A cinnamaldehyde derivative-based 1-hydroxy-1-sulfonic acid sodium salt structured compound, a preparation method and application thereof

Abstract

The application discloses a cinnamaldehyde derivative-based 1-hydroxy-1-sulfonic acid sodium salt structured compound and a preparation method and application thereof, and belongs to the technical field of agricultural chemical preparation. The structural general formula of the compound is shown as formula (I). The preparation method of the compound comprises the following steps: dropping a homogeneous phase B system composed of sodium bisulfite, a quaternary phosphonium salt phase transfer catalyst and water into a homogeneous phase A system composed of a compound shown as formula (II) and an organic solvent to perform a nucleophilic addition reaction, so as to obtain the compound shown as formula (I). The preparation method is simple, the reaction condition is mild, the obtained compound is good in environmental compatibility, has high biological activity on soil pathogens (bacteria, fungi, root knot nematodes and the like), can be widely used for the prevention and treatment of soil-borne diseases, and provides material guarantee for safe production of crops.

Description

Technical Field

[0001] This invention belongs to the field of agricultural chemicals technology, specifically relating to a sodium 1-hydroxy-1-sulfonate salt compound based on cinnamaldehyde derivatives, its preparation method, and its application. Background Technology

[0002] Soil-borne diseases are diseases caused by pathogens (fungi, bacteria, nematodes, and viruses, etc.) that exist part or most of their life cycle in the soil, infecting the roots or stems of plants under suitable conditions. In recent years, intensive production and continuous cropping have led to an increase in the accumulation of pathogens in the soil, and soil-borne diseases have become increasingly severe year by year, thus becoming an important factor limiting crop yield and quality, and seriously hindering the sustainable development of agriculture. For a long time, fumigants such as calcium cyanamide, dazomet, sulfuryl fluoride, 1,3-dichloropropene, dimethyl disulfide, methyl methacrylate, and methyl bromide have achieved good results in controlling soil-borne diseases. However, these traditional fumigants have various limitations, such as high toxicity to humans and animals, large dosage, high cost, increased resistance of pests, damage to the ecological environment, unstable activity in soil, susceptibility to environmental conditions, and harm to the planting of crops in the lower strata. They cannot meet the needs of modern agricultural production. Developing efficient, safe, green, and low-cost alternative technologies and products to traditional soil fumigants is an urgent need in the current prevention and control of soil-borne diseases.

[0003] Cinnamaldehyde is an aldehyde organic compound naturally found in the volatile oils of plants such as cinnamon, cassia bark, and bay leaves. To further enhance the bioactivity of cinnamaldehyde, various derivatives have been obtained by modifying its benzene ring, α-carbon, or β-carbon. Compared to cinnamaldehyde, the developed derivatives exhibit superior bioactivity. However, in the prior art, no compounds with a 1-hydroxy-1-sulfonate sodium salt structure based on cinnamaldehyde derivatives have been reported, and they have not been used in agricultural production as agents for controlling soil-borne diseases. Summary of the Invention

[0004] To find novel compounds with efficient, safe, and environmentally friendly structures for controlling soil-borne diseases, this invention utilizes a nucleophilic addition reaction between cinnamaldehyde derivatives and sodium bisulfite to obtain a series of compounds containing 1-hydroxy-1-sulfonate sodium salt structures for the first time. Indoor bioactivity assays and pot experiments show that these compounds have high bioactivity against soil-borne diseases and can be used for the control of plant soil-borne diseases, providing material support for safe crop production. In other words, the purpose of this invention is to provide a 1-hydroxy-1-sulfonate sodium salt structure compound based on cinnamaldehyde derivatives, its preparation method, and its applications, exhibiting high activity against plant pathogenic fungi, bacteria, and nematodes.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] In a first aspect, the general structural formula of the sodium 1-hydroxy-1-sulfonate salt compound based on cinnamaldehyde derivative provided by the present invention is shown in formula (I):

[0007]

[0008] In formula (I): R1 is substituted in a mono-, di-, or tri-substituted manner, and each substituent is independently selected from hydrogen, halogen, nitro, hydroxyl, phenyl, halomethyl, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkyl disubstituted amino, and C1-C4 alkyl acyloxy.

[0009] R2 is selected from any one of hydrogen, halogen, and phenyl;

[0010] R3 is selected from any one of hydrogen, halogen, C1-C6 alkyl, and phenyl;

[0011] Among them, R1, R2, and R3 are not all hydrogen at the same time, and when R1 is Cl and is in position 4, R2 is not chlorine.

[0012] In this invention, the term "C1-C4 alkyl" refers to a straight-chain or branched alkyl group having 1-4 carbon atoms, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0013] The term "C1-C4 alkoxy" refers to straight-chain or branched alkoxy groups with 1-4 carbon atoms, including but not limited to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy.

[0014] The term "C1-C4 alkyl disubstituted amino" refers to an alkyl disubstituted amino group with 1-4 carbon atoms, such as dimethylamino, diethylamino, dipropylamino, and dibutylamino.

[0015] The term "C1-C4 alkyl acyloxy" refers to alkyl acyloxy groups with 1-4 carbon atoms, including but not limited to methyl acyloxy, ethyl acyloxy, propyl acyloxy, and butyl acyloxy.

[0016] The term "halomethyl" refers to a group formed by replacing one, two, or three hydrogen atoms of a methyl group with a halogen atom, including but not limited to monohalomethyl, dihalomethyl, and trihalomethyl, such as monofluoromethyl, difluoromethyl, or trifluoromethyl.

[0017] The halogens in R1, R2, and R3, or the halogens in the halogenation, are all selected from F, Cl, Br, or I.

[0018] As an example, the compound represented by formula (I) is any one of the following formulas (I-01) to (I-38):

[0019] Formula (I-01): R1 is 2-NO2, R2 is H, R3 is H;

[0020] Equation (I-02): R1 is 2-F, R2 is H, R3 is H;

[0021] Formula (I-03): R1 is 2-Br, R2 is H, and R3 is H;

[0022] Formula (I-04): R1 is 2-Cl, R2 is H, R3 is H;

[0023] Equation (I-05): R1 is 2-OCH3, R2 is H, and R3 is H;

[0024] Formula (I-06): R1 is 2-OH, R2 is H, R3 is H;

[0025] Formula (I-07): R1 is 3-NO2, R2 is H, R3 is H;

[0026] Equation (I-08): R1 is 3-OCH3, R2 is H, and R3 is H;

[0027] Equation (I-09): R1 is 3-CH3, R2 is H, and R3 is H;

[0028] Equation (I-10): R1 is 3-F, R2 is H, R3 is H;

[0029] Equation (I-11): R1 is 3-Cl, R2 is H, and R3 is H;

[0030] Equation (I-12): R1 is 3-Br, R2 is H, and R3 is H;

[0031] Equation (I-13): R1 is 3-CF3, R2 is H, and R3 is H;

