Mechanical chemical synthesis method of sulfonyl methyl benzoic acid compound

Abstract

The invention discloses a mechanochemical synthesis method of a sulfonyl methyl benzoic acid compound, which comprises the following steps: mixing benzyl substituted benzoic acid, aryl sodium sulfinate and an inorganic substance, and carrying out solid-phase nucleophilic substitution reaction through mechanochemical grinding under a solvent-free condition to obtain the sulfonyl methyl benzoic acid compound. Cheap and easily available aryl sodium sulfinate and benzyl substituted benzoic acid are used as raw materials, the target product is prepared by carrying out nucleophilic substitution reaction under a solid phase condition by adopting mechanochemical grinding, the synthesis process is simple, convenient, green and environment-friendly, and the obtained target product is high in yield and purity and suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of pharmaceutical chemical intermediates, in particular to a mechanochemical synthesis method of sulfonamidomethyl benzoic acid compounds. BACKGROUND

[0002] Organic compounds containing sulfonamide groups exhibit wide application value in the fields of organic synthesis chemistry, medicinal chemistry and material science. Sulfonamide group is a strong electron-withdrawing group, which can significantly affect the key physical and chemical properties of the molecule, such as biological activity and acidity. Due to the strong electron-withdrawing property of the sulfonamide group, the adjacent carbon atom is prone to form a stable α-carbon anion under the action of base, and this intermediate can undergo nucleophilic substitution or addition reaction with various electrophilic reagents, thereby deriving target products with diverse structures. In addition, trans-olefin compounds can be selectively synthesized through aldehyde alcohol type reaction of sulfone and subsequent elimination, which makes aryl alkyl sulfone a key intermediate for the synthesis of various natural products.

[0003] In drug molecule design, sulfonamide group is often used as a bioisostere of carbonyl or carboxyl group. Due to its similar volume and charge distribution characteristics to these groups, it not only maintains or enhances the biological activity after introducing small molecules, but also effectively adjusts the solubility, acidity and alkalinity of the molecule, and optimizes the interaction between the drug and the target as a hydrogen bond acceptor. The inherent stability of the sulfonamide structure also helps to improve the metabolic stability and bioavailability of the drug, and prolong its in vivo action time. Among sulfonamide organic compounds, benzoic acid compounds containing sulfonamide methyl are particularly widely used in the development of new chemical reactions and the synthesis of new drugs (such as cardiovascular drugs) due to their unique properties.

[0004] At present, there are many methods for synthesizing sulfonamide methyl benzoic acid compounds reported.

[0005] For example, the synthesis of sulfonamide methyl benzoic acid compounds was first reported in the literature (Journal of Chemical and Engineering Data, 1987, 32(4), 483-485). This method uses aryl thiol and benzyl chloride compounds as starting materials, first reacts to form a thioether intermediate, and then undergoes an oxidation step to obtain the final target sulfonamide product. The reaction route is as follows: .

[0006] This route has obvious defects: first, the thiol reagent used usually has an unbearable stench, which is extremely unfriendly to experimental operators and the environment; second, the multi-step reaction process involves an oxidation step, which not only increases the complexity of the process, but also brings potential environmental pollution and safety risks.

[0007] Another document (Organic Letters, 2005, 7(14), 2973-2975) reports an improved synthesis method. The process uses a benzyl carbonate compound to react with sodium benzenesulfinate in the presence of a noble metal palladium catalyst to synthesize the target product in one step. The reaction scheme is as follows: .

[0008] Although this method avoids the use of foul-smelling thiophenol and simplifies the steps, its core is the use of expensive palladium catalyst. This will significantly increase the raw material cost in industrial production, and there may be a metal residue problem. For large-scale production of pharmaceutical intermediates that need to strictly control costs, its economy is poor.

