A process for the simultaneous production of pyroxasulfone and acetone

Abstract

The application belongs to the technical field of pesticide synthesis, and particularly relates to a method for simultaneously producing metrafenone and acetone, which comprises the following steps: taking a compound shown in formula I as an intermediate, reacting the intermediate with isopropyl alcohol under the action of a titanium-silicon molecular sieve to obtain metrafenone and acetone under an oxygen-containing gas; formula I. The application can selectively convert isopropyl alcohol into acetone with high selectivity while oxidizing the intermediate into metrafenone, and acetone is also a high-value-added organic solvent and chemical raw material, which significantly improves the atomic economy and overall economic benefit of the reaction. Meanwhile, the application uses an oxygen-containing gas to replace hydrogen peroxide in the traditional synthesis process, and the oxygen-containing gas is cheap and safe, which greatly reduces the safety hazard in the production process of metrafenone using hydrogen peroxide as a raw material.

Description

Technical Field

[0001] This invention belongs to the field of pesticide synthesis technology, and in particular relates to a method for simultaneously producing sulfonylpyrazole and acetone. Background Technology

[0002] Pyroxasulfone is a pre-emergence herbicide developed by Japan Combinatorial Chemicals Co., Ltd. Its chemical name is 3-[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)pyrazol-4-ylmethylsulfonyl]-4,5-dihydro-5,5-dimethyl-1,2-isoxaazole, and its molecular formula is C2. 12 H 14 F5N3O4S, with a molecular weight of 391.32, is widely used in crops such as wheat, corn, rice, and sunflower. Compared to the traditional herbicide acetochlor, sulfonylpyrazole requires a smaller dosage, has a longer residual effect, and possesses promising market prospects. The chemical structural formula of sulfonylpyrazole is as follows: .

[0003] Currently, most preparation processes for sulfonylpyrazole use hydrogen peroxide and metal catalysts as the oxidation system. For example, Chinese invention patent application CN121717797A discloses a synthesis process for sulfonylpyrazole, with the specific reaction route as follows: Figure 1 As shown, the solution of intermediate 5 reacts directly with hydrogen peroxide in the presence of a catalyst to obtain sulfonylpyrazole. The catalyst is sodium tungstate or molybdenum trioxide. Chinese invention patent application CN111393427A discloses a method for synthesizing sulfonylpyrazole, the specific reaction route of which is as follows: Figure 2 As shown, under catalytic conditions, intermediate VIII is oxidized with hydrogen peroxide to obtain sulfonylpyrazine IX. The catalyst is sodium tungstate and acid. Chinese invention patent application CN113831333A discloses a method for synthesizing sulfonylpyrazine, the specific synthetic route of which is as follows... Figure 3 As shown, the thioether obtained by hydroxymethylation, etherification and condensation reacts with hydrogen peroxide in the presence of a catalyst to produce sulfopyrazol, wherein the catalyst is one of sodium tungstate and ammonium molybdate.

[0004] In the preparation of sulfonylpyrazine, the above-mentioned technical solutions all use an oxidation system composed of hydrogen peroxide and a metal catalyst, which has the following disadvantages: (1) All of the above technical solutions use hydrogen peroxide. Hydrogen peroxide is a strong oxidant. The reaction releases a lot of heat, which requires high equipment corrosion resistance and operating temperature. It poses a safety risk and will generate a large amount of waste liquid.

[0005] (2) The catalyst used is a metal catalyst, which dissolves in the reaction system during the reaction process. After the reaction is completed, it cannot be recovered and reused by simple filtration, which increases the burden of wastewater treatment.

[0006] (3) Only the single synthesis of sulfopyrazole product is considered, without considering the high-value utilization of by-products. Summary of the Invention

[0007] The purpose of this invention is to provide a method for simultaneously producing sulfonylpyrazole and acetone, in order to solve the problem that the existing technology uses hydrogen peroxide and metal catalysts as an oxidation system in the synthesis of sulfonylpyrazole, which generates a large amount of waste liquid and does not consider the high-value utilization of by-products.

[0008] To achieve the above objectives, the present invention provides a method for simultaneously producing sulfonylpyrazole and acetone, comprising the following steps: Using the compound shown in Formula I as an intermediate, the intermediate reacts with isopropanol under the action of titanium silicate molecular sieve in the presence of oxygen-containing gas to obtain sulfopyrazole and acetone. Formula I.

[0009] To address the issues of low safety, large wastewater volume, and lack of high-value utilization of byproducts in existing technologies for producing sulfopyrazine, which utilize hydrogen peroxide and metal catalysts, this invention proposes a new reaction system. This system replaces traditional hydrogen peroxide with oxygen-containing gas and isopropanol, and replaces traditional metal catalysts with titanium-silicon molecular sieves. The oxygen-containing gas offers advantages of high safety and low cost. The titanium-silicon molecular sieve, as a heterogeneous catalyst, is easy to separate and can be used for extended periods. Furthermore, isopropanol not only acts as an organic solvent but also reacts with oxygen in the oxygen-containing gas to produce acetone and water.

[0010] Preferably, the molar ratio of the intermediate to isopropanol is 1:6-10.

[0011] Preferably, the reaction temperature is 50-60℃, the reaction time is 1-3h, and the partial pressure of oxygen in the oxygen-containing gas in the reaction system is 0.1-2MPa.