[0032] Equation (I-14): R1 is 4-F, R2 is H, R3 is H;

[0033] Equation (I-15): R1 is 4-Cl, R2 is H, and R3 is H;

[0034] Equation (I-16): R1 is 4-Br, R2 is H, and R3 is H;

[0035] Equation (I-17): R1 is 4-I, R2 is H, R3 is H;

[0036] Equation (I-18): R1 is 4-CH3, R2 is H, and R3 is H;

[0037] Equation (I-19): R1 is 4-CH(CH3)2, R2 is H, and R3 is H;

[0038] Equation (I-20): R1 is 4-OCH3, R2 is H, and R3 is H;

[0039] Formula (I-21): R1 is 4-OH, R2 is H, and R3 is H;

[0040] Equation (I-22): R1 is 4-C6H5, R2 is H, R3 is H;

[0041] Equation (I-23): R1 is 4-CF3, R2 is H, R3 is H;

[0042] Equation (I-24): R1 is 4-N(CH3CH2)2, R2 is H, and R3 is H;

[0043] Formula (I-25): R1 is 3-OCH3 and 4-OH, R2 is H, and R3 is H;

[0044] Formula (I-26): R1 is 3,5-OCH3 and 4-OH, R2 is H, and R3 is H;

[0045] Equation (I-27): R1 is 2,6-F, R2 is H, and R3 is H;

[0046] Equation (I-28): R1 is 2,3-Cl, R2 is H, and R3 is H;

[0047] Equation (I-29): R1 is 2-Cl,6-F, R2 is H, and R3 is H;

[0048] Equation (I-30): R1 is 3-OCH3, 4-OCOCH3, R2 is H, and R3 is H;

[0049] Equation (I-31): R1 is 2,3,4-CH3, R2 is H, and R3 is H;

[0050] Equation (I-32): R1 is 4-F, R2 is F, R3 is F;

[0051] Equation (I-33): R1 is H, R2 is H, and R3 is Br;

[0052] Equation (I-34): R1 is H, R2 is H, and R3 is CH3;

[0053] Equation (I-35): R1 is H, R2 is H, R3 is -C6H5;

[0054] Equation (I-36): R1 is H, R2 is H, and R3 is -CH2CH2CH2CH2CH2CH3;

[0055] Equation (I-37): R1 is H, R2 is H, and R3 is Cl;

[0056] Equation (I-38): R1 is H, R2 is -C6H5, and R3 is Cl.

[0057] In a second aspect, the present invention provides a method for preparing the compound represented by any one of the formulas (I) above, comprising the following steps:

[0058]

[0059] In equation (II): R1, R2, and R3 are defined in the same way as in equation (I);

[0060] A homogeneous phase B system, consisting of sodium bisulfite, a quaternary phosphine salt phase transfer catalyst, and water, was added dropwise to a homogeneous phase A system, consisting of the compound shown in formula (II) and an organic solvent, to carry out a nucleophilic addition reaction, yielding the compound shown in formula (I).

[0061] In the above preparation method, the quaternary phosphine salt phase transfer catalyst is one or more of tetrabutylphosphine bromide, tetrabutylphosphine chloride, hexadecyltributylphosphine bromide, and hexadecyltributylphosphine chloride.

[0062] The amount of the quaternary phosphine salt phase transfer catalyst is 0.25% to 5% of the molar amount of sodium bisulfite, such as 0.25%, 0.5%, 0.75%, 0.8%, 1%, 1.25%, or 2%.

[0063] As an example, 250 to 750 mmol of the sodium bisulfite is dissolved in 100 mL of water, such as 250 mmol, 300 mmol, 400 mmol, 500 mmol or 750 mmol of sodium bisulfite dissolved in 100 mL of water.

[0064] In the above preparation method, further, the molar ratio of the compound shown in formula (II) to the sodium bisulfite is 1.0:(1.0 to 3.0), such as 1.0:1.0, 1.0:1.2, 1.0:1.6, 1.0:2.0 or 1.0:3.0;

[0065] The organic solvent is one or more of methanol, ethanol, n-propanol, isopropanol, dichloromethane, acetonitrile, ethyl acetate, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), cyclohexane, and cyclohexanone.

[0066] As an example, each 250 mmol of the compound represented by formula (II) is dissolved in 150 mL of the organic solvent.

[0067] In the above preparation method, the nucleophilic addition reaction is carried out at room temperature and pressure for a reaction time of 3h to 6h, such as 3h, 3.5h, 4h, 5h or 6h.

[0068] In this invention, the term "normal temperature" refers to a temperature of 20-25°C, and unless otherwise specified in the embodiments of this invention, it refers to 25°C; the term "normal pressure" refers to one standard atmosphere (101 kPa).

[0069] In the above preparation method, the reaction process is further monitored using thin-layer chromatography (TLC);

[0070] The method further includes the following steps after the reaction is completed: the system is desolventized by vacuum distillation (e.g., rotary evaporation), washed and filtered to remove sodium bisulfite, and the obtained solid is recrystallized to obtain the compound shown in formula (I).

[0071] Thirdly, the present invention provides the use of the compound of formula (I) described in any of the preceding claims in any of the following:

[0072] A1. Inhibit soil-borne plant pathogens or prepare products that inhibit soil-borne plant pathogens;

[0073] A2. Inhibiting Ralstonia solanacearum or preparing products that inhibit Ralstonia solanacearum;

[0074] A3. Inhibit soil-borne Botrytis cinera Pers or prepare products that inhibit soil-borne Botrytis cinera Pers.

[0075] Fourthly, the present invention provides the use of the compound of formula (I) described in any of the preceding claims in any of the following:

[0076] B1. Inhibit soil-borne plant pathogenic fungi or prepare products that inhibit soil-borne plant pathogenic fungi;

[0077] B2. Inhibit Sclerotinia sclerotiorum or prepare products that inhibit Sclerotinia sclerotiorum;

[0078] B3. Inhibit Fusarium oxysporum or prepare products that inhibit Fusarium oxysporum.

[0079] Fifthly, the present invention provides the use of the compound of formula (I) described in any of the preceding claims in any of the following:

[0080] C1. Inhibiting nematodes or preparing products that inhibit nematodes;

[0081] C2. Inhibit southern root-knot nematode (Meloidogyne incognita) or prepare products that inhibit southern root-knot nematode (Meloidogyne incognita).

[0082] In a sixth aspect, the present invention provides the use of the compound of formula (I) described in any of the preceding claims in the prevention and control of soil-borne diseases or in the preparation of products for the prevention and control of soil-borne diseases.

[0083] The soil pathogens of the soil-borne diseases mentioned above are any one of soil-borne plant pathogenic bacteria, soil-borne plant pathogenic fungi, or nematodes.

[0084] The preferred soil-borne plant pathogens are Ralstonia solanacearum or Botrytis cinera Pers.

