Hydrazino formate compound as well as preparation method and application thereof

Abstract

The invention relates to a carbazate compound as well as a preparation method and application thereof. The carbazate compound is a compound shown in a formula (I), or an isotope labeled compound thereof, or an optical isomer, a geometric isomer, a tautomer or an isomer mixture thereof, or a pharmaceutically acceptable salt thereof. The carbazate compound provided by the invention shows broad-spectrum antibacterial activity on plant pathogenic bacteria such as pathogenic fungi; the invention relates to the field of pesticide preparations, in particular to a pesticide preparation for tobacco alternaria alternata pathogenic bacteria, cabbage black spot pathogenic bacteria, tomato early blight pathogenic bacteria, apple anthracnose pathogenic bacteria, corn curvularia pathogenic bacteria, wheat scab pathogenic bacteria, watermelon fusarium wilt pathogenic bacteria, potato dry rot pathogenic bacteria, rice blast pathogenic bacteria, pumpkin fusarium wilt pathogenic bacteria, cotton fusarium wilt pathogenic bacteria, apple ring rot pathogenic bacteria and apple rot pathogenic bacteria. The compound shows excellent bacteriostatic activity on plasmopara viticola, powdery mildew of muskmelon and the like. (I)

Description

Technical Field

[0001] This application relates to the field of plant antibacterial agents, specifically to a hydrazine carbamate compound, its preparation method, and its uses. Background Technology

[0002] Plant pathogenic fungi are one of the major biological threats affecting stable and high global grain yields. During the field growth and storage stages, the combined occurrence of fungal diseases can lead to a 25% reduction in the yield of major grain crops. 35% of agricultural products are contaminated with fungal toxins, further reducing their commercial value and market competitiveness. Although measures such as agricultural control, disease-resistant breeding, and biological agents are being promoted, chemical fungicides still hold an irreplaceable position in integrated pest management due to their rapid effectiveness, low cost, and ease of use.

[0003] Statistics show that the rational use of fungicides can save approximately 15% of global grain production annually, playing a vital role in ensuring food supply and stabilizing farmers' income. Since the 1960s, nearly 200 active fungicide ingredients have been commercially applied, forming a multi-category, multi-variety product system that provides important support for modern agricultural production.

[0004] However, long-term, high-frequency use has led to a decline in the efficacy of some traditional fungicides and an increase in the risk of reinfection in the field. Agricultural production is increasingly demanding alternatives that are highly efficient, safe, and have a long-lasting effect. Therefore, developing novel fungicides with good environmental compatibility and low risk to non-target organisms is of great significance for ensuring sustainable agricultural development and food security. Summary of the Invention

[0005] For the sake of brevity, the term “compound of formula (N) (such as compound of formula (I))” as used below may also encompass any optical isomer, geometric isomer, tautomer or mixture of isomers of compound of formula (N), or an agriculturally acceptable salt.

[0006] The term "optical isomer" refers to the various isomers formed when a compound has one or more chiral centers, each of which can exist in either an R or S configuration. Optical isomers include all diastereomers, enantiomers, meso compounds, racemates, or mixtures thereof. For example, optical isomers can be separated by chiral chromatography or by chiral synthesis.

[0007] The term "geometric isomer" refers to the fact that when a compound contains a double bond, it can exist as cis isomers, trans isomers, E-isomers, and Z-isomers. Geometric isomers include cis isomers, trans isomers, E-isomers, Z-isomers, or mixtures thereof.

[0008] The term "tautomer" refers to an isomer that results from the rapid movement of an atom in a molecule to two different positions. Those skilled in the art will understand that tautomers can interconvert and may coexist in an equilibrium state under certain conditions.

[0009] Unless otherwise specified, the reference herein to “compound of formula (N) (such as compound of formula (I))” also includes isotopically labeled compounds obtained by replacing any one atom of that compound with its isotopic atom. That is, the present invention includes all agriculturally acceptable isotopically labeled compounds of formula (N), wherein one or more atoms are replaced by atoms of the same atomic number but different atomic mass or mass number that exist in nature.

[0010] Examples of isotopes suitable for inclusion in the compounds of this invention include isotopes of hydrogen, such as... 2 H(D) and 3 H(T), isotopes of carbon, such as 11 C 13 C and 14 C, isotopes of chlorine, such as 37 Cl, an isotope of fluorine, such as 18 F, an isotope of iodine, such as 123 I and 125 I, isotopes of oxygen, such as 15 O、 17 O and 18 O.

[0011] Isotope-labeled compounds of formula (N) can generally be prepared by conventional techniques known to those skilled in the art or by using a suitable isotope-labeling reagent instead of the previously used unlabeled reagent, in a manner similar to that described in the examples and preparations appended herein.

[0012] Compounds of formula (N) may exist in the form of agriculturally acceptable salts, such as acid addition salts and / or base addition salts of compounds of formula (N). Unless otherwise specified, “agriculturally acceptable salts” as used herein includes acid addition salts or base addition salts that may appear in compounds of formula (N).

[0013] Agriculturally acceptable salts of compounds of formula (N) include their acid addition salts and base addition salts. Suitable acid addition salts are formed from acids that form non-toxic salts. Examples include, but are not limited to: acetates, adipates, aspartates, benzoates, benzenesulfonates, bicarbonates / carbonates, hydrogen sulfates / sulfates, borates, camphor sulfonates, citrates, cyclohexylamine sulfonates, ethanedisulfonates, formates, fumarates, gluconate, glucuronates, glucuronates, hexafluorophosphates, 2-(4-hydroxybenzyl)benzoates, hydrochlorides / chlorides, hydrobromines / bromines, hydroiodides / iodides, 2-hydroxyethanesulfonates, lactates, malates, maleates, malonates, methanesulfonates, methyl sulfates, naphthalates, 2-naphthalenesulfonates, nicotinates, nitrates, orotates, oxalates, hexadecates, phosphates / hydrogen phosphates / dihydrogen phosphates, pyroglutamates, gluconate, stearates, salicylates, tannins, tartrates, toluenesulfonates, and trifluoroacetates. Suitable base addition salts are formed by bases that form non-toxic salts. Examples include, but are not limited to: ammonium salts, aluminum, arginine, calcium, choline, diethylamine, diethanolamine, glycine, lysine, magnesium, meglumine, ethanolamine, potassium, sodium, lithium, tromethamine, and zinc salts. They can also form acid and base hemisalts, such as hemisulfates and hemicalcium salts. Methods for preparing agriculturally acceptable salts of the compounds described herein are known to those skilled in the art.

