Sulfide oxidation catalyst, preparation method thereof and preparation method of sulfonepyraclostrobin

Abstract

The present invention provides a thioether oxidation catalyst, a preparation method thereof and a preparation method of sulfonepyraclostrobin. The preparation method includes: step S1, a selenium source and a first solvent are formulated into a first solution; step S2, a Lewis acid source is added to the first solution, and after the first mixing, a second solution is obtained; step S3, an organic base ligand source is added to the second solution, and after the second mixing, a third solution is obtained; step S4, the third solution is subjected to a solvent thermal reaction at 100 DEG C to 150 DEG C to obtain a thioether oxidation catalyst. The present invention combines a selenium source, a Lewis acid source and an organic base ligand source in a specific order and condition, and ultimately forms a structurally special, inorganic-organic hybridized selenite catalyst under solvent thermal conditions. The active atom utilization rate of the obtained catalyst is high, and the adsorption property to the reactant molecules is strong, which is conducive to the deep oxidation of the reactant, accelerates the oxidation of thioether to sulfone, and improves the selectivity and production efficiency of the reaction.

Description

Technical Field

[0001] The present invention relates to the field of organic synthesis, and in particular to a sulfide oxidation catalyst, a preparation method thereof, and a preparation method of sulfonepyraclostrobin. Background Art

[0002] As a new generation of highly effective broad-spectrum herbicide, sulfonepyraclostrobin has received extensive attention and application in agricultural production in recent years due to its unique chemical structure and excellent biological activity. Its mechanism of action is mainly to interfere with the biosynthesis of very long chain fatty acids (VLCFA) in plants, inhibit the early growth of seedlings, and thus effectively control weed infestations in crop fields. The synthesis of sulfonepyraclostrobin intermediates, especially the oxidation of sulfide intermediates, is a key technology in its production process. This step directly determines the quality and yield of the final product. At present, the main technical routes for the oxidation of sulfide in sulfonepyraclostrobin involve a variety of catalyst systems. Common catalysts include tungsten metal catalysts, precious metal complexes, inorganic acids and ionic liquids. They each have certain advantages, but they also expose some technical bottlenecks in practical applications.

[0003] CN111393427A uses sodium tungstate as a catalyst and hydrogen peroxide as an oxidant to directly oxidize sulfides into sulfone products with a content exceeding 99%. However, the reaction time is long, requiring 8-10 hours, and the catalyst is difficult to separate and recycle, making it unsuitable for industrial production. CN115850254A uses palladium or copper catalysts, which are expensive and complex to synthesize, resulting in low product yields. CN114716429A uses a functionalized acidic ionic liquid catalyst to enhance the oxidizing power of hydrogen peroxide, with the best reported results achieving a purity of 95.5% and a yield of 99.2%. However, the use of ionic liquids as catalysts has drawbacks such as high preparation costs, complex processes, difficulty in recycling, and inability to achieve continuous batch production.

[0004] In other words, the main catalysts for oxidizing existing sulfide intermediates to produce sulfonepyraclostrobin are tungsten metal catalysts, precious metal complexes, inorganic acids, ionic liquids, etc., but there are the following problems: 1. The process is intermittent and has high process risks. It is limited by the heat and mass transfer of the intermittent equipment itself. The reaction time is generally long, resulting in poor selectivity of the product sulfone; 2. The catalyst system is relatively concentrated, mainly tungsten catalysts or precious metals, and the catalyst cost is relatively expensive.

[0005] Based on this, there is an urgent need to develop a new catalyst system for the oxidation of sulfur-containing ether sulfone pyraclostrobin intermediates, which can not only significantly reduce production costs and simplify the production process, but also be suitable for continuous production processes, while maintaining the efficiency and selectivity of the reaction, reducing the impact on the environment, and providing a more optimized and sustainable solution for the industrial production of sulfone pyraclostrobin. Summary of the Invention

[0006] The main purpose of the present invention is to provide a sulfide oxidation catalyst, a preparation method thereof and a preparation method of sulfonepyraclostrobin, so as to solve the problem that the catalysts in the prior art cannot catalyze the oxidation of sulfur-containing sulfonepyraclostrobin intermediates with high conversion rate and high selectivity, and prepare sulfonepyraclostrobin with high yield.

[0007] To achieve the above-mentioned objectives, a first aspect of the present invention provides a method for preparing a sulfide oxidation catalyst, comprising: step S1, preparing a selenium source and a first solvent into a first solution; step S2, adding a Lewis acid source to the first solution, and obtaining a second solution after a first mixing; step S3, adding an organic base ligand source to the second solution, and obtaining a third solution after a second mixing; and step S4, subjecting the third solution to a solvothermal reaction at 100°C to 150°C to obtain a sulfide oxidation catalyst.

[0008] Furthermore, the first solvent includes water and acetonitrile, and the molar ratio of the selenium source to water is 1:(20-90), and the volume ratio of water to acetonitrile in the first solvent is (2-3):1; and / or step S1 is performed at 30°C-40°C.

[0009] Furthermore, in step S2, the molar ratio of the selenium source to the Lewis acid source is 1:(0.1-3.0); and / or, the first mixing time is 0.5h-1.0h, and the first mixing is performed at 25±2°C.

[0010] Furthermore, in step S3, the molar ratio of the selenium source to the organic base ligand source is 1:(0.8-2.0); and / or the second mixing time is 0.5h-1.0h, and the second mixing is performed at 30°C-40°C.

[0011] Furthermore, in step S4, the reaction temperature of the solvothermal reaction is 110° C. to 130° C., and the reaction time is 8 h to 15 h.

[0012] Furthermore, the selenium source is selected from one or more of elemental selenium, selenium oxide, selenite and selenate; selenite is selected from one or more of sodium selenite, potassium selenite, zinc selenite and barium selenite; selenate is selected from one or more of sodium selenate, zinc selenate, copper selenate and potassium selenate; the Lewis acid source is selected from one or more of a metal source and an ammonium source; the metal source is selected from one or more of a zinc source, a vanadium source, an iron source, a molybdenum source, an aluminum source, a titanium source and a copper source; the metal source is in the form of one or more of a nitrate, a basic sulfate, a chloride, a potassium salt and an ammonium salt. The ammonium source is added in the form of chloride; the organic base ligand source is selected from one or more of ethylenediamine, triethylamine, 1,8-diazabicyclo[5,4,0]-undec-7-ene, 1,5-diazabicyclo[4,3,0]-5-nonene, 1,4-diazabicyclo[2,2,2]octane, N-methylpyrrolidine and tert-butylamine; preferably, the Lewis acid source is selected from one or more of zinc nitrate, zinc chloride, ammonium metavanadate, ferric nitrate, ammonium heptamolybdate, aluminum nitrate, titanyl sulfate, potassium metatitanate, copper chloride and ammonium chloride.

[0013] A second aspect of the present invention provides a sulfide oxidation catalyst, which is prepared by the above-mentioned preparation method of the sulfide oxidation catalyst.

[0014] A third aspect of the present invention provides a method for preparing sulfonepyrazoline, wherein a sulfonepyrazoline intermediate containing a sulfide is oxidized with hydrogen peroxide in the presence of a sulfide oxidation catalyst to obtain sulfonepyrazoline; the sulfide-containing sulfonepyrazoline intermediate has a structure shown in the following formula I:

[0015]

[0016] Formula I.

[0017] Furthermore, before the oxidation reaction, the preparation method of sulfonepyraclostrobin further includes the step of activating the sulfide oxidation catalyst. The activation treatment includes: mixing hydrogen peroxide and the sulfide oxidation catalyst in an organic solvent, and stirring for 1 hour to 2 hours to activate the sulfide oxidation catalyst; wherein the molar ratio of hydrogen peroxide to the sulfide oxidation catalyst is (0.5-1.0):1.

[0018] Furthermore, in the oxidation reaction, the feed rate of the sulfide oxidation catalyst is 0.1 g / min to 0.2 g / min; the feed rate of the sulfide-containing sulfonepyraclostrobin intermediate is 1.2 g / min to 1.5 g / min; the hydrogen peroxide is added dropwise at a rate of 1.0 g / min to 1.5 g / min; the retention time of the hydrogen peroxide is 0.5 h to 2 h, and the reaction temperature of the oxidation reaction is 40° C. to 65° C.