[0085] The preferred soil-borne plant pathogenic fungi are Sclerotinia sclerotiorum or Fusarium oxysporum.

[0086] The preferred nematode is the southern root-knot nematode (Meloidogyne incognita).

[0087] The present invention has the following beneficial effects:

[0088] The preparation method of this invention is simple, the reaction conditions are mild, the resulting compound has good environmental compatibility, and it has high biological activity against soil pathogens (bacteria, fungi, root-knot nematodes, etc.). It can be widely used for the prevention and control of soil-borne diseases, providing material support for safe crop production. Attached Figure Description

[0089] Figure 1 The preparation route for the compound shown in formula (I) of this invention is as follows. Detailed Implementation

[0090] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation on the invention in any way.

[0091] Unless otherwise specified, the methods used in the following embodiments are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following embodiments are commercially available.

[0092] Test strain: Ralstonia solanacearum strain GMI1000, which is described in the literature "Xu Yan, Song Wen, Zhu Dan, et al. Identification of inhibitory activity of propolis residue extract against Ralstonia solanacearum [J]. Sericultural Science. 2018, (2). DOI:10.13441 / j.cnki.cykx.2018.02.004.", which is available to the public from the applicant. This biological material is only used to repeat the relevant experiments of this invention and shall not be used for other purposes.

[0093] Botrytis cinera Pers strain B05.10, described in the literature "Li Boya. Mechanism of Wuyi mycin in controlling grape gray mold and its study on delaying the development of drug resistance in gray mold [D]. Hebei Agricultural University, 2023.", is available to the public from the applicant. This biological material is only used to repeat the relevant experiments of this invention and may not be used for other purposes.

[0094] The *Sclerotinia sclerotiorum* strain 1980, described in the literature “Liu Yong, Zhang Yuyu, Fu Yanping, et al. Functional analysis of autophagy-related genes SsATG5 and SsATG8 in *Sclerotinia sclerotiorum* [J]. Journal of Plant Protection, 2024(2).”, is available to the public from the applicant. This biological material is only for repeating the relevant experiments of this invention and may not be used for other purposes.

[0095] Fusarium oxysporum strain F-1, described in the literature “Xiao Jiling, Xiong Yi, Liang Zhihuai, et al. Preliminary study on the control effect and mechanism of Fusarium oxysporum F-1 on strawberry gray mold [J]. Chinese Journal of Biological Control, 2022, 38(4):6.DOI:10.16409 / j.cnki.2095-039x.2022.04.010.”, is available to the public from the applicant. This biological material is only for repeating the relevant experiments of this invention and shall not be used for other purposes.

[0096] Reference reagent: Sodium cinnamaldehyde bisulfite, with the structural formula shown as Cin-Sod, is described in the literature "Zhang Yuanyuan. Synthesis and quantitative structure-activity relationship of cinnamaldehyde antibacterial derivatives [D]. Northeast Forestry University, 2013." The public can refer to the provided literature for preparation, or obtain it from the applicant.

[0097]

[0098] Example 1: Preparation of compound I-01

[0099] 44.25 g (250 mmol) of (2E)-3-(2-nitrophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 66.08 g of a white solid, with a yield of 94.07%. 1 ¹H NMR (400MHz, D₂O) δ: 8.21 (m, 1H), 7.88-7.71 (m, 2H), 7.66 (m, 1H), 7.16 (m, 1H), 6.41 (m, 1H), 4.69 (m, 1H), 4.28 (m, 1H). Product structural formula is shown in I-01.

[0100]

[0101] Example 2: Preparation of compound I-02

[0102] 37.53 g (250 mmol) of (2E)-3-(2-fluorophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 58.49 g of a yellow solid, with a yield of 92.07%. 1 ¹H NMR (400MHz, D₂O) δ: 8.19 (m, 1H), 7.82-7.69 (m, 2H), 7.65 (m, 1H), 7.13 (m, 1H), 6.38 (m, 1H), 4.64 (m, 1H), 4.22 (m, 1H). Product structural formula is shown as I-O₂.

[0103]

[0104] Example 3: Preparation of compound I-03

[0105] 52.77 g (250 mmol) of (2E)-3-(2-bromophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 63.81 g of a brown solid, with a yield of 81.01%. 1 ¹H NMR (400MHz, D₂O) δ: 8.18 (m, 1H), 7.83-7.70 (m, 2H), 7.61 (m, 1H), 7.08 (m, 1H), 6.35 (m, 1H), 4.61 (m, 1H), 4.18 (m, 1H). Product structural formula is shown in I-O3.

[0106] (I-03)

[0107] Example 4: Preparation of compound I-04

[0108] 41.65 g (250 mmol) of (2E)-3-(2-chlorophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 65.22 g of a yellow solid, with a yield of 96.41%. 1 ¹H NMR (400MHz, D₂O) δ: 8.18 (m, 1H), 7.83-7.67 (m, 2H), 7.59 (m, 1H), 7.08 (m, 1H), 6.40 (m, 1H), 4.70 (m, 1H), 4.27 (m, 1H). Product structural formula is shown in I-04.

[0109]

[0110] Example 5: Preparation of compound I-05

[0111] 40.55 g (250 mmol) of (2E)-3-(2-methoxyphenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of ethanol by stirring at room temperature. 31.28 g (300 mmol) of sodium bisulfite and 0.50 g (1.50 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 4 hours of reaction, water and ethanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from ethanol and dried to obtain 61.23 g of a white solid, with a yield of 92.01%. 1 ¹H NMR (400MHz, D₂O) δ: 8.23 ​​(m, 1H), 7.90–7.75 (m, 2H), 7.58 (m, 1H), 7.22 (m, 1H), 6.43 (m, 1H), 4.70 (m, 1H), 4.21 (m, 1H), 3.88 (s, 3H). Product structural formula is shown in I-05.

[0112]

[0113] Example 6: Preparation of compound I-06

[0114] 37.04 g (250 mmol) of (2E)-3-(2-hydroxyphenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of ethanol by stirring at room temperature. 26.00 g (250 mmol) of sodium bisulfite and 0.37 g (1.25 mmol) of tetrabutylphosphine chloride were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 6 hours of reaction, water and ethanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from ethanol and dried to obtain 57.08 g of a white solid, with a yield of 90.55%. 1 ¹H NMR (400MHz, D₂O) δ: 7.55 (m, 1H), 7.08 (m, 1H), 6.88 (m, 1H), 6.79 (m, 1H), 6.71 (m, 1H), 6.11 (m, 1H), 4.72 (m, 1H), 4.16 (m, 1H). Product structural formula is shown in I-06.