[0014] Agriculturally acceptable carriers for compounds of formula (N) include, but are not limited to, surfactants, including ionic or nonionic surfactants. The surfactants include emulsifiers, dispersants, or wetting agents. The emulsifiers may be polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty amines, and commercially available emulsifiers; the dispersants include sodium lignosulfonate, dispersing agents, calcium lignosulfonate, or methylnaphthalenesulfonate formaldehyde condensate, etc.; the wetting agents include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, or alkylnaphthalenesulfonate, etc. Pesticide-acceptable carriers include solid carriers and / or liquid carriers. Preferably, the solid carriers include natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicate, such as talc; magnesium aluminum silicate, such as kaolinite, montmorillonite, and mica; white carbon black, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; and amine salts such as ammonium sulfate and hexamethylenediamine. Preferably, the liquid carrier comprises water and an organic solvent; when water is used as a solvent or diluent, the organic solvent can be used as an auxiliary agent or antifreeze additive. Preferably, the organic solvent includes aromatic hydrocarbons (e.g., benzene, xylene, or toluene), chlorinated hydrocarbons (e.g., chlorobenzene, vinyl chloride, chloroform, or dichloromethane), aliphatic hydrocarbons (e.g., petroleum fractions, cyclohexane, or light mineral oil), alcohol solvents (e.g., isopropanol, butanol, ethylene glycol, glycerol, or cyclohexanol), ether solvents, ester solvents, ketone solvents (e.g., acetone, cyclohexanone, or N-methylpyrrolidone), or dimethylformamide, etc.

[0015] Some compounds of the present invention may exist in both unsolvated and solvated forms (including hydrated forms). Generally, compounds of formula (N) are included within the scope of the present invention, whether they exist in solvated or unsolvated forms.

[0016] Some compounds of the present invention may exist in different crystal forms or amorphous forms. Regardless of the form in which they exist, compounds of formula (N) are included within the scope of the present invention.

[0017] To avoid ambiguity, the terms used in this article are defined below. Unless otherwise stated, the meanings of the terms used in this article are as follows.

[0018] When used herein, the term “substituted” means that one or more (preferably 1 to 5, more preferably 1 to 3) specific hydrogen atoms in a molecule are independently replaced by the corresponding number of substituents.

[0019] When used in this document, the term "independently" means that when the number of substituents exceeds one, these substituents may be the same or different.

[0020] When used herein, the terms “optional” or “optionally” indicate that the event described may or may not occur. For example, “optionally substituted” means that the group may be unsubstituted or substituted.

[0021] In a first aspect, this application provides a hydrazine carbamate compound, which is a compound of formula (I), or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer, or mixture of isomers thereof, or a pharmaceutically acceptable salt thereof.

[0022] (I) in, Each R 1 Each is independently selected from halogens; Each R 2 Each is independently selected from halogen, methyl, trifluoromethyl, or trifluoromethoxy; and X is selected from the following: —CH2—, —CH2CH2—, —CH2CH2CH2—, —CH2OCH2CH2—, —CH2CH2CH2CH2—, or —OCH2CH2OCH2CH2—. n and m are each independently selected from any integer from 0 to 5. Furthermore, where R 2 Not 3-trifluoromethyl, and R 1 and R 2 Not all are Cl, and when X is selected from bond, —CH2— or —CH2CH2—, n and m are not all 0.

[0023] In one embodiment of the present invention, the halogen may be selected from fluorine, chlorine, bromine or iodine.

[0024] In one embodiment of the invention, n and m are each independently selected from 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2.

[0025] In one embodiment of the present invention, when n is 1, R 1 It is selected from 4-fluoro, 4-chloro, 4-bromine or 4-iodine.

[0026] In another embodiment of the invention, when m is 1, R 2 Selected from 2-fluoro, 3-fluoro, 4-fluoro, 3-chloro, 4-chloro, 3-bromo, 4-bromo, 4-iodine, 3-methyl, 4-methyl, 4-trifluoromethyl, or 4-trifluoromethoxy; or when m is 2, R 2 It is selected from 2,4-difluoro, 3,4-difluoro, 3,5-difluoro, 2-fluoro-3-chloro, 2-fluoro-4-chloro, or 4-fluoro-3-chloro.

[0027] In a preferred embodiment of the present invention, X is selected from —CH2CH2CH2—, —CH2OCH2CH2—, —CH2CH2CH2CH2— or —OCH2CH2OCH2CH2—.

[0028] In a second aspect, this application also provides a method for preparing the above-mentioned hydrazine carbamate compounds, which includes the following steps: condensing the compound of formula (II) with the compound of formula (III), or their corresponding hydrochloride, sulfate or acetate, to obtain the compound of formula (I); (II) (III).

[0029] In one embodiment of the present invention, (R) in the compound of formula (II) 1 The types and positions of )n are similar to those of (R) in compound (I). 1 )n corresponds; and (R) in compound (III) 2 The type and position of m are similar to those of (R) in compound (I). 2 )m corresponds.

[0030] In one embodiment of the invention, compound (II) and compound (III), or their corresponding hydrochloride, sulfate, or acetate, undergo a direct condensation reaction in the presence of a condensing agent to obtain compound (I). Further, the molar ratio of compound (II) to compound (III), or the molar ratio of the hydrochloride, sulfate, or acetate of compound (II) to compound (III) can be 1–1.5:1, preferably 1.2–1.4:1. The condensing agent includes EDCI and / or HOBT.

[0031] In a third aspect, this application also provides a bactericidal composition comprising at least one of the hydrazine carbamate compounds described in the first aspect of this application as an active ingredient; and optionally, a pesticide-acceptable carrier and / or adjuvant.

[0032] The bactericidal composition of this application can be applied in the form of a formulation, wherein the hydrazine carbamate compound is dissolved or dispersed in a carrier as an active component or formulated into a formulation for easier dispersion when used as a bactericidal composition. The bactericidal composition can be formulated into various dosage forms, such as soluble powders, dispersible liquids, emulsifiable concentrates, suspensions, aqueous suspensions, microemulsions, emulsions, water-in-oil emulsions, and water-dispersible granules. When the bactericidal composition of this application is applied in the form of a formulation, the preferred mass percentage of the hydrazine carbamate compound is 200%. 500 mg / L, more preferably 300 mg / L 400 mg / L.

[0033] The bactericidal composition of this application may contain one or more other insecticides, fungicides, herbicides, plant growth regulators, or fertilizers.

[0034] In a fourth aspect, this application also provides the use of the hydrazine carbamate compounds described in the first aspect or the bactericidal compositions described in the third aspect for controlling plant diseases caused by plant pathogens; preferably for use in agriculture, forestry, horticulture, and sanitation.