[0009] In view of the huge application potential and market demand of sulfoncarboxylic compounds, it is of great industrial application value and technical necessity to develop a new synthesis route that is simple to operate, low in cost, environmentally friendly and suitable for industrial production. SUMMARY

[0010] The present application can realize low-cost, convenient and safe and environmentally friendly production of sulfoncarboxylic compounds by providing a mechanochemical synthesis method of sulfoncarboxylic compounds, solving the problems of using foul-smelling raw materials, noble metal catalysts, high environmental pollution and high cost in the prior art.

[0011] To solve the above technical problems, the present application provides a mechanochemical synthesis method of sulfoncarboxylic compounds, characterized in that a benzyl-substituted benzoic acid and sodium arylsulfinate are used as raw materials, inorganic substances are used as solid inorganic carriers, and a solid-phase nucleophilic substitution reaction is carried out by mechanical chemical grinding under solvent-free conditions to obtain a sulfoncarboxylic compound. The general structure of the benzyl-substituted benzoic acid is shown in formula (II), and the leaving group X on the benzyl group is selected from chlorine or bromine. The general structure of the sodium arylsulfinate is shown in formula (I). The general structure of the sulfoncarboxylic compound is shown in formula (III). (I), (II), (III), In formula (I) and formula (III), Ar is a substituted or unsubstituted aryl group.

[0012] In a preferred embodiment of the present application, Ar is at least one of phenyl, C1-C4 alkyl-substituted phenyl, halogen-substituted phenyl, nitro-substituted phenyl, C1-C4 alkoxy-substituted phenyl, trifluoromethyl-substituted phenyl, 1-naphthyl, 2-naphthyl, 2-pyridyl, 3-pyridyl, or 4-pyridyl.

[0013] In a preferred embodiment of the present application, Ar is at least one of phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,4,6-trifluorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-dimethylphenyl, 1-naphthyl, 2-naphthyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2,5-difluorophenyl, 2,4,6-trimethylphenyl, 2,4,6-trichlorophenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, or 4-tert-butylphenyl.

[0014] In a preferred embodiment of the present application, the inorganic substance is at least one of an oxide, a chloride, a sulfate, a carbonate, silica gel, a titanate, or a molecular sieve.

[0015] In a preferred embodiment of the present application, the inorganic substance is at least one of zinc oxide, aluminum oxide, magnesium chloride, sodium chloride, barium chloride, potassium aluminum sulfate dodecahydrate, kaolin, montmorillonite, sodium sulfate, barium sulfate, magnesium sulfate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, strontium carbonate, magnesium carbonate, calcium carbonate, barium titanate, SiO2-Al2O3, Fe2O3-Cr2O3-K2O, powdered molecular sieve, or silica gel.

[0016] In a preferred embodiment of the present application, the inorganic substance is at least one of silica gel, barium titanate, potassium aluminum sulfate dodecahydrate, zinc oxide, or aluminum oxide.

[0017] In a preferred embodiment of the present application, the mechanical chemical grinding is performed in a ball mill at a rotation speed of 300-500 rpm for 30-120 minutes, and the mass ratio of grinding balls to reaction material is 10:1 to 50:1. In a preferred embodiment of the present application, the reaction temperature is 20-50°C.

[0018] In a preferred embodiment of the present application, the molar ratio of the benzyl-substituted benzoic acid to sodium arylsulfinate is 1:1 to 1.2.

[0019] In a preferred embodiment of the present application, the mass ratio of the benzyl-substituted benzoic acid to the inorganic substance is 1:10-20.

