1-hydroxy-1-sodium sulfonate structural compound based on cinnamyl aldehyde derivative as well as preparation method and application of 1-hydroxy-1-sodium sulfonate structural compound

Abstract

The invention discloses a cinnamyl aldehyde derivative-based 1-hydroxy-1-sodium sulfonate structural compound as well as a preparation method and application thereof, and belongs to the technical field of preparation of agricultural chemicals. The structural general formula of the compound is shown as a formula (I). The preparation method of the compound comprises the following steps: dropwise adding a homogeneous phase B system consisting of sodium hydrogen sulfite, a quaternary phosphonium salt phase transfer catalyst and water into a homogeneous phase A system consisting of a compound shown in a formula (II) and an organic solvent, and carrying out nucleophilic addition reaction to obtain the compound shown in the formula (I). The preparation method is simple, reaction conditions are mild, and the obtained compound is good in environmental compatibility, has high biological activity on soil pathogens (bacteria, fungi, root-knot nematode and the like), can be widely applied to prevention and treatment of soil-borne diseases, and provides material guarantee for safe production of crops.

Description

Technical Field

[0001] The present invention belongs to the technical field of agricultural chemicals, and in particular relates to a 1-hydroxy-1-sulfonic acid sodium salt structure compound based on a cinnamaldehyde derivative, and a preparation method and application thereof. Background Art

[0002] Soilborne diseases are caused by pathogens (fungi, bacteria, nematodes, viruses, etc.) that reside partly or largely in the soil during their life cycle, infecting plant roots or stems under favorable conditions. In recent years, intensive crop production and continuous tillage practices have led to an accumulation of pathogens in the soil, exacerbating the severity of soilborne diseases. These diseases have become a major factor limiting crop yield and quality, seriously hindering the sustainable development of agriculture. For a long time, fumigants represented by calcium cyanamide, dazomethan, sulfuryl fluoride, 1,3-dichloropropylene, dimethyl disulfide, methamphetamine and methyl bromide have been used to fumigate soil and achieve good results in the prevention and control of 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 the soil, susceptibility of activity to environmental conditions, and harm to crop planting. They are unable to adapt well to the needs of modern agricultural planting and production. The development of 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 present in the volatile oils of plants such as cinnamon, cassia bark, and bay leaves. To further enhance the biological activity of cinnamaldehyde, modifications have been made on its benzene ring, α-carbon, or β-carbon to produce a variety of derivatives. These developed derivatives exhibit superior biological activity compared to cinnamaldehyde. However, no prior art reports have identified compounds with the structure of 1-hydroxy-1-sulfonic acid sodium salts based on cinnamaldehyde derivatives, let alone their application in agricultural production as agents for controlling soil-borne diseases. Summary of the Invention

[0004] To identify novel compounds for the effective, safe, and environmentally friendly prevention and treatment of soil-borne diseases, this invention utilizes a nucleophilic addition reaction between cinnamaldehyde derivatives and sodium bisulfite to yield, for the first time, a series of compounds containing the structure of 1-hydroxy-1-sulfonic acid sodium salt. Indoor bioactivity assays and potted plant experiments demonstrate that these compounds exhibit high bioactivity against soil-borne diseases and can be used to prevent and treat soil-borne plant diseases, providing a material guarantee for crop production safety. Specifically, the present invention provides a cinnamaldehyde derivative-based 1-hydroxy-1-sulfonic acid sodium salt structure compound, its preparation method, and its application, which exhibits high activity against plant pathogenic fungi, bacteria, and nematodes.

[0005] To achieve the above object, the present invention adopts the following technical solutions:

[0006] In the first aspect, the general structural formula of the 1-hydroxy-1-sulfonic acid sodium salt structure compound based on the 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 any one of hydrogen, halogen, nitro, hydroxy, 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] Wherein, R1, R2, and R3 are not hydrogen at the same time, and when R1 is Cl and is at the 4-position, R2 is not chlorine.

[0012] In the present invention, the term "C1-C4 alkyl" refers to a straight-chain or branched alkyl group having 1 to 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 a straight or branched chain alkoxy group having 1 to 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 amino group disubstituted by an alkyl group having 1 to 4 carbon atoms, such as dimethylamino, diethylamino, dipropylamino, and dibutylamino;

[0015] The term "C1-C4 alkyl acyloxy" refers to an alkyl acyloxy group having 1 to 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 when a halogen atom replaces one, two or three hydrogen atoms in a methyl group, including but not limited to monohalomethyl, dihalomethyl, trihalomethyl, such as monofluoromethyl, difluoromethyl or trifluoromethyl;

[0017] Wherein, the halogen in R1, R2, and R3 or the halogen in the halogenated radical is 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, and R3 is H;