[0115]

[0116] Example 7: Preparation of compound I-07

[0117] 44.25 g (250 mmol) of (2E)-3-(3-nitrophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 64.72 g of a white solid, with a yield of 92.13%. 1 ¹H NMR (400MHz, D₂O) δ: 8.16 (m, 1H), 8.04 (1, 2H), 7.71 (m, 1H), 6.68 (m, 1H), 6.51 (m, 1H), 4.72 (m, 1H), 4.38 (m, 1H). Product structural formula is shown in I-07.

[0118]

[0119] Example 8: Preparation of compound I-08

[0120] 40.55 g (250 mmol) of (2E)-3-(3-methoxy)phenylprop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of ethanol by stirring at room temperature. 41.60 g (400 mmol) of sodium bisulfite and 1.34 g (4.00 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 4 hours of reaction, water and ethanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from ethanol to obtain 57.67 g of a white solid, which was dried, yielding 86.66%. 1 ¹H NMR (400MHz, D₂O) δ: 7.49 (m, 1H), 7.18 (m, 1H), 7.13 (m, 1H), 6.96 (m, 1H), 6.65 (m, 1H), 6.28 (m, 1H), 4.64 (m, 1H), 4.35 (m, 1H), 3.81 (s, 3H). Product structural formula is shown in I-08.

[0121]

[0122] Example 9: Preparation of compound I-09

[0123] 36.55 g (250 mmol) of (2E)-3-(3-methylphenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 26.00 g (250 mmol) of sodium bisulfite and 0.67 g (2.00 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 5 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 51.67 g of a white solid, with a yield of 82.61%. 1 ¹H NMR (400MHz, D₂O) δ: 7.58 (m, 1H), 7.33 (m, 1H), 7.21 (m, 1H), 6.91 (m, 1H), 6.79 (m, 1H), 6.23 (m, 1H), 4.74 (m, 1H), 4.25 (m, 1H), 2.38 (s, 3H). Product structural formula is shown in I-09.

[0124]

[0125] Example 10: Preparation of compound I-10

[0126] 37.53 g (250 mmol) of (2E)-3-(3-fluorophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 54.78 g of a white solid, with a yield of 86.22%. 1 ¹H NMR (400MHz, D₂O) δ: 7.53 (m, 1H), 7.38 (m, 1H), 7.33–7.29 (m, 2H), 6.71 (m, 1H), 6.34 (m, 1H), 4.79 (m, 1H), 4.42 (m, 1H). Product structural formula is shown in I-10.

[0127]

[0128] Example 11: Preparation of compound I-11

[0129] 41.65 g (250 mmol) of (2E)-3-(3-chlorophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 62.56 g of a yellow solid, with a yield of 92.48%. 1 ¹H NMR (400MHz, D₂O) δ: 7.52 (m, 1H), 7.36 (m, 1H), 7.32–7.28 (m, 2H), 6.67 (m, 1H), 6.24 (m, 1H), 4.72 (m, 1H), 4.37 (m, 1H). Product structural formula is shown in I-11.

[0130]

[0131] Example 12: Preparation of compound I-12

[0132] 52.77 g (250 mmol) of (2E)-3-(3-bromophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 66.95 g of a brown solid, with a yield of 84.00%. 1 ¹H NMR (400MHz, D₂O) δ: 7.48 (m, 1H), 7.34 (m, 1H), 7.28–7.19 (m, 2H), 6.65 (m, 1H), 6.14 (m, 1H), 4.61 (m, 1H), 4.14 (m, 1H). Product structural formula is shown in I-12.

[0133]

[0134] Example 13: Preparation of compound I-13

[0135] 50.04 g (250 mmol) of (2E)-3-[3-(trifluoromethyl)phenyl]prop-2-enal was dissolved in 150 mL of methanol in a 500 mL single-necked flask at room temperature by stirring. 31.20 g (300 mmol) of sodium bisulfite and 1.26 g (3.75 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 5 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 60.73 g of white solid, with a yield of 79.87%. 1 ¹H NMR (400MHz, D₂O) δ: 7.62 (m, 1H), 7.52-7.48 (m, 2H), 7.16 (m, 1H), 6.68 (m, 1H), 6.17 (m, 1H), 4.74 (m, 1H), 4.37 (m, 1H). Product structural formula is shown in I-13.

[0136]

[0137] Example 14: Preparation of compound I-14

[0138] 37.53 g (250 mmol) of (2E)-3-(4-fluorophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 26.00 g (250 mmol) of sodium bisulfite and 1.68 g (5.00 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3.5 h of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 51.57 g of a white solid, with a yield of 81.17%. 1 ¹H NMR (400MHz, D₂O) δ: 7.80-6.74 (m, 4H), 6.71 (m, 1H), 6.43 (m, 1H), 4.82 (m, 1H), 4.41 (m, 1H). Product structural formula is shown in I-14.

[0139]

[0140] Example 15: Preparation of compound I-15

[0141] 41.65 g (250 mmol) of (2E)-3-(4-chlorophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 26.00 g (250 mmol) of sodium bisulfite and 1.68 g (5.00 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3.5 h of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 57.56 g of a yellow solid, with a yield of 85.08%. 1 ¹H NMR (400MHz, D₂O) δ: 7.70-6.61 (m, 4H), 6.56 (m, 1H), 6.23 (m, 1H), 4.76 (m, 1H), 4.32 (m, 1H). Product structural formula is shown in I-15.

[0142]

[0143] Example 16: Preparation of compound I-16

[0144] 52.77 g (250 mmol) of (2E)-3-(4-bromophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 1.68 g (5.00 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3.5 h of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 68.31 g of a brown solid, with a yield of 86.72%. 1 ¹H NMR (400MHz, D₂O) δ: 7.60-6.52 (m, 4H), 6.45 (m, 1H), 6.16 (m, 1H), 4.63 (m, 1H), 4.21 (m, 1H). Product structural formula is shown in I-16.

[0145]

[0146] Example 17: Preparation of compound I-17

[0147] 64.52 g (250 mmol) of (2E)-3-(4-iodophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 1.68 g (5.00 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3.5 h of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 73.49 g of a white solid, with a yield of 81.19%. 1 ¹H NMR (400MHz, D₂O) δ: 7.70-6.61 (m, 4H), 6.51 (m, 1H), 6.02 (m, 1H), 4.66 (m, 1H), 4.21 (m, 1H). Product structural formula is shown in I-17.

[0148]

[0149] Example 18: Preparation of compound I-18

[0150] 36.55 g (250 mmol) of (2E)-3-(4-methylphenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of isopropanol and stirred thoroughly at room temperature to dissolve. 26.00 g (250 mmol) of sodium bisulfite and 0.84 g (2.50 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and isopropanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from isopropanol and dried to give 47.29 g of a white solid, with a yield of 75.60%. 1 ¹H NMR (400MHz, D₂O) δ: 7.62 (m, 2H), 7.41 (m, 2H), 6.65 (m, 1H), 6.25 (m, 1H), 4.73 (m, 1H), 4.36 (m, 1H). Product structural formula is shown in I-18.