[0012] By adopting the above technical solution, the contact between the intermediate and isopropanol with the titanium-silicon molecular sieve is carried out under an oxygen-containing gas. The oxygen-containing gas can be pure oxygen or a mixture of pure oxygen and inactive gases. The inactive gas refers to a gas that does not chemically interact with the reactants (intermediate and isopropanol) and the reaction products (sulfonium pyrazol and acetone), such as nitrogen and / or group zero element gases (e.g., argon). The amount of oxygen in the oxygen-containing gas is generally 0.1-99% by volume, preferably 0.5-60% by volume, and more preferably 20-50% by volume. The oxygen-containing gas can also be air. When using air as the oxygen-containing gas, air can be used directly, or the air can be purified to remove particulate matter before use. The function of the oxygen in the oxygen-containing gas is to react with isopropanol in an oxidation reaction, producing acetone and water, thus oxidizing the intermediate into the finished product. The amount of oxygen used is determined to achieve the above function. Generally, the amount of oxygen used is such that the partial pressure of oxygen in the reaction system is 0.01-5 MPa, preferably 0.05-3 MPa, and more preferably 0.1-2 MPa.

[0013] Preferably, a peroxide is added during the reaction process, and the molar ratio of the peroxide to the intermediate is 0.0005-0.05:1.

[0014] By adopting the above technical solution, the conversion rate of raw materials and the selectivity of products in the reaction can be further improved. The peroxide refers to a compound containing an -OO- bond in its molecular structure, and can be hydrogen peroxide and / or organic peroxides. Organic peroxides are substances formed by replacing one or two hydrogen atoms in the hydrogen peroxide molecule with organic groups. The organic peroxide is preferably R1-OO-R2, where R1 and R2 may be the same or different, and each can be H or C4-C. 12 Straight-chain or branched alkyl groups R3 is C4-C 12 The peroxide is a straight-chain or branched alkyl group, where R1 and R2 are not both H. Specific examples of peroxides may include, but are not limited to: hydrogen peroxide, tert-butyl hydrogen peroxide, ethylbenzene hydrogen peroxide, cumene hydrogen peroxide, cyclohexyl hydrogen peroxide, peracetic acid, peroxypropionic acid, dicumene peroxide, di-tert-butyl peroxide, benzoyl peroxide, and dodecyl peroxide.

[0015] Preferably, the titanium-silicon molecular sieve is one or more of the following: MFI structure titanium-silicon molecular sieve (e.g., TS-1), MEL structure titanium-silicon molecular sieve (e.g., TS-2), BEA structure titanium-silicon molecular sieve (e.g., Ti-Beta), MWW structure titanium-silicon molecular sieve (e.g., Ti-MCM-22), hexagonal structure titanium-silicon molecular sieve (e.g., Ti-MCM-41, Ti-SBA-15), MOR structure titanium-silicon molecular sieve (e.g., Ti-MOR), TUN structure titanium-silicon molecular sieve (e.g., Ti-TUN), and other structures of titanium-silicon molecular sieve (e.g., Ti-ZSM-48).

[0016] Preferably, the titanium-silicon molecular sieve includes at least an MFI structure titanium-silicon molecular sieve, wherein the surface silicon-to-titanium ratio of the MFI structure titanium-silicon molecular sieve is not lower than the bulk silicon-to-titanium ratio.

[0017] More preferably, the titanium-silicon molecular sieve is at least partially titanium-silicon molecular sieve TS-1, and the surface silicon-to-titanium ratio of titanium-silicon molecular sieve TS-1 is not lower than the bulk silicon-to-titanium ratio. This can further improve the catalytic performance of the titanium-silicon molecular sieve and further extend its single-pass service life. More preferably, the ratio of the surface silicon-to-titanium ratio to the bulk silicon-to-titanium ratio is 1.2 or higher. More preferably, the ratio of the surface silicon-to-titanium ratio to the bulk silicon-to-titanium ratio is 1.2-5. More preferably, the ratio of the surface silicon-to-titanium ratio to the bulk silicon-to-titanium ratio is 1.5-4.5. More preferably, the ratio of the surface silicon-to-titanium ratio to the bulk silicon-to-titanium ratio is 2.5-4.5. Even more preferably, the ratio of the surface silicon-to-titanium ratio to the bulk silicon-to-titanium ratio is 2-3. The silicon-to-titanium ratio refers to the molar ratio of silicon oxide to titanium oxide. The surface silicon-to-titanium ratio is determined by X-ray photoelectron spectroscopy, and the bulk silicon-to-titanium ratio is determined by X-ray fluorescence spectroscopy.

[0018] Preferably, the preparation method of the MFI-structured titanium-silicon molecular sieve includes the following steps: Inorganic silicon source was dispersed in an aqueous solution containing titanium source and alkali source template agent to obtain a dispersion. After the dispersion was allowed to stand, it was placed in a sealed reaction vessel and crystallized in sequence through stages (1), (2) and (3). After crystallization, the resulting mixture was dried and calcined to obtain titanium silicon molecular sieve with MFI structure.

[0019] The titanium-silicon molecular sieve TS-1 prepared by the above-described method can further improve the catalytic performance and extend the service life of the titanium-silicon molecular sieve.

[0020] The alkali source template agent can be any of the template agents commonly used in the synthesis of titanium silicate molecular sieves. For example, the alkali source template agent can be one or more of quaternary ammonium bases, aliphatic amines, and aliphatic alcoholic amines. Quaternary ammonium bases can be various organic quaternary ammonium bases, aliphatic amines can be compounds formed by replacing at least one hydrogen atom in various NH3 groups with an aliphatic hydrocarbon group (such as an alkyl group), and aliphatic alcoholic amines can be compounds formed by replacing at least one hydrogen atom in various NH3 groups with a hydroxyl-containing aliphatic group (such as an alkyl group).

[0021] The general chemical structural formula of quaternary ammonium bases is as follows: , In the above formula, R1, R2, R3 and R4 are each C1-C4 alkyl groups, including straight-chain alkyl groups of C1-C4 and branched alkyl groups of C3-C4. Specific examples of R1, R2, R3 and R4 may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.

