Hydrazine formate compound, and preparation method and use thereof

Abstract

This application relates to a hydrazine carbamate compound, its preparation method, and its uses. The hydrazine carbamate compound is a compound of formula (I) or formula (II), or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer, or mixture of isomers thereof, or a pharmaceutically acceptable salt thereof. The hydrazine carbamate compounds provided in this application exhibit broad-spectrum antibacterial activity against plant pathogens such as pathogenic fungi, particularly against *Tobacco Red Spot*, *Chinese Cabbage Black Spot*, *Tomato Early Blight*, *Apple Anthracnose*, *Curvularia*, *Wheat Fusarium*, *Watermelon Fusarium*, *Potato Dry Rot*, *Rice Blast*, *Pumpkin Fusarium*, *Cotton Fusarium*, *Apple Ring Spot*, *Apple Rot*, *Grape Downy Mildew*, and *Melon Powdery Mildew*. (I) (II).

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 widely recognized as the leading biological threat to stable and high global food yields. The combined effects of fungal infections in the field and storage stages can cause yield reductions of 25%-35% in major food crops, and the accompanying fungal toxin contamination further weakens their commercial and market value. Despite the continuous promotion of agricultural control, disease-resistant breeding, and biological agents, chemical fungicides still hold an irreplaceable position in integrated pest management due to their advantages of rapid effectiveness, low cost, and ease of use.

[0003] Statistics show that the rational use of fungicides can save about 15% of global grain production each year, which is of great significance for ensuring food supply and stabilizing farmers' income. Since the 1960s, nearly 200 active ingredients have been put into commercial application, forming a multi-category and multi-variety product system that supports modern agricultural production.

[0004] However, long-term, high-frequency use has led to a decline in the efficacy of some traditional fungicides and an increased risk of reinfection in the field. The demand for efficient, safe, and long-lasting alternatives is becoming increasingly urgent in agricultural production. Developing new fungicides with good environmental compatibility and low risk to non-target organisms has become an important task for ensuring sustainable agricultural production 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) hydrogen atoms in a group are independently replaced by the corresponding number of substituents.

[0019] When used in this document, the term "independently" means that when there are more than one substituent, 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] As used herein, the term "alkyl" refers to a saturated aliphatic hydrocarbon, including straight-chain and branched groups. In some embodiments, the alkyl group has, for example, 1-6 or 1-3 carbon atoms. For example, the term "C1-C6 alkyl" refers to a straight-chain or branched group having 1-6 carbon atoms. The term "C1-C6 alkyl" includes, in its definition, the term "C1-C6 alkyl". 1-6 "alkyl", "C1-C3 alkyl" and "C1-C4 alkyl". Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, isopentyl, neopentyl, (R)-2-methylbutyl, (S)-2-methylbutyl, 3-methylbutyl, 2,3-dimethylpropyl, 2,3-dimethylbutyl, hexyl, etc.

[0022] As used herein, the term "haloalkyl" refers to an alkyl group having one or more halogen substituents (at most fully haloalkyl, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom). For example, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group having one or more halogen substituents (at most fully haloalkyl, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom). As another example, the term "C1 haloalkyl" refers to a methyl group having one, two, or three halogen substituents. Examples of haloalkyl groups include: CF3, C2F5, CHF2, CH2F, CH2CF3, CH2Cl, CF(CF3)2, etc.

[0023] In a first aspect, this application provides a hydrazine carbamate compound, which is a compound of formula (I) or formula (II), or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer, or mixture of isomers thereof, or a pharmaceutically acceptable salt thereof.

[0024] (I) (II) in, Each R 1 Each is independently selected from halogens, C1-C6 alkyl groups, and C1-C6 haloalkyl groups; Each R 2 Each is independently selected from halogens, C1-C6 alkyl groups, C1-C6 haloalkyl groups, C1-C3 alkoxy groups, or C1-C3 haloalkoxy groups; and n and m are each independently selected from any integer between 0 and 5.