[0019] By applying the technical solution of the present invention, a selenium source, a Lewis acid source, and an organic base ligand source are reacted in a specific order and under specific conditions, and finally a structurally special, inorganic-organic hybrid selenite catalyst is formed under solvent thermal conditions. The obtained catalyst has a high active atom utilization rate and strong adsorption to reactant molecules, which is conducive to the deep oxidation of the reactants, accelerates the oxidation of sulfides to sulfones, improves the selectivity of the reaction, and also improves production efficiency. At the same time, the catalyst prepared by the present invention has the remarkable characteristics of fast reaction speed, mild reaction conditions, and high product purity. In addition, the preparation process of the present invention is simple, the reagents or catalysts are cheap, the catalyst can be recycled and reused, and the catalyst can be continuously produced in a coil, reducing the adverse effects of large reaction heat release and high process risks, providing feasibility for industrial production. DETAILED DESCRIPTION

[0020] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the embodiments.

[0021] As described in the background art, the catalysts in the prior art have the problem of being unable to catalyze the oxidation of sulfur-containing sulfonepyraclostrobin intermediates with high conversion and high selectivity, and to prepare sulfonepyraclostrobin in high yield. In order to solve the above technical problems, the first aspect of the present invention provides a method for preparing a sulfide oxidation catalyst, comprising: step S1, preparing a first solution from a selenium source and a first solvent; step S2, adding a Lewis acid source to the first solution, and obtaining a second solution after a first mixing; step S3, adding an organic base ligand source to the second solution, and obtaining a third solution after a second mixing; step S4, subjecting the third solution to a solvothermal reaction at 100°C to 150°C to obtain a sulfide oxidation catalyst.

[0022] The technical solution of the present invention is to combine the selenium source, Lewis acid source and organic base ligand source in a specific order and under specific conditions to finally form a structurally special inorganic-organic hybrid selenite catalyst under solvent thermal conditions. IV O3] 2-The unique triangular pyramidal configuration of the group allows it to be covalently bonded with an organic base to form an inorganic-organic hybrid selenite. In the crystal structure of the resulting compound, the MO (metal-oxygen bond, or ammonia molecule bond) polyhedron is connected to the SeO3 triangular pyramid to form an inorganic layer, and the layers are connected to each other by means of coordination bonds with the organic ligands to form a multidimensional structure. Specifically, during the reaction process, the selenium source is first dissolved to uniformly disperse it and provide a suitable reaction medium for subsequent reactions. Subsequently, a Lewis acid source is added to the stirred solution, and the selenium compound and the metal ions provided by the Lewis acid are preliminarily connected through coordination bonds to form a polyhedron. Thereafter, an organic base ligand is added, which further forms coordination bonds with the selenium compound and the metal ions provided by the Lewis acid. In this step, the precursor containing the inorganic layer begins to form, and the SeO3 triangular pyramid of selenium is connected to the polyhedron of the Lewis acid central ion, preliminarily constructing the basic unit of the inorganic layer. Finally, the system is transferred into a hydrothermal reactor and subjected to a solvothermal reaction to strengthen the connection between the formed inorganic layer and the organic ligand and promote further improvement of the structure.

[0023] The catalyst prepared by the present invention exhibits significant characteristics such as fast reaction speed, mild reaction conditions, and high product purity. Furthermore, the preparation process is simple, reagents or catalysts are inexpensive, the catalyst is recyclable, and continuous production of the catalyst in coils is achieved, reducing the adverse effects of high reaction heat release and high process risks, thus facilitating industrial production.

[0024] Furthermore, the first solvent preferably comprises water and acetonitrile, and the molar ratio of the selenium source to water is 1:(20-90), more preferably 1:(20-50), thereby reducing the formation of unnecessary selenium clusters, thereby making the resulting catalyst have higher activity and better selectivity. The volume ratio of water to acetonitrile in the first solvent is preferably (2-3):1, so as to provide good solubility and more suitable polarity, which facilitates more uniform mixing of the selenium source with the Lewis acid and organic base, thereby forming a more structurally stable catalyst. Furthermore, step S1 is preferably carried out at 30°C to 40°C to achieve higher solubility and stability, providing a more optimal reaction medium for the subsequent synthesis of the catalyst.

[0025] In several typical embodiments, the molar ratio of the selenium source to the Lewis acid source is 1:(0.1-3.0).

[0026] In step S2, the molar ratio of the selenium source to the Lewis acid source is preferably 1:(0.1-2.0), thereby promoting the formation of a more stable hybrid structure between the Lewis acid source and the selenium source, while reducing excessive passivation of the catalyst active sites, thereby improving the catalytic performance of the resulting catalyst. Furthermore, in step S2, the first mixing time is preferably 0.5 h to 1.0 h, and the first mixing is performed at 25±2°C to facilitate more complete contact and reaction between the selenium source and the Lewis acid source, forming more evenly distributed active centers, and further improving the activity and stability of the catalyst in the sulfide oxidation reaction.

[0027] In several typical embodiments, the molar ratio of the selenium source to the organic base ligand source is 1:(0.8-2.0).

[0028] In step S3, in order to promote the organic base to form a more stable coordination bond between the inorganic layers, thereby more significantly optimizing the structure of the obtained catalyst and improving its catalytic performance, the molar ratio of the selenium source to the organic base ligand source is preferably 1: (0.8~1.2); and / or, the second mixing time is 0.5h~1.0h, and the second mixing is carried out at 30℃~40℃.

[0029] In the above preparation process, a complete catalyst structure is finally formed through a solvothermal reaction in step S4. Preferably, the solvothermal reaction temperature is 110°C to 130°C, and the reaction time is 8 hours to 15 hours. This temperature range and reaction time can more effectively promote the deep crystallization of the catalyst precursor and the coordination connection of the organic base ligand, forming a hybrid selenite catalyst with a three-dimensional structure and higher activity and selectivity.

[0030] In several typical embodiments, the selenium source is selected from one or more of elemental selenium, selenium oxide, selenite and selenate; selenite is selected from one or more of sodium selenite, potassium selenite, zinc selenite and barium selenite, and selenate is selected from one or more of sodium selenate, zinc selenate, copper selenate and potassium selenate; the Lewis acid source is selected from one or more of a metal source and an ammonium source, and the metal source is selected from one or more of a zinc source, a vanadium source, an iron source, a molybdenum source, an aluminum source, a titanium source and a copper source; the metal source is added in the form of one or more of a nitrate, a basic sulfate, a chloride, a potassium salt and an ammonium salt, and the ammonium source is added in the form of a chloride; the organic base ligand source is selected from one or more of ethylenediamine, triethylamine, 1,8-diazabicyclo[5,4,0]-undec-7-ene, 1,5-diazabicyclo[4,3,0]-5-nonene, 1,4-diazabicyclo[2,2,2]octane, N-methylpyrrolidine and tert-butylamine. Among them, especially the zinc source, vanadium source, iron source, molybdenum source, titanium source and copper source in the metal source, can use the empty or partially filled d orbital to receive the lone pair of electrons of the ligand; the aluminum source can use the empty valence layer s and p orbitals to accept the lone pair of electrons of the ligand; and the ammonium source uses the empty orbital formed by the sp3 hybridization of the nitrogen atom to coordinate, and finally forms an inorganic layer in the form of a MO (metal-oxygen bond, or ammonia molecular bond) polyhedron, connected to the SeO3 triangular pyramid to form an inorganic layer, forming a sulfide oxidation catalyst with stable structure and excellent catalytic performance. And further preferably, the Lewis acid source is selected from one or more of zinc nitrate, zinc chloride, ammonium metavanadate, iron nitrate, ammonium heptamolybdate, aluminum nitrate, titanyl sulfate, potassium metatitanate, copper chloride and ammonium chloride. These salts have higher compatibility with the above-mentioned reaction system provided by the present invention, thereby helping to form a more stable catalyst structure and improve its catalytic performance.