[0035] In one embodiment of the present invention, an effective amount of the hydrazine carbamate compound as described above, or the fungicide composition as described above, is applied to plants, plant propagation materials, or subsequently grown plant organs and cultivation media, cultivation materials, or cultivation spaces; or an effective amount of the hydrazine carbamate compound as described above, or the fungicide composition as described above, is used to prevent or control pathogenic fungi in the roots of wood.

[0036] Preferably, an effective amount of the hydrazine carbamate compound or the fungicide composition as described above is applied to the leaves, stems, roots, seeds, or soil.

[0037] In one set of embodiments, the pathogen is preferably a pathogenic fungus, including but not limited to Ascomycota, Basidiomycota, Plasmodiophoromycota, Oomycota, Chytridiomycota, Zygomycota, and Deuteromycota; preferably, it is an Ascomycota or Oomycota pathogenic fungus, such as Ascomycetes or Oomycetes pathogenic fungi. Preferably, the plant pathogen is *Tobacco Red Spot Pathogen*, *Chinese Cabbage Black Spot Pathogen*, *Tomato Early Blight Pathogen*, *Apple Anthracnose Pathogen*, *Curviflora Pathogen*, *Wheat Fusarium Root Pathogen*, *Watermelon Fusarium Fissula*, *Potato Dry Rot Pathogen*, *Rice Blast Pathogen*, *Pumpkin Fusarium Fissula*, *Cotton Fusarium Fissula*, *Apple Ring Spot Pathogen*, *Apple Rot Pathogen*, *Grape Downy Mildew Pathogen*, or *Melon Powdery Mildew Pathogen*.

[0038] In one embodiment of the present invention, the plant disease is a plant disease caused by *Tobacco Red Spot Pathogen*, *Chinese Cabbage Black Spot Pathogen*, *Tomato Early Blight Pathogen*, *Apple Anthracnose Pathogen*, *Curviflora Pathogen*, *Wheat Fusarium Head Blight Pathogen*, *Watermelon Fusarium Wilt Pathogen*, *Potato Dry Rot Pathogen*, *Rice Blast Pathogen*, *Pumpkin Fusarium Wilt Pathogen*, *Cotton Fusarium Wilt Pathogen*, *Apple Ring Spot Pathogen*, *Apple Rot Pathogen*, *Grape Downy Mildew Pathogen*, or *Melon Powdery Mildew Pathogen*.

[0039] Those skilled in the art will understand that the definitions and preferences described in one aspect of this application also apply to other aspects. Those skilled in the art will appreciate that embodiments of various aspects of this application can be combined in various ways without departing from the subject matter and spirit of this application, and these combinations are also included within the scope of this application.

[0040] Research has shown that, compared with existing technologies, the hydrazine carbamate compounds provided in this application exhibit broad-spectrum antibacterial activity against plant pathogens such as pathogenic fungi, particularly showing excellent inhibitory activity against Tobacco Red Spot Pathogen, Chinese Cabbage Black Spot Pathogen, Tomato Early Blight Pathogen, Apple Anthracnose Pathogen, Corn Curvularia Pathogen, Wheat Fusarium Root Pathogen, Watermelon Fusarium Fissula ... Detailed Implementation

[0041] The present invention will be further illustrated below with reference to embodiments, but these embodiments do not limit the scope of the invention; unless otherwise stated, all reactants used in each embodiment are obtained commercially; the instruments and equipment used in the synthesis experiments and product analysis are all conventional instruments and equipment commonly used in organic synthesis.

[0042] Those skilled in the art will understand that the compounds of this invention can also be synthesized using other synthetic routes. Although the specific raw materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar raw materials and conditions. Furthermore, the preparation methods described below can be further modified according to the disclosure of this invention using conventional chemical methods well known to those skilled in the art. For example, appropriate groups may be protected during the reaction process, etc.

[0043] Example 1 55 The structural formulas of hydrazine carbamate compounds are as follows: (I) Example 1 All compounds in group 55 conform to the structure of compound (I), where R 1 and R 2 The types and positions are shown in Table 1, but based on differences in group selection, compounds 1 and 10... 11, 15, 27 28, 34, and 53 are not within the scope of this invention.

[0044] Table 1: Compounds from Examples 1-55

[0045] Preparation methods of the compounds in Examples 1-55: Synthesis of the intermediate benzyl chloroformate: Substituted benzyl alcohol (5.0 mmol) and dichloromethane (DCM, 30 mL) were added to a 100 mL round-bottom flask. The resulting solution was cooled to... At 20 °C, solid triphosgene (0.89 g, 3.0 mmol) was added, and the mixture was stirred for 10 minutes. While stirring, a solution of triethylamine (0.78 g, 7.0 mmol) in dichloromethane (10 mL) was slowly added dropwise. After the addition was complete, the cold bath was removed, and the mixture was stirred at room temperature for 4 hours to terminate the reaction. The reaction mixture was washed successively with distilled water (50 mL) and saturated brine (2 × 50 mL). The solvent was removed from the organic phase under reduced pressure to obtain the corresponding benzyl chloroformate. The latter was used directly in subsequent reactions without purification.

[0046] Example 1 Synthesis of Compound 55: (Substituted) phenylhydrazine hydrochloride (5.0 mmol), pyridine (0.87 g, 11 mmol), and tetrahydrofuran (15 mL) were added to a 100 mL round-bottom flask and stirred at 0 °C for 15 minutes. Then, a solution of (substituted) benzyl chloroformate (1.02 g, 6.0 mmol) in tetrahydrofuran (5 mL) prepared above was slowly added dropwise. After the addition was complete, the reaction mixture was stirred at room temperature for 8 hours to stop the reaction. 30 mL of distilled water was added to the reaction system, and the mixture was extracted with ethyl acetate (3 × 20 mL). The organic phases were combined, washed with saturated brine (2 × 20 mL), and dried over anhydrous sodium sulfate. The mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was separated by silica gel column chromatography using a petroleum ether-ethyl acetate mixture as the eluent to obtain the product of Example 1. Compounds of 55.