[0025] In one embodiment of the present invention, the halogen may be selected from fluorine, chlorine, bromine or iodine; the C1-C6 alkyl may be selected from methyl, ethyl, n-propyl or isopropyl; the C1-C6 haloalkyl may be selected from trifluoromethyl, trichloromethyl, trifluoroethyl or heptafluoroisopropyl; the C1-C3 alkoxy may be selected from methoxy or ethoxy; and / or the C1-C3 haloalkoxy may be selected from trifluoromethoxy.

[0026] In one embodiment of the present invention, each R 1 Each is independently selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, methoxy, or trifluoromethyl; and each R 2 Each is independently selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, methoxy, trifluoromethyl, or trifluoromethoxy.

[0027] 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.

[0028] In one embodiment of the present invention, when n is 1, R 1 Selected from 4-fluoro or 4-chloro.

[0029] 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-trifluoromethoxy, 4-methyl, or 4-ethyl; or when m is 2, R 2 Selected from 2,4-difluoro, 3,4-difluoro, or 3-chloro-4-fluoro.

[0030] 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 (III) with substituted phenylhydrazine or naphthalenehydrazine, or their corresponding hydrochloride, sulfate or acetate, to obtain the compound of formula (I) or the compound of formula (II). (III).

[0031] In one embodiment of the present invention, the structural formula of the substituted phenylhydrazine or its corresponding hydrochloride salt can be: The type and position of (R)n are the same as those of (R)n in compound (I). 1 )n corresponds; and the structural formula of naphthalenehydrazine or its corresponding hydrochloride can be .

[0032] In one embodiment of the invention, the compound of formula (III) undergoes a direct condensation reaction with a substituted phenylhydrazine or naphthylhydrazine, or its corresponding hydrochloride, sulfate, or acetate, in the presence of a condensing agent to obtain the compound of formula (I) or formula (II). Further, the molar ratio of the compound of formula (III) to the substituted phenylhydrazine or naphthylhydrazine, or the molar ratio of the compound of formula (III) to the hydrochloride, sulfate, or acetate of the substituted phenylhydrazine or naphthylhydrazine, can be 1–1.5:1, preferably 1.2–1.4:1. The aforementioned condensing agent may include, for example, EDCI and / or HOBT.

[0033] 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.

[0034] 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 mass percentage of the hydrazine carbamate compound is preferably 200-500 mg / L, more preferably 300-400 mg / L.

[0035] The bactericidal composition of this application may contain one or more other insecticides, fungicides, herbicides, plant growth regulators or fertilizers.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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*.

[0040] 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*.

[0041] 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.

[0042] 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 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

[0043] The invention is further illustrated below with reference to specific embodiments; however, these embodiments do not limit the scope of the invention. Unless otherwise stated, all reactants used in the embodiments were obtained commercially; the instruments and equipment used in the synthesis experiments and product analysis were conventional instruments and equipment commonly used in organic synthesis.

[0044] 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.

[0045] Examples 1-26 The structural formulas of hydrazine carbamate compounds are as follows: (I) (II) Examples 1-25 are compounds of formula (I), wherein R 1 and R 2 The types and locations are shown in Table 1. Example 26 is a compound of formula (II).

[0046] Table 1: Compounds from Examples 1-26

[0047] Preparation methods of Examples 1-24: Preparation of intermediate A: A magnetic stir bar, 20 mL of dimethylformamide, and 2.0 g (50 mmol) of 60% (w / w) sodium hydride were added sequentially to a reaction flask. A dimethylformamide solution containing 2.95 g (25 mmol) of 1,6-hexanediol was added to the system at room temperature with stirring. After stirring for half an hour, benzyl bromide or substituted benzyl bromide (25 mmol) was added, and stirring was continued for 2.5 h. While stirring, 120 mL of saturated ammonium chloride aqueous solution was added dropwise to the reaction flask. The aqueous phase was extracted with 3 × 100 mL of ethyl acetate, and the organic phase was washed with saturated brine. The organic phase was desolvated under reduced pressure, and the residue was separated by silica gel column chromatography using petroleum ether-ethyl acetate (4:1, v / v) as the eluent to obtain the corresponding compound A.

