Patents
Method for preparing sulfone by catalytic oxidation of thioether Download PDFInfo
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- 150000003457 sulfones Chemical class 0.000 title claims abstract description 31
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 20
- -1 sulfone compounds Chemical class 0.000 claims abstract description 15
- 229940126062 Compound A Drugs 0.000 claims abstract description 13
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012074 organic phase Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 9
- UGMXRPVWWWDPFC-UHFFFAOYSA-N 1-(bromomethyl)pyrene Chemical compound C1=C2C(CBr)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 UGMXRPVWWWDPFC-UHFFFAOYSA-N 0.000 claims description 8
- ZDDDFDQTSXYYSE-UHFFFAOYSA-N 1-ethylsulfanylpropane Chemical compound CCCSCC ZDDDFDQTSXYYSE-UHFFFAOYSA-N 0.000 claims description 8
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 7
- NGDMLQSGYUCLDC-UHFFFAOYSA-N pyren-1-ylmethanol Chemical compound C1=C2C(CO)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 NGDMLQSGYUCLDC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004451 qualitative analysis Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003220 pyrenes Chemical class 0.000 description 3
- PLKAKCXVZMGSKI-UHFFFAOYSA-N 2-thiophen-2-yloxythiophene Chemical compound C=1C=CSC=1OC1=CC=CS1 PLKAKCXVZMGSKI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- KBSPJIWZDWBDGM-UHFFFAOYSA-N 1-Methylpyrene Chemical class C1=C2C(C)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 KBSPJIWZDWBDGM-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- XQFOTRFIVZLGOW-UHFFFAOYSA-N COC1=CC=CC(=C1)C2=CC=CC=C2SC Chemical compound COC1=CC=CC(=C1)C2=CC=CC=C2SC XQFOTRFIVZLGOW-UHFFFAOYSA-N 0.000 description 1
- 229910019501 NaVO3 Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical class N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of synthesis of sulfone compounds, and particularly relates to a method for preparing sulfone by catalytic oxidation of thioether. The method for preparing the sulfone by catalytic oxidation of the thioether comprises the following steps: catalyst, thioether and 30 percent of H by mass fraction2O2Mixing the aqueous solution in a reaction bottle, and stirring at room temperature for 3-6h to obtain sulfone; the catalyst, thioether and H2O2The molar ratio of (1: 10000: 50000); the catalyst is prepared by reacting8[SiW10O36]·12H2Adding NaVO into hydrochloric acid solution of O3Stirring the solution for 5min, filtering to obtain bright yellow filtrate, dropwise adding a chloroform solution of a compound A into the bright yellow filtrate, continuously stirring for 5h, and collecting a solid, wherein the solid is the catalyst. The catalyst used in the method for preparing the sulfone by catalyzing the thioether has high conversion number, and the preparation of the sulfone can be realized at room temperature without using an organic solvent in the reaction process.
Description
Technical Field
The invention belongs to the technical field of synthesis of sulfone compounds, and particularly relates to a method for preparing sulfone by catalytic oxidation of thioether.
Background
Sulfoxide compounds and sulfone compounds are very important organic intermediates, and have wide application in aspects of organic synthetic chemistry, biology, pharmacology, petroleum desulfurization, industrial application and the like. Therefore, the research on the preparation of the sulfone compound by oxidizing the thioether compound has important theoretical and practical application values. In recent years, catalytic oxidation systems using inexpensive and safe aqueous hydrogen peroxide as an oxidizing agent have been used in various catalytic oxidation reactions, including the oxidation of thioethers to sulfones. However, the conventional catalytic systems generally have the following disadvantages: 1. the use of large amounts of solvent. In order to mix the reaction system sufficiently, a large amount of organic solvent is used, which makes purification and post-treatment of the product troublesome. 2. The amount of catalyst required is large, the conversion number (TON, TON is the number of moles of product/moles of catalyst) is generally low; 3. the reaction temperature is high and the reaction time is long.
For example, chinese patent publication No. CN 106111213 a, entitled "synthesis method of catalyst capable of performing catalytic oxidation reaction of organic substances in aqueous phase" discloses a catalyst, and specifically discloses a technical scheme for preparing sulfone compounds by using the catalyst: the catalyst with the molar ratio of 1:400:1200, the dimethyl sulfide and 30% hydrogen peroxide can form stable emulsion in a water phase, the stable emulsion is stirred for 1.5 hours at room temperature, the conversion rate reaches 99%, and the selectivity of the product sulfone reaches 94% -96%. Wherein the conversion number of the catalyst is about 372, and the conversion number of the catalyst is lower.