[0151]

[0152] Example 19: Preparation of compound I-19

[0153] 43.56 g (250 mmol) of (2E)-3-[4-(prop-2-yl)phenyl]prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of ethanol and dissolved thoroughly by stirring at room temperature. 26.00 g (250 mmol) of sodium bisulfite and 0.84 g (2.50 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the above single-necked flask until the reaction was complete, while stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and ethanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from ethanol and dried to obtain 42.84 g of white solid, with a yield of 61.59%. 1 ¹H NMR (400MHz, D₂O) δ: 7.64 (m, 2H), 7.31 (m, 2H), 6.66 (m, 1H), 6.23 (m, 1H), 5.23 (m, 1H), 4.72 (m, 1H), 4.38 (m, 1H), 1.31 (m, 6H). Product structural formula is shown in I-19.

[0154]

[0155] Example 20: Preparation of compound I-20

[0156] 40.55 g (250 mmol) of (2E)-3-(4-methoxy)phenylprop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of ethanol by stirring at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 0.84 g (2.50 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 4 hours of reaction, water and ethanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from ethanol and dried to obtain 58.33 g of a white solid, with a yield of 87.65%. 1 ¹H NMR (400MHz, D₂O) δ: 7.66 (m, 2H), 7.13 (m, 2H), 6.65 (m, 1H), 6.29 (m, 1H), 4.74 (m, 1H), 4.34 (m, 1H), 3.83 (s, 3H). Product structural formula is shown in I-20.

[0157]

[0158] Example 21: Preparation of compound I-21

[0159] 37.04 g (250 mmol) of ((2E)-3-(4-hydroxyphenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of ethanol and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 0.84 g (2.50 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the above single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 4 hours of reaction, water and ethanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from ethanol and dried to obtain 52.93 g of white solid, with a yield of 83.96%. 1 ¹H NMR (400MHz, D₂O) δ: 7.72-6.65 (m, 4H), 6.50 (m, 1H), 6.04 (m, 1H), 4.67 (m, 1H), 4.23 (m, 1H). Product structural formula is shown in I-21.

[0160]

[0161] Example 22: Preparation of compound I-22

[0162] 52.07 g (250 mmol) of (2E)-3-(4-phenylphenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of dichloromethane and stirred thoroughly at room temperature to dissolve. 78.00 g (750 mmol) of sodium bisulfite and 1.26 g (3.75 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the above single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and dichloromethane were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 60.42 g of white solid, with a yield of 77.39%. 1 ¹H NMR (400MHz, D₂O) δ: 7.81 (m, 2H), 7.50-7.42 (m, 7H), 6.63 (m, 1H), 6.21 (m, 1H), 4.79 (m, 1H), 4.44 (m, 1H). Product structural formula is shown in I-22.

[0163]

[0164] Example 23: Preparation of compound I-23

[0165] 50.04 g (250 mmol) of (2E)-3-[3-(trifluoromethyl)phenyl]prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 12.6 g (3.75 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 6 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 58.14 g of a yellow solid, with a yield of 76.46%. 1 ¹H NMR (400MHz, D₂O) δ: 7.58 (m, 2H), 7.49 (m, 2H), 6.59 (m, 1H), 6.22 (m, 1H), 4.75 (m, 1H), 4.36 (m, 1H). Product structural formula is shown in I-23.

[0166]

[0167] Example 24: Preparation of compound I-24

[0168] 50.82 g (250 mmol) of (2E)-3-[4-(diethylamino)phenyl]prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of DMF and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 0.84 g (2.50 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the above single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 6 hours of reaction, water and DMF were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 56.92 g of a yellow solid, with a yield of 74.10%. 1 ¹H NMR (400MHz, D₂O) δ: 7.68 (m, 2H), 6.88 (m, 2H), 6.64 (m, 1H), 6.28 (m, 1H), 4.79 (m, 1H), 4.21 (m, 1H), 3.42 (m, 6H), 1.32 (m, 6H). Product structural formula is shown in I-24.

[0169]

[0170] Example 25: Preparation of compound I-25

[0171] 44.55 g (250 mmol) of (2E)-3-(3-hydroxy-4-methoxyphenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 78.00 g (750 mmol) of sodium bisulfite and 12.6 g (3.75 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 61.13 g of a yellow solid, with a yield of 86.65%. 1 ¹H NMR (400MHz, D₂O) δ: 7.20 (m, 2H), 7.11 (m, 1H), 6.58 (m, 1H), 6.17 (m, 1H), 4.67 (m, 1H), 4.21 (m, 1H), 3.74 (s, 3H). Product structural formula is shown in I-25.

[0172]

[0173] Example 26: Preparation of compound I-26

[0174] 52.05 g (250 mmol) of (2E)-3-(4-hydroxy-3,5-dimethoxyphenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 0.84 g (2.50 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 5 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 64.52 g of a yellow solid, with a yield of 82.66%. 1 ¹H NMR (400MHz, D₂O) δ: 6.81 (m, 2H), 6.59 (m, 1H), 6.26 (m, 1H), 4.77 (m, 1H), 4.31 (m, 1H), 3.82 (s, 6H). Product structural formula is shown in I-26.

[0175]

[0176] Example 27: Preparation of compound I-27

[0177] 42.04 g (250 mmol) of (2E)-3-(2,6-difluorophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 39.89 g of a white solid, with a yield of 58.63%. 1 ¹H NMR (400MHz, D₂O) δ: 7.23 (m, 1H), 7.11 (m, 2H), 6.83 (m, 1H), 6.19 (m, 1H), 4.82 (m, 1H), 3.92 (m, 1H). Product structural formula is shown in I-27.

[0178]

[0179] Example 28: Preparation of compound I-28

[0180] 50.26 g (250 mmol) of (2E)-3-(2,3-dichlorophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 5 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 63.81 g of a yellow solid, with a yield of 83.67%. 1 ¹H NMR (400MHz, D₂O) δ: 7.53-7.18 (m, 3H), 6.90 (m, 1H), 6.01 (m, 1H), 5.88 (m, 1H), 4.71 (m, 1H). Product structural formula is shown in I-28.

[0181]

[0182] Example 29: Preparation of compound I-29

[0183] 46.15 g (250 mmol) of (2E)-3-(2-chloro-6-fluorophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 6 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 60.02 g of a yellow solid, with a yield of 83.19%. 1 ¹H NMR (400MHz, D₂O) δ: 7.48-7.11 (m, 3H), 6.88 (m, 1H), 6.04 (m, 1H), 5.81 (m, 1H), 4.69 (m, 1H). Product structural formula is shown in I-29.