[0047] The physicochemical properties and nuclear magnetic resonance spectral data of the compounds in Examples 1-55 are as follows: Example 1: N'-Phenylated Benzyl Formate

[0048] Pale yellow solid, yield 57%. mp 95-96℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.16 (s,1H), 7.69 (s, 1H), 7.43 – 7.22 (m, 5H), 7.13 (t, J = 7.8 Hz, 2H), 6.70 (d, J =7.3 Hz, 1H), 6.67 (d, J= 7.8 Hz, 2H), 5.08 (s, 2H). Example 2: N'-o-fluorophenylhydrazine benzyl ester

[0049] White solid, yield 34%. mp 92-93℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.25 (s,1H), 7.74 (s, 1H), 7.46 – 7.12 (m, 5H), 7.06 (ddd, J = 12.2, 8.0, 1.4 Hz, 1H),7.00 (t, J = 7.7 Hz, 1H), 6.77 (d, J = 8.3 Hz, 1H), 6.71 (ddt, J = 7.8, 4.7, 2.3Hz, 1H), 5.10 (s, 2H). Example 3: N'-m-fluorophenylhydrazine benzyl ester

[0050] White solid, yield 49%. mp 93-94℃; 1 H NMR (400 MHz, DMSO) δ 9.27 (s, 1H), 8.04 (s, 1H), 7.46 – 7.23 (m, 5H), 7.15 (td, J = 8.2, 6.7 Hz, 1H), 6.51 (ddd, J =8.3, 2.2, 0.9 Hz, 1H), 6.49 – 6.44 (m, 1H), 6.40 (dt, J = 11.7, 2.3 Hz, 1H),5.10 (s, 2H). Example 4: N'-p-Fluorophenylhydrazine benzyl ester

[0051] Pink solid, yield 46%. mp 117-119℃; 1 H NMR (400 MHz, DMSO) δ 9.27 (s,1H), 7.74 (s, 1H), 7.38 (dd, J = 20.3, 7.5 Hz, 5H), 7.01 (t,J = 8.9 Hz, 2H), 6.74 (dd, J = 9.0, 4.6 Hz, 2H), 5.13 (s, 2H). Example 5: N'-m-chlorophenylhydrazine benzyl ester

[0052] White solid, yield 38%. mp 10³-10⁵℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.28 (s,1H), 8.04 (s, 1H), 7.37 (d, J = 12.4 Hz, 5H), 7.15 (t, J = 7.9 Hz, 1H), 6.72 (dd, J = 7.8, 2.0 Hz, 1H), 6.66–6.59 (m, 2H), 5.10 (s, 2H). Example 6: N'-p-chlorophenylhydrazine benzyl ester

[0053] Pink solid, yield 43%. 110-112℃; 1 H NMR (400 MHz, DMSO) δ 9.30 (s, 1H), 7.95 (s, 1H), 7.45 – 7.31 (m, 5H), 7.21 (d, J = 8.9 Hz, 2H), 6.74 (d, J = 8.9 Hz, 2H), 5.13 (s, 2H). Example 7: N'-(3-bromophenyl)hydrazinocarbamate benzyl ester

[0054] White solid, yield 52%. mp 99-101℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.27 (s,1H), 8.02 (s, 1H), 7.36 (d, J = 19.2 Hz, 5H), 7.09 (t, J = 8.0 Hz, 1H), 6.85 (dd, J = 7.9, 1.9 Hz, 1H), 6.80 (t,J = 2.0 Hz, 1H), 6.70 – 6.62 (m, 1H), 5.10 (s,2H). Example 8: N'-p-bromophenylhydrazine benzyl ester

[0055] Pink solid, yield 54%. mp 117-119℃; 1 H NMR (400 MHz, DMSO) δ 9.29 (s,1H), 7.96 (s, 1H), 7.43 – 7.17 (m, 7H), 6.77 – 6.59 (m, 2H), 5.12 (s, 2H). Example 9: N'-p-iodophenylhydrazine carbamate

[0056] Pink solid, yield 52%. mp 127-128℃; 1 H NMR (400 MHz, DMSO) δ 9.25 (s,1H), 7.93 (s, 1H), 7.48 – 7.11 (m, 7H), 6.53 (d, J = 8.9 Hz, 1H), 5.09 (s, 2H). Example 10: N'-p-nitrophenylhydrazine benzyl ester

[0057] Reddish-brown solid, yield 53%. mp 131-133℃; 1 H NMR (400 MHz, DMSO) δ 9.60 (s,1H), 9.06 (s, 1H), 8.17 – 8.02 (m, 2H), 7.49–7.25 (m, 5H), 6.84–6.69 (m, 2H), 5.14 (s, 2H). Example 11: N'-m-trifluoromethylphenylhydrazine benzyl ester

[0058] White solid, yield 59%. mp 79-81℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.37 (s,1H), 8.21 (s, 1H), 7.54 – 7.09 (m, 6H), 7.02 (d,J = 7.6 Hz, 1H), 6.98 – 6.90(m, 2H), 5.12 (s, 2H). Example 12: N'-p-trifluoromethylphenylhydrazine benzyl ester

[0059] Pale yellow solid, yield 53%. mp 136-137℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.38(s, 1H), 8.39 (s, 1H), 7.48 (d, J = 8.5 Hz, 2H), 7.44 – 7.22 (m, 5H), 6.80 (d, J = 8.4 Hz, 2H), 5.12 (s, 2H). Example 13: N'-(m-methylphenyl)hydrazine benzyl formate

[0060] Pale yellow solid, yield 34%. mp 93-95℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.14 (s,1H), 7.62 (s, 1H), 7.45 – 7.10 (m, 5H), 7.01 (t, J = 8.1 Hz, 1H), 6.51 (d, J =7.4 Hz, 1H), 6.47 (dd, J = 6.9, 2.2 Hz, 2H), 5.09 (s, 2H), 2.19 (s, 3H). Example 14: N'-p-Tolylhydrazinocarbamate

[0061] Pink solid, yield 40%. mp 10³-10⁵℃; 1 H NMR (400 MHz, DMSO) δ 9.14 (s,1H), 7.54 (s, 1H), 7.47 – 7.09 (m, 5H), 6.96 (d, J = 8.1 Hz, 2H), 6.60 (d, J=8.5 Hz, 2H), 5.09 (s, 2H), 2.18 (s, 3H). Example 15: N'-p-isopropylphenylhydrazine benzyl ester

[0062] Pale yellow solid, yield 44%. mp 74-76℃; 1 H NMR (400 MHz, DMSO) δ 9.16 (s,1H), 7.56 (s, 1H), 7.45–7.18 (m, 5H), 7.02 (d, J = 8.1 Hz, 2H), 6.69 – 6.54 (m,2H), 5.10 (s, 2H), 2.77 (p, J = 6.9 Hz, 1H), 1.16 (d, J = 6.9 Hz, 6H). Example 16: N'-(4-methoxyphenyl)hydrazinocarbamate benzyl ester

[0063] Pale yellow powder, yield 50%. mp 117-118℃; 1 H NMR (400 MHz, DMSO) δ 9.28 (s,1H), 7.99 (s, 1H), 7.42 – 7.29 (m, 5H), 7.14 (d, J = 8.5 Hz, 2H), 6.77 – 6.70 (m, 2H), 5.10 (s, 2H). Example 17: N'-(2,3-difluorophenyl)hydrazinocarbamate benzyl ester