[0022] The general chemical structural formula of aliphatic amines is as follows: , In the above formula, n is an integer of 1 or 2. When n is 1, R 5 It is a C1-C6 alkyl group, including straight-chain C1-C6 alkyl groups and branched C3-C6 alkyl groups, and specific examples may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl, and n-hexyl. When n is 2, R 5 It is a C1-C6 alkylene, including C1-C6 straight-chain alkylene and C3-C6 branched alkylene, and specific examples may include, but are not limited to: methylene, ethylene, n-propylene, n-butylene, n-pentylene or n-hexylene.

[0023] The general chemical structural formula of aliphatic alcoholamines is as follows: , In the above formula, m R 6 Whether identical or different, each is a C1-C4 alkylene group, including C1-C4 straight-chain alkylene groups and C3-C4 branched alkylene groups, specific examples of which may include, but are not limited to: methylene, ethylene, n-propylene, and n-butylene; m is 1, 2, or 3.

[0024] Specific examples of the alkali source template agent may include, but are not limited to, one or more of the following: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide (including various isomers of tetrapropylammonium hydroxide, such as tetra-n-propylammonium hydroxide and tetraisopropylammonium hydroxide), tetrabutylammonium hydroxide (including various isomers of tetrabutylammonium hydroxide, such as tetra-n-butylammonium hydroxide and tetraisobutylammonium hydroxide), ethylamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylenediamine, monoethanolamine, diethanolamine, and triethanolamine. More preferably, the alkali source template agent is one or more of the following: tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. More preferably, the alkali source template agent is tetrapropylammonium hydroxide.

[0025] The titanium source can be an inorganic titanium salt and / or an organic titanate, preferably an organic titanate. The inorganic titanium salt can be one or more of TiCl4, Ti(SO4)2, and TiOCl2; the organic titanate can be selected from general formula R. 7 The compound represented by 4TiO4, where R 7 It is an alkyl group having 1-6 carbon atoms, preferably an alkyl group having 2-4 carbon atoms.

[0026] The inorganic silicon source can be silica gel and / or silica sol, preferably silica gel. The mass percentage of SiO2 in the silica sol can be 10% or more, preferably 15% or more, and more preferably 20% or more.

[0027] Preferably, the silicon source is SiO2, the titanium source is TiO2, the alkali source template agent is N, and the molar ratio of silicon source, titanium source, alkali source template agent and water in the dispersion is preferably 100:(1-6):(8-25):(200-1500), more preferably 100:(2-5):(10-20):(400-1000).

[0028] Preferably, in stage (1), the crystallization is carried out at 80-150℃ for 6-72h, in stage (2), the temperature is lowered to below 70℃ and the residence time is more than 0.5h, and in stage (3), the temperature is raised to 120-200℃ and re-crystallized for 6-96h.

[0029] Preferably, the reaction is carried out in a reaction vessel or a fixed-bed reactor.

[0030] Preferably, when the reaction is carried out in a reactor, the weight ratio of the intermediate to the titanium-silicon molecular sieve is 20:0.5-2; when the reaction is carried out in a fixed-bed reactor, the weight hourly space velocity of the intermediate is 3-5 h⁻¹. -1 .

[0031] The present invention, by adopting the above-described technical solution, has at least the following beneficial effects compared with the prior art: (1) The present invention uses oxygen-containing gas to replace hydrogen peroxide in the prior art. Oxygen-containing gas is cheap and safe, which greatly reduces the safety hazards in the production process of sulfopyrazole using hydrogen peroxide as a raw material, and also significantly reduces the amount of wastewater.

[0032] (2) This invention uses titanium-silicon molecular sieves as catalysts. When the reaction is carried out in the reactor, the catalyst can be directly recovered through simple filtration, reducing the cost of raw materials. In addition, a fixed-bed reactor can be used for the reaction, which is more suitable for continuous industrial production. Catalysts such as sodium tungstate and ammonium molybdate in the prior art are difficult to use for continuous production in a fixed-bed reactor.

[0033] (3) While oxidizing the intermediate to sulfopyrazole, the present invention can also selectively convert isopropanol into acetone. Acetone is also a high-value organic solvent and chemical raw material, which improves the atom economy and overall economic benefits of the reaction.

[0034] (4) This invention can be carried out efficiently at low temperature and medium-low pressure, without the need for strong acid or high temperature and high pressure. The reaction conditions are mild and the product selectivity is high, which is conducive to the industrial production of two products, sulfopyrazole and acetone. Attached Figure Description

[0035] Figure 1 The synthetic route of sulfonylpyrazine in Chinese invention patent application CN121717797A; Figure 2 The synthetic route of sulfonylpyrazine in Chinese invention patent application CN111393427A; Figure 3 The synthetic route of sulfonylpyrazine in Chinese invention patent application CN113831333A; Figure 4 This is a synthetic route diagram of sulfonylpyrazole in this invention. Detailed Implementation

[0036] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with embodiments. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the technical solutions of this invention are within the scope of protection of this invention.

[0037] The chemical structural formulas of the intermediates used in all the following examples are as follows: The CAS number is 656825-92-2.

[0038] The intermediates and other raw materials mentioned above, as well as those in the examples, can all be purchased.

[0039] Example 1 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: (1) At room temperature (20℃), 22.5g of tetraethyl orthosilicate and 7.0g of tetrapropylammonium hydroxide as a template agent were mixed and 59.8g of distilled water were added. After stirring and mixing, the mixture was hydrolyzed at atmospheric pressure and 60℃ for 1.0h to obtain a hydrolyzed solution of tetraethyl orthosilicate. Under vigorous stirring, a solution consisting of 1.1g of tetrabutyl titanate and 5.0g of anhydrous isopropanol was slowly added to the hydrolyzed solution. The resulting mixture was stirred at 75℃ for 3h to obtain a clear and transparent colloid. This colloid was placed in a stainless steel sealed reactor and kept at 170℃ for 36h to obtain a mixture of crystallized products. The mixture of crystallized products was filtered, and the solid material was collected, washed with water, dried at 110℃ for 60min, and then calcined at 500℃ for 6h to obtain titanium silicon molecular sieve TS-1 with a titanium oxide content of 2.8% by weight and a surface silicon-to-titanium ratio / bulk phase silicon-to-titanium ratio of 1.05. The surface silicon-to-titanium ratio was determined by X-ray photoelectron spectroscopy, and the bulk silicon-to-titanium ratio was determined by X-ray fluorescence spectroscopy.