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0038] Formula (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] Formula (I-22): R1 is 4-C6H5, R2 is H, and R3 is H;

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

[0042] Formula (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] Formula (I-27): R1 is 2,6-F, R2 is H, and R3 is H;

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

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

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

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

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

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

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

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

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

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

[0056] Formula (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 a compound represented by any one of the above formula (I), comprising the following steps:

[0058]

[0059] In formula (II): R1, R2, and R3 are as defined in formula (I);

[0060] A homogeneous phase B system consisting of sodium bisulfite, a quaternary phosphonium salt phase transfer catalyst and water is added dropwise to a homogeneous phase A system consisting of a compound represented by formula (II) and an organic solvent to carry out a nucleophilic addition reaction to obtain a compound represented by formula (I).

[0061] In the above preparation method, further, 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 phosphonium salt phase transfer catalyst is 0.25-5% of the molar amount of the sodium bisulfite, such as 0.25%, 0.5%, 0.75%, 0.8%, 1%, 1.25%, and 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 is dissolved in 100 mL of water.

[0064] In the above preparation method, further, the molar ratio of the compound represented by formula (II) to the sodium bisulfite is 1.0: (1.0-3.0), 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, 250 mmol of the compound represented by formula (II) is dissolved in 150 mL of the organic solvent.

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

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

[0069] In the above preparation method, thin layer chromatography (TLC) is further used to track the reaction progress;

[0070] After the reaction is completed, the method further comprises the following steps: desolventizing the system by distillation (such as rotary evaporation), washing and filtering to remove sodium bisulfite, and recrystallizing the obtained solid to obtain the compound represented by formula (I).

[0071] In a third aspect, the present invention provides the use of the compound represented by formula (I) described in any one of the above in any of the following:

[0072] A1. Inhibition of soil-borne plant pathogenic bacteria or preparation of products for inhibiting soil-borne plant pathogenic bacteria;

[0073] A2. Inhibition of Ralstonia solanacearum or preparation of a product for inhibition of Ralstonia solanacearum;

[0074] A3. Inhibiting soil-borne Botrytis cinera Pers or preparing a product for inhibiting soil-borne Botrytis cinera Pers.

[0075] In a fourth aspect, the present invention provides the use of the compound represented by formula (I) described in any one of the above in any one of the following:

[0076] B1. Inhibiting soil-borne plant pathogenic fungi or preparing products for inhibiting soil-borne plant pathogenic fungi;

[0077] B2. Inhibition of Sclerotinia sclerotiorum or preparation of a product that inhibits Sclerotinia sclerotiorum;

[0078] B3. Inhibiting Fusarium oxysporum or preparing a product for inhibiting Fusarium oxysporum.

[0079] In a fifth aspect, the present invention provides the use of the compound represented by formula (I) described in any one of the above in any one of the following:

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

[0081] C2. Inhibiting the southern root-knot nematode (Meloidogyne incognita) or preparing a product for inhibiting the southern root-knot nematode (Meloidogyne incognita).

[0082] In a sixth aspect, the present invention provides use of the compound represented by formula (I) as described in any one of the above items in preventing and controlling soil-borne diseases or preparing products for preventing and controlling soil-borne diseases;

[0083] The soil pathogen of the soil-borne disease is any one of soil-borne plant pathogenic bacteria, soil-borne plant pathogenic fungi or nematodes;

[0084] The soil-borne plant pathogenic bacteria are preferably Ralstonia solanacearum or Botrytis cinera Pers;

[0085] The soil-borne plant pathogenic fungus is preferably Sclerotinia sclerotiorum or Fusarium oxysporum;

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

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

[0088] The preparation method of the present invention is simple, the reaction conditions are mild, the obtained compound has good environmental compatibility, and has high biological activity against soil pathogens (bacteria, fungi, root-knot nematodes, etc.). It can be widely used in the prevention and treatment of soil-borne diseases, providing material guarantee for the safe production of crops. BRIEF DESCRIPTION OF THE DRAWINGS

[0089] Figure 1 This is the preparation route of the compound represented by formula (I) of the present invention. DETAILED DESCRIPTION

[0090] The present invention will be further described in detail below in conjunction with specific embodiments. The examples provided are only for illustrating the present invention and are not intended to limit the scope of the present invention. The examples provided below can serve as a guide for further improvements by those skilled in the art and are not intended to limit the present invention in any way.

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

[0092] Test strain: Ralstonia solanacearum strain GMI1000, which is recorded in the document "Xu Yan, Song Wen, Zhu Dan, et al. Identification of the inhibitory activity of propolis residue extract against Ralstonia solanacearum [J]. Sericulture Science. 2018, (2). DOI: 10.13441 / j.cnki.cykx.2018.02.004." The public can obtain it from the applicant. The biological material is only used to repeat the relevant experiments of the present invention and cannot be used for other purposes.