[0031] In several particularly typical embodiments, the Lewis acid source includes a vanadium source (specifically, ammonium metavanadate) and a zinc source (specifically, zinc chloride), with the molar ratio of the vanadium source to the zinc source being 1:(0.4-0.5); or, the Lewis acid source includes a vanadium source (specifically, ammonium metavanadate) and a copper source (specifically, copper chloride), with the molar ratio of the vanadium source to the copper source being 1:(0.4-0.5). In these two types of solutions, the two Lewis acid sources can form a more stable three-dimensional network structure in combination with the selenium source, resulting in the resulting catalyst exhibiting more stable catalytic activity and high product selectivity during the catalytic process.

[0032] A second aspect of the present invention provides a sulfide oxidation catalyst prepared by the above-described method for preparing a sulfide oxidation catalyst. The steps of the above-described method ultimately form a compound that not only exhibits highly efficient catalytic performance but also exhibits multidimensional structural complexity. The resulting catalyst exhibits high active atom utilization and strong adsorption for reactant molecules, facilitating deep oxidation of the reactants, accelerating the oxidation of sulfides to sulfones, improving reaction selectivity, and enhancing production efficiency.

[0033] It should be noted that due to the particularity of the material field and the limitations of existing testing and characterization methods, it is difficult to conduct a comprehensive quantitative characterization of the complex crystal structure and microstructure of the catalyst obtained above, but the performance test results show that the catalyst obtained in this application has better catalytic oxidation performance, and is particularly suitable for the oxidation reaction of sulfonepyraclostrobin intermediates containing sulfide with hydrogen peroxide under the action of a sulfide oxidation catalyst to obtain sulfonepyraclostrobin.

[0034] A third aspect of the present invention provides a method for preparing sulfonepyrazoline, wherein a sulfonepyrazoline intermediate containing a sulfide is oxidized with hydrogen peroxide in the presence of a sulfide oxidation catalyst to obtain sulfonepyrazoline; the sulfide-containing sulfonepyrazoline intermediate has a structure shown in the following formula I:

[0035]

[0036] Formula I.

[0037] In the above-mentioned method for preparing sulfonepyraclostrobin, the mechanism of sulfide oxidation is as follows: first, hydrogen peroxide forms a hydrogen bond between the oxygen atom and the sulfur atom of the sulfide, making the sulfide active. The activated sulfide undergoes an oxidation reaction with hydrogen peroxide, wherein the sulfur atom of the sulfide undergoes an electrophilic attack with the oxygen atom to form an SO single bond, thereby generating a thiol intermediate. This intermediate further forms a hydrogen bond with chlorine peroxide. The activated thiol undergoes an oxidation reaction with chlorine peroxide, wherein the sulfur atom of the thiol undergoes an electrophilic attack with the oxygen atom to form an S=O double bond (i.e., sulfoxide). The sulfoxide undergoes another oxidation reaction to become a sulfone.

[0038] Based on this, the catalyst provided by the present invention has a selenite structure coordinated by three oxygen atoms, which is a trigonal pyramid (pseudo-tetrahedron) structure similar to that of an ammonia molecule. IV There is a pair of active lone electron pairs on HSeO3. - 、Se2O5 2- Acid radicals such as Se IVThe pair of active lone electron pairs on the molecule can be considered as an invisible structure-directing agent. This allows them to form non-centrosymmetric structures in stereochemistry, thus giving the compound some interesting physical and chemical properties. Specifically, the covalently bonded compound (C2N2H8) prepared in Example 1 of the present invention is 0.5 Zn3SeO3: This compound crystallizes in the P21 / n space group. Both zinc ions are hexacoordinated and form an octahedral structure with oxygen and nitrogen atoms. Two ZnO5N octahedra and one ZnO6 octahedron form Zn3O by sharing edges. 12 N2 trimers, which form chains by sharing vertex oxygen atoms, are then connected by SeO3 tetrahedra to form a two-dimensional layered structure. This novel ligand structure improves the atomic utilization of the catalyst during the reaction, facilitates the adsorption and deep oxidation of reactants, accelerates the oxidation of sulfides to sulfones, and improves the selectivity and production efficiency of the reaction.

[0039] In particular, the resulting structure is particularly suitable for the oxidation reaction of a sulfoether-containing sulfonepyrazoline intermediate with hydrogen peroxide in the presence of a sulfoether oxidation catalyst to produce sulfopyrazoline. This is because this structure can more accurately adsorb the sulfoether intermediate of sulfopyrazoline, promoting its oxidation reaction with hydrogen peroxide, making the reaction pathway more direct, reducing the formation of byproducts, and improving the purity of sulfopyrazoline.

[0040] In several typical embodiments, before the oxidation reaction, the application further includes a step of activating the sulfide oxidation catalyst, the activation treatment comprising: mixing hydrogen peroxide and the sulfide oxidation catalyst in an organic solvent, and stirring for 1 hour to 2 hours to activate the sulfide oxidation catalyst; wherein the molar ratio of hydrogen peroxide to the sulfide oxidation catalyst is (0.5-1.0):1.

[0041] Activation treatment involves pre-contacting the catalyst with hydrogen peroxide to activate the catalyst's surface active centers, enabling a faster initiation of the subsequent oxidation reaction and enhancing its catalytic activity. An activation time of 1 to 2 hours is particularly effective. Within this timeframe, the catalyst's active centers are more fully activated without the passivation or structural changes that can occur with excessive activation times, resulting in an optimal catalytic state. A molar ratio of (0.5 to 1.0):1 more effectively promotes the binding of hydrogen peroxide as an oxidant to the catalyst, allowing for more precise control of the degree of activation. This results in a faster catalyst response in the subsequent oxidation reaction and more efficient catalytic oxidation of the sulfide intermediate to form pyraclostrobin.

[0042] In the above activation process, the mass concentration of hydrogen peroxide is further preferably 25% to 50%. The interaction of hydrogen peroxide with the catalyst and reactants within this concentration range is more moderate, so as to better maintain the structural stability of the catalyst while achieving activation.

[0043] In the oxidation reaction, the feed rate of the sulfide oxidation catalyst is 0.1g / min~0.2g / min; the feed rate of the sulfide-containing sulfonepyraclostrobin intermediate is 1.2g / min~1.5g / min; the hydrogen peroxide is added dropwise, and the dropwise addition rate is 1.0g / min~1.5g / min. The preferred feed rate promotes more uniform contact between the reactants and the catalyst during the reaction. Under these reaction conditions, the active sites of the catalyst can more effectively contact the sulfide intermediate, accelerating the oxidation reaction, allowing the reaction to proceed smoothly and efficiently in continuous production, thereby improving production efficiency. The preferred retention time of hydrogen peroxide is 0.5h~2.0h, and the reaction temperature of the oxidation reaction is 40℃~65℃, which can make the thermodynamic conditions of the reaction more suitable, thereby better balancing the reaction rate and product selectivity.

[0044] Furthermore, the sulfide-containing sulfonepyraclostrobin intermediate is preferably added in the form of an intermediate solution, and the concentration of the sulfide-containing sulfonepyraclostrobin intermediate in the intermediate solution is 0.5±0.02 g / mL. At this concentration, the active ingredient in the intermediate solution can more fully contact the active sites on the catalyst surface, thereby further accelerating the oxidation reaction while maintaining the stability of the reaction system.

[0045] The present application is further described in detail below with reference to specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in this application.

[0046] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0047] Example 1

[0048] A preparation method of a sulfide oxidation catalyst:

[0049] (1) Weigh 250 g (13.88 mol) of deionized water and 125 mL of acetonitrile (i.e., water:acetonitrile = 2:1, volume ratio), then weigh 30.8 g (0.278 mol) of selenium dioxide and add them to the mixture. Stir at 40°C until completely dissolved to obtain a first solution. The molar ratio of selenium dioxide to water is 1:50.

[0050] (2) Add 37.9 g (0.278 mol) of zinc chloride (i.e., zinc source, selenium source: zinc source = 1:1, molar ratio) to the first solution, stir vigorously at room temperature (25 ± 2 ° C) for 1 h, and wait until it is completely dissolved to obtain a second solution.