[0040] (2) In a reactor, under the presence of oxygen-containing gas (an atmosphere formed by oxygen with a purity of 99%), the intermediate and isopropanol were reacted with the titanium silicate molecular sieve TS-1 raw powder prepared in step (1) as a catalyst. The molar ratio of the intermediate to isopropanol was 1:8, the weight ratio of the intermediate to the catalyst was 20:1, the temperature was 50°C, the pressure was 2.8 MPa (gauge pressure), and the oxygen partial pressure was 1.8 MPa. After reacting for 2 hours, the resulting reaction mixture was filtered, and the collected liquid mixture was analyzed by gas chromatography. The filtered titanium silicate molecular sieve was directly fed into the reactor for the next reaction, and the reaction was continuously cyclical. The experimental results of the first and 40th cycles are listed in Table 1.

[0041] Example 2 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: Titanium silicate molecular sieve TS-1 was prepared using the same method as step (1) of Example 1, and the intermediate was oxidized using the same method as step (2) of Example 1, except that the reaction temperature was 60°C. The experimental results are listed in Table 1.

[0042] Example 3 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: Titanium silicate molecular sieve TS-1 was prepared using the same method as in step (1) of Example 1, and the intermediate was oxidized using the same method as in step (2) of Example 1. The difference was that in step (2), hydrogen peroxide (provided in the form of 30% by weight hydrogen peroxide) was added to the reactor, so that the contact reaction of the intermediate and isopropanol with the titanium silicate molecular sieve TS-1 raw powder prepared in step (1) as a catalyst was carried out in the presence of hydrogen peroxide, wherein the molar ratio of hydrogen peroxide to intermediate was 0.0005:1. The experimental results are listed in Table 1.

[0043] Example 4 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: Titanium silicate molecular sieve TS-1 was prepared using the same method as in step (1) of Example 1, and the intermediate was oxidized using the same method as in step (2) of Example 1. The difference was that in step (2), hydrogen peroxide (provided in the form of 30% by weight hydrogen peroxide) was added to the reactor, so that the contact reaction of the intermediate and isopropanol with the titanium silicate molecular sieve TS-1 raw powder prepared in step (1) as a catalyst was carried out in the presence of hydrogen peroxide, wherein the molar ratio of hydrogen peroxide to intermediate was 0.05:1. The experimental results are listed in Table 1.

[0044] Example 5 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: The intermediate was oxidized using the same method as in Example 4, except that in step (2), an equal amount of cumene hydroperoxide was used instead of hydrogen peroxide. The experimental results are listed in Table 1.

[0045] Comparative Example 1 The intermediate was oxidized using the same method as in Example 1, except that the titanium silicate molecular sieve TS-1 was not used in step (2). The experimental results are listed in Table 1.

[0046] Comparative Example 2 The intermediate was oxidized using the same method as in Example 1, except that dichloroethane was used instead of isopropanol in step (2). The experimental results are listed in Table 1.

[0047] Comparative Example 3 The intermediate was oxidized using the same method as in Example 1, except that nitrogen was used instead of oxygen in step (2). The experimental results are listed in Table 1.

[0048] Comparative Example 4 The intermediate was oxidized using the same method as in Example 1, except that in step (2), isopropanol was not used; instead, hydrogen peroxide (provided as 30% by weight hydrogen peroxide) was used, with a molar ratio of hydrogen peroxide to intermediate of 4:1. The experimental results are listed in Table 1.

[0049] Table 1. Preparation results of Examples 1-5 and Comparative Examples 1-4

[0050] As shown in Table 1, Examples 1-5 all achieved effective conversion of the intermediate, with high selectivity of the finished product, and co-produced acetone. In Example 2, the increased reaction temperature slightly improved the conversion rate, indicating that temperature adjustment had little impact on the reaction. Examples 3-5 added a small amount of peroxide, which slightly improved the conversion rate and selectivity, and also increased the catalyst's lifespan. The amount of peroxide added in this invention is small and has almost no impact on subsequent processing. Furthermore, it should be noted that the addition of peroxide did not significantly affect the reaction results; even without the aforementioned peroxide, the conversion rate of the raw materials, the selectivity of the finished product, and acetone remained at a high level. In Comparative Example 1, no catalyst was added during the reaction, resulting in a significant decrease in the conversion rates of the intermediate and isopropanol. In Comparative Example 2, no isopropanol was added during the reaction, resulting in a severe decrease in the conversion rate and selectivity of the intermediate. In Comparative Example 3, no oxygen was added during the reaction, and the reaction did not occur. Comparative Examples 1-3 demonstrate that in this invention, the three conditions of titanium silicate molecular sieve as catalyst, isopropanol, and oxygen as reactants are indispensable. Comparative Example 4, without the addition of isopropanol but using a large amount of hydrogen peroxide, showed higher conversion and selectivity of the intermediate. However, the use of large amounts of hydrogen peroxide resulted in higher costs and lower safety. After 40 cycles, the catalytic performance also significantly decreased. In contrast, the catalysts in Examples 1-5 were recycled more frequently. Comparative Example 4 and Examples 1-5 demonstrate that the oxidation system composed of titanium-silicon molecular sieves, oxygen-containing gas, and isopropanol in this invention can replace the oxidation system using hydrogen peroxide and metal catalysts in the prior art. This not only reduces the use of hydrogen peroxide and wastewater volume but also improves the cycle performance of the catalytic reaction. Therefore, the method of this invention can not only oxidize the intermediate to obtain high product selectivity but also yield the byproduct acetone. Furthermore, the method of this invention avoids the problem of increased equipment throughput caused by hydrogen peroxide being provided in hydrogen peroxide form when hydrogen peroxide is used as the oxidant.