[0093] Botrytis cinera Pers strain B05.10, described in the document "Li Boya. Study on the mechanism of wuyimycin in preventing and controlling grape gray mold and its delay in gray mold resistance [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 the present invention and cannot be used for other purposes.

[0094] Sclerotinia sclerotiorum strain 1980 is recorded in the document "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).", which can be obtained by the public from the applicant. The biological material is only used to repeat the relevant experiments of the present invention and cannot be used for other purposes.

[0095] Fusarium oxysporum strain F-1 is recorded in the document "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 Biocontrol, 2022, 38(4): 6. DOI: 10.16409 / j.cnki.2095-039x.2022.04.010." The public can obtain it from the applicant. The biological material is only used to repeat the relevant experiments of the present invention and cannot be used for other purposes.

[0096] Control agent: cinnamaldehyde sodium bisulfite, with the structural formula shown as Cin-Sod, is recorded in the document "Zhang Yuanyuan. Synthesis of cinnamaldehyde antibacterial derivatives and their quantitative structure-activity relationship [D]. Northeast Forestry University, 2013." The public can prepare it with reference to the provided document, or obtain it from the applicant.

[0097]

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

[0099] 44.25 g (250 mmol) of (2E)-3-(2-nitrophenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 3-hour reaction, water and methanol were removed by rotary evaporation, and the mixture was washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 66.08 g of a white solid, with a yield of 94.07%. 1 H NMR (400 MHz, 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). The product structure is shown in I-01.

[0100]

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

[0102] 37.53 g (250 mmol) of (2E)-3-(2-fluorophenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. The reaction progress was monitored by thin-layer chromatography. After the 3-hour reaction, water and methanol were removed by rotary evaporation, and the mixture was washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 58.49 g of a yellow solid, with a yield of 92.07%. 1 H NMR (400 MHz, 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). The product structure is shown in FIG1-02.

[0103]

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

[0105] 52.77 g (250 mmol) of (2E)-3-(2-bromophenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until complete, with stirring at room temperature. The reaction solution gradually became turbid, with the formation of solids. The reaction progress was monitored by thin-layer chromatography. After the 3-h reaction, water and methanol were removed by rotary evaporation, and the mixture was washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried from methanol to obtain 63.81 g of a brown solid, with a yield of 81.01%. 1 H NMR (400 MHz, 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). The product structure is shown as I-03.

[0106] (I-03)

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

[0108] 41.65 g (250 mmol) of (2E)-3-(2-chlorophenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 3-hour reaction, water and methanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 65.22 g of a yellow solid, with a yield of 96.41%. 1 H NMR (400 MHz, 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). The product structure is shown as I-04.

[0109]

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

[0111] 40.55 g (250 mmol) of (2E)-3-(2-methoxyphenyl)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. 31.28 g (300 mmol) of sodium bisulfite and 0.50 g (1.50 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. The reaction progress was monitored by thin-layer chromatography. After the 4-hour reaction, water and ethanol were removed by rotary evaporation, and the mixture was washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with ethanol to obtain 61.23 g of a white solid, with a yield of 92.01%. 1 H NMR (400 MHz, 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). The product structure is shown in FIG1-05.

[0112]

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

[0114] 37.04 g (250 mmol) of (2E)-3-(2-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. 26.00 g (250 mmol) of sodium bisulfite and 0.37 g (1.25 mmol) of tetrabutylphosphonium chloride were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 6-hour reaction, water and ethanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with ethanol to obtain 57.08 g of a white solid, with a yield of 90.55%. 1 H NMR (400 MHz, 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). The product structure is shown as I-06.

[0115]

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

[0117] 44.25 g (250 mmol) of (2E)-3-(3-nitrophenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 3-hour reaction, water and methanol were removed by rotary evaporation, and the mixture was washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 64.72 g of a white solid, with a yield of 92.13%. 1 H NMR (400 MHz, 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). The product structure is shown as I-07.

[0118]

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

[0120] 40.55 g (250 mmol) of (2E)-3-(3-methoxy)phenylprop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of ethanol and stirred thoroughly at room temperature to dissolve. 41.60 g (400 mmol) of sodium bisulfite and 1.34 g (4.00 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 4-hour reaction, water and ethanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized from ethanol to obtain 57.67 g of a white solid, dried in a yield of 86.66%. 1 H NMR (400 MHz, 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). The product structure is shown in FIG1-08.

[0121]

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

[0123] 36.55 g (250 mmol) of (2E)-3-(3-methylphenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 26.00 g (250 mmol) of sodium bisulfite and 0.67 g (2.00 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 5-hour reaction, water and methanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 51.67 g of a white solid, with a yield of 82.61%. 1 H NMR (400 MHz, 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). The product structure is shown in FIG1-09.