[0048] The physicochemical properties and NMR spectra of compounds A1-A3 are as follows: 6-Benzyloxy-1-hexanol (A1): Colorless liquid, yield 48%. 1 H NMR (400 MHz, CDCl3) δ 7.37–7.26 (m, 5H), 4.50 (s, 2H), 3.61 (t, J = 6.6 Hz, 2H), 3.47 (t, J= 6.6 Hz, 2H), 1.69 (s, 1H), 1.67–1.53 (m, 4H), 1.45–1.31 (m, 4H). 6-(4-Fluorobenzoxy)-1-hexanol (A2): Colorless liquid, yield 52%. 1 H NMR (400 MHz, CDCl3) δ7.34–7.27 (m, 2H), 7.06–6.98 (m, 2H), 4.45 (s, 2H), 3.61 (t, J = 6.6 Hz, 2H), 3.46 (t, J = 6.6 Hz, 2H), 1.74 (s, 1H), 1.67–1.53 (m, 4H), 1.44–1.31 (m, 4H). 6-(4-chlorobenzyloxy)-1-hexanol (A3): colorless liquid, yield 55%. 1 H NMR (400 MHz, CDCl3) δ7.34–7.22 (m, 4H), 4.46 (s, 2H), 3.63 (t, J = 6.6 Hz, 2H), 3.46 (t, J = 6.5 Hz, 2H), 1.68–1.52 (m, 4H), 1.48 (s, 1H), 1.44–1.32 (m, 4H). Preparation of Intermediate B: A magnetic stir bar, dichloromethane (50 mL), and intermediate A (10.0 mmol) were added to a reaction flask and stirred until the solid was completely dissolved. The resulting solution was then cooled to 0 °C, and triphosgene (1.48 g, 5.0 mmol, 0.5 eq.) was added, followed by stirring for 15 minutes. Then, a dichloromethane solution (10 mL) of pyridine (1.19 g, 1.21 mL, 15.0 mmol, 1.5 eq.) was slowly added dropwise at 0 °C with stirring. After addition, the cold bath was removed, and the reaction solution was allowed to warm to room temperature naturally while stirring for 3 h. 60 mL of water was added to the reaction solution, and the aqueous phase was extracted with dichloromethane. The organic phases were combined, washed twice with saturated brine, and dried over anhydrous sodium sulfate. The organic phases were dissolved under reduced pressure, and the residue obtained was intermediates B1–B3. The latter did not require further purification and was directly used for the synthesis of compound C.

[0049] The physicochemical properties and NMR spectra of compounds B1–B3 are as follows: 6-Benzyloxyhexyl chloroformate (B1), colorless liquid, yield 72%. 1H NMR (400 MHz, CDCl3) δ 7.31– 7.19 (m, 5H), 4.43 (s, 2H), 4.23 (t, J = 6.7 Hz, 2H), 3.40 (t, J = 6.4 Hz, 2H), 1.71 – 1.61 (m, 2H), 1.60 – 1.51 (m, 2H), 1.40 – 1.27 (m, 4H). 6-(4-fluorobenzyloxy)hexyl chloroformate (B2), colorless liquid, yield 73%. 1 H NMR (400 MHz, CDCl3)δ 7.36 – 7.29 (m, 2H), 7.09 – 7.01 (m, 2H), 4.48 (s, 2H), 4.34 (t, J = 6.7 Hz, 2H), 3.48 (t, J = 6.4 Hz, 2H), 1.82 – 1.71 (m, 2H), 1.69 – 1.62 (m, 2H), 1.50 –1.37 (m, 4H). 6-(4-chlorobenzyloxy)hexyl chloroformate (B3), colorless liquid, yield 70%. 1 H NMR (400 MHz, CDCl3)δ 7.35 – 7.25 (m, 4H), 4.46 (s, 2H), 4.31 (t, J = 6.6 Hz, 2H), 3.46 (t, J = 6.4Hz, 2H), 1.79 – 1.68 (m, 2H), 1.66 – 1.58 (m, 2H), 1.47 – 1.35 (m, 4H). Preparation methods of compounds C1-C26 in Examples 1-26: Add a magnetic flux, tetrahydrofuran (20 mL), and phenylhydrazine, or substituted phenylhydrazine or 2-naphthylhydrazine hydrochloride (3.0 mmol) to the reaction flask, and stir until the solid is completely dissolved. Add pyridine or triethylamine (3.3–6.3 mmol) to the mixture at room temperature. Cool the reaction solution to 0 °C, and then add a tetrahydrofuran solution of compound B (3.3 mmol) dropwise with stirring. After the addition is complete, remove the cold bath and stir at room temperature for 6 h. Evaporate the tetrahydrofuran under reduced pressure, and add 40 mL of water to the residue. Extract the resulting aqueous solution with ethyl acetate and dry to anhydrous sodium sulfate. Filter, remove the solvent from the filtrate under reduced pressure, and perform silica gel column chromatography on the residue using petroleum ether-ethyl acetate (6:1, v / v) as eluent to give hydrazine carbamate compounds C1–C26.