[0051] (3) Control the temperature to 30 to 40°C, and add 16.7 g (0.278 mol) of ethylenediamine (i.e., organic base ligand source, selenium dioxide: ethylenediamine = 1:1, molar ratio) dropwise to the second solution. The addition time is mainly based on temperature control. After the addition is completed, keep warm and stir for 0.5 h to obtain the third solution.

[0052] (4) The third solution system was transferred into a hydrothermal reactor, heated to 110°C, and reacted for 8 hours.

[0053] (5) After the reaction is completed, the mixture is cooled to room temperature and filtered. The product is then washed twice with purified water and acetonitrile, each time using 200 mL. The washed solid is placed in an oven and dried at 60°C for 10 h to obtain a sulfide oxidation catalyst.

[0054] Example 2

[0055] A preparation method of a sulfide oxidation catalyst:

[0056] (1) Weigh 250 g (13.88 mol) of deionized water and 125 mL of acetonitrile (water:acetonitrile = 2:1, volume ratio), then weigh 96.08 g (0.556 mol) of sodium selenite and add them to the mixture. Stir at 35°C until completely dissolved to obtain a first solution. The molar ratio of sodium selenite to water is 1:25.

[0057] (2) Add 64.99 g (0.556 mol) of ammonium metavanadate and 37.86 g (0.278 mol) of zinc chloride (i.e., vanadium source, selenium source: vanadium source: zinc source = 1:1:0.5, molar ratio) to the first solution, stir vigorously at room temperature (25±2°C) for 1 h, and wait until all of them are dissolved to obtain a second solution.

[0058] (3) Control the temperature to 30 to 40°C, and add 56.22 g (0.555 mol) of triethylamine (i.e., organic base ligand source, sodium selenite: triethylamine = 1:1, molar ratio) dropwise to the second solution. The addition time is mainly based on temperature control. After the addition is completed, the mixture is stirred for 0.5 h to obtain a third solution.

[0059] (4) The third solution system was transferred into a hydrothermal reactor, heated to 120°C, and reacted for 15 hours.

[0060] (5) After the reaction is completed, the mixture is cooled to room temperature and filtered. The product is then washed twice with purified water and acetonitrile, each time using 200 mL. The washed solid is placed in an oven and dried at 80°C for 8 h to obtain a sulfide oxidation catalyst.

[0061] Example 3

[0062] A preparation method of a sulfide oxidation catalyst:

[0063] (1) Weigh 250 g (13.88 mol) of deionized water and 125 mL of acetonitrile (water:acetonitrile = 2:1, volume ratio), then weigh 87.47 g (0.463 mol) of sodium selenate and add them to the mixture. Stir at 35°C until completely dissolved to obtain a first solution. The molar ratio of sodium selenate to water is 1:30.

[0064] (2) Add 81.73 g (0.07 mol) of ammonium heptamolybdate (i.e., molybdenum source, selenium source: molybdenum source = 1:1.06, molar ratio) to the first solution, stir vigorously at room temperature (25±2°C) for 0.5 h, and wait until it is completely dissolved to obtain a second solution.

[0065] (3) Control the temperature to 30 to 40°C, and add 46.85 g (0.463 mol) of triethylamine (i.e., organic base ligand source, sodium selenate: triethylamine = 1:1, molar ratio) dropwise to the second solution. The addition time is mainly based on temperature control. After the addition is completed, the mixture is stirred for 0.5 h to obtain a third solution.

[0066] (4) The third solution system was transferred into a hydrothermal reactor, heated to 125°C, and reacted for 10 hours.

[0067] (5) After the reaction is completed, the mixture is cooled to room temperature and filtered. The product is then washed twice with purified water and acetonitrile, each time using 200 mL. The washed solid is placed in an oven and dried at 70°C for 10 h to obtain a sulfide oxidation catalyst.

[0068] Example 4

[0069] A preparation method of a sulfide oxidation catalyst:

[0070] (1) Weigh 250 g (13.88 mol) of deionized water and 125 mL of acetonitrile (water:acetonitrile = 2:1, volume ratio), then weigh 80.06 g (0.463 mol) of sodium selenite and add them to the mixture. Stir at 35°C until completely dissolved to obtain a first solution. The molar ratio of sodium selenite to water is 1:30.

[0071] (2) Add 10.58 g (0.066 mol) of titanyl sulfate (i.e., titanium source, selenium source: titanium source = 1:0.143, molar ratio) to the first solution and stir vigorously at room temperature (25 ± 2 ° C) for 0.5 h until it is completely dissolved to obtain a second solution.

[0072] (3) Control the temperature between 30 and 40°C, and add 39.42 g (0.463 mol) of N-methylpyrrolidine (NMP) (i.e., an organic base ligand source, sodium selenite:NMP = 1:1, molar ratio) dropwise to the second solution. The addition time is mainly controlled by temperature control. After the addition is completed, the mixture is stirred for 0.5 h to obtain a third solution.

[0073] (4) The third solution system was transferred into a hydrothermal reactor, heated to 110°C, and reacted for 15 hours.

[0074] (5) After the reaction is completed, the mixture is cooled to room temperature and filtered. The product is then washed twice with purified water and acetonitrile, each time using 200 mL. The washed solid is placed in an oven and dried at 80°C for 10 h to obtain a sulfide oxidation catalyst.

[0075] Example 5

[0076] A preparation method of a sulfide oxidation catalyst:

[0077] (1) Weigh 250 g (13.88 mol) of deionized water and 125 mL of acetonitrile (i.e., water:acetonitrile = 2:1, volume ratio), then weigh 61.64 g (0.556 mol) of selenium dioxide and add them to the mixture. Stir at 35°C until completely dissolved to obtain a first solution. The molar ratio of selenium dioxide to water is 1:50.

[0078] (2) Add 37.35 g (0.278 mol) of copper chloride and 64.99 g of ammonium metavanadate (0.556 mol) (i.e., copper source, selenium source: copper source: vanadium source = 1:0.5:1, molar ratio) to the first solution, stir vigorously at room temperature (25 ± 2 ° C) for 1 h, and wait until they are completely dissolved to obtain a second solution.

[0079] (3) Control the temperature between 30 and 40°C, and add 84.58 g (0.556 mol) of 1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU) (i.e., an organic base ligand source, selenium dioxide:DBU = 1:1, molar ratio) dropwise to the second solution. The addition time is mainly controlled by temperature control. After the addition is completed, the mixture is stirred for 1 hour to obtain a third solution.

[0080] (4) The third solution system was transferred into a hydrothermal reactor, heated to 110°C, and reacted for 12 hours.

[0081] (5) After the reaction is completed, the mixture is cooled to room temperature and filtered. The product is then washed twice with purified water and acetonitrile, each time using 200 mL. The washed solid is placed in an oven and dried at 65°C for 12 h to obtain a sulfide oxidation catalyst.

[0082] Example 6

[0083] A preparation method of a sulfide oxidation catalyst:

[0084] (1) Weigh 250 g (13.88 mol) of deionized water and 125 mL of acetonitrile (water:acetonitrile = 2:1, volume ratio), then weigh 80.06 g (0.463 mol) of sodium selenite and add them to the mixture. Stir at 35°C until completely dissolved to obtain a first solution. The molar ratio of sodium selenite to water is 1:20.

[0085] (2) Add 81.74 g (0.07 mol) of ammonium heptamolybdate (i.e., molybdenum source, selenium source: molybdenum source = 1:0.15, molar ratio) to the first solution, stir vigorously at room temperature (25±2°C) for 1 h, and wait until it is completely dissolved to obtain a second solution.

[0086] (3) Control the temperature between 30 and 40 °C, and add 51.93 g (0.463 mol) of 1,4-diazabicyclo[2,2,2]octane (DABCO) (i.e., organic base ligand source, sodium selenite:DABCO = 1:1, molar ratio) dropwise to the second solution. The addition time is mainly controlled by temperature control. After the addition is completed, the mixture is stirred for 1 hour to obtain a third solution.

[0087] (4) The third solution system was transferred into a hydrothermal reactor, heated to 120°C, and reacted for 12 hours.

[0088] (5) After the reaction is completed, the mixture is cooled to room temperature and filtered. The product is then washed twice with purified water and acetonitrile, each time using 200 mL. The washed solid is placed in an oven and dried at 65°C for 12 h to obtain a sulfide oxidation catalyst.