The chinese patent publication No. CN 108558716a, "a method for preparing sulfone compound by oxidizing thioether under static condition" discloses: adding a silicon dioxide emulsifier and phosphotungstic acid in a mass ratio of 3:1 into a mixed solvent of toluene and water in a volume ratio of 1:2, adding 1 equivalent of a thioether compound, carrying out ultrasonic treatment for 10 minutes to obtain an emulsion system, finally adding 5 equivalents of hydrogen peroxide in a mass ratio of 30%, and standing at room temperature for 5 hours; after the reaction is finished, ethyl acetate solvent is used for extraction, and then the organic phase is distilled and purified to obtain the sulfone compound product. The process requires the use of large amounts of toluene and the number of conversions of the catalyst is low.
Therefore, research into a method for preparing a sulfone compound, which has a higher conversion number and does not require the use of an organic solvent, is still necessary.
Disclosure of Invention
The invention provides a method for preparing sulfone by catalytic oxidation of thioether, wherein the catalyst used in the method for preparing sulfone by catalytic oxidation of thioether has high conversion number, and the preparation of sulfone can be realized at room temperature without using an organic solvent in the reaction process.
The method for preparing the sulfone by catalytic oxidation of the thioether adopts the following technical scheme: catalyst, thioether and 30 percent of H by mass fraction2O2Mixing the water solution in a reaction bottle, and stirring at room temperature for 3-6h to obtain sulfone; the catalyst, thioether and H2O2The molar ratio of (1: 10000: 50000); the catalyst is prepared by reacting8[SiW10O36]·12H2Adding NaVO into hydrochloric acid solution of O3Stirring the solution for 5min, filtering to obtain bright yellow filtrate, dropwise adding chloroform solution of compound A into the bright yellow filtrate, stirring for 5 hr, collecting solid,the solid is the catalyst; the structural formula of the compound A is as follows:
wherein the molecular formula of the catalyst is as follows: [ C ]35H50N+]4[H2SiV2W10O40]。
Preferably, after the reaction is completed by stirring at room temperature, ethyl acetate is added to the reaction system to extract the sulfone obtained.
Preferably, the synthesis method of the compound A is as follows: dissolving the brominated pyrene crystal in toluene, adding hexadecyl tertiary amine, stirring at 50 ℃ for 48 hours to generate white solid precipitate in the stirring process, and filtering, washing and drying to obtain the compound A.
Preferably, the molar ratio of the brominated pyrene crystals to the hexadecyl tertiary amine is 1: 1.
Preferably, when compound a is synthesized, the washing refers to washing the white solid precipitate with toluene.
Preferably, the preparation method of the brominated methyl pyrene comprises the following steps: under the protection of inert gas or nitrogen, adding pyrene methanol and newly steamed toluene into a reaction bottle; cooling to 0 ℃, adding phosphorus tribromide into the reaction bottle, and stirring for 30 min; heating to room temperature, and stirring until the reaction liquid in the reaction bottle is clear; after the reaction is finished, adding a saturated sodium carbonate solution into the reaction bottle, and layering; collecting the organic phase obtained by layering, washing and drying the organic phase; and (3) evaporating to remove toluene in the organic phase, cooling, crystallizing, filtering, and drying in vacuum to obtain the brominated pyrene crystal.
Preferably, the mass-to-volume ratio of the pyrene methanol to the phosphorus tribromide is 2:1, the mass of the pyrene methanol is calculated in g, and the volume of the phosphorus tribromide is calculated in mL.
Preferably, when the brominated formazan pyrene crystal is prepared, the washing is water/saturated brine washing, and the drying of the organic phase is drying of the organic phase by anhydrous magnesium sulfate.
Preferably, the sulfides include, but are not limited to, thioanisole, 3-methoxyphenylthioanisole, p-methylthiophene, and ethylpropylsulfide.
The invention has the beneficial effects that: the catalyst used in the method for preparing the sulfone by catalytic oxidation of the thioether has high conversion number, and can be generated at room temperature without adding a solvent in the reaction process.