[0050] The physicochemical properties and NMR spectra of compounds C1–C26 are as follows: Example 1, chemical name N′-phenylhydrazine carboxylic acid (6 - Benzyloxyhexyl ester (referred to as compound C1): Yellow oily liquid, yield 94%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.00 (s, 1H), 7.63 (d, J = 2.0 Hz,1H), 7.40–7.22 (m, 5H), 7.18–7.05 (m, 2H), 6.73–6.61 (m, 3H), 4.44 (s, 2H),3.99 (t, J = 6.7 Hz, 2H), 3.41 (dt, J = 10.2, 6.2 Hz, 2H), 1.65–1.12 (m, 8H). Example 2, chemically named N′-(2-fluorophenyl)hydrazinocarboxylic acid (6 - Benzyloxyhexyl ester (denoted as compound C2): yellow oily liquid, yield 37%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.09 (s, 1H), 7.67 (s, 1H), 7.40–7.21 (m, 5H), 7.10–6.93 (m, 2H), 6.81–6.61 (m, 2H), 4.44 (s, 2H), 4.00(t, J = 6.6 Hz, 2H), 3.42 (t, J = 6.5 Hz, 2H), 1.67–1.12 (m, 8H). Example 3, chemically named N′-(3-fluorophenyl)hydrazinocarboxylic acid (6 - Benzyloxyhexyl ester (referred to as compound C3): yellow oily liquid, yield 79%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.11 (s, 1H), 7.98 (s, 1H),7.39–7.22 (m, 5H), 7.14 (td, J = 8.1, 6.7 Hz, 1H), 6.55–6.34 (m, 3H), 4.44 (s,2H), 4.01 (t, J = 6.7 Hz, 2H), 3.41 (td, J = 6.6, 3.7 Hz, 2H), 1.66–1.13 (m, 8H). Example 4, chemically named N′-(4-fluorophenyl)hydrazinocarboxylic acid (6 - Benzyloxyhexyl ester (compound C4): yellow solid, yield 76%. mp 71–73 °C. 1 H NMR (400 MHz, DMSO- d 6) δ 9.03 (s, 1H), 7.70–7.51 (d, J = 1.6 Hz, 1H), 7.40–7.24 (m, 5H), 7.02–6.91 (m, 2H), 6.71–6.60 (m,2H), 4.44 (s, 2H), 3.99 (t, J = 6.8 Hz, 2H), 3.41 (td, J = 6.4, 3.4 Hz, 2H),1.64–1.12 (m, 8H). Example 5, chemically named N′-(3-chlorophenyl)hydrazinocarboxylic acid (6 - Benzyloxyhexyl ester (referred to as compound C5): yellow oily liquid, yield 82%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.12 (s, 1H), 7.98 (s, 1H),7.40–7.21 (m, 5H), 7.14 (t, J = 8.0 Hz, 1H), 6.75–6.55 (m, 3H), 4.44 (s, 2H), 4.00 (t, J = 6.7 Hz, 2H), 3.41 (td,J = 6.7, 3.5 Hz, 2H), 1.66–1.13 (m, 8H). Example 6, chemically named N′-(4-chlorophenyl)hydrazinocarboxylic acid (6 - Benzyloxyhexyl ester (denoted as compound C6): yellow solid, yield 74%. mp 60–62 °C. 1 H NMR (400 MHz, DMSO- d 6) δ 9.07 (s, 1H), 7.84 (d, J = 1.9 Hz, 1H), 7.39–7.23 (m, 5H), 7.20–7.10 (m, 2H), 6.70–6.60 (m, 2H), 4.44 (s, 2H), 3.99 (t, J = 6.7 Hz, 2H), 3.47–3.36 (m, 2H), 1.64–1.12 (m, 8H). Example 7, chemically named N′-(3-bromophenyl)hydrazinocarboxylic