[0089] Example 7

[0090] A preparation method of a sulfide oxidation catalyst:

[0091] The only difference between this embodiment and embodiment 1 is that in step (1), the amount of water is changed so that the volume ratio of water to acetonitrile is changed to 1:1; at the same time, the stirring temperature is changed to 25°C. Specifically:

[0092] (1) Weigh 100 g (5.56 mol) of deionized water and 100 mL of acetonitrile (i.e., water:acetonitrile = 1:1, volume ratio), then weigh 30.8 g (0.278 mol) of selenium dioxide and add them to the mixture. Stir at 25°C until completely dissolved to obtain a first solution. The molar ratio of selenium dioxide to water is 1:20.

[0093] Example 8

[0094] A preparation method of a sulfide oxidation catalyst:

[0095] The only difference between this embodiment and embodiment 1 is that in step (1), the amount of water is changed so that the molar ratio of selenium dioxide to water is changed to 1:100, and the volume ratio of water to acetonitrile is changed to 4:1; at the same time, the stirring temperature is changed to 45°C. Specifically:

[0096] (1) Weigh 500 g (27.8 mol) of deionized water and 125 mL of acetonitrile (i.e., water:acetonitrile = 4:1, volume ratio), then weigh 30.8 g (0.278 mol) of selenium dioxide and add them, and stir at 45°C until completely dissolved to obtain a first solution. The molar ratio of selenium dioxide to water is 1:100.

[0097] Example 9

[0098] A preparation method of a sulfide oxidation catalyst:

[0099] The only difference between this embodiment and embodiment 1 is that in step (2), the amount of zinc source is changed so that the molar ratio of selenium source to zinc source is changed to 1:0.05; and the stirring time is changed to 0.4h. Specifically:

[0100] (2) Add 1.89 g (0.0139 mol) of zinc chloride (i.e., zinc source, selenium source: zinc source = 1:0.05, molar ratio) to the first solution and stir vigorously at room temperature (25 ± 2 ° C) for 0.4 h until it is completely dissolved to obtain a second solution.

[0101] Example 10

[0102] A preparation method of a sulfide oxidation catalyst:

[0103] The only difference between this embodiment and embodiment 1 is that in step (2), the amount of zinc source is changed so that the molar ratio of selenium source to zinc source is changed to 1:3.5; and the stirring time is changed to 1.2 h. Specifically:

[0104] (2) Add 132.62 g (0.973 mol) of zinc chloride (i.e., zinc source, selenium source: zinc source = 1:3.5, molar ratio) to the first solution, and stir vigorously at room temperature (25 ± 2 ° C) for 1.2 h until it is completely dissolved to obtain a second solution.

[0105] Example 11

[0106] A preparation method of a sulfide oxidation catalyst:

[0107] The only difference between this embodiment and embodiment 1 is that in step (3), the amount of ethylenediamine is changed so that the molar ratio of selenium dioxide to ethylenediamine is changed to 1:0.5; at the same time, the stirring temperature is changed to 50°C and the stirring time is changed to 0.4h.

[0108] (3) Control the temperature at 50°C and add 8.35 g (0.139 mol) of ethylenediamine (i.e., organic base ligand source, selenium dioxide: ethylenediamine = 1:0.5, molar ratio) dropwise to the second solution. The addition time is mainly based on temperature control. After the addition is completed, keep warm and stir for 0.4 h to obtain the third solution.

[0109] Example 12

[0110] A preparation method of a sulfide oxidation catalyst:

[0111] The only difference between this embodiment and embodiment 1 is that in step (3), the amount of ethylenediamine is changed so that the molar ratio of selenium dioxide to ethylenediamine is changed to 1:2.5; at the same time, the stirring temperature is changed to 25°C and the stirring time is changed to 1.2 hours. Specifically:

[0112] (3) Control the temperature at 25°C and add 41.8 g (0.695 mol) of ethylenediamine (i.e., organic base ligand source, selenium dioxide: ethylenediamine = 1:2.5, molar ratio) dropwise to the second solution. The addition time is mainly based on temperature control. After the addition is completed, keep warm and stir for 1.2 hours to obtain the third solution.

[0113] Example 13

[0114] A preparation method of a sulfide oxidation catalyst:

[0115] The only difference between this embodiment and embodiment 1 is that in step (4), the temperature of the solvent thermal reaction is changed to 100°C and the time is changed to 18 hours.

[0116] Example 14

[0117] A preparation method of a sulfide oxidation catalyst:

[0118] The only difference between this embodiment and embodiment 1 is that in step (4), the temperature of the solvent thermal reaction is changed to 150° C. and the time is changed to 6 h.

[0119] Comparative Example 1

[0120] A preparation method of a sulfide oxidation catalyst:

[0121] (1) Weigh 250 g (13.88 mol) of deionized water and 125 mL of acetonitrile (i.e., water:acetonitrile = 2:1, volume ratio), then weigh 30.8 g (0.278 mol) of selenium dioxide and add them to the mixture. Stir at 40°C until completely dissolved to obtain a first solution. The molar ratio of selenium dioxide to water is 1:50.

[0122] (2) Control the temperature to 30 to 40°C, and add 16.7 g (0.278 mol) of ethylenediamine (i.e., organic base ligand source, selenium dioxide: ethylenediamine = 1:1, molar ratio) dropwise to the first solution. The addition time is mainly based on temperature control. After the addition is completed, keep warm and stir for 0.5 h to obtain the second solution.

[0123] (3) The second solution system was transferred into a hydrothermal reactor, heated to 110°C, and reacted for 8 hours.

[0124] (4) After the reaction is completed, the mixture is cooled to room temperature and filtered. The product is then washed twice with purified water and acetonitrile, each time using 200 mL. The washed solid is placed in an oven and dried at 60°C for 10 h to obtain a sulfide oxidation catalyst.

[0125] That is, the only difference between this comparative example and Example 1 is that no Lewis acid source is added.

[0126] Comparative Example 2

[0127] A preparation method of a sulfide oxidation catalyst:

[0128] (1) Weigh 250 g (13.88 mol) of deionized water and 125 mL of acetonitrile (i.e., water:acetonitrile = 2:1, volume ratio), then weigh 30.8 g (0.278 mol) of selenium dioxide and add them to the mixture. Stir at 40°C until completely dissolved to obtain a first solution. The molar ratio of selenium dioxide to water is 1:50.

[0129] (2) Add 37.9 g (0.278 mol) of zinc chloride (i.e., zinc source, selenium source: zinc source = 1:1, molar ratio) to the first solution, stir vigorously at room temperature (25 ± 2 ° C) for 1 h, and wait until it is completely dissolved to obtain a second solution.

[0130] (3) The second solution system was transferred into a hydrothermal reactor, heated to 110°C, and reacted for 8 hours.

[0131] (4) After the reaction is completed, the mixture is cooled to room temperature and filtered. The product is then washed twice with purified water and acetonitrile, each time using 200 mL. The washed solid is placed in an oven and dried at 60°C for 10 h to obtain a sulfide oxidation catalyst.

[0132] That is, the only difference between this comparative example and Example 1 is that no organic base ligand source is added.

[0133] Comparative Example 3

[0134] A preparation method of a sulfide oxidation catalyst:

[0135] (1) Weigh 250 g (13.88 mol) of deionized water and 125 mL of acetonitrile (i.e., water:acetonitrile = 2:1, volume ratio), then weigh 30.8 g (0.278 mol) of selenium dioxide and add them to the mixture. Stir at 40°C until completely dissolved to obtain a first solution. The molar ratio of selenium dioxide to water is 1:50.

[0136] (2) Add 37.9 g (0.278 mol) of zinc chloride (i.e., zinc source, selenium source: zinc source = 1:1, molar ratio) to the first solution, stir vigorously at room temperature (25 ± 2 ° C) for 1 h, and wait until it is completely dissolved to obtain a second solution.

[0137] (3) Control the temperature to 30 to 40°C, and add 16.7 g (0.278 mol) of acetic acid (i.e., the organic base ligand source, selenium dioxide: acetic acid = 1:1, molar ratio) dropwise to the second solution. The addition time is mainly based on temperature control. After the addition is completed, the mixture is stirred for 0.5 h to obtain a third solution.