[0020] The present application has the following advantages: the mechanical-chemical synthesis method of the sulfonamidomethyl benzoic acid compound uses cheap and readily available, non-toxic and stable arylsulfinate sodium and benzyl-substituted benzoic acid as raw materials, and combines a solvent-free solid-phase reaction system to realize green process and safe production from the source; through the mechanical-chemical grinding technology, the contact area of the reactants is greatly increased and a unique surface effect is induced under the synergistic action of a specific solid inorganic substance reaction medium, so that the nucleophilic substitution reaction is efficiently completed in one step, and the oxidation step and noble metal catalysts required in the traditional process are successfully omitted, so that the process flow is greatly simplified and the production cost is significantly reduced; the process condition of the present application is mild and the operation is simple, and a high yield and high purity target product can be obtained, which exhibits excellent reaction efficiency and economy, and is very suitable for industrial scale-up production. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 FIG. 8 is a nuclear magnetic resonance spectrum of 4-bromo-3-[(phenylsulfonyl)methyl]benzoic acid prepared in the mechanical-chemical synthesis method of the sulfonamidomethyl benzoic acid compound according to a preferred embodiment of the present application. DETAILED DESCRIPTION

[0022] The preferred embodiments of the present application will be described in detail below with reference to the accompanying drawings, so that the advantages and features of the present application can be more easily understood by those skilled in the art, and the scope of protection of the present application can be more clearly defined.

[0023] The present application discloses a mechanical-chemical synthesis method of a sulfonamidomethyl benzoic acid compound, which uses benzyl-substituted benzoic acid shown in formula (I) and arylsulfinate sodium shown in formula (II) as raw materials, and mixes the substances in a mass ratio of 1:1-1.2, and then performs a solid-phase nucleophilic substitution reaction in a ball mill under the assistance of inorganic substances and under solvent-free conditions at 20-50°C to obtain a sulfonamidomethyl benzoic acid compound shown in formula (III); The reaction process is as follows: wherein X is a leaving group selected from chlorine or bromine; and Ar is an aryl group, specifically at least one of phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,4,6-trifluorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-dimethylphenyl, 1-naphthyl, 2-naphthyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2,5-difluorophenyl, 2,4,6-trimethylphenyl, 2,4,6-trichlorophenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, or 4-tert-butylphenyl.

[0024] wherein the mass ratio of the benzyl-substituted benzoic acid to the inorganic substance is 1:10-20. Specifically, the inorganic substance is a solid inorganic carrier, specifically at least one of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, strontium carbonate, magnesium carbonate, calcium carbonate, magnesium chloride, sodium chloride, barium chloride, silica gel, barium titanate, potassium aluminum sulfate dodecahydrate, kaolin, montmorillonite, zinc oxide, aluminum oxide, sodium sulfate, barium sulfate, magnesium sulfate, SiO2-Al2O3, Fe2O3-Cr2O3-K2O, or a powdered molecular sieve.

[0025] The present application finds that, under solvent-free mechanochemical grinding conditions, the addition of a specific inorganic substance as a reaction medium can greatly increase the contact area between the reactants and provide a unique surface effect, thereby efficiently promoting the occurrence of nucleophilic substitution reactions.

[0026] The content of the present application is described in detail below through specific examples.

[0027] Example 1 Synthesis of 4-[(phenylsulfonyl)methyl]benzoic acid The substrate 4-chloromethylbenzoic acid (1.7 g, 10 mmol), sodium benzenesulfinate (2 g, 12 mmol) and sodium chloride (25 g) were added together into a stainless steel ball mill jar, and stainless steel balls were added to make the mass ratio of grinding balls to reaction mass 20:1. The tightly capped ball mill jar was placed on a planetary ball mill and the reaction was mechanically ground at 25 °C at a rotation speed of 500 rpm for 60 min. After the reaction was completed, the solid reaction mass was extracted twice with ethyl acetate, the organic phases were combined, washed with water, concentrated, and the residue was separated and purified by column chromatography [eluent: V(petroleum ether):V(ethyl acetate)=8:1] to obtain 2.4 g of the target product with a yield of 87%;1H (NMR, d6-DMSO): 13.32 (brs, 1H), 7.85 (d, 2H), 7.72-7.70 (m, 3H), 7.64-7.60 (m, 2H), 7.27 (d, 2H), 4.81 (s, 2H). Example 2 Synthesis of 3-[(benzenesulfonyl)methyl]benzoic acid The substrate 3-chloromethylbenzoic acid (1.7 g, 10 mmol), sodium benzenesulfinate (2 g, 12 mmol) and barium titanate (25 g) were added together into a stainless steel ball mill jar, and stainless steel balls were added to make the mass ratio of grinding balls to reaction mass 20:1. The tightly capped ball mill jar was placed on a planetary ball mill and the reaction was mechanically ground at 25 °C at a rotation speed of 500 rpm for 60 min. After the reaction was completed, the solid reaction mass was extracted twice with ethyl acetate, the organic phases were combined, washed with water, concentrated, and the residue was separated and purified by column chromatography [eluent: V(petroleum ether):V(ethyl acetate)=5:1] to obtain 2.6 g of the target product with a yield of 94%;1H (NMR, d6-DMSO): 13.04 (brs, 1H), 7.91-7.89 (m, 1H), 7.79 (s, 1H), 7.74-7.72 (m, 3H), 7.63-7.59 (m, 2H), 7.46-7.39 (m, 2H), 4.81 (s, 2H).