[0051] Example 6 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: (1) In this embodiment, the titanium-silicon molecular sieve used as raw material is prepared by the following method, specifically including the following steps: First, tetrabutyl titanate (titanium source) was dissolved in an aqueous solution of tetrapropylammonium hydroxide (alkali source template agent). Then, silica gel (silicon source) was added to obtain a dispersion. In this dispersion, the molar ratio of silicon source:titanium source:alkali source template agent:water was 100:4:12:400, where silicon source was calculated as SiO2, titanium source as TiO2, and alkali source template agent as N. The dispersion was sealed in a beaker with sealing film and allowed to stand at room temperature (25°C) for 24 hours. Then, it was stirred magnetically at 35°C for 2 hours to redisperse the dispersion. The redispersed dispersion was transferred to a sealed reactor. The crystallization process consisted of three stages: the first stage was crystallization at 140℃ for 6 hours; the second stage was cooling the mixture to 30℃ and holding it for 2 hours; and the third stage was continued in the sealed reactor at 170℃ for 12 hours (wherein, the heating rate from room temperature to the crystallization temperature of the first stage was 2℃ / min, the cooling rate from the crystallization temperature of the first stage to the processing temperature of the second stage was 5℃ / min, and the heating rate from the processing temperature of the second stage to the crystallization temperature of the third stage was 10℃ / min). The resulting crystallized product was taken out and dried directly at 110℃ for 2 hours without filtration and washing, and then calcined at 550℃ for 3 hours to obtain titanium-silicon molecular sieve TS-1. The XRD phase diagram of the obtained sample was consistent with that of the titanium-silicon molecular sieve TS-1 prepared in step (1) of Example 1, indicating that the obtained sample was a titanium-silicon molecular sieve with an MFI structure; in the Fourier transform infrared spectrum, at 960 cm⁻¹ -1 The presence of absorption peaks nearby indicates that titanium has entered the molecular sieve framework. In this titanium-silicon molecular sieve, the titanium oxide content is 3.5% by weight, and the surface silicon-to-titanium ratio / bulk silicon-to-titanium ratio is 2.58.

[0052] (2) The intermediate was oxidized using the same method as in step (2) of Example 1, except that the titanium-silicon molecular sieve TS-1 prepared in step (1) of this Example was used. The experimental results are listed in Table 2.

[0053] Example 7 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: (1) Titanium silicate molecular sieve TS-1 was prepared using the same method as in step (1) of Example 6, except that the crystallization temperature of the third stage was also 140℃. The Fourier transform infrared spectrum of the obtained titanium silicate molecular sieve with MFI structure was at 960 cm⁻¹. -1 Absorption peaks also appeared nearby, indicating that titanium has entered the molecular sieve framework. In this titanium-silicon molecular sieve, the surface silicon-to-titanium ratio / bulk silicon-to-titanium ratio is 4.21, and the titanium oxide content is 3.1% by weight.

[0054] (2) The intermediate was oxidized using the same method as in step (2) of Example 1, except that the titanium-silicon molecular sieve TS-1 prepared in step (1) of this example was used. The experimental results are listed in Table 2.

[0055] Example 8 This embodiment provides a method for simultaneously producing sulfonylpyrazine and acetone, including the following steps: (1) Titanium silicate molecular sieve TS-1 was prepared using the same method as in step (1) of Example 6, except that the crystallization temperature of the first stage was 110℃. The Fourier transform infrared spectrum of the obtained titanium silicate molecular sieve with MFI structure was at 960 cm⁻¹. -1 Absorption peaks also appeared nearby, indicating that titanium has entered the molecular sieve framework. In this titanium-silicon molecular sieve, the surface silicon-to-titanium ratio / bulk silicon-to-titanium ratio is 2.37, and the titanium oxide content is 3.2% by weight.

[0056] (2) The intermediate was oxidized using the same method as in step (2) of Example 1, except that the titanium-silicon molecular sieve TS-1 prepared in step (1) of this example was used. The experimental results are listed in Table 2.

[0057] Example 9 This embodiment provides a method for simultaneously producing sulfonylpyrazine and acetone, including the following steps: (1) Titanium silicate molecular sieve TS-1 was prepared using the same method as in step (1) of Example 6, except that the crystallization time in the first stage was 12 h. The Fourier transform infrared spectrum of the obtained titanium silicate molecular sieve with MFI structure was at 960 cm⁻¹. -1 Absorption peaks also appeared nearby, indicating that titanium has entered the molecular sieve framework. In this titanium-silicon molecular sieve, the surface silicon-to-titanium ratio / bulk silicon-to-titanium ratio is 3.78, and the titanium oxide content is 3.4% by weight.

[0058] (2) The intermediate was oxidized using the same method as in step (2) of Example 1, except that the titanium-silicon molecular sieve TS-1 prepared in step (1) of this example was used. The experimental results are listed in Table 2.

[0059] Example 10 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: (1) Using the same steps as in Example 6 (1), the Fourier transform infrared spectrum of the titanium-silicon molecular sieve with the MFI structure obtained is at 960 cm⁻¹. - An absorption peak also appears near ¹, indicating that titanium has entered the molecular sieve framework. In this titanium-silicon molecular sieve, the surface silicon-to-titanium ratio / bulk silicon-to-titanium ratio is 2.75, and the titanium oxide content is 3.1% by weight.

[0060] (2) The intermediate was oxidized using the same method as in step (2) of Example 1, except that the titanium-silicon molecular sieve TS-1 prepared in step (1) of this example was used. The experimental results are listed in Table 2.