[0184]

[0185] Example 30: Preparation of compound I-30

[0186] 59.55 g (250 mmol) of 5-fluoro-4-[(1E)-2-formylvinyl]-2-methoxyphenyl ester was dissolved in a 500 mL single-necked flask containing 150 mL of ethyl acetate by stirring at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 12.6 g (3.75 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and ethyl acetate were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 71.29 g of a yellow solid, with a yield of 83.33%. 1 ¹H NMR (400MHz, D₂O) δ: 7.41 (m, 1H), 7.33 (m, 1H), 7.22 (m, 1H), 6.58 (m, 1H), 6.16 (m, 1H), 4.71 (m, 1H), 3.88 (m, 1H), 3.79 (s, 3H), 2.17 (s, 3H). Product structural formula is shown in I-30.

[0187]

[0188] Example 31: Preparation of compound I-31

[0189] 43.56 g (250 mmol) of (2E)-3-(3,4,5-trimethylphenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of ethanol by stirring at room temperature. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and ethanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from ethanol and dried to obtain 48.56 g of a white solid, with a yield of 69.81%. 1 ¹H NMR (400MHz, D₂O) δ: 7.13 (m, 2H), 6.63 (m, 1H), 6.28 (m, 1H), 4.81 (m, 1H), 4.28 (m, 1H), 2.40 (m, 6H), 2.23 (s, 3H). Product structural formula is shown in I-31.

[0190]

[0191] Example 32: Preparation of compound I-32

[0192] 46.53 g (250 mmol) of (2E)-2,3-difluoro-3-(4-fluorophenyl)prop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 1.68 g (5.00 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 5 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 53.56 g of a white solid, with a yield of 73.85%. 1 ¹H NMR (400MHz, D₂O) δ: 7.41 (m, 2H), 7.33 (m, 2H), 4.72 (m, 1H), 4.08 (m, 1H). Product structural formula is shown in I-32.

[0193]

[0194] Example 33: Preparation of compound I-33

[0195] 52.77 g (250 mmol) of (2Z)-2-bromo-3-phenylprop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of DMF and stirred thoroughly at room temperature to dissolve. 78.00 g (750 mmol) of sodium bisulfite and 2.52 g (7.5 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the above single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 4 hours of reaction, water and DMF were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from DMF and dried to obtain 61.32 g of a yellow solid, with a yield of 77.85%. 1 ¹H NMR (400MHz, D₂O) δ: 7.62 (m, 2H), 7.37 (m, 2H), 7.19 (m, 1H), 7.02 (m, 1H), 5.71 (m, 1H), 4.74 (m, 1H). Product structural formula is shown in I-33.

[0196]

[0197] Example 34: Preparation of compound I-34

[0198] 36.55 g (250 mmol) of (2E)-2-methyl-3-phenylprop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of DMF and stirred thoroughly at room temperature to dissolve. 78.00 g (750 mmol) of sodium bisulfite and 2.52 g (7.5 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the above single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and DMF were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from DMF and dried to obtain 39.58 g of white solid, with a yield of 63.28%. 1 ¹H NMR (400MHz, D₂O) δ: 7.64 (m, 2H), 7.39 (m, 2H), 7.22 (m, 1H), 6.98 (m, 1H), 5.73 (m, 1H), 4.77 (m, 1H), 1.83 (s, 3H). Product structural formula is shown in I-34.

[0199] (I-34)

[0200] Example 35: Preparation of compound I-35

[0201] 52.07 g (250 mmol) of (2E)-2,3-diphenylprop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of DMF and stirred thoroughly at room temperature to dissolve. 78.00 g (750 mmol) of sodium bisulfite and 2.52 g (7.5 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the above single-necked flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and DMF were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from DMF and dried to obtain 64.71 g of white solid, with a yield of 82.89%. 1 ¹H NMR (400MHz, D₂O) δ: 7.81 (m, 2H), 7.52 (m, 2H), 7.33 (m, 1H), 7.22 (m, 3H), 6.91 (m, 2H), 6.48 (m, 1H), 4.81 (m, 1H), 4.22 (m, 1H). Product structural formula is shown in I-35.

[0202]

[0203] Example 36: Preparation of compound I-36

[0204] 54.08 g (250 mmol) of 2-[(E)-phenylmethylene]octanal was dissolved in 150 mL of methanol in a 500 mL single-necked flask at room temperature by stirring. 52.00 g (500 mmol) of sodium bisulfite and 0.84 g (2.50 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 4 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 62.67 g of a white solid, with a yield of 78.26%. 1 ¹H NMR (400MHz, D₂O) δ: 7.66 (m, 2H), 7.35 (m, 3H), 6.27 (m, 1H), 4.71 (m, 1H), 4.28 (m, 1H), 2.88 (m, 2H), 1.32 (m, 8H), 0.89 (t, 3H). Product structural formula is shown in I-36.

[0205]

[0206] Example 37: Preparation of compound I-37

[0207] 41.65 g (250 mmol) of (2Z)-2-chloro-3-phenylprop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of methanol by stirring thoroughly at room temperature. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 6 hours of reaction, water and methanol were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtration to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 57.91 g of a white solid, with a yield of 85.60%. 1 ¹H NMR (400MHz, D₂O) δ: 7.63 (m, 2H), 7.37 (m, 3H), 6.68 (m, 1H), 4.55 (m, 1H), 4.15 (m, 1H). Product structural formula is shown in I-37.

[0208]

[0209] Example 38: Preparation of compound I-38

[0210] 52.07 g (250 mmol) of 3,3-diphenylprop-2-enal was dissolved in a 500 mL single-necked flask containing 150 mL of acetonitrile by stirring at room temperature. 52.00 g (500 mmol) of sodium bisulfite and 1.68 g (5.00 mmol) of tetrabutylphosphine bromide were dissolved in 100 mL of deionized water at room temperature, and then slowly added dropwise to the same flask until the reaction was complete, with stirring at room temperature. The reaction solution gradually became turbid, and a solid was produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 hours of reaction, water and acetonitrile were removed by rotary evaporation, followed by washing three times with 600 mL of deionized water and filtering to remove sodium bisulfite. The resulting solid was recrystallized from methanol and dried to obtain 52.78 g of a white solid, with a yield of 67.61%. 1 ¹H NMR (400MHz, D₂O) δ: 7.33-7.29 (m, 10H), 6.16 (m, 1H), 4.82 (m, 1H), 4.16 (m, 1H). Product structural formula is shown in I-38.

[0211]

[0212] Table 1. Structural formula of reactant II and appearance, purification method and yield of compound (I).

[0213]

[0214]

[0215]

[0216]

[0217] Test Example 1: Inhibitory effect against Ralstonia solanacearum

[0218] The inhibitory effect of the compound of this invention on Ralstonia solanacearum was tested using the shake-flask method. Specifically, the compound of this invention was dissolved in DMF containing 6% Tween 80 and diluted with deionized water to prepare a series of concentration gradient solutions. The drug solution was then mixed evenly with liquid LB medium in an Erlenmeyer flask to prepare a drug-loaded medium. 1 mL of (10) of liquid LB medium was added to the above LB medium. 8 The bacterial culture (CFU) was placed in an Erlenmeyer flask and incubated at 28-30°C on a shaker at 150 rpm. -1 Cultured, each treatment was repeated three times. After 24 hours, 200 μL of culture medium was collected and the absorbance (OD) at 600 nm was measured. 600 The EC value of each drug is calculated using the DPS data processing system. 50 Value. The control reagents were cinnamaldehyde and sodium cinnamaldehyde bisulfite, numbered Cin and Cin-Sod, respectively.