[0028] Example 3 Synthesis of 2-[(benzenesulfonyl)methyl]benzoic acid The substrate 2-chloromethylbenzoic acid (1.7 g, 10 mmol), sodium benzenesulfinate (2 g, 12 mmol) and silica gel (30 g) were added together into a stainless steel ball mill jar, and stainless steel balls were added to give a mass ratio of grinding balls to reaction mass of 20:1. The tightly capped ball mill jar was placed on a planetary ball mill and the reaction was mechanically ground at 25 °C at a speed of 500 rpm for 60 min. After the reaction was completed, the solid reaction mass was extracted with ethyl acetate twice, the organic phases were combined, washed with water, concentrated, and the residue was purified by column chromatography [eluent: V(petroleum ether):V(ethyl acetate) = 5:1] to give the target product 2.5 g, yield 91%;1H (NMR, d6-DMSO): 13.08 (brs, 1H), 7.89-7.85 (m, 3H), 7.59 (t, 2H), 7.68-7.62 (m, 1H), 7.13-7.09 (m, 2H), 7.09-7.04 (m, 1H), 4.80 (s, 2H).

[0029] Example 4 Synthesis of 4-[[(4-methylphenyl)sulfonyl]methyl]benzoic acid The substrate 2-chloromethylbenzoic acid (1.7 g, 10 mmol), sodium benzenesulfinate (2 g, 12 mmol) and silica gel (30 g) were added together into a stainless steel ball mill jar, and stainless steel balls were added to give a mass ratio of grinding balls to reaction mass of 20:1. The tightly capped ball mill jar was placed on a planetary ball mill and the reaction was mechanically ground at 25 °C at a speed of 500 rpm for 60 min. After the reaction was completed, the solid reaction mass was extracted with ethyl acetate twice, the organic phases were combined, washed with water, concentrated, and the residue was purified by column chromatography [eluent: V(petroleum ether):V(ethyl acetate) = 5:1] to give the target product 2.5 g, yield 91%;1H (NMR, d6-DMSO): 13.08 (brs, 1H), 7.89-7.85 (m, 3H), 7.59 (t, 2H), 7.68-7.62 (m, 1H), 7.13-7.09 (m, 2H), 7.09-7.04 (m, 1H), 4.80 (s, 2H). The substrate 4-chloromethylbenzoic acid (1.7 g, 10 mmol), sodium p- chlorobenzenesulfinate (2.2 g, 11 mmol) and zinc oxide (25 g) were added together into a stainless steel ball mill jar, and stainless steel balls were added to give a mass ratio of grinding balls to reaction mass of 20:1. The tightly capped ball mill jar was placed on a planetary ball mill and the reaction was mechanically ground at 25 °C at a speed of 500 rpm for 60 min. After the reaction was completed, the solid reaction mass was extracted twice using ethyl acetate, the organic phases were combined, washed with water, concentrated, and the residue was purified by column chromatography [eluent: V(petroleum ether):V(ethyl acetate) = 4:1] to give the target product 2.9 g in a yield of 93%;1H (NMR, d6-DMSO): 13.29 (br s, 1H), 7.79 (d, 2H), 7.72 (d, 2H), 7.61 (d, 2H), 7.26 (d, 2H), 4.81 (s, 2H). The substrate 4-chloromethylbenzoic acid (1.7 g, 10 mmol), sodium p- chlorobenzenesulfinate (2.2 g, 11 mmol) and zinc oxide (25 g) were added together into a stainless steel ball mill jar, and stainless steel balls were added to give a mass ratio of grinding balls to reaction mass of 20:1. The tightly capped ball mill jar was placed on a planetary ball mill and the reaction was mechanically ground at 25 °C at a speed of 500 rpm for 60 min. After the reaction was completed, the solid reaction mass was extracted twice using ethyl acetate, the organic phases were combined, washed with water, concentrated, and the residue was purified by column chromatography [eluent: V(petroleum ether):V(ethyl acetate) = 4:1) to give the target product 2.9 g in a yield of 93%;1H (NMR, d6-DMSO): 13.29 (br s, 1H), 7.79 (d, 2H), 7.72 (d, 2H), 7.61 (d, 2H), 7.26 (d, 2H), 4.81 (s, 2H).