The method for preparing the sulfone by catalytic oxidation of the thioether has the advantages that the conversion rate can reach more than 93 percent, the selectivity can reach more than 90 percent, and the conversion number can reach more than 8370.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1 preparation of the catalyst
(1) Synthesis of Compound A
Under the protection of Ar gas, 1.0g of pyrene methanol was placed in a three-necked flask, and 50mL of freshly distilled toluene was added to the three-necked flask. The three-necked flask was cooled to 0 ℃ and then 0.5mL of phosphorus tribromide was added dropwise to the system. After the addition was complete, stirring was continued at this temperature for 30 min. Stirring was then carried out at room temperature until the solution was clear. After completion of the reaction, 26mL of a saturated sodium carbonate solution was added to cause separation, and the organic phase was washed twice with 26mL of water and saturated brine, respectively. Then, the mixture is dried by using anhydrous magnesium sulfate, filtered, most of toluene is evaporated by using a rotary evaporator, the mixture is cooled and crystallized to obtain bromomethylpyrene crystals, and the bromomethylpyrene crystals are filtered and dried in vacuum to obtain 0.8g of bromomethylpyrene. 0.8g of bromomethylpyrene was dissolved in 16mL of toluene, and an equimolar amount of hexadecyl tertiary amine was added to the system, and stirred at 50 ℃ for 48 hours, during which a white precipitate appeared. After completion of the reaction, filtration was carried out, and the solid was washed with a small amount of toluene. Drying in vacuum to obtain the compound A. The structural formula is as follows:
(2) preparation of catalyst by using compound A as raw material
0.27mmol of K8[SiW10O36]·12H2O (synthetic methods see: ref. A.T ez and G. Herv, Inorg. Synth.,1990,27,85.) quickly dissolved in 2.8mL of 1mol/L HCl solution, 1.1mL of NaVO3The solution (0.5mol/L) was added, stirred for 5 minutes and filtered to give a bright yellow filtrate. 50mL of a chloroform solution in which 0.27mmol of Compound A was dissolved was added dropwise to the above solution (K)8[SiW10O36]·12H2O hydrochloric acid solution), continuously stirring for 5 hours, collecting the solid, washing with ethanol for 3 times, and drying at 50 ℃ to obtain the catalyst. The molecular formula of the catalyst is as follows: [ C ]35H50N+]4[H2SiV2W10O40]。
EXAMPLE 2 catalytic oxidation of thioether to sulfone (all catalysts used were as prepared in example 1)
(1) Mu mol of catalyst, 10mmol of thioanisole and 50mmol of 30% hydrogen peroxide are mixed and stirred at room temperature, and the mixture reacts for 3 hours. After the reaction is finished, ethyl acetate solvent is used for extraction, a Gas Chromatograph (GC) is used for detecting the conversion rate and selectivity after an organic phase is dried, and a gas chromatography-mass spectrometer (GC-MS) is used for carrying out qualitative analysis on the product. According to calculation, the conversion rate of the sulfone prepared by taking the thioanisole as a raw material is 98%, the selectivity is 90%, and the conversion number (TON) is 8820.
(2) Mu mol of the catalyst, 10mmol of thiophenyl ether and 50mmol of 30% hydrogen peroxide were mixed and stirred at room temperature, and reacted for 6 hours. After the reaction is finished, ethyl acetate solvent is used for extraction, a Gas Chromatograph (GC) is used for detecting the conversion rate and selectivity after an organic phase is dried, and a gas chromatography-mass spectrometer (GC-MS) is used for carrying out qualitative analysis on the product. According to calculation, the sulfone is prepared by taking the thiophenyl ether as a raw material, the conversion rate is 99%, the selectivity is 99%, and the conversion number (TON)9801 is obtained.
(3) Mu mol of catalyst, 10mmol of 3-methoxy-thiobenzoxide and 50mmol of 30% hydrogen peroxide are mixed and stirred at room temperature for reaction for 6 hours. Conversion 93%, selectivity 90%, conversion number (TON) 8370.
(4) Mu mol of catalyst, 10mmol of p-methyl thiobenzoxide and 50mmol of 30% hydrogen peroxide are mixed and stirred at room temperature, and the reaction is carried out for 6 hours. After the reaction is finished, ethyl acetate solvent is used for extraction, a Gas Chromatograph (GC) is used for detecting the conversion rate and selectivity after an organic phase is dried, and a gas chromatography-mass spectrometer (GC-MS) is used for carrying out qualitative analysis on the product. By calculation, the conversion rate of the sulfone prepared by taking the p-methyl phenyl sulfide as a raw material is 97%, the selectivity is 99%, and the conversion number (TON)9603 is obtained.