[0064] White solid, yield 37%. mp 106-107℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.26 (s,1H), 7.67 (s, 1H), 7.45 – 7.06 (m, 6H), 6.97 – 6.68 (m, 2H), 5.09 (s, 2H). Example 18: N'-(3,4-difluorophenyl)hydrazine benzyl formate

[0065] White solid, yield 35%. mp 100-101℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.28 (s,1H), 7.94 (s, 1H), 7.42 – 7.30 (m, 5H), 7.20 (dt, J = 10.6, 9.0 Hz, 1H), 6.59(ddd, J = 12.9, 6.9, 2.7 Hz, 1H), 6.52 – 6.43 (m, 1H), 5.10 (s, 2H). Example 19: N'-(3,5-difluorophenyl)hydrazine benzyl formate

[0066] White solid, yield 38%. mp 143-144℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.34 (s,1H), 8.33 (s, 1H), 7.37 (t, J = 9.2 Hz, 5H), 6.43 (tt, J = 9.4, 2.4 Hz, 1H), 6.27(dd, J = 10.1, 2.3 Hz, 2H), 5.11 (s, 2H). Example 20: N'-(2-fluoro-4-chlorophenyl)hydrazinocarbamate benzyl ester

[0067] White solid, yield 45%. mp 98-99℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.31 (s,1H), 7.93 (s, 1H), 7.44 – 7.32 (m, 4H), 7.26 (dd, J = 11.6, 2.3 Hz, 1H), 7.08(dd, J = 8.7, 1.9 Hz, 1H), 6.76 (t, J = 9.0 Hz, 1H), 5.10 (s, 2H). Example 21: N'-(3-chloro-4-fluorophenyl)hydrazine benzyl carboxylate

[0068] Pale yellow powder, yield 44%. mp 108-109℃; 1 H NMR (400 MHz, DMSO) δ 9.32 (s,1H), 7.97 (s, 1H), 7.43 – 7.31 (m, 5H), 7.20 (t, J = 9.0 Hz, 1H), 6.78 (dd, J =6.3, 2.8 Hz, 1H), 6.68 (ddd, J = 9.0, 4.0, 2.8 Hz, 1H), 5.12 (s, 2H). Example 22: N'-p-fluorophenylhydrazine carboxylic acid (2-p-fluorophenyl) benzyl ester

[0069] Pink solid, yield 58%. mp 110-112℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.20 (s,1H), 7.68 (s, 1H), 7.42 (d, J = 5.7 Hz, 2H), 7.22 (t, J = 8.7 Hz, 2H), 6.98 (t, J =8.9 Hz, 2H), 6.66 (dd, J = 9.0, 4.6 Hz, 2H), 5.06 (s, 2H). Example 23: N'-p-fluorophenylhydrazine carboxylic acid (2-p-chlorophenyl) benzyl ester

[0070] White solid, yield 31%. mp 129-131℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.26 (s,1H), 7.71 (s, 1H), 7.50 – 7.30 (m, 4H), 7.00 (t, J = 8.7 Hz, 2H), 6.70 (dd, J =8.8, 4.6 Hz, 2H), 5.10 (s, 2H). Example 24: N'-p-fluorophenylhydrazine carboxylic acid (2-p-chlorophenyl) benzyl ester

[0071] Pale yellow solid, yield 33%. mp 135-137℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.24(s, 1H), 7.69 (s, 1H), 7.60 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 6.99(t, J = 8.9 Hz, 2H), 6.66 (dd, J = 9.0, 4.6 Hz, 2H), 5.06 (s, 2H). Example 25: N'-p-fluorophenylhydrazine carboxylic acid (2-p-iodophenyl) benzyl ester

[0072] Yellow solid, yield 26%. mp 134-135℃; 1 H NMR (400 MHz, DMSO) δ 9.24 (s,1H), 7.76 (d, J = 7.9 Hz, 2H), 7.68 (s, 1H), 7.19 (d, J = 7.9 Hz, 2H), 6.99 (t, J =8.9 Hz, 2H), 6.67 (dd, J = 9.0, 4.6 Hz, 2H), 5.04 (s, 2H). Example 26: p-Fluorobenzyl N'-chlorophenylhydrazine carboxylate

[0073] Reddish-brown solid, yield 37%. mp 89-90℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.25 (s,1H), 7.91 (s, 1H), 7.44 (t, J = 7.0 Hz, 2H), 7.28 – 7.13 (m, 4H), 6.68 (d, J =8.9 Hz, 2H), 5.08 (s, 2H). Example 27: p-Chlorobenzyl chlorophenylhydrazine carboxylate

[0074] Pale yellow solid, yield 35%. mp 101-102℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.27(s, 1H), 7.90 (s, 1H), 7.54 7.11 (m, 6H), 6.72–6.61 (m, 2H), 5.08 (s, 2H). Example 28: N'-Phenylhydrazinocarboxylate

[0075] Yellow solid, yield 56%. mp 105-107℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.64 (s,1H), 7.85 (s, 1H), 7.40 (t, J = 7.9 Hz, 2H), 7.17 (td, J = 10.1, 9.3, 5.4 Hz,5H), 6.74 (dd, J = 16.1, 7.8 Hz, 3H). Example 29: N'-p-Fluorophenylhydrazine carboxylate

[0076] Yellow solid, yield 56%. mp 133-134 ℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.67 (s,1H), 7.83 (s, 1H), 7.40 (t, J = 7.7 Hz, 2H), 7.26–6.98 (m, 5H), 6.81–6.73 (m, 2H). Example 30: N'-p-chlorophenylhydrazine carboxylate

[0077] White solid, yield 40%. 138-140℃; 1 H NMR (400 MHz, DMSO) δ 9.75 (d, J = 1.7Hz, 1H), 8.08 (d, J = 1.8 Hz, 1H), 7.41 (t, J= 7.7 Hz, 2H), 7.33–7.11 (m, 5H), 6.91–6.70 (m, 2H). Example 31: N'-p-bromophenylhydrazine carboxylate

[0078] Yellow solid, yield 60%. 120-121℃; 1 H NMR (400 MHz, DMSO) δ 9.73 (s, 1H), 8.08 (s, 1H), 7.47 – 7.31 (m, 4H), 7.27 – 7.12 (m, 3H), 6.80 – 6.69 (m, 2H). Example 32: N'-p-iodophenylhydrazine carboxylate

[0079] White solid, yield 40%. 140-141℃; 1 H NMR (400 MHz, DMSO) δ 9.71 (d, J = 1.7Hz, 1H), 8.07 (d, J = 1.8 Hz, 1H), 7.52 – 7.34 (m, 4H), 7.26 – 7.11 (m, 3H), 6.67 – 6.59 (m, 2H). Example 33: N'-p-Tolylhydrazinoformate