[0030] Example 7 4-[[(4- Bromophenyl)sulfonyl]methyl]benzoic acid The substrate 4-chloromethylbenzoic acid (1.7 g, 10 mmol), sodium p-bromobenzenesulfinate (2.7 g, 11 mmol) and barium titanate 25 g) were added together into a stainless steel ball mill jar, and stainless steel balls were added to make the mass ratio of grinding balls to reaction materials 20:1. The tightly covered ball mill jar was placed on a planetary ball mill, and the reaction was mechanically ground at 25°C and a rotation speed of 500 rpm for 60 min. After the reaction was completed, the solid reaction was extracted twice with ethyl acetate, the organic phases were combined, washed with water, concentrated, and the residue was separated and purified by column chromatography [eluent: V(petroleum ether):V(ethyl acetate)=4:1] to obtain 3.4 g of the target product with a yield of 96%; 1H (NMR, d6-DMSO): 13.31 (brs, 1H), 7.86 (d, 2H), 7.76 (d, 2H), 7.60 (d, 2H), 7.19 (d, 2H), 4.78 (s, 2H).

[0031] Example 8 4-bromo-3-[(benzenesulfonyl)methyl]benzoic acid The substrate 4-bromo-3-bromomethylbenzoic acid (1.5 g, 5 mmol), sodium benzenesulfinate (1 g, 6 mmol) and barium titanate (15 g) were added together into a stainless steel ball mill jar, and stainless steel balls were added to make the mass ratio of grinding balls to reaction materials 20:1. The tightly covered ball mill jar was placed on a planetary ball mill, and the reaction was mechanically ground at 25°C and a rotation speed of 500 rpm for 60 min. After the reaction was completed, the solid reaction was extracted twice with ethyl acetate, the organic phases were combined, washed with water, concentrated, and the residue was separated and purified by column chromatography [eluent: V(petroleum ether):V(ethyl acetate)=3:1] to obtain 1.7 g of the target product with a yield of 96%; 1H (NMR, d6-DMSO): 13.31 (brs, 1H), 7.95 (s, 1H), 7.83-7.70 (m, 5H), 7.65-7.61 (m, 2H), 4.91 (s, 2H). The nuclear magnetic resonance spectrum is shown in the accompanying drawings. The present application uses inexpensive and readily available sodium aryl sulfinate and benzyl-type substituted benzoic acid as raw materials, and uses simple physical operations such as grinding, extrusion, shearing and friction to induce changes in the chemical and physical properties of the reactants. The target product sulfonated carboxylic acid is prepared under solid phase reaction conditions; the yield and purity of the obtained target product are high, the operation is simple and convenient, and the process is green and environmentally friendly. Figure 1 The present application uses inexpensive and readily available sodium aryl sulfinate and benzyl-type substituted benzoic acid as raw materials, and uses simple physical operations such as grinding, extrusion, shearing and friction to induce changes in the chemical and physical properties of the reactants. The target product sulfonated carboxylic acid is prepared under solid phase reaction conditions; the yield and purity of the obtained target product are high, the operation is simple and convenient, and the process is green and environmentally friendly. The above is only an embodiment of the present application, and does not limit the patent scope of the present application, and any equivalent structure or equivalent process transformation using the content of the specification and