[0124]

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

[0126] 37.53 g (250 mmol) of (2E)-3-(3-fluorophenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. The reaction progress was monitored by thin-layer chromatography. After the 3-h reaction, water and methanol were removed by rotary evaporation, and the mixture was washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 54.78 g of a white solid, with a yield of 86.22%. 1 H NMR (400 MHz, 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). The product structure is shown in I-10.

[0127]

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

[0129] 41.65 g (250 mmol) of (2E)-3-(3-chlorophenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 3-hour reaction, water and methanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 62.56 g of a yellow solid, with a yield of 92.48%. 1 H NMR (400 MHz, 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). The product structure is shown in I-11.

[0130]

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

[0132] 52.77 g (250 mmol) of (2E)-3-(3-bromophenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. The reaction progress was monitored by thin-layer chromatography. After the 3-h reaction, water and methanol were removed by rotary evaporation, and the mixture was washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried from methanol to obtain 66.95 g of a brown solid, with a yield of 84.00%. 1 H NMR (400 MHz, 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). The product structure is shown in I-12.

[0133]

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

[0135] 50.04 g (250 mmol) of (2E)-3-[3-(trifluoromethyl)phenyl]prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 31.20 g (300 mmol) of sodium bisulfite and 1.26 g (3.75 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 5-hour reaction, water and methanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 60.73 g of a white solid, with a yield of 79.87%. 1 H NMR (400 MHz, 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). The product structure 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 placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 26.00 g (250 mmol) of sodium bisulfite and 1.68 g (5.00 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After 3.5 h of reaction, water and methanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 51.57 g of a white solid, with a yield of 81.17%. 1 H NMR (400 MHz, D2O) δ: 7.80-6.74 (m, 4H), 6.71 (m, 1H), 6.43 (m, 1H), 4.82 (m, 1H), 4.41 (m, 1H). The product structure is shown in I-14.

[0139]

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

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

[0142]

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

[0144] 52.77 g (250 mmol) of (2E)-3-(4-bromophenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 1.68 g (5.00 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. The reaction progress was monitored by thin-layer chromatography. After 3.5 h of reaction, water and methanol were removed by rotary evaporation, and the mixture was washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried from methanol to obtain 68.31 g of a brown solid, with a yield of 86.72%. 1 H NMR (400 MHz, D2O) δ: 7.60-6.52 (m, 4H), 6.45 (m, 1H), 6.16 (m, 1H), 4.63 (m, 1H), 4.21 (m, 1H). The product structure 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 placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 1.68 g (5.00 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. The reaction progress was monitored by thin-layer chromatography. After the reaction was completed after 3.5 h, water and methanol were removed by rotary evaporation, and the mixture was washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 73.49 g of a white solid, with a yield of 81.19%. 1 H NMR (400 MHz, D2O) δ: 7.70-6.61 (m, 4H), 6.51 (m, 1H), 6.02 (m, 1H), 4.66 (m, 1H), 4.21 (m, 1H). The product structure is shown in I-17.

[0148]

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

[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 isopropyl alcohol and thoroughly stirred at room temperature for dissolution. 26.00 g (250 mmol) of sodium bisulfite and 0.84 g (2.50 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until completion of the reaction. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 3-hour reaction, water and isopropyl alcohol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried from isopropyl alcohol to obtain 47.29 g of a white solid, with a yield of 75.60%. 1 H NMR (400 MHz, 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). The product structure is shown in I-18.

[0151]

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

[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 stirred thoroughly at room temperature to dissolve. 26.00 g (250 mmol) of sodium bisulfite and 0.84 g (2.50 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 3-hour reaction, water and ethanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with ethanol to obtain 42.84 g of a white solid, with a yield of 61.59%. 1 H NMR (400 MHz, 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). The product structure 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 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 tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 4-hour reaction, water and ethanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with ethanol to obtain 58.33 g of a white solid, with a yield of 87.65%. 1 H NMR (400 MHz, 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). The product structure 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 tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until completion of the reaction. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. The reaction progress was monitored by thin-layer chromatography. After the 4-hour reaction, water and ethanol were removed by rotary evaporation, and the mixture was washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with ethanol to obtain 52.93 g of a white solid with a yield of 83.96%. 1 H NMR (400 MHz, D2O) δ: 7.72-6.65 (m, 4H), 6.50 (m, 1H), 6.04 (m, 1H), 4.67 (m, 1H), 4.23 (m, 1H). The product structure is shown in I-21.