[0219] The results of the indoor toxicity of the compounds of this invention against Ralstonia solanacearum are shown in Table 2.

[0220] Table 2. Results of indoor toxicity tests of the compounds of this invention against Ralstonia solanacearum.

[0221]

[0222]

[0223] The in vitro toxicity results of the compounds described in this invention against Ralstonia solanacearum showed that the compounds of this invention have good inhibitory effects on Ralstonia solanacearum. In particular, sample I-32 showed good inhibitory effects against the EC50 of Ralstonia solanacearum. 50 The value can reach 57.69 mg / L.

[0224] Test Example 2: Inhibitory effect against soil-borne Botrytis cinera Pers.

[0225] The inhibitory effect of the compound described in this invention on Botrytiscinera Pers was tested using the mycelial growth rate method.

[0226] The compound described in this invention was dissolved in a solvent and prepared as a stock solution using a 0.1% Tween 80 aqueous solution. The stock solution was mixed with PDA medium and poured into a culture medium to prepare a drug-containing medium. 5mm bacterial discs were inoculated, and each treatment was repeated three times. The control agents were cinnamaldehyde and sodium cinnamaldehyde bisulfite, labeled Cin and Cin-Sod, respectively. When the colony diameter of the blank control reached approximately 8cm, the colony diameter was measured using the cross-crossing method. The inhibition rate of each compound against the pathogen was calculated according to formula (1):

[0227] Inhibition rate (%) = (Coronary diameter of control group (mm) - Colony diameter of treatment group (mm)) / (Coronary diameter of control group (mm) - 5mm) × 100% (1)

[0228] The results of the indoor toxicity of the compounds described in this invention against soil-borne Botrytis cinera Pers are shown in Table 3.

[0229] Table 3. Indoor toxicity results of compounds against soil-borne Botrytis cinera Pers.

[0230]

[0231]

[0232] The in vitro toxicity results of the compounds described in this invention against soil-borne Botrytis cinera Pers showed that the compounds of this invention have good inhibitory effects on all Botrytis cinera species. In particular, sample number I-13 showed good inhibitory effects against Botrytis cinera persica via EC50. 50 The value can reach 60.51 mg / L.

[0233] Test Example 3: Inhibitory effect against Sclerotinia sclerotiorum

[0234] The inhibitory effect of the compound described in this invention on Sclerotinia sclerotiorum was tested using the mycelial growth rate method.

[0235] The compound described in this invention was dissolved in a solvent and prepared as a stock solution using a 0.1% Tween 80 aqueous solution. The stock solution was mixed with PDA medium and poured into a culture medium to prepare a drug-containing medium. 5mm bacterial discs were inoculated, and each treatment was repeated three times. The control agents were cinnamaldehyde and sodium cinnamaldehyde bisulfite, labeled Cin and Cin-Sod, respectively. When the colony diameter of the blank control reached approximately 8cm, the colony diameter was measured using the cross-crossing method. The inhibition rate of each compound against the pathogen was calculated according to formula (1):

[0236] Inhibition rate (%) = (Coronary diameter of control group (mm) - Colony diameter of treatment group (mm)) / (Coronary diameter of control group (mm) - 5mm) × 100% (1)

[0237] The results of the indoor toxicity of the compounds described in this invention against Sclerotinia sclerotiorum are shown in Table 4.

[0238] Table 4. Indoor toxicity results of compounds against *Sclerotinia sclerotiorum*.

[0239]

[0240] The in vitro toxicity results of the compounds described in this invention against *Sclerotinia sclerotiorum* showed that the compounds of this invention exhibited good inhibitory effects against *Sclerotinia sclerotiorum*. In particular, sample number I-27 showed significant inhibitory effects against *Sclerotinia sclerotiorum*. 50 The value can reach 75.39 mg / L.

[0241] Test Example 4: Inhibitory effect against Fusarium oxysporum

[0242] The inhibitory effect of the compound described in this invention on Fusarium oxysporum was tested using the mycelial growth rate method.

[0243] The compound described in this invention was dissolved in a solvent and prepared as a stock solution using a 0.1% Tween 80 aqueous solution. The stock solution was mixed with PDA medium and poured into a culture medium to prepare a drug-containing medium. 5mm bacterial discs were inoculated, and each treatment was repeated three times. The control agents were cinnamaldehyde and sodium cinnamaldehyde bisulfite, labeled Cin and Cin-Sod, respectively. When the colony diameter of the blank control reached approximately 8cm, the colony diameter was measured using the cross-crossing method. The inhibition rate of each compound against the pathogen was calculated according to formula (1):

[0244] Inhibition rate (%) = (Coronary diameter of control group (mm) - Colony diameter of treatment group (mm)) / (Coronary diameter of control group (mm) - 5mm) × 100% (1)

[0245] The results of the indoor toxicity of the compounds described in this invention against Fusarium oxysporum are shown in Table 5.

[0246] Table 5. Indoor toxicity results of compounds against Fusarium oxysporum.

[0247]

[0248] The in vitro toxicity results of the compounds described in this invention against *Fusarium oxysporum* showed that the compounds of this invention exhibited good inhibitory effects against *Fusarium oxysporum*. In particular, sample I-23 showed a significant EC50 inhibition against *Fusarium oxysporum*. 50 The value can reach 118.35 mg / L.

[0249] Test Example 5: Bioactivity against Southern Root-Knot Nematode

[0250] The bioactivity of the compounds obtained in this invention against southern root-knot nematodes was tested using the second-instar larval immersion method.

[0251] The compound described in this invention was dissolved in an organic solvent and diluted to 100 mg / L with 0.1% Triton aqueous solution. 100 μL of the solution and 100 μL of nematode solution (approximately 50 second-instar larvae) were mixed in a 96-well plate, with each treatment repeated three times. A Triton aqueous solution containing only the solvent was used as a blank control. The control agents were cinnamaldehyde and cinnamaldehyde sodium bisulfite, labeled Cin and Cin-Sod, respectively. After incubating the 96-well plates at 25°C for 24 and 48 hours, the mortality was examined under a stereomicroscope, and the nematode mortality rate was calculated using the following formula:

[0252] Mortality rate (%) = number of dead nematodes / total number of tested nematodes × 100% (2);

[0253] The results of the indoor toxicity of the compounds described in this invention against southern root-knot nematodes are shown in Table 6.