[0138] (4) The third solution system was transferred into a hydrothermal reactor, heated to 110°C, and reacted for 8 hours.

[0139] (5) After the reaction is completed, the mixture is cooled to room temperature and filtered. The product is then washed twice with purified water and acetonitrile, each time using 200 mL. The washed solid is placed in an oven and dried at 60°C for 10 h to obtain a sulfide oxidation catalyst.

[0140] That is, the only difference between this comparative example and Example 1 is that in step (3), an equimolar amount of acetic acid is used to replace ethylenediamine.

[0141] Comparative Example 4

[0142] A preparation method of a sulfide oxidation catalyst:

[0143] (1) Weigh 250 g (13.88 mol) of deionized water and 125 mL of acetonitrile (i.e., water:acetonitrile = 2:1, volume ratio), then weigh 30.8 g (0.278 mol) of selenium dioxide and add them to the mixture. Stir at 40°C until completely dissolved to obtain a first solution. The molar ratio of selenium dioxide to water is 1:50.

[0144] (2) Add 37.9 g (0.278 mol) of zinc chloride (i.e., zinc source, selenium source: zinc source = 1:1, molar ratio) to the first solution, stir vigorously at room temperature (25 ± 2 ° C) for 1 h, and wait until it is completely dissolved to obtain a second solution.

[0145] (3) Control the temperature to 30 to 40°C, and add 16.7 g (0.278 mol) of ethylenediamine (i.e., organic base ligand source, selenium dioxide: ethylenediamine = 1:1, molar ratio) dropwise to the second solution. The addition time is mainly based on temperature control. After the addition is completed, keep warm and stir for 0.5 h to obtain the third solution.

[0146] (4) The third solution system was transferred into a hydrothermal reactor, heated to 80°C, and reacted for 8 hours.

[0147] (5) After the reaction is completed, the mixture is cooled to room temperature and filtered. The product is then washed twice with purified water and acetonitrile, each time using 200 mL. The washed solid is placed in an oven and dried at 60°C for 10 h to obtain a sulfide oxidation catalyst.

[0148] Comparative Example 5

[0149] A preparation method of a sulfide oxidation catalyst:

[0150] (1) Weigh 250 g (13.88 mol) of deionized water and 125 mL of acetonitrile (i.e., water:acetonitrile = 2:1, volume ratio), then weigh 30.8 g (0.278 mol) of selenium dioxide and add them to the mixture. Stir at 40°C until completely dissolved to obtain a first solution. The molar ratio of selenium dioxide to water is 1:50.

[0151] (2) Add 37.9 g (0.278 mol) of zinc chloride (i.e., zinc source, selenium source: zinc source = 1:1, molar ratio) to the first solution, stir vigorously at room temperature (25 ± 2 ° C) for 1 h, and wait until it is completely dissolved to obtain a second solution.

[0152] (3) Control the temperature to 30 to 40°C, and add 16.7 g (0.278 mol) of ethylenediamine (i.e., organic base ligand source, selenium dioxide: ethylenediamine = 1:1, molar ratio) dropwise to the second solution. The addition time is mainly based on temperature control. After the addition is completed, keep warm and stir for 0.5 h to obtain the third solution.

[0153] (4) The third solution system was transferred into a hydrothermal reactor, heated to 160°C, and reacted for 8 hours.

[0154] (5) After the reaction is completed, the mixture is cooled to room temperature and filtered. The product is then washed twice with purified water and acetonitrile, each time using 200 mL. The washed solid is placed in an oven and dried at 60°C for 10 h to obtain a sulfide oxidation catalyst.

[0155] Application Example 1

[0156] The sulfide oxidation catalyst obtained in Example 1 was used as the catalyst.

[0157] Before use, the catalyst system was preliminarily activated: 100 mL of acetonitrile was added to a round-bottom flask, and then 31.49 g of a 30% dual oxidation catalyst precursor was added, wherein the molar ratio of hydrogen peroxide to sulfide oxidation catalyst was 0.5:1, and the activation time was 1 h.

[0158] (1) Catalytic oxidation of sulfides:

[0159] After activation, the catalyst system was fed into the coil at a rate of 0.1 g / min, a thioether solution in acetonitrile (concentration 0.52 g / ml) was fed at a rate of 1.5 g / min, and hydrogen peroxide was fed at a rate of 1 g / min. The reaction temperature was 65°C, and hydrogen peroxide was added dropwise at multiple points throughout the process, with a retention time of 0.5 h. Liquid phase analysis of the reaction results is shown in Table 1.

[0160] (2) Catalytic oxidation of sulfonepyraclostrobin intermediate containing sulfide to obtain sulfonepyraclostrobin:

[0161] After activation, the catalyst system was fed at a rate of 0.1 g / min. An acetonitrile solution of the thioether-containing pyrazoline intermediate (concentration 0.52 g / ml) was fed at a rate of 1.2 g / min, and hydrogen peroxide was fed at a rate of 1.5 g / min into the coil. The reaction temperature was 40°C, and hydrogen peroxide was added dropwise at multiple locations throughout the process, with a retention time of 2 hours. Liquid phase analysis of the reaction revealed a 100% feed conversion and a 97% selectivity for the pyrazoline product.

[0162] The reaction scheme in this process is as follows.

[0163]

[0164] Application Example 2

[0165] The sulfide oxidation catalyst obtained in Example 2 was used as the catalyst.

[0166] Before use, the catalyst system was preliminarily activated: 100 mL of acetonitrile was added to a round-bottom flask, and then 31.49 g of a 30% dual oxidation catalyst precursor was added, wherein the molar ratio of hydrogen peroxide to sulfide oxidation catalyst was 1:0.8, and the activation time was 1.5 h.

[0167] (1) Catalytic oxidation of sulfides:

[0168] After activation, the catalyst system was fed into the coil at a rate of 0.2 g / min, a thioether solution in acetonitrile (concentration 0.52 g / ml) was fed at a rate of 1.5 g / min, and hydrogen peroxide was fed at a rate of 1 g / min. The reaction temperature was 55°C, and hydrogen peroxide was added dropwise at multiple points throughout the process, with a retention time of 1 hour. Liquid phase analysis of the reaction results is shown in Table 1.

[0169] (2) Catalytic oxidation of sulfonepyraclostrobin intermediate containing sulfide to obtain sulfonepyraclostrobin:

[0170] After activation, the catalyst system was fed at a rate of 0.2 g / min. An acetonitrile solution of the sulfide-containing pyrazoline intermediate (concentration 0.52 g / ml) was fed at a rate of 1.5 g / min, and hydrogen peroxide was fed at a rate of 1.5 g / min into the coil. The reaction temperature was 65°C, and hydrogen peroxide was added dropwise at multiple points throughout the process, with a retention time of 0.5 h. Liquid phase chromatography revealed a 100% feed conversion and 98% selectivity for the pyrazoline product.

[0171] Application Example 3

[0172] The sulfide oxidation catalyst obtained in Example 3 was used as the catalyst.

[0173] Before use, the catalyst system was preliminarily activated: 100 mL of acetonitrile was added to a round-bottom flask, and then 41.99 g of a 30% dual oxidation catalyst precursor was added, wherein the molar ratio of hydrogen peroxide to sulfide oxidation catalyst was 1:1, and the activation time was 2 h.

[0174] (1) Catalytic oxidation of sulfides:

[0175] After activation, the catalyst system was fed into the coil at a rate of 0.2 g / min, a thioether solution in acetonitrile (concentration 0.52 g / ml) was fed at a rate of 1.5 g / min, and hydrogen peroxide was fed at a rate of 1 g / min. The reaction temperature was 55°C, and hydrogen peroxide was added dropwise at multiple points throughout the process, with a retention time of 1 hour. Liquid phase analysis of the reaction results is shown in Table 1.