[0160]

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

[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 thoroughly stirred at room temperature for dissolution. 78.00 g (750 mmol) of sodium bisulfite and 1.26 g (3.75 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until completion of the reaction. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 3-hour reaction, water and dichloromethane were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 60.42 g of a white solid, with a yield of 77.39%. 1 H NMR (400 MHz, 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). The product structure is shown in I-22.

[0163]

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

[0165] 50.04 g (250 mmol) of (2E)-3-[3-(trifluoromethyl)phenyl]prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and thoroughly stirred at room temperature for dissolution. 52.00 g (500 mmol) of sodium bisulfite and 12.6 g (3.75 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until complete, with stirring at room temperature. The reaction solution gradually became turbid, with the formation of solids. Thin-layer chromatography was used to track the reaction progress. After the 6-hour reaction, water and methanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 58.14 g of a yellow solid, with a yield of 76.46%. 1 H NMR (400 MHz, 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). The product structure 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 tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 6-hour reaction, water and DMF were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 56.92 g of a yellow solid, with a yield of 74.10%. 1 H NMR (400 MHz, 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). The product structure is shown in I-24.

[0169]

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

[0171] 44.55 g (250 mmol) of (2E)-3-(3-hydroxy-4-methoxyphenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 78.00 g (750 mmol) of sodium bisulfite and 12.6 g (3.75 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 3-hour reaction, water and methanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried from methanol to obtain 61.13 g of a yellow solid, with a yield of 86.65%. 1 H NMR (400 MHz, 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). The product structure 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 placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 0.84 g (2.50 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to monitor the reaction progress. After 5 h of reaction, water and methanol were removed by rotary evaporation, and the solution was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized from methanol and dried to yield 64.52 g of a yellow solid, with a yield of 82.66%. 1 H NMR (400 MHz, 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). The product structure 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 placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to monitor the reaction progress. After the 3-h reaction, water and methanol were removed by rotary evaporation. The solution was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized from methanol and dried to yield 39.89 g of a white solid, with a yield of 58.63%. 1 H NMR (400 MHz, 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). The product structure is shown in I-27.

[0178]

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

[0180] 50.26 g (250 mmol) of (2E)-3-(2,3-dichlorophenyl)prop-2-enal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to monitor the reaction progress. After 5 h of reaction, water and methanol were removed by rotary evaporation. The solution was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized from methanol and dried to yield 63.81 g of a yellow solid, with a yield of 83.67%. 1 H NMR (400 MHz, D2O) δ: 7.53-7.18 (m, 3H), 6.90 (m, 1H), 6.01 (m, 1H), 5.88 (m, 1H), 4.71 (m, 1H). The product structure 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 placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. The reaction progress was monitored by thin-layer chromatography. After the 6-hour reaction, water and methanol were removed by rotary evaporation, and the mixture was washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 60.02 g of a yellow solid, with a yield of 83.19%. 1 H NMR (400 MHz, D2O) δ: 7.48-7.11 (m, 3H), 6.88 (m, 1H), 6.04 (m, 1H), 5.81 (m, 1H), 4.69 (m, 1H). The product has the same structural formula as 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 acetate was placed in a 500 mL single-necked flask containing 150 mL of ethyl acetate and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 12.6 g (3.75 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. The reaction progress was monitored by thin-layer chromatography. After the 3-hour reaction, the water and ethyl acetate were removed by rotary evaporation, and the mixture was washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 71.29 g of a yellow solid, with a yield of 83.33%. 1 H NMR (400 MHz, 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). The product structure 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 placed in a 500 mL single-necked flask containing 150 mL of ethanol and stirred thoroughly at room temperature to dissolve. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to monitor the reaction progress. After the 3-h reaction, water and ethanol were removed by rotary evaporation. The solution was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized from ethanol and dried to yield 48.56 g of a white solid, with a yield of 69.81%. 1 H NMR (400 MHz, 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). The product structure is the same as I-31.

[0190]

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

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

[0193]

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

[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 thoroughly stirred at room temperature for dissolution. 78.00 g (750 mmol) of sodium bisulfite and 2.52 g (7.5 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 4-hour reaction, water and DMF were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried using DMF to obtain 61.32 g of a yellow solid, with a yield of 77.85%. 1 H NMR (400 MHz, 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). The product structure 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 tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 3 h reaction, water and DMF were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried using DMF to obtain 39.58 g of a white solid, with a yield of 63.28%. 1 H NMR (400 MHz, 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). The product structure is shown in I-34.

[0199] (I-34)

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

[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 tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the flask until complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to monitor the reaction progress. After 3 h of reaction, water and DMF were removed by rotary evaporation. The solution was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized from DMF and dried to yield 64.71 g of a white solid, with a yield of 82.89%. 1 H NMR (400 MHz, 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). The product structure is shown in I-35.