[0254] Table 6 shows the results of the indoor toxicity of the compounds against the southern root-knot nematode (Meloidogyne incognita).

[0255]

[0256] Note: +0-20%; ++20-40%; +++40-60%; ++++60-80%; +++++80-100%.

[0257] The indoor toxicity results of the compounds described in this invention against southern root-knot nematodes (Meloidogyne incognita) show that the compounds of this invention have good control effects against southern root-knot nematodes.

[0258] Test Example 6: Bioactivity against Southern Root-Knot Nematode

[0259] The bioactivity of the compound described in this invention against the southern root-knot nematode (Meloidogyne incognita) was tested using a nematode soil column experiment.

[0260] First, 250g of soil containing nematodes was placed into a 30cm high empty PE pipe to prepare a soil column. Then, the compound described in this invention was dissolved in DMF containing 6% Tween 80, and then diluted with deionized water to 200-500mg / L. -1 Add 90 mL of the agent to the soil column, and repeat each treatment three times; use a DMF aqueous solution containing only the same concentration of Tween 80 as a blank control. Place the soil column at room temperature (25℃) for two weeks, examine the mortality under a stereomicroscope, and calculate the nematode inhibition rate (%) according to formula (1):

[0261] Inhibition rate (%) = Number of nematodes in the treated soil column (number of nematodes) / Total number of nematodes in the control group (number of nematodes) × 100% (1)

[0262] The results of the indoor toxicity of the compounds described in this invention against southern root-knot nematodes are shown in Table 7.

[0263] Table 7. Indoor toxicity results of the compounds described in this invention against southern root-knot nematode (Meloidogyne incognita).

[0264]

[0265]

[0266] The indoor toxicity results of the compounds described in this invention against southern root-knot nematodes (Meloidogyne incognita) show that the compounds of this invention have good control effects against southern root-knot nematodes.

[0267] As can be seen from test examples 1-6, the compound represented by formula (I) of the present invention has good biological activity against Ralstonia solanacearum, Botrytis cinera Pers, Sclerotinia sclerotiorum, Fusarium oxysporum, and Meloidogyne incognita.

[0268] The present invention has been described in detail above. Those skilled in the art will recognize that the invention can be practiced in a wide range of ways with equivalent parameters, concentrations, and conditions without departing from its spirit and scope. While specific embodiments have been provided, it should be understood that further modifications can be made to the invention. In summary, according to the principles of the invention, this application is intended to include any changes, uses, or improvements to the invention, including modifications made using conventional techniques known in the art that depart from the scope disclosed herein.

Claims

1. The compound shown in formula (I): Formula (I) The compound represented by formula (I) is any one of the following: Equation (I-09): R1 is 3-CH3, R2 is H, and R3 is H; Equation (I-10): R1 is 3-F, R2 is H, R3 is H; Equation (I-13): R1 is 3-CF3, R2 is H, and R3 is H; Equation (I-14): R1 is 4-F, R2 is H, R3 is H; Equation (I-18): R1 is 4-CH3, R2 is H, and R3 is H; Equation (I-23): R1 is 4-CF3, R2 is H, R3 is H; Equation (I-27): R1 is 2, 6-F, R2 is H, R3 is H; Equation (I-28): R1 is 2,3-Cl, R2 is H, and R3 is H; Equation (I-29): R1 is 2-Cl, 6-F, R2 is H, R3 is H; Equation (I-31): R1 is 2, 3, 4-CH3, R2 is H, and R3 is H; Equation (I-32): R1 is 4-F, R2 is F, and R3 is F.

2. A method for preparing the compound according to claim 1, comprising the following steps: Equation (II) In equation (II): R1, R2, and R3 are defined in the same way as in equation (I); A homogeneous phase B system, consisting of sodium bisulfite, a quaternary phosphine salt phase transfer catalyst, and water, was added dropwise to a homogeneous phase A system, consisting of the compound shown in formula (II) and an organic solvent, to carry out a nucleophilic addition reaction, yielding the compound shown in formula (I).

3. The preparation method according to claim 2, characterized in that: The quaternary phosphine salt phase transfer catalyst is one or more of tetrabutylphosphine bromide, tetrabutylphosphine chloride, and hexadecyltributylphosphine bromide. The amount of the quaternary phosphine salt phase transfer catalyst used is 0.25 to 5% of the molar amount of sodium bisulfite.

4. The preparation method according to claim 2 or 3, characterized in that: The molar ratio of the compound shown in formula (II) to the sodium bisulfite is 1.0:(1.0 to 3.0). The organic solvent is one or more of methanol, ethanol, n-propanol, isopropanol, dichloromethane, acetonitrile, ethyl acetate, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, cyclohexane, and cyclohexanone.

5. The preparation method according to any one of claims 2-3, characterized in that: The nucleophilic addition reaction was carried out at room temperature and pressure for 3 to 6 hours.

6. The use of the compound of claim 1 in inhibiting soil-borne plant pathogens or in the preparation of products that inhibit soil-borne plant pathogens.

7. The application according to claim 6, characterized in that: The soil-borne plant pathogenic bacteria is *Laurella multocida* (…). Ralstonia solanacearum ).

8. The application according to claim 6, characterized in that: The soil-borne plant pathogenic bacteria is soil-borne Botrytis cinerea (… Botrytis cinera Pers).

9. The use of the compound of claim 1 in inhibiting soil-borne plant pathogenic fungi or in the preparation of products that inhibit soil-borne plant pathogenic fungi.

10. The application according to claim 9, characterized in that: The soil-borne plant pathogenic fungus is *Sclerotinia sclerotiorum* (… Sclerotinia sclerotiorum ).

11. The application according to claim 9, characterized in that: The soil-borne plant pathogenic fungus is *Fusarium oxysporum* (…). Fusarium oxysporum ).

12. The use of the compound of claim 1 in inhibiting nematodes or in the preparation of products that inhibit nematodes.

13. The application according to claim 12, characterized in that: The nematode is the southern root-knot nematode ( Meloidogyne incognita ).

14. The use of the compound of claim 1 in the prevention and control of soil-borne diseases or in the preparation of products for the prevention and control of soil-borne diseases; The soil pathogens of the soil-borne diseases mentioned are any one of soil-borne plant pathogenic bacteria, soil-borne plant pathogenic fungi, or nematodes.

15. The application according to claim 14, characterized in that: The soil-borne plant pathogenic bacteria is *Laurella multocida* (…). Ralstonia solanacearum ) or soil-borne Botrytis cinerea ( Botrytis cinerea Pers).

16. The application according to claim 14, characterized in that: The soil-borne plant pathogenic fungus is *Sclerotinia sclerotiorum* (… Sclerotinia sclerotiorum ) or Fusarium oxysporum ( Fusarium oxysporum ).

17. The application according to claim 14, characterized in that: The nematode is the southern root-knot nematode ( Meloidogyne unknown ).

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