[0176] (2) Catalytic oxidation of sulfonepyraclostrobin intermediate containing sulfide to obtain sulfonepyraclostrobin:

[0177] After activation, the catalyst system was fed at a rate of 0.1 g / min. An acetonitrile solution of the sulfide-containing pyrazoline intermediate (concentration 0.52 g / ml) was fed at a rate of 1.2 g / min, and hydrogen peroxide was fed at a rate of 1 g / min into the coil. The reaction temperature was 55°C, and hydrogen peroxide was added dropwise at multiple locations with a retention time of 1 hour. Liquid phase chromatography revealed a 100% feed conversion and 99% selectivity for the pyrazoline product.

[0178] Application Example 4

[0179] The sulfide oxidation catalyst obtained in Example 4 was used as the catalyst.

[0180] Before use, the catalyst system was preliminarily activated: 100 mL of acetonitrile was added to a round-bottom flask, and then 41.99 g of a 30% dual oxidation catalyst precursor was added, wherein the molar ratio of hydrogen peroxide to sulfide oxidation catalyst was 1:1.5, and the activation time was 1.5 h.

[0181] Catalytic oxidation of sulfides:

[0182] After activation, the catalyst system was fed into the coil at a rate of 0.1 g / min, the thioether in acetonitrile solution (concentration 0.52 g / ml) was fed at a rate of 1.5 g / min, and the hydrogen peroxide was fed at a rate of 1 g / min. The reaction temperature was 50°C, and the hydrogen peroxide was added dropwise at multiple points throughout the process, with a retention time of 1 hour. Liquid phase analysis of the reaction results is shown in Table 1.

[0183] Application Example 5

[0184] The sulfide oxidation catalyst obtained in Example 5 was used as the catalyst.

[0185] Before use, the catalyst system was preliminarily activated: 100 mL of acetonitrile was added to a round-bottom flask, and then 56.68 g of a 30% dual oxidation catalyst precursor was added, wherein the molar ratio of hydrogen peroxide to sulfide oxidation catalyst was 1:2, and the activation time was 1.5 h.

[0186] Catalytic oxidation of sulfides:

[0187] After activation, the catalyst system was fed into the coil at a rate of 0.1 g / min, a thioether solution in acetonitrile (concentration 0.52 g / ml) was fed at a rate of 1.5 g / min, and hydrogen peroxide was fed at a rate of 1 g / min. The reaction temperature was 40°C, and hydrogen peroxide was added dropwise at multiple points throughout the process, with a retention time of 0.5 h. Liquid phase analysis of the reaction results is shown in Table 1.

[0188] Application Example 6

[0189] The sulfide oxidation catalyst obtained in Example 6 was used as the catalyst.

[0190] Before use, the catalyst system was preliminarily activated: 100 mL of acetonitrile was added to a round-bottom flask, and then 52.48 g of a 30% dual oxidation catalyst precursor was added, wherein the molar ratio of hydrogen peroxide to sulfide oxidation catalyst was 1:2.5, and the activation time was 1 h.

[0191] Catalytic oxidation of sulfides:

[0192] After activation, the catalyst system was fed into the coil at a rate of 0.15 g / min, the thioether in acetonitrile solution (concentration 0.52 g / ml) was fed at a rate of 1.5 g / min, and the hydrogen peroxide was fed at a rate of 1 g / min. The reaction temperature was 40°C, and the hydrogen peroxide was added dropwise at multiple points throughout the process, with a retention time of 1 hour. Liquid phase analysis of the reaction results is shown in Table 1.

[0193] Application Example 7

[0194] The sulfide oxidation catalyst obtained in Example 7 was used as the catalyst, and activation was performed according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0195] Application Example 8

[0196] The sulfide oxidation catalyst obtained in Example 8 was used as the catalyst, and activation was carried out according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0197] Application Example 9

[0198] The sulfide oxidation catalyst obtained in Example 9 was used as the catalyst, and activation was carried out according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0199] Application Example 10

[0200] The sulfide oxidation catalyst obtained in Example 10 was used as the catalyst, and activation was performed according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0201] Application Example 11

[0202] The sulfide oxidation catalyst obtained in Example 11 was used as the catalyst, and activation was performed according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0203] Application Example 12

[0204] The sulfide oxidation catalyst obtained in Example 12 was used as the catalyst, and activation was performed according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0205] Application Example 13

[0206] The sulfide oxidation catalyst obtained in Example 13 was used as the catalyst, and activation was performed according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0207] Application Example 14

[0208] The sulfide oxidation catalyst obtained in Example 15 was used as the catalyst, and activation was carried out according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0209] Application Example 15

[0210] In this application example, the system after the reaction in application example 5 was filtered, and the catalyst was recovered to obtain a recovered catalyst.

[0211] Afterwards, the recovered catalyst was used as the catalyst and the same reaction conditions as in Application Example 5 were followed to again carry out catalytic oxidation of sulfide. The reaction results were tested using a liquid phase test, as shown in Table 1.

[0212] Application Example 16

[0213] The sulfide oxidation catalyst obtained in Example 1 was used as the catalyst, and the activation treatment was changed to:

[0214] Take 100 mL of acetonitrile, then add all the sulfide oxidation catalyst obtained in Example 1 into a round-bottom flask, and then add 31.49 g of 30% dual oxidation catalyst precursor, wherein the molar ratio of hydrogen peroxide to sulfide oxidation catalyst is 0.2:1, and the activation time is 2 h.

[0215] Then, catalytic oxidation of sulfide was carried out under the same conditions as in Application Example 1. The reaction results were tested in liquid phase and are shown in Table 1.

[0216] Application Example 17

[0217] The sulfide oxidation catalyst obtained in Example 1 was used as the catalyst, and the activation treatment was changed to:

[0218] Take 100 mL of acetonitrile, then add all the sulfide oxidation catalyst obtained in Example 1 into a round-bottom flask, and then add 31.49 g of 30% dual oxidation catalyst precursor, wherein the molar ratio of hydrogen peroxide to sulfide oxidation catalyst is 2:1, and the activation time is 0.2 h.

[0219] Then, catalytic oxidation of sulfide was carried out under the same conditions as in Application Example 1. The reaction results were tested in liquid phase and are shown in Table 1.

[0220] Application Example 18

[0221] The sulfide oxidation catalyst obtained in Example 1 was used as the catalyst for the catalytic oxidation of the sulfide-containing sulfonepyraclostrobin intermediate. The catalyst was activated according to the conditions in Example 1, and the catalytic oxidation conditions of the sulfide-containing sulfonepyraclostrobin intermediate were changed to:

[0222] After activation, the catalyst system was fed at a rate of 0.5 g / min. An acetonitrile solution of the sulfide-containing pyrazoline intermediate (concentration 0.2 g / ml) was fed at a rate of 0.5 g / min, and hydrogen peroxide was fed at a rate of 0.5 g / min into the coil. The reaction temperature was 70°C, and hydrogen peroxide was added dropwise at multiple points throughout the process, with a retention time of 3 hours. Liquid phase analysis of the reaction revealed a 91% feed conversion and 83% selectivity for the pyrazoline product.

[0223] Comparative Application Example 1

[0224] The sulfide oxidation catalyst obtained in Comparative Example 1 was used as the catalyst, and activation was carried out according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0225] Application Comparative Example 2

[0226] The sulfide oxidation catalyst obtained in Comparative Example 2 was used as the catalyst, and activation was carried out according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0227] Application Comparative Example 3

[0228] The sulfide oxidation catalyst obtained in Comparative Example 3 was used as the catalyst, and activation was carried out according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0229] Comparative Application Example 4

[0230] The sulfide oxidation catalyst obtained in Comparative Example 4 was used as the catalyst, and activation was carried out according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0231] Comparative Application Example 5

[0232] The sulfide oxidation catalyst obtained in Comparative Example 5 was used as the catalyst, and activation was carried out according to the conditions in Application Example 1 to achieve catalytic oxidation of sulfide. The reaction results were tested in liquid phase, as shown in Table 1.

[0233] Table 1

[0234]

[0235] From the above description, it can be seen that, compared to the comparative examples, the above-described embodiments of the present invention achieve the preparation of a structurally unique, inorganic-organic hybrid selenite catalyst. The resulting catalyst accelerates the oxidation of sulfides to sulfones, improves reaction selectivity, and enhances production efficiency. It is particularly suitable for the oxidation reaction of a sulfonepyrazoline intermediate containing a sulfide with hydrogen peroxide in the presence of a sulfide oxidation catalyst to obtain sulfonepyrazoline.