[0061] Example 11 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: (1) Titanium silicate molecular sieve TS-1 was prepared using the same method as in step (1) of Example 6, except that the second stage involved cooling to 30°C and holding for 0.2 h. The Fourier transform infrared spectrum of the obtained titanium silicate molecular sieve with MFI structure was at 960 cm⁻¹. - An absorption peak also appears near ¹, indicating that titanium has entered the molecular sieve framework. In this titanium-silicon molecular sieve, the surface silicon-to-titanium ratio / bulk silicon-to-titanium ratio is 1.14, and the titanium oxide content is 2.4% by weight.

[0062] (2) The intermediate was oxidized using the same method as in step (2) of Example 1, except that the titanium-silicon molecular sieve TS-1 prepared in step (1) of this example was used. The experimental results are listed in Table 2.

[0063] Example 12 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: (1) Titanium silicate molecular sieve TS-1 was prepared using the same method as in step (1) of Example 6, except that the second stage was omitted. The Fourier transform infrared spectrum of the obtained titanium silicate molecular sieve with MFI structure was at 960 cm⁻¹. - An absorption peak also appears near ¹, indicating that titanium has entered the molecular sieve framework. In this titanium-silicon molecular sieve, the surface silicon-to-titanium ratio / bulk silicon-to-titanium ratio is 1.08, and the titanium oxide content is 2.5% by weight.

[0064] (2) The intermediate was oxidized using the same method as in step (2) of Example 1, except that the titanium-silicon molecular sieve TS-1 prepared in step (1) of this Example was used. The experimental results are listed in Table 2.

[0065] Example 13 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: (1) Titanium silicate molecular sieve TS-1 was prepared using the same method as in step (1) of Example 6. The difference was that, when preparing titanium silicate molecular sieve TS-1, the aqueous dispersion was not allowed to stand at room temperature for 12 hours, but was directly fed into the reactor for crystallization. The Fourier transform infrared spectrum of the obtained titanium silicate molecular sieve with MFI structure was at 960 cm⁻¹. - An absorption peak also appears near ¹, indicating that titanium has entered the molecular sieve framework. In this titanium-silicon molecular sieve, the titanium oxide content is 3.5% by weight, and the surface silicon-to-titanium ratio / bulk silicon-to-titanium ratio is 1.18.

[0066] (2) The intermediate was oxidized using the same method as in step (2) of Example 1, except that the titanium-silicon molecular sieve TS-1 prepared in step (1) of this example was used. The experimental results are listed in Table 2.

[0067] Table 2 Preparation results of Examples 6-13

[0068] As shown in Table 2, the surface silicon-to-titanium ratio / bulk silicon-to-titanium ratio of the titanium-silicon molecular sieves prepared in Examples 6-10 ranges from 2.37 to 4.21, with an initial intermediate conversion rate of 76-80%. After 45-60 cycles, they still achieve a conversion rate of 69-74% and a selectivity of 85-89%. In contrast, Examples 11-12 (with a surface silicon-to-titanium ratio of 1.08-1.14) show a lower conversion rate after 35 cycles, with a selectivity dropping to 58-59% and a selectivity decreasing to 80-85%, indicating a significantly shortened lifespan. Therefore, to further improve the catalyst lifespan in this invention, titanium-silicon molecular sieves with a higher surface silicon-to-titanium ratio / bulk silicon-to-titanium ratio can be prepared following the staged crystallization steps in Examples 6-10.

[0069] Example 14 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: Molded titanium silicate molecular sieve TS-1 (volume average particle size of 150 μm, based on the total amount of molded titanium silicate molecular sieve TS-1, the content of titanium silicate molecular sieve TS-1 is 75 wt%, the content of silicon oxide is 25 wt%, and the titanium silicate molecular sieve TS-1 is prepared by the same method as step (1) of Example 1)) was packed into a micro fixed-bed reactor to form an equal-diameter catalyst bed. The intermediate and isopropanol were fed into the reactor from the feed port located at the bottom of the reactor to react with the titanium silicate molecular sieve TS-1. During the reaction, oxygen-containing gas (a mixture of 99% pure oxygen and 99% pure nitrogen, wherein the volume ratio of oxygen to nitrogen is 0.25:1) was continuously introduced into the reactor. The molar ratio of the intermediate to isopropanol was 1:10, and the weight hourly space velocity of the intermediate was 4 h⁻¹. -1 The temperature inside the catalyst bed is 60℃, the pressure inside the reactor is 0.8MPa (gauge pressure), and the oxygen partial pressure is 0.16MPa.

[0070] The reaction mixture output from the reactor was analyzed by liquid chromatography during operation, and the experimental results are listed in Table 3.

[0071] Example 15 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: The intermediate was oxidized using the same method as in Example 14, except that an equal mass of shaped hollow titanium-silicon molecular sieves (volume average particle size of 150 μm, with the content of hollow titanium-silicon molecular sieves being 75 wt% and the content of silicon oxide being 25 wt% based on the total amount of shaped hollow titanium-silicon molecular sieves) was used. The experimental results are listed in Table 3. Both the hollow titanium-silicon molecular sieves and silicon oxide mentioned above are commercially available. The hollow titanium-silicon molecular sieves were purchased from Hunan Jianchang Petrochemical Co., Ltd., under the brand name HTS.

[0072] Example 16 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: The intermediate was oxidized using the same method as in Example 14. The difference was that, while maintaining the total catalyst loading in the reactor, a shaped hollow titanium-silicon molecular sieve (same as in Example 15) was first loaded into the reactor, followed by a shaped titanium-silicon molecular sieve TS-1 (same as in Example 14, prepared using the same method as step (1) of Example 1). This allowed the intermediate and isopropanol to first pass through the bed formed by the shaped hollow titanium-silicon molecular sieve, and then through the bed formed by the shaped titanium-silicon molecular sieve TS-1. The weight ratio of the shaped hollow titanium-silicon molecular sieve to the shaped titanium-silicon molecular sieve TS-1 was 1:1, and the inner diameter of the catalyst bed formed by the shaped titanium-silicon molecular sieve TS-1 was the same as that formed by the shaped hollow titanium-silicon molecular sieve. The experimental results are listed in Table 3.