[0202]

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

[0204] 54.08 g (250 mmol) of 2-[(E)-phenylmethylidene]octanal was placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 0.84 g (2.50 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until the reaction was complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to track the reaction progress. After the 4-hour reaction, water and methanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried with methanol to obtain 62.67 g of a white solid, with a yield of 78.26%. 1 H NMR (400 MHz, 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). The product structure 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 placed in a 500 mL single-necked flask containing 150 mL of methanol and stirred thoroughly at room temperature to dissolve. 26.00 g (250 mmol) of sodium bisulfite and 0.42 g (1.25 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the single-necked flask until complete, with stirring at room temperature. The reaction solution gradually became turbid, with the formation of solids. Thin-layer chromatography was used to track the progress of the reaction. After the 6-hour reaction, water and methanol were removed by rotary evaporation, and the mixture was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized and dried from methanol to obtain 57.91 g of a white solid, with a yield of 85.60%. 1 H NMR (400 MHz, D2O) δ: 7.63 (m, 2H), 7.37 (m, 3H), 6.68 (m, 1H), 4.55 (m, 1H), 4.15 (m, 1H). The product structure 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 placed in a 500 mL single-necked flask containing 150 mL of acetonitrile and stirred thoroughly at room temperature to dissolve. 52.00 g (500 mmol) of sodium bisulfite and 1.68 g (5.00 mmol) of tetrabutylphosphonium bromide were dissolved in 100 mL of deionized water at room temperature and then slowly added dropwise to the same flask until complete. The reaction was stirred at room temperature. The reaction solution gradually became turbid and solids were produced. Thin-layer chromatography was used to monitor the reaction progress. After the 3-hour reaction, water and acetonitrile were removed by rotary evaporation. The solution was then washed and filtered three times with 600 mL of deionized water to remove the sodium bisulfite. The resulting solid was recrystallized from methanol and dried to yield 52.78 g of a white solid, with a yield of 67.61%. 1 H NMR (400 MHz, D2O) δ: 7.33-7.29 (m, 10H), 6.16 (m, 1H), 4.82 (m, 1H), 4.16 (m, 1H). The product structure 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 on Ralstonia solanacearum

[0218] The inhibitory effect of the compound of the present invention on Ralstonia solanacearum was tested by the shake flask method. Specifically, the compound of the present invention was dissolved in DMF containing 6% Tween 80 and diluted with deionized water to form a series of concentration gradient solutions. The drug solution was mixed with liquid LB medium in a conical flask to prepare the drug-containing medium. 1 mL (10 8 CFU) of bacterial solution and place the conical flask in a shaker at 28-30℃ at 150 rpm min -1 Each treatment was repeated three times. After 24 hours, 200 μL of culture medium was taken to measure the absorbance at 600 nm (OD 600 ), and the EC of each drug was calculated using the DPS data processing system. 50 The control agents were cinnamaldehyde and cinnamaldehyde sodium bisulfite, coded as Cin and Cin-Sod, respectively.

[0219] Table 2 shows the indoor toxicity results of the compounds of the present invention against Ralstonia solanacearum.

[0220] Table 2 Results of indoor toxicity test of the compounds of the present invention against Ralstonia solanacearum

[0221]

[0222]

[0223] The results of the indoor toxicity test of the compounds of the present invention against Ralstonia solanacearum showed that the compounds of the present invention had a good inhibitory effect on Ralstonia solanacearum. In particular, sample No. Ⅰ-32 had a good inhibitory effect on the EC 50 The value can reach 57.69 mg / L.

[0224] Test Example 2: Inhibitory Effect on Soil-Borne Botrytis Cinera Pers

[0225] The mycelial growth rate method was used to test the inhibitory effect of the compounds of the present invention on soil-borne Botrytiscinera Pers.

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

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

[0228] The indoor toxicity results of the compounds of the present 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 indoor toxicity test results of the compounds of the present invention on soil-borne Botrytis cinera Pers showed that the compounds of the present invention had a good inhibitory effect on Botrytis cinera Pers. In particular, sample No. Ⅰ-13 had an EC 50 The value can reach 60.51 mg / L.

[0233] Test Example 3: Inhibitory Effect on Sclerotinia sclerotiorum

[0234] The mycelial growth rate method was used to test the inhibitory effect of the compounds of the present invention on Sclerotinia sclerotiorum.

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

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

[0237] Table 4 shows the indoor toxicity results of the compounds of the present invention against Sclerotinia sclerotiorum.

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

[0239]

[0240] The results of the indoor toxicity test of the compounds of the present invention against Sclerotinia sclerotiorum showed that the compounds of the present invention had a good inhibitory effect on Sclerotinia sclerotiorum. In particular, sample No. Ⅰ-27 had an EC 50 The value can reach 75.39 mg / L.