[0236] Specifically, by comparing Examples 7 and 8 with Examples 1 to 6, it can be seen that the molar ratio of the selenium source to water, the volume ratio of water to acetonitrile in the preferred step (1), and the temperature conditions in the preferred step S1 can help to more evenly mix the selenium source with the Lewis acid and the organic base, thereby forming a catalyst with a more stable structure.

[0237] Comparing Examples 9 and 10 with Examples 1 to 6, it can be seen that the preferred molar ratio of the selenium source to the Lewis acid source can promote the Lewis acid source and the selenium source to form a more stable hybrid structure, while reducing excessive passivation of the catalyst active sites, thereby improving the catalytic performance of the resulting catalyst.

[0238] Comparing Examples 11 and 12 with Examples 1 to 6, it can be seen that the preferred molar ratio of the selenium source to the organic base ligand source and the temperature conditions of the second mixing can promote the organic base to form more stable coordination bonds between the inorganic layers, thereby more significantly optimizing the structure of the obtained catalyst and improving its catalytic performance.

[0239] Comparing Examples 13 and 14 with Examples 1 to 6, it can be seen that the preferred temperature and time of the solvothermal reaction can more effectively promote the deep crystallization of the catalyst precursor and the coordination connection of the organic base ligand, thereby forming a hybrid selenite catalyst with higher activity and selectivity and a three-dimensional structure.

[0240] By comparing Examples 1 to 5, it can be seen that: when the Lewis acid source includes a vanadium source (specifically, ammonium metavanadate) and a zinc source (specifically, zinc chloride), and the molar ratio of the vanadium source to the zinc source is 1:(0.4~0.5); or, when the Lewis acid source includes a vanadium source (specifically, ammonium metavanadate) and a copper source (specifically, copper chloride), and the molar ratio of the vanadium source to the copper source is 1:(0.4~0.5), the two Lewis acid sources can be respectively combined with the selenium source to form a more stable three-dimensional network structure, so that the resulting catalyst exhibits more stable catalytic activity and high product selectivity during the catalytic process.

[0241] Furthermore, it can be seen from Application Example 15 that the catalyst provided by the present invention can still exhibit excellent catalytic activity after being recycled and reused.

[0242] In the catalytic oxidation process of sulfide, by comparing Application Examples 16 and 17 with Application Example 1, it can be seen that the molar ratio of hydrogen peroxide to the sulfide oxidation catalyst and the activation time during the activation treatment of the sulfide oxidation catalyst are preferably such that the active centers of the catalyst can be more fully activated, thereby obtaining a better catalytic state, thereby more accurately controlling the degree of activation, so that in the subsequent oxidation reaction, the catalyst can respond more quickly and more efficiently catalyze the oxidation of the sulfide intermediate.

[0243] During the catalytic oxidation of the sulfide-containing sulfonepyrazoline intermediate, the feed rate of each raw material and the catalytic temperature and time conditions are preferably selected to promote more effective contact between the active sites of the catalyst and the sulfide intermediate, accelerate the oxidation reaction, and enable the reaction to proceed smoothly and efficiently in continuous production, ultimately achieving a better balance between reaction rate and product selectivity. Furthermore, the sulfide-containing sulfonepyrazoline intermediate is preferably added in the form of an intermediate solution, and the concentration of the sulfide-containing sulfonepyrazoline intermediate in the intermediate solution is 0.5±0.02 g / mL, thereby further accelerating the oxidation reaction while maintaining the stability of the reaction system.

[0244] It should be noted that the terms "first," "second," and the like in the specification and claims of this application are used to distinguish similar objects, and are not necessarily used to describe a specific order or precedence. It should be understood that the terms used in this manner are interchangeable where appropriate, so that the embodiments of the application described herein can, for example, be implemented in an order other than that described herein.

[0245] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A method for preparing a sulfide oxidation catalyst, characterized in that: include: Step S1, preparing a selenium source and a first solvent into a first solution; Step S2, adding a Lewis acid source to the first solution, and obtaining a second solution after a first mixing; Step S3, adding an organic base ligand source to the second solution, and performing a second mixing to obtain a third solution; Step S4, subjecting the third solution to a solvothermal reaction at 100° C. to 150° C. to obtain the sulfide oxidation catalyst; The molar ratio of the selenium source to the Lewis acid source is 1:(0.1-2.0); The molar ratio of the selenium source to the organic base ligand source is 1:(0.8-1.2); The Lewis acid source is selected from one or more of a metal source and an ammonium source, and the metal source is selected from one or more of a zinc source, a vanadium source, an iron source, a molybdenum source, an aluminum source, a titanium source, and a copper source; The organic base ligand source is selected from one or more of ethylenediamine, triethylamine, 1,8-diazabicyclo[5,4,0]-undec-7-ene, 1,5-diazabicyclo[4,3,0]-5-nonene, 1,4-diazabicyclo[2,2,2]octane, N-methylpyrrolidine and tert-butylamine.

2. The method for preparing a sulfide oxidation catalyst according to claim 1, wherein: In the step S1, The first solvent comprises water and acetonitrile, and the molar ratio of the selenium source to the water is 1:(20-90); in the first solvent, the volume ratio of the water to the acetonitrile is (2-3):1; and / or, The step S1 is performed at 30°C to 40°C.

3. The method for preparing a sulfide oxidation catalyst according to claim 2, wherein: In the step S2, The first mixing time is 0.5 h to 1.0 h, and the first mixing is performed at 25±2° C.

4. The method for preparing a sulfide oxidation catalyst according to any one of claims 1 to 3, characterized in that: In the step S3, The second mixing time is 0.5 h to 1.0 h, and the second mixing is performed at 30° C. to 40° C.

5. The method for preparing a sulfide oxidation catalyst according to any one of claims 1 to 3, characterized in that: In step S4, the reaction temperature of the solvent thermal reaction is 110° C. to 130° C., and the reaction time is 8 h to 15 h.

6. The method for preparing a sulfide oxidation catalyst according to any one of claims 1 to 3, characterized in that: The selenium source is selected from one or more of selenium oxide, selenite and selenate; the selenite is selected from one or more of sodium selenite, potassium selenite, zinc selenite and barium selenite; the selenate is selected from one or more of sodium selenate, zinc selenate, copper selenate and potassium selenate; The metal source is added in the form of one or more of nitrate, basic sulfate, chloride, potassium salt and ammonium salt, and the ammonium source is added in the form of chloride.

7. A sulfide oxidation catalyst, characterized in that: The sulfide oxidation catalyst is prepared by the preparation method of the sulfide oxidation catalyst according to any one of claims 1 to 6.

8. A method for preparing sulfonepyraclostrobin, characterized in that: The sulfonepyrazoline intermediate containing sulfoether is oxidized with hydrogen peroxide in the presence of the sulfide oxidation catalyst of claim 7 to obtain the sulfonepyrazoline; the sulfonepyrazoline intermediate containing sulfoether has a structure shown in the following formula I: Formula I.

9. The method for preparing sulfonepyraclostrobin according to claim 8, wherein Before the oxidation reaction, the method for preparing sulfonepyraclostrobin further comprises the step of activating the sulfide oxidation catalyst, wherein the activation treatment comprises: In an organic solvent, hydrogen peroxide and the sulfide oxidation catalyst are mixed and stirred for 1 to 2 hours to activate the sulfide oxidation catalyst; Wherein, the molar ratio of the hydrogen peroxide to the sulfide oxidation catalyst is 1:(0.8~2.5).

10. The method for preparing sulfonepyraclostrobin according to claim 8 or 9, characterized in that: In the oxidation reaction, The feed rate of the sulfide oxidation catalyst is 0.1 g / min to 0.2 g / min; The feed rate of the sulfide-containing sulfone metachloride intermediate is 1.2 g / min to 1.5 g / min; The hydrogen peroxide solution is added dropwise at a rate of 1.0 g / min to 1.5 g / min; The retention time of the hydrogen peroxide solution is 0.5h~2.0h, and the reaction temperature of the oxidation reaction is 40°C~65°C.

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