[0073] Example 17 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: The intermediate was oxidized using the same method as in Example 16. The difference was that, while keeping the loading amounts of both the hollow titanium-silicon molecular sieve and the TS-1 molecular sieve constant, the ratio of the inner diameter of the catalyst bed filled with the hollow titanium-silicon molecular sieve to the inner diameter of the catalyst bed filled with the TS-1 molecular sieve was 2:1. The experimental results are listed in Table 3.

[0074] Example 18 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: The intermediate was oxidized using the same method as in Example 17, except that tert-butyl hydrogen peroxide was also introduced into the reactor through a feed inlet located at the bottom of the reactor, so that the contact reaction was carried out in the presence of tert-butyl hydrogen peroxide, wherein the molar ratio of tert-butyl hydrogen peroxide to the intermediate was 0.02:1. The experimental results are listed in Table 3.

[0075] Example 19 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: The intermediate was oxidized using the same method as in Example 18, except that the titanium-silicon molecular sieve TS-1 in the molded titanium-silicon molecular sieve TS-1 was prepared using the following method: First, tetrabutyl titanate (titanium source) was dissolved in an aqueous solution of tetrapropylammonium hydroxide (alkali source template agent). Then, silica gel (silicon source) was added to obtain a dispersion. The molar ratio of silicon source:titanium source:alkali source template agent:water in this dispersion was 100:2:10:600. The silicon source was calculated as SiO2, the titanium source as TiO2, and the alkali source template agent as N. The dispersion was sealed in a beaker with sealing film and allowed to stand at 40°C for 10 hours. Then, it was stirred magnetically at 25°C for 0.5 hours to redisperse the dispersion. The redispersed dispersion was transferred to a sealed reactor and crystallized in three stages. The first stage involved crystallization at 130℃ for 8 hours. The second stage involved cooling the mixture to 50℃ and holding it there for 5 hours. The third stage involved continued crystallization at 170℃ for 16 hours in the sealed reactor (where the heating rate from room temperature to the first-stage crystallization temperature was 1℃ / min, the cooling rate from the first-stage crystallization temperature to the second-stage processing temperature was 10℃ / min, and the heating rate from the second-stage processing temperature to the third-stage crystallization temperature was 20℃ / min). The resulting crystallized product was removed and dried directly at 120℃ for 3 hours without filtration or washing, followed by calcination at 580℃ for 2 hours to obtain titanium silicate molecular sieves. The Fourier transform infrared spectrum of the obtained titanium silicate molecular sieve with an MFI structure showed that at 960 cm⁻¹... - An absorption peak also appeared near ¹, indicating that titanium has entered the molecular sieve framework. In this titanium-silicon molecular sieve, the surface silicon-to-titanium ratio / bulk silicon-to-titanium ratio is 2.25, and the titanium oxide content is 2.6% by weight. The experimental results are listed in Table 3.

[0076] Example 20 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: The intermediate was oxidized using the same method as in Example 19. The difference was that, while keeping the loading amounts of both the hollow titanium-silicon molecular sieve and the TS-1 molecular sieve constant, the ratio of the inner diameter of the catalyst bed filled with the hollow titanium-silicon molecular sieve to the inner diameter of the catalyst bed filled with the TS-1 molecular sieve was 1:2. The experimental results are listed in Table 3.

[0077] Example 21 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: The intermediate was oxidized using the same method as in Example 19. The difference was that, while keeping the loading amounts of both the hollow titanium-silicon molecular sieve and the TS-1 molecular sieve constant, the ratio of the inner diameter of the catalyst bed filled with the hollow titanium-silicon molecular sieve to the inner diameter of the catalyst bed filled with the TS-1 molecular sieve was 1:1. The experimental results are listed in Table 3.

[0078] Example 22 This embodiment provides a method for simultaneously producing sulfonylpyrazole and acetone, including the following steps: (1) The volume average particle size of the shaped titanium silicon molecular sieve TS-1 used in this embodiment is 500 μm. Based on the total amount of shaped titanium silicon molecular sieve TS-1, the content of titanium silicon molecular sieve TS-1 is 85% by weight and the content of silicon oxide is 15% by weight. The titanium silicon molecular sieve TS-1 is prepared by the following method.

[0079] First, tetrabutyl titanate (titanium source) is dissolved in an aqueous solution of tetrapropylammonium hydroxide (alkali source template agent). Then, silica gel (silicon source) is added to obtain a dispersion. In this dispersion, the molar ratio of silicon source: titanium source: alkali source template agent: water is 100:5:18:1000. The silicon source is calculated as SiO2, the titanium source is calculated as TiO2, and the alkali source template agent is calculated as N. The above dispersion was sealed in a beaker with sealing film and allowed to stand at 45°C for 8 hours. The settled dispersion was then transferred to a sealed reactor for crystallization in three stages. The first stage involved crystallization at 140°C for 6 hours. The second stage involved cooling the mixture to 40°C and holding it there for 1 hour. The third stage continued crystallization at 160°C for 12 hours in the sealed reactor (the heating rate from room temperature to the first stage crystallization temperature was 5°C / min, the cooling rate from the first stage crystallization temperature to the second stage processing temperature was 5°C / min, and the heating rate from the second stage processing temperature to the third stage crystallization temperature was 5°C / min). The resulting crystallized product was removed and dried directly at 110°C for 2 hours without filtration or washing, followed by calcination at 550°C for 3 hours to obtain a titanium-silicon molecular sieve. The Fourier transform infrared spectrum of the obtained titanium-silicon molecular sieve with an MFI structure showed a peak at 960 cm⁻¹. - The presence of an absorption peak near ¹ indicates that titanium has entered the molecular sieve framework. In this titanium-silicon molecular sieve, the surface silicon-to-titanium ratio / bulk silicon-to-titanium ratio is 2.71, and the titanium oxide content is 4.3% by weight.