[0241] Test Example 4: Inhibitory Effect on Fusarium oxysporum

[0242] The mycelial growth rate method was used to test the inhibitory effect of the compounds of the present invention on Fusarium oxysporum.

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

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

[0245] Table 5 shows the indoor toxicity results of the compounds of the present invention against Fusarium oxysporum.

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

[0247]

[0248] The indoor toxicity test results of the compounds of the present invention against Fusarium oxysporum showed that the compounds of the present invention had a good inhibitory effect on Fusarium oxysporum. In particular, sample No. I-23 had an EC 50 The value can reach 118.35 mg / L.

[0249] Test Example 5: Biological activity against southern root-knot nematode

[0250] The biological activity of the compound obtained in the present invention against the southern root-knot nematode was tested by the second-instar larvae immersion method.

[0251] The compound of the present invention was dissolved in an organic solvent and diluted to 100 mg / L by adding a 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 culture plate. Each treatment was 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, designated Cin and Cin-Sod, respectively. The 96-well plates were placed in a 25°C incubator for 24 and 48 hours. After incubation, the mortality of the nematodes was examined under a stereomicroscope and the nematode mortality rate was calculated using the following formula:

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

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

[0254] Table 6 Indoor toxicity results of compounds against 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 of the present invention on the southern root-knot nematode (Meloidogyne incognita) show that the compounds of the present invention have a good control effect on the southern root-knot nematode.

[0258] Test Example 6: Biological activity against southern root-knot nematode

[0259] The biological activity of the compounds of the present invention against the southern root-knot nematode (Meloidogyne incognita) was tested using a nematode soil column test.

[0260] First, 250 g of soil containing nematodes was placed into a 30 cm high empty PE tube to prepare a soil column. Then, the compound of the present invention was dissolved in DMF containing 6% Tween 80 and diluted with deionized water to 200, 500 mg L -1 90 mL of the agent was added to the soil column, and each treatment was repeated three times. A DMF aqueous solution containing only the same concentration of Tween 80 was used as a blank control. The soil column was placed at room temperature (25°C) for two weeks. The mortality was examined under a stereomicroscope and the nematode inhibition rate (%) was calculated according to formula (1):

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

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

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

[0264]

[0265]

[0266] The indoor toxicity results of the compounds of the present invention on the southern root-knot nematode (Meloidogyne incognita) show that the compounds of the present invention have a good control effect on the southern root-knot nematode.

[0267] It can be seen from Test Examples 1-6 that 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. For those skilled in the art, without departing from the purpose and scope of the present invention, can implement the present invention in a wider range under equivalent parameters, concentration and conditions. Although the present invention provides specific embodiments, it should be understood that the present invention can be further improved. In a word, according to the principle of the present invention, the application is intended to include any variation, purposes or improvements of the present invention, including departing from the disclosed scope in the application and the changes made with conventional techniques known in the art.

Claims

1. Compound represented by formula (I): In formula (I), R1 is substituted in a mono-, di- or tri-substituted manner, and each substituent is independently selected from any one of hydrogen, halogen, nitro, hydroxy, phenyl, halomethyl, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkyl disubstituted amino, and C1-C4 alkyl acyloxy; R2 is selected from any one of hydrogen, halogen, and phenyl; R3 is selected from any one of hydrogen, halogen, C1-C6 alkyl, and phenyl; in, R1, R2, and R3 are not hydrogen at the same time, and when R1 is Cl and is at the 4-position, R2 is not chlorine.