[0080] Pale yellow solid, yield 45%. 118-119℃; 1 H NMR (400 MHz, DMSO) δ 9.62 (s, 1H), 7.69 (s, 1H), 7.46 – 6.89 (m, 7H), 6.70 (d, J = 8.3 Hz, 2H), 2.19 (s, 3H). Example 34: (2-Phenyl)ethyl N'-phenylhydrazine carboxylate

[0081] Pale yellow solid, yield 46%. mp 77-78℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.03 (s, 1H), 7.64 (d, J= 2.1 Hz, 1H), 7.42 – 6.97 (m, 7H), 6.66 (dd, J = 26.1, 7.6 Hz, 3H), 4.23 (t, J = 6.8 Hz, 2H), 2.90 (t, J = 6.8 Hz, 2H). Example 35: N'-p-fluorophenylhydrazine carboxylic acid (2-phenyl)ethyl ester

[0082] Pale yellow solid, yield 54%. mp 75-77℃; 1 H NMR (400 MHz, DMSO) δ 9.06 (s,1H), 7.61 (d, J = 2.1 Hz, 1H), 7.43 – 7.13 (m, 2H), 7.09–6.91 (m, 2H), 6.74–6.53 (m, 2H), 4.24 (q, J = 7.9 Hz, 2H), 2.96–2.81 (m, 2H). Example 36: N'-2-phenylethyl p-chlorophenylhydrazine carboxylate

[0083] Pink solid, yield 32%. mp 10³-10⁴℃; 1 H NMR (400 MHz, DMSO) δ 9.13 (s,1H), 7.86 (d, J = 1.9 Hz, 1H), 7.42–7.11 (m, 7H), 6.75–6.59 (m, 2H), 4.25 (t, J =6.8 Hz, 2H), 3.40 (s, 2H). Example 37: Ethyl N'-phenylhydrazine carboxylic acid (2-p-fluorophenyl)

[0084] Yellow solid, yield 29%. 116-117℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.03 (s, 1H), 7.64 (s, 1H), 7.37 – 7.04 (m, 6H), 6.66 (dd, J= 28.3, 7.6 Hz, 3H), 4.22 (t, J =6.8 Hz, 2H), 2.89 (t, J = 6.8 Hz, 2H). Example 38: (3-Phenyl)propyl N'-phenylhydrazine carboxylate

[0085] Pale yellow solid, yield 44%. mp 59-61℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.07 (s,1H), 7.67 (s, 1H), 7.42–7.07 (m, 7H), 6.69 (t, J = 7.5 Hz, 3H), 4.00 (t, J = 6.5Hz, 2H), 2.66 (t, J = 7.8 Hz, 2H), 1.88 (t, J = 7.5 Hz, 2H). Example 39: N'-p-chlorophenylhydrazine carboxylic acid (3-phenyl)propyl ester

[0086] Pale yellow solid, yield 36%. mp 104-105℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.13(s, 1H), 7.86 (s, 1H), 7.46 – 7.06 (m, 7H), 6.69 (d, J = 8.4 Hz, 2H), 4.00 (t, J = 6.8 Hz, 2H), 2.66 (t, J = 7.7 Hz, 2H), 2.03–1.79 (m, 2H). Example 40: (4-phenyl)butyl N'-phenylhydrazine carboxylate

[0087] White solid, yield 48%. mp 62-63℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.00 (s, 1H), 7.64 (d, J= 1.9 Hz, 1H), 7.43–6.97 (m, 7H), 6.78–6.54 (m, 3H), 4.03 (t, J =6.0 Hz, 2H), 2.60 (d, J = 7.5 Hz, 2H), 1.61 (q, J = 10.1, 8.2 Hz, 3H), 1.41 (s,1H). Example 41: (4-phenyl)butyl N'-o-fluorophenylhydrazine carboxylate

[0088] Orange-red oily substance, yield 33%; 1 H NMR (400 MHz, DMSO) δ 9.10 (s, 1H), 7.68 (s,1H), 7.32 – 6.62 (m, 9H), 4.05 (s, 2H), 2.60 (q, J = 7.3 Hz, 2H), 1.70 – 1.32(m, 4H). Example 42: (4-phenyl)butyl N'-m-fluorophenylhydrazine carboxylate

[0089] Orange-red oily substance, yield 46%; 1 H NMR (400 MHz, DMSO) δ 9.13 (s, 1H), 8.00 (s,1H), 7.35 – 7.03 (m, 6H), 6.55 – 6.36 (m, 3H), 4.06 (s, 2H), 2.60 (dt, J =14.7, 7.1 Hz, 2H), 1.96 – 1.35 (m, 4H). Example 43: (4-phenyl)butyl N'-p-fluorophenylhydrazine carboxylate

[0090] Yellow solid, yield 43%. mp 57-58℃; 1 H NMR (400 MHz, DMSO) δ 9.05 (s, 1H), 7.36 – 6.49 (m, 10H), 4.04 (s, 2H), 2.61 (t, J = 6.7 Hz, 2H), 1.61 (s, 4H). Example 44: (4-phenyl)butyl N'-m-chlorophenylhydrazine carboxylate

[0091] Orange-red oily substance, yield 43%; 1 H NMR (400 MHz, DMSO) δ 9.11 (s, 1H), 7.96 (d, J = 1.8 Hz, 1H), 7.34 – 7.01 (m, 6H), 6.75 – 6.56 (m, 3H), 4.05 (s, 2H), 2.60(d, J = 7.8 Hz, 2H), 1.61 (s, 4H). Example 45: N'-4-phenyl)butyl N'-chlorophenylhydrazine carboxylate

[0092] White solid, yield 35%. mp 69-70℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.07 (s,1H), 7.83 (s, 1H), 7.33–7.04 (m, 7H), 6.73–6.59 (m, 2H), 4.03 (s, 2H), 2.60(t, J = 6.9 Hz, 2H), 1.60 (s, 4H). Example 46: (4-phenyl)butyl N'-m-bromophenylhydrazine carboxylate

[0093] Orange-red oily substance, yield 43%; 1 H NMR (400 MHz, DMSO) δ 9.14 (s, 1H), 7.98 (d, J = 1.8 Hz, 1H), 7.38 – 6.60 (m, 9H), 4.06 (d, J = 5.3 Hz, 2H), 2.72 – 2.56 (m,2H), 1.62 (s, 4H). Example 47: N'-4-phenyl)butyl p-bromophenylhydrazine carboxylate