acid (6 - Benzyloxyhexyl ester (referred to as compound C7): yellow liquid, yield 53%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.11 (s, 1H), 7.96 (d, J = 1.8 Hz,1H), 7.38–7.23 (m, 5H), 7.07 (t, J = 8.0 Hz, 1H), 6.86–6.77 (m, 2H), 6.66 (dd, J = 8.3, 2.2 Hz, 1H), 4.44 (s, 2H), 4.01 (t, J = 6.6 Hz, 2H), 3.41 (tt, J = 9.3,4.8 Hz, 2H), 1.66–1.13 (m, 8H). Example 8, chemically named N′-(4-bromophenyl)hydrazinocarboxylic acid ( 6- Benzyloxyhexyl ester (referred to as compound C8): yellow liquid, yield 59%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.07 (s, 1H), 7.86 (d, J= 1.9 Hz,1H), 7.40–7.19 (m, 7H), 6.66–6.57 (m, 2H), 4.44 (s, 2H), 3.99 (t, J = 6.8 Hz, 2H), 3.42 (t, J = 6.5 Hz, 2H), 1.64–1.13 (m, 8H). Example 9, chemically named N′-(4-trifluoromethoxyphenyl)hydrazinocarboxylic acid (6 - Benzyloxyhexyl ester (referred to as compound C9): Yellow liquid, yield 56%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.11 (s, 1H), 7.92 (s,1H), 7.39–7.23 (m, 5H), 7.13 (d, J = 8.6 Hz, 2H), 6.71 (dd, J = 8.9, 1.5 Hz, 2H), 4.44 (s, 2H), 4.00 (t, J = 6.9 Hz, 2H), 3.50–3.37 (m, 2H), 1.66–1.16 (m, 8H). Example 10, chemically named N′-(4-methylphenyl)hydrazinocarboxylic acid (6 - Benzyloxyhexyl ester (referred to as compound C10): Yellow liquid, yield 36%. 1 H NMR (400 MHz, DMSO- d 6) δ 8.96 (s, 1H), 7.45 (s, 1H),7.37–7.27 (m, 5H), 6.93 (d, J = 8.2 Hz, 2H), 6.60 (d, J = 8.4 Hz, 2H), 4.44 (s, 2H), 3.99 (t, J = 6.8 Hz, 2H), 3.45–3.38 (m, 2H), 2.16 (s, 3H), 1.63–1.46 (m, 4H), 1.39–1.25 (m, 4H). Example 11, chemically named N′-(4-ethylphenyl)hydrazinocarboxylic acid (6 - Benzyloxyhexyl ester (referred to as compound C11): Yellow liquid, yield 59%. 1 H NMR (400 MHz, DMSO- d6) δ 8.97 (s, 1H), 7.47 (s, 1H),7.38–7.28 (m, 5H), 6.96 (d, J = 8.3 Hz, 2H), 6.60 (d, J = 8.4 Hz, 2H), 4.44 (s,2H), 3.98 (t, J = 6.7 Hz, 2H), 3.41 (td, J = 6.7, 3.4 Hz, 2H), 2.45 (t, J = 7.6 Hz, 2H), 1.64–1.46 (m, 4H), 1.38–1.26 (m, 4H), 1.11 (t, J = 7.6 Hz, 3H). Example 12, chemically named N′-(2,4-difluorophenyl)hydrazinocarboxylic acid (6 - Benzyloxyhexyl ester (compound C12): Yellow solid, yield 65%. mp 43–44 °C. 1 H NMR (400 MHz, DMSO- d 6) δ 9.10 (s, 1H), 7.60 (s, 1H), 7.38–7.24 (m, 5H), 7.12 (ddd, J = 11.8, 8.9, 2.8 Hz, 1H), 6.93–6.85 (m, 1H), 6.74 (td, J = 9.3, 5.6 Hz, 1H), 4.44 (s, 2H), 4.00 (t, J = 6.7 Hz, 2H), 3.42 (t, J = 6.4 Hz, 2H), 1.66–1.13 (m, 8H). Example 13, chemically named N′-(3,4-difluorophenyl)hydrazinocarboxylic