[0080] (2) The volume average particle size of the shaped hollow titanium silicon molecular sieve used in this embodiment is 500 μm. Based on the total amount of the shaped hollow titanium silicon molecular sieve, the content of hollow titanium silicon molecular sieve (from the same source as in Example 15) is 90% by weight and the content of silicon oxide is 10% by weight.

[0081] First, a shaped hollow titanium-silicon molecular sieve is packed into a fixed-bed reactor, followed by the shaped titanium-silicon molecular sieve TS-1 prepared in this embodiment. This allows the intermediate and isopropanol to pass through the bed formed by the shaped hollow titanium-silicon molecular sieve first, and then through the bed formed by the shaped titanium-silicon molecular sieve TS-1. The weight ratio of the shaped hollow titanium-silicon molecular sieve to the shaped titanium-silicon molecular sieve TS-1 is 5:1, and the ratio of the inner diameter of the catalyst bed filled with the shaped hollow titanium-silicon molecular sieve to the inner diameter of the catalyst bed filled with the shaped titanium-silicon molecular sieve TS-1 is also 5:1.

[0082] The intermediate and isopropanol were fed into the reactor through the feed inlet located at the bottom of the reactor to react with the titanium silicate molecular sieve TS-1. During the reaction, oxygen-containing gas (a mixture of 99% pure oxygen and 99% pure nitrogen, with a volume ratio of 0.5:1) was continuously introduced into the reactor. The molar ratio of the intermediate to isopropanol was 1:12, and the weight hourly space velocity (WHSV) of the intermediate was 8 h⁻¹. - ¹. The temperature inside the catalyst bed is 60℃, the pressure inside the reactor is 1.6MPa (gauge pressure), and the oxygen partial pressure is 0.53MPa.

[0083] During operation, the material output from the reactor was analyzed by gas chromatography, and the experimental results are listed in Table 3.

[0084] Table 3. Preparation results of Examples 14-22

[0085] As can be seen from Table 3, the reaction time in the fixed-bed reactor for all examples was 2 hours, the conversion rate of the intermediate was 86-93%, the selectivity of the finished product was 92-96%, and the selectivity of acetone was 95-99%. This proves that the reaction between the intermediate and isopropanol to produce sulfopyrazol and acetone can be carried out not only in a reaction vessel but also in a fixed-bed reactor, which facilitates subsequent continuous production and is conducive to achieving large-scale industrial production.

[0086] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for simultaneously producing sulfonylpyrazol and acetone, characterized in that: Includes the following steps: Using the compound shown in Formula I as an intermediate, the intermediate reacts with isopropanol under the action of titanium silicate molecular sieve in the presence of oxygen-containing gas to obtain sulfopyrazole and acetone. Formula I.

2. The method for simultaneously producing sulfonylpyrazol and acetone according to claim 1, characterized in that: The molar ratio of the intermediate to isopropanol is 1:6-10.

3. The method for simultaneously producing sulfonylpyrazol and acetone according to claim 1, characterized in that: The reaction temperature is 50-60℃, the reaction time is 1-3h, and the partial pressure of oxygen in the oxygen-containing gas in the reaction system is 0.1-2MPa.

4. The method for simultaneously producing sulfonylpyrazol and acetone according to claim 1, characterized in that: Peroxide was also added during the reaction, with a molar ratio of peroxide to intermediate of 0.0005-0.05:

1.

5. The method for simultaneously producing sulfonylpyrazol and acetone according to claim 1, characterized in that: The titanium-silicon molecular sieve is one or more of the following: MFI structure, MEL structure, BEA structure, MWW structure, hexagonal structure, MOR structure, TUN structure, and Ti-ZSM-48.

6. A method for simultaneously producing sulfonylpyrazol and acetone according to claim 5, characterized in that: Titanium-silicon molecular sieves include at least MFI-structured titanium-silicon molecular sieves, and the surface silicon-to-titanium ratio of the MFI-structured titanium-silicon molecular sieve is not lower than the bulk silicon-to-titanium ratio.

7. A method for simultaneously producing sulfonylpyrazol and acetone according to claim 6, characterized in that: The preparation method of MFI structured titanium silicate molecular sieve includes the following steps: Inorganic silicon source was dispersed in an aqueous solution containing titanium source and alkali source template agent to obtain a dispersion. After the dispersion was allowed to stand, it was placed in a sealed reaction vessel and crystallized in sequence through stages (1), (2) and (3). After crystallization, the resulting mixture was dried and calcined to obtain titanium silicon molecular sieve with MFI structure.

8. A method for simultaneously producing sulfonylpyrazol and acetone according to claim 7, characterized in that: Stage (1) Crystallize at 80-150℃ for 6-72h, Stage (2) Cool down to below 70℃ and stay for more than 0.5h, Stage (3) Raise to 120-200℃ and recrystallize for 6-96h.

9. A method for simultaneously producing sulfonylpyrazol and acetone according to claim 1, characterized in that: The reaction takes place in a reaction vessel or a fixed-bed reactor.

10. A method for simultaneously producing sulfonylpyrazol and acetone according to claim 9, characterized in that: When the reaction is carried out in a reactor, the weight ratio of the intermediate to the titanium-silicon molecular sieve is 20:0.5-2; when the reaction is carried out in a fixed-bed reactor, the weight hourly space velocity of the intermediate is 3-5 h⁻¹. -1 .

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