2. The compound according to claim 1, characterized in that: The compound represented by formula (I) is any one of the following formulas (I-01) to (I-38): Formula (I-01): R1 is 2-NO2, R2 is H, and R3 is H; Formula (I-02): R1 is 2-F, R2 is H, and R3 is H; Formula (I-03): R1 is 2-Br, R2 is H, and R3 is H; Formula (I-04): R1 is 2-Cl, R2 is H, and R3 is H; Formula (I-05): R1 is 2-OCH3, R2 is H, and R3 is H; Formula (I-06): R1 is 2-OH, R2 is H, and R3 is H; Formula (I-07): R1 is 3-NO2, R2 is H, and R3 is H; Formula (I-08): R1 is 3-OCH3, R2 is H, and R3 is H; Formula (I-09): R1 is 3-CH3, R2 is H, and R3 is H; Formula (I-10): R1 is 3-F, R2 is H, and R3 is H; Formula (I-11): R1 is 3-Cl, R2 is H, and R3 is H; Formula (I-12): R1 is 3-Br, R2 is H, and R3 is H; Formula (I-13): R1 is 3-CF3, R2 is H, and R3 is H; Formula (I-14): R1 is 4-F, R2 is H, and R3 is H; Formula (I-15): R1 is 4-Cl, R2 is H, and R3 is H; Formula (I-16): R1 is 4-Br, R2 is H, and R3 is H; Formula (I-17): R1 is 4-I, R2 is H, and R3 is H; Formula (I-18): R1 is 4-CH3, R2 is H, and R3 is H; Formula (I-19): R1 is 4-CH(CH3)2, R2 is H, and R3 is H; Formula (I-20): R1 is 4-OCH3, R2 is H, and R3 is H; Formula (I-21): R1 is 4-OH, R2 is H, and R3 is H; Formula (I-22): R1 is 4-C6H5, R2 is H, and R3 is H; Formula (I-23): R1 is 4-CF3, R2 is H, and R3 is H; Formula (I-24): R1 is 4-N(CH3CH2)2, R2 is H, and R3 is H; Formula (I-25): R1 is 3-OCH3 and 4-OH, R2 is H, and R3 is H; Formula (I-26): R1 is 3,5-OCH3 and 4-OH, R2 is H, and R3 is H; Formula (I-27): R1 is 2,6-F, R2 is H, and R3 is H; Formula (I-28): R1 is 2,3-Cl, R2 is H, and R3 is H; Formula (I-29): R1 is 2-Cl, 6-F, R2 is H, and R3 is H; Formula (I-30): R1 is 3-OCH3,4-OCOCH3, R2 is H, and R3 is H; Formula (I-31): R1 is 2,3,4-CH3, R2 is H, and R3 is H; Formula (I-32): R1 is 4-F, R2 is F, and R3 is F; Formula (I-33): R1 is H, R2 is H, and R3 is Br; Formula (I-34): R1 is H, R2 is H, and R3 is CH3; Formula (I-35): R1 is H, R2 is H, and R3 is -C6H5; Formula (I-36): R1 is H, R2 is H, and R3 is -CH2CH2CH2CH2CH2CH3; Formula (I-37): R1 is H, R2 is H, and R3 is Cl; Formula (I-38): R1 is H, R2 is -C6H5, and R3 is Cl.

3. A method for preparing the compound according to claim 1 or 2, comprising the steps of: In formula (II): R1, R2, and R3 are as defined in formula (I); A homogeneous phase B system consisting of sodium bisulfite, a quaternary phosphonium salt phase transfer catalyst and water is added dropwise to a homogeneous phase A system consisting of a compound represented by formula (II) and an organic solvent to carry out a nucleophilic addition reaction to obtain a compound represented by formula (I).

4. The preparation method according to claim 3, wherein: The quaternary phosphonium salt phase transfer catalyst is one or more of tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, hexadecyltributylphosphonium bromide, and hexadecyltributylphosphonium chloride; The amount of the quaternary phosphonium salt phase transfer catalyst used is 0.25-5% of the molar amount of the sodium bisulfite.

5. The preparation method according to claim 3 or 4, characterized in that: The molar ratio of the compound represented by formula (II) to the sodium bisulfite is 1.0:(1.0-3.0); 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.

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

7. Use of the compound according to claim 1 or 2 in any of the following: A1. Inhibition of soil-borne plant pathogenic bacteria or preparation of products for inhibiting soil-borne plant pathogenic bacteria; A2. Inhibition of Ralstonia solanacearum or preparation of a product for inhibition of Ralstonia solanacearum; A3. Inhibiting soil-borne Botrytis cinera Pers or preparing a product for inhibiting soil-borne Botrytis cinera Pers.

8. Use of the compound according to claim 1 or 2 in any of the following: B1. Inhibiting soil-borne plant pathogenic fungi or preparing products for inhibiting soil-borne plant pathogenic fungi; B2. Inhibition of Sclerotinia sclerotiorum or preparation of a product that inhibits Sclerotinia sclerotiorum; B3. Inhibiting Fusarium oxysporum or preparing a product for inhibiting Fusarium oxysporum.

9. Use of the compound according to claim 1 or 2 in any of the following: C1. Inhibiting nematodes or preparing products that inhibit nematodes; C2. Inhibiting the southern root-knot nematode (Meloidogyne incognita) or preparing a product for inhibiting the southern root-knot nematode (Meloidogyne incognita).

10. Use of the compound according to claim 1 or 2 in preventing and controlling soil-borne diseases or in preparing products for preventing and controlling soil-borne diseases; The soil pathogen of the soil-borne disease is any one of soil-borne plant pathogenic bacteria, soil-borne plant pathogenic fungi or nematodes; The soil-borne plant pathogenic bacteria are preferably Ralstonia solanacearum or Botrytis cinera Pers; The soil-borne plant pathogenic fungus is preferably Sclerotinia sclerotiorum or Fusarium oxysporum; The nematode is preferably the southern root-knot nematode (Meloidogyne incognita).

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