(5) Mu mol of the catalyst, 10mmol of ethyl propyl sulfide and 50mmol of 30% hydrogen peroxide were mixed and stirred at room temperature, and reacted for 6 hours. After the reaction is finished, ethyl acetate solvent is used for extraction, a Gas Chromatograph (GC) is used for detecting the conversion rate and selectivity after an organic phase is dried, and a gas chromatography-mass spectrometer (GC-MS) is used for carrying out qualitative analysis on the product. According to calculation, the conversion rate of the sulfone prepared by taking the ethyl propyl sulfide as a raw material is 98%, the selectivity is 97%, and the conversion number (TON) is 9506.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The method for preparing the sulfone by catalytic oxidation of the thioether is characterized in that a catalyst, the thioether and 30 mass percent of H2O2Mixing the aqueous solution in a reaction bottle, stirring at room temperature for reaction for 3-6h to prepare the sulfone; the catalyst, thioether and H2O2The molar ratio of (1: 10000: 50000); the catalyst is prepared by reacting8[SiW10O36]·12H2Adding NaVO into hydrochloric acid solution of O3Stirring the solution for 5min, filtering to obtain bright yellow filtrate, dropwise adding a chloroform solution of a compound A into the bright yellow filtrate, continuously stirring for 5h, and collecting a solid, wherein the solid is the catalyst; the structural formula of the compound A is as follows:
2. the method for preparing sulfone by catalytic oxidation of thioether according to claim 1, wherein after the reaction is completed by stirring at room temperature, ethyl acetate is added to the reaction system to extract the sulfone obtained.
3. The process for the catalytic oxidation of a thioether to a sulfone according to claim 1, wherein the compound a is synthesized by the following steps: dissolving 1-bromomethylpyrene crystals in toluene, adding hexadecyl tertiary amine, stirring at 50 ℃ for 48 hours to generate white solid precipitate in the stirring process, filtering, washing and drying in vacuum to obtain the compound A.
4. The method for preparing sulfone by catalytic oxidation of thioether according to claim 3, wherein the molar ratio of the 1-bromomethylpyrene crystals to the hexadecyl tertiary amine is 1: 1.
5. The process for preparing sulfone by catalytic oxidation of thioether according to claim 3, wherein, in the synthesis of compound A, the washing is carried out by washing the precipitate of white solid with toluene.
6. The method for preparing sulfone from thioether through catalytic oxidation according to any one of claims 3 to 5, wherein 1-bromomethylpyrene is prepared by the following steps: under the protection of inert gas or nitrogen, adding pyrene methanol and newly steamed toluene into a reaction bottle; cooling to 0 ℃, adding phosphorus tribromide into the reaction bottle, and stirring for 30 min; heating to room temperature, and stirring until the reaction liquid in the reaction bottle is clear; after the reaction is finished, adding a saturated sodium carbonate solution into the reaction bottle, and layering; collecting the organic phase obtained by layering, washing and drying the organic phase; and (3) evaporating to remove a proper amount of toluene in the organic phase, cooling, crystallizing, filtering, and drying in vacuum to obtain the 1-bromomethylpyrene crystal.
7. The method of claim 6, wherein the mass to volume ratio of pyrene methanol to phosphorus tribromide is 2:1, the mass of pyrene methanol is in g, and the volume of phosphorus tribromide is in mL.
8. The method of claim 6, wherein the washing step is performed with water/saturated brine, and the drying step is performed with anhydrous magnesium sulfate.
9. The method of claim 1, wherein said sulfides include, but are not limited to, thioanisole, 3-methoxybenzathione, p-methylbenzathione, and ethylpropyl sulfide.
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| CN201910747846.4A CN110590617B (en) | 2019-08-14 | 2019-08-14 | Method for preparing sulfone by catalytic oxidation of thioether |
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| CN201910747846.4A CN110590617B (en) | 2019-08-14 | 2019-08-14 | Method for preparing sulfone by catalytic oxidation of thioether |
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| Publication Number | Publication Date |
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| CN110590617A CN110590617A (en) | 2019-12-20 |
| CN110590617B true CN110590617B (en) | 2022-02-18 |
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