acid (6 - Benzyloxyhexyl ester (referred to as compound C13): Yellow liquid, yield 64%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.10 (s, 1H), 7.87 (s, 1H),7.38–7.24 (m, 5H), 7.19 (dt, J = 10.7, 9.0 Hz, 1H), 6.58 (ddd, J= 13.0, 6.9, 2.7Hz, 1H), 6.46 (dq, J = 9.0, 2.6, 2.0 Hz, 1H), 4.44 (s, 2H), 4.00 (t, J = 6.7 Hz, 2H), 3.41–3.32 (m, 2H), 1.64–1.22 (m, 8H). Example 14, chemically named N′-(3-chloro-4-fluorophenyl)hydrazinocarboxylic acid (6 - Benzyloxyhexyl ester (referred to as compound C14): Yellow oily liquid, yield 91%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.13 (s, 1H), 7.89 (d, J = 2.1 Hz, 1H), 7.39–7.23 (m, 5H), 7.18 (t, J = 9.1 Hz, 1H), 6.75 (dd, J =6.3, 2.7 Hz, 1H), 6.65 (dt, J = 9.0, 3.4 Hz, 1H), 4.44 (s, 2H), 4.01 (t, J = 6.7Hz, 2H), 3.41 (t, J = 6.4 Hz, 2H), 1.75–1.12 (m, 8H). Example 15, chemical name N′-phenylhydrazine carboxylic acid (p-fluorobenzyloxy)hexyl ester (denoted as compound C15): yellow liquid, yield 89%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.00 (s, 1H), 7.64 (s, 1H), 7.39–7.32 (m, 2H), 7.23–7.05 (m, 4H), 6.72–6.55 (m, 3H), 4.42 (s, 2H), 3.99 (t, J =6.8 Hz, 2H), 3.40 (dt, J = 11.3, 6.2 Hz, 2H), 1.66–1.21 (m, 8H). Example 16, chemically named N′-p-fluorophenylhydrazine carboxylic acid (6 - p-Fluorobenyl(2-fluorobenzyl)hexyl ester (compound C16): Yellow liquid, 93% yield. 1H NMR (400 MHz, DMSO- d 6) δ 9.03 (s, 1H), 7.60 (s, 1H), 7.35 (dd, J = 8.5, 5.8 Hz, 2H), 7.20–7.12 (m, 2H), 7.01–6.93 (m, 2H), 6.68–6.61(m, 2H), 4.42 (s, 2H), 3.98 (t, J = 6.6 Hz, 2H), 3.40 (tt, J = 10.8, 5.5 Hz, 2H),1.64–1.22 (m, 8H). Example 17, chemically named N′-p-chlorophenylhydrazine carboxylic acid (6 - p-Fluorochlorobenzyloxyethyl ester (compound C17): Yellow liquid, yield 55%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.08 (s, 1H), 7.84 (s, 1H), 7.39–7.30 (m, 2H), 7.21–7.09 (m, 4H), 6.71–6.62 (m, 2H), 4.42 (s, 2H), 3.99(t, J = 6.9 Hz, 2H), 3.41 (m, 2H), 1.65–1.21 (m, 8H). Example 18, chemically named N′-p-bromophenylhydrazine carboxylic acid (6 - p-Fluorobenyl(2-fluorobenzyl)hexyl ester (compound C18): Yellow liquid, yield 64%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.07 (s, 1H), 7.85 (s, 1H), 7.42–7.04 (m, 6H), 6.63 (dd, J = 8.8, 2.6 Hz, 2H), 4.41 (s, 2H), 3.99 (t, J = 7.3Hz, 2H), 3.40 (t, J = 6.6 Hz, 2H), 1.68–1.12 (m, 8H). Example 19, chemically named N′-p-trifluoromethoxyphenylhydrazine carboxylic acid (6 - p-Fluorobenyl(2-fluorobenzyl)hexyl ester (compound C19): yellow liquid, yield 56%. 