[0094] White solid, yield 46%. mp 73-75℃; 1H NMR (400 MHz, DMSO) δ 9.07 (s, 1H),7.85 (d, J = 1.8 Hz, 1H), 7.33 – 6.95 (m, 6H), 6.70 – 6.56 (m, 2H), 4.03 (s,2H), 2.60 (t, J = 6.8 Hz, 2H), 1.60 (s, 4H). Example 48: N'-p-Tolylhydrazinocarboxylic acid (4-phenyl)butyl ester

[0095] Yellow solid, yield 36%. mp 76-77℃; 1 H NMR (400 MHz, DMSO) δ 8.97 (s, 1H), 7.46 (s, 1H), 7.36 – 7.01 (m, 5H), 6.93 (d, J = 8.2 Hz, 2H), 6.67 – 6.52 (m,2H), 4.02 (s, 2H), 2.59 (d, J = 7.4 Hz, 2H), 2.16 (s, 3H), 1.71 – 1.32 (m, 4H). Example 49: N'-(2,4-difluorophenyl)hydrazinocarboxylic acid (4-phenyl)butyl ester

[0096] Orange-red oily substance, yield 43%; 1 H NMR (400 MHz, DMSO) δ 9.11 (s, 1H), 7.62 (s,1H), 7.33 – 7.07 (m, 6H), 6.88 (tt, J = 8.6, 1.9 Hz, 2H), 6.74 (dt, J = 9.5, 4.7Hz, 2H), 4.04 (s, 2H), 2.59 (dt, J = 15.1, 7.1 Hz, 2H), 1.60 (qd, J = 9.4, 4.0Hz, 3H), 1.51 – 1.33 (m, 1H). Example 50: N'-(3,4-difluorophenyl)hydrazinocarboxylic acid (4-phenyl)butyl ester

[0097] Orange-red oily substance, yield 45%; 1 H NMR (400 MHz, DMSO) δ 9.13 (s, 1H), 7.89 (s,1H), 7.52 – 6.85 (m, 6H), 6.78 – 6.33 (m, 2H), 4.05 (t, J = 5.9 Hz, 2H), 2.60(t, J = 5.9 Hz, 2H), 1.82 – 1.33 (m, 4H). Example 51: N'-(3-chloro-2-fluorophenyl)hydrazinocarboxylic acid (4-phenyl)butyl ester

[0098] Pale yellow solid, yield 55%. mp 87-88℃; 1 H NMR (400 MHz, DMSO) δ 9.21 (s,1H), 8.03 (s, 1H), 7.45 – 6.55 (m, 8H), 4.06 (s, 2H), 2.60 (q, J = 7.1 Hz, 2H),1.89 – 1.32 (m, 4H). Example 52: N'-(3-chloro-4-fluorophenyl)hydrazinocarboxylic acid (4-phenyl)butyl ester

[0099] Yellow solid, yield 48%. mp 57-59℃; 1 H NMR (400 MHz, DMSO) δ 9.14 (s, 1H), 7.89 (s, 1H), 7.48 – 6.45 (m, 8H), 4.05 (s, 2H), 2.60 (s, 2H), 1.78 – 1.35 (m, 4H). Example 53: N'-Phenylated carboxylic acid (2-phenoxy) ethyl ester

[0100] Light yellow powder, yield 60%. mp 90-91℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.18 (s, 1H), 7.68 (d, J = 1.9 Hz, 1H), 7.41–7.07 (m, 4H), 6.96 (t,J = 7.5 Hz, 3H), 6.74–6.62 (m, 3H), 4.26 (dt, J = 72.1, 4.3 Hz, 4H). Example 54: N'-Phenylated hydrazinoic acid (2-benzyloxy) ethyl ester

[0101] Pale yellow solid, yield 59%. mp 60-62℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.13 (s,1H), 7.67 (s, 1H), 7.43–7.24 (m, 5H), 7.12 (t, J = 7.7 Hz, 2H), 6.80–6.60 (m,3H), 4.52 (s, 2H), 4.18 (t, J = 4.7 Hz, 2H), 3.62 (q, J = 6.0, 5.4 Hz, 2H). Example 55: Ethyl N'-phenylhydrazine carboxylic acid [2-(2-benzyloxyethoxy)] ester

[0102] Pale yellow solid, yield 48%. mp 69-70℃; 1 H NMR (400 MHz, DMSO- d 6) δ 9.13 (s, 1H), 7.66 (d, J = 2.0 Hz, 1H), 7.43 – 7.25 (m, 2H), 7.12 (t, J = 7.9 Hz, 2H), 6.94 (t, J = 7.7 Hz, 3H), 6.71 – 6.63 (m, 3H), 4.12 (dt, J = 26.2, 4.7 Hz, 4H), 3.72 (dt, J = 38.8, 4.7 Hz, 4H). Bioactivity test examples In vitro antibacterial activity test: In vitro antibacterial activity was determined using the linear hyphal growth rate method: The test bacterium was *Tobacco Star Bacterium* (YC, *Tobacco Star Bacterium*). Alternaria alternata ), black spot fungus of Chinese cabbage (BH, Alternaria brassicae ), tomato early blight pathogen (FZ, Alternaria solani Apple anthracnose fungus (PT, Colletotrichum gloeosporioides ), corn curvularia (YW, Curvularia lunate ), wheat scab (XC, Fusarium gramineae ), Fusarium wilt of watermelon (XK, Fusarium oxysporum f. sp. snowy ), potato dry rot fungus (MG, Fusarium solani Rice blast fungus (SD, Rice blast ), the fungus that causes wilt of pumpkin (NK, Fusarium bulbiferum ), cotton wilt pathogen (MK, Fusarium oxysporum f. sp. dirty dishes Apple ring rot fungus (PL, Physalospora little bird Apple rot pathogen (PF, The waltz of evil The culture medium was PDA. The test compound was prepared into a test solution of a certain concentration using 5% (v / v) dimethyl sulfoxide (DMSO). The test solution was mixed thoroughly with a certain volume of sterile PDA culture medium to obtain a test medium containing 50 mg / L of the test compound. Each experiment was performed in triplicate, and the antibacterial activity was expressed as the average inhibition rate. Standards of the antibacterial agents carbendazim and boscalid were used as positive controls. The results are shown in Tables 2 and 3.