the accompanying drawings, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A mechanochemical synthesis method of a sulfonmethybenzoic acid compound, characterized by, A sulfonamidomethyl benzoic acid compound is obtained by a solid phase nucleophilic substitution reaction of a benzyl-substituted benzoic acid and sodium aryl sulfinate as raw materials and inorganic substance as solid inorganic carrier under solvent-free condition through mechanical chemical grinding; The benzyl-substituted benzoic acid has a general structure as shown in formula (II), and a leaving group X on the benzyl group is selected from chlorine or bromine; The sodium aryl sulfinate has a general structure as shown in formula (I); The sulfonamidomethyl benzoic acid compound has a general structure as shown in formula (III); (I), (II), (III), In formula (I) and formula (III), Ar is a substituted or unsubstituted aryl group.

2. The method of claim 1, wherein, The Ar is at least one of a phenyl group, a C1-C4 alkyl-substituted phenyl group, a halogen-substituted phenyl group, a nitro-substituted phenyl group, a C1-C4 alkoxy-substituted phenyl group, a trifluoromethyl-substituted phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group.

3. The method of claim 2, wherein, The Ar is at least one of a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2,4,6-trifluorophenyl group, a 2-bromophenyl group, a 3-bromophenyl group, a 4-bromophenyl group, a 2-iodophenyl group, a 3-iodophenyl group, a 4-iodophenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,4-dimethylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-nitrophenyl group, a 3-nitrophenyl group, a 4-nitrophenyl group, a 2,5-difluorophenyl group, a 2,4,6-trimethylphenyl group, a 2,4,6-trichlorophenyl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-trifluoromethylphenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group or a 4-tert-butylphenyl group.

4. The method of claim 1, wherein, The inorganic substance is at least one of an oxide, a chloride, a sulfate, a carbonate, silica gel, a titanate or a molecular sieve.

5. The method of claim 4, wherein, The inorganic substance is at least one of zinc oxide, aluminum oxide, magnesium chloride, sodium chloride, barium chloride, potassium aluminum sulfate dodecahydrate, kaolin, montmorillonite, sodium sulfate, barium sulfate, magnesium sulfate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, strontium carbonate, magnesium carbonate, calcium carbonate, barium titanate, SiO2-Al2O3, Fe2O3-Cr2O3-K2O, powdered molecular sieve or silica gel.

6. The method of claim 5, wherein, The inorganic substance is at least one of silica gel, barium titanate, potassium aluminum sulfate dodecahydrate, zinc oxide or aluminum oxide.

7. The method of claim 1, wherein, The mechanical chemical grinding is performed in a ball mill at a rotation speed of 300-500 rpm for 30-120 minutes, and the mass ratio of grinding ball to reaction material is 10:1 to 50:

1.

8. The method of claim 1, wherein, The reaction temperature is 20-50℃.

9. The method of claim 1, wherein, The molar ratio of the benzyl-substituted benzoic acid to the sodium aryl sulfinate is 1:1-1.

2.

10. The method of claim 1, wherein, The mass ratio of the benzyl-substituted benzoic acid to the inorganic substance is 1:10-20.

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