[0103] Table 2: Inhibition rate (%) of example compounds against some plant pathogenic fungi at 50 mg / L

[0104] *MG: Potato dry rot pathogen; FZ: Tomato early blight pathogen; BH: Chinese cabbage black spot pathogen; YC: Tobacco scab pathogen; YW: Maize curvature spore pathogen; PT: Apple anthracnose pathogen. Table 3: Inhibition rate (%) of example compounds against some plant pathogenic fungi at 50 mg / L

[0105] *MK: Fusarium wilt of cotton; XK: Fusarium wilt of watermelon; XC: Fusarium head blight of wheat; NK: Fusarium wilt of pumpkin; PF: Apple rot fungus; SD: Rice blast fungus; PL: Apple ring spot fungus Pot experiment on resistance to downy mildew: Preparation of test solution: Dissolve the test compound in an appropriate amount of dimethyl sulfoxide (DMSO) containing 10% by mass of OP-10 (octylphenol polyoxyethylene ether-10) to prepare a stock solution of 150 mg / mL. Before the test, dilute with water to prepare a test solution of 200 mg / L.

[0106] Assay method: Using *Phyllostachys edulis* as the test fungus and potted grapevines as the test plants, the antibacterial activity of the compounds was determined using the leaf spore germination method. The spores of the test fungus were prepared into 10... 5 A suspension with a spore count / mL concentration was sprayed onto the underside of grape leaves for inoculation. After inoculation, the plants were first placed in a high-humidity isolation room at room temperature for 24 hours, then transferred to a greenhouse with controlled humidity and temperature for 48 hours, and finally placed in a high-humidity environment for 24 hours. Afterward, the plants were moved to a natural environment, and once the moisture on the leaf surface had evaporated naturally, infected leaves were removed from the plants and sprayed with the test solution. After the moisture on the leaf surface had evaporated naturally, the petioles were immersed in water, and then the leaves were incubated in a high-humidity environment for 72 hours. The experimental results were evaluated by comparing the percentage of spore-covered area on the leaves of the experimental and control groups.

[0107] Pot experiment on resistance to powdery mildew: Preparation of test solution: Dissolve the test compound in an appropriate amount of dimethyl sulfoxide (DMSO) containing 10% by mass of OP-10 (octylphenol polyoxyethylene ether-10) to prepare a stock solution of 150 mg / mL. Before the test, dilute with water to prepare a test solution of 200 mg / L.

[0108] Test leaves: Using *Powdery mildew fungus* as the test fungus and melon seedlings as the test plants, the antibacterial activity of the compound was determined using the leaf spore germination method. The specific method was basically the same as the pot antibacterial test for downy mildew fungus mentioned above. Thirty melon seedlings were used in each experiment, grown in sterilized compost. The melon plants inoculated with the *Powdery mildew* spore suspension were placed in a high-humidity environment for 24 hours, and then sprayed with the test solution. Five days later, the antibacterial effect was evaluated using the same method as the pot antibacterial test for downy mildew fungus mentioned above.

[0109] Table 4 shows the control indices of example compounds 1, 4, 7, 11, 18, 21, 22, 24, 26, 29, 35, 43, 45, 52, 54, and 55 against grape downy mildew and melon powdery mildew.

[0110] Table 4: Control index of example compounds against grape downy mildew and melon powdery mildew*

[0111] Note: In the table, *0 indicates that the efficacy is less than 50%, 1 indicates that the efficacy is 50-80%, and 2 indicates that the efficacy is greater than 80%.

[0112] From Table 2 As shown in Figure 4, at a concentration of 50 μg / mL, most of the tested compounds exhibited highly efficient and broad-spectrum in vitro inhibitory activity against the 13 tested plant pathogens. Some compounds showed control efficacy of over 80% against powdery mildew of melon and downy mildew of grape at a concentration of 200 ppm, demonstrating potential applications in the preparation of plant antimicrobial agents and serving as active or synergistic components for such agents.

[0113] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0114] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0115] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A hydrazine carbamate compound, which is a compound of formula (I), or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer, or mixture of isomers thereof, or a pharmaceutically acceptable salt thereof. （I） in, Each R 1 Each is independently selected from halogens; Each R 2 Each is independently selected from halogen, methyl, trifluoromethyl, or trifluoromethoxy; X is selected from the following: —CH2—, —CH2CH2—, —CH2CH2CH2—, —CH2OCH2CH2—, —CH2CH2CH2CH2—, or —OCH2CH2OCH2CH2—. n and m are each independently selected from any integer from 0 to 5. Furthermore, where R 2 Not 3-trifluoromethyl, and R 1 and R 2 Not all are Cl, and when X is selected from bond, —CH2— or —CH2CH2—, n and m are not all 0.

2. The hydrazine carbamate compound according to claim 1, wherein the halogen is selected from fluorine, chlorine, bromine or iodine.

3. The hydrazine carbamate compound according to claim 1, wherein n is 1, R 1 It is selected from 4-fluoro, 4-chloro, 4-bromine or 4-iodine.

4. The hydrazine carbamate compound according to claim 1, wherein m is 1, R 2 Selected from 2-fluoro, 3-fluoro, 4-fluoro, 3-chloro, 4-chloro, 3-bromo, 4-bromo, 4-iodine, 3-methyl, 4-methyl, 4-trifluoromethyl, or 4-trifluoromethoxy; or m is 2, R 2 It is selected from 2,4-difluoro, 3,4-difluoro, 3,5-difluoro, 2-fluoro-3-chloro, 2-fluoro-4-chloro, or 4-fluoro-3-chloro.

5. The hydrazine carbamate compound according to claim 1, wherein X is selected from —CH2CH2CH2—, —CH2OCH2CH2—, —CH2CH2CH2CH2— or —OCH2CH2OCH2CH2—.

6. A method for preparing a hydrazine carbamate compound according to any one of claims 1-5, comprising the following steps: The compound of formula (II) is condensed with the compound of formula (III), or their corresponding hydrochloride, sulfate or acetate, to obtain the compound of formula (I); (II) (III)。 7. A fungicidal composition comprising at least one of the hydrazine carbamate compounds according to any one of claims 1–5 as an active ingredient, and optionally a pesticide-acceptable carrier and / or adjuvant.

8. Use of the hydrazine carbamate compound according to any one of claims 1–5 or the bactericidal composition according to claim 7, for controlling plant diseases caused by plant pathogens.

9. The use according to claim 8, wherein, The plant pathogen is a plant pathogenic fungus. Preferably, the plant pathogenic fungus is selected from the phylum Plasmomycota, Oomycota, Chytridiomycota, Zygomycota, Ascomycota, Basidiomycota, or Deuteromycota.

10. The use according to claim 9, wherein, The plant pathogens are selected from the following pathogens: tobacco red spot pathogen, Chinese cabbage black spot pathogen, tomato early blight pathogen, apple anthracnose pathogen, corn curvature spore pathogen, wheat scab pathogen, watermelon wilt pathogen, potato dry rot pathogen, rice blast pathogen, pumpkin wilt pathogen, cotton wilt pathogen, apple ring rot pathogen, apple rot pathogen, grape downy mildew pathogen, or melon powdery mildew pathogen.

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