1H NMR (400 MHz, DMSO- d 6) δ 9.11 (s, 1H), 7.92 (s, 1H), 7.40–7.29 (m, 2H), 7.21–7.06 (m, 4H), 6.76–6.65 (m, 2H), 4.42 (s, 2H), 4.00 (t, J = 6.7 Hz, 2H), 3.40 (m, 2H), 1.65–1.22 (m, 8H). Example 20, chemically named N′-(3-chloro-4-fluorophenyl)hydrazinocarboxylic acid (6 - p-Fluorobenyl(2-fluorobenzyl)hexyl ester (denoted as compound C20): Yellow liquid, yield 61%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.11 (s, 1H), 7.87 (d, J = 2.0 Hz, 1H), 7.39–7.30 (m, 2H), 7.22–7.10 (m, 3H), 6.74 (dd, J = 6.4, 2.8Hz, 1H), 6.64 (ddd, J = 9.0, 3.9, 2.8 Hz, 1H), 4.42 (s, 2H), 4.00 (t, J = 6.8 Hz, 2H), 3.40 (dt, J = 12.5, 5.5 Hz, 2H), 1.65–1.20 (m, 8H). Example 21, chemical name: N′-phenylhydrazine carboxylic acid (6 - p-chlorobenzyloxyhexyl ester (designated as compound C21): yellow solid, yield 48%. mp 49–50 °C. 1 H NMR (400 MHz, DMSO- d 6) δ 9.00 (s, 1H), 7.63 (s, 1H), 7.44–7.25 (m, 4H), 7.12 (t, J = 7.8 Hz, 2H), 6.67 (t, J = 8.0 Hz, 3H), 4.43 (s, 2H), 4.00 (t, J = 6.7 Hz, 2H), 3.48–3.36 (m, 2H), 1.65–1.12 (m, 8H). Example 22, chemically named N′-(4-fluorophenyl)hydrazinocarboxylic acid (6 - p-chlorobenzyloxyhexyl ester (denoted as compound C22): yellow liquid, yield 50%. 1 H NMR (400 MHz, DMSO- d 6) δ 9.04 (s, 1H), 7.62 (s, 1H), 7.45–7.27 (m, 4H), 7.03–6.90 (m, 2H), 6.67 (dd, J = 8.9, 4.6 Hz, 2H), 4.43 (s,2H), 3.99 (t, J = 6.8 Hz, 2H), 3.48–3.38 (m, 2H), 1.66–1.12 (m, 8H). Example 23, chemically named N′-(4-chlorophenyl)hydrazinocarboxylic acid (6 - p-chlorobenzyloxyhexyl ester (compound C23): Yellow solid, yield 44%. mp 56–57 °C. 1 H NMR (400 MHz, DMSO- d 6) δ 9.08 (s, 1H), 7.84 (s, 1H), 7.44–7.28 (m, 4H), 7.20–7.11 (m, 2H), 6.70–6.62 (m, 2H), 4.43 (s, 2H), 3.99 (t, J = 6.9 Hz, 2H), 3.42 (t, J = 6.5 Hz, 2H), 1.66–1.12 (m, 8H). Example 24, chemically named N′-(4-bromophenyl)hydrazinocarboxylic acid (6 - p-chlorobenzyloxyhexyl ester (compound C24): Yellow solid, yield 53%. mp 66–67 °C. 1 H NMR (400 MHz, DMSO- d 6) δ 9.08 (s, 1H), 7.86 (s, 1H), 7.44–7.21 (m, 6H), 6.62 (d, J = 8.6 Hz, 2H), 4.43 (s, 2H), 4.00(t, J = 6.7 Hz, 2H), 3.42 (t, J = 6.5 Hz, 2H), 1.65–1.20 (m, 8H). Example 25, chemically named N′-(3-chloro-4-fluorophenyl)hydrazinocarboxylic acid (6 - p-chlorobenzyloxyhexyl ester (compound C25): Yellow solid, yield 37%. mp 42–43 °C. 1 H NMR (400 MHz, DMSO- d 6) δ 9.12 (s,1H), 7.87 (s, 1H), 7.45–7.28 (m, 4H), 7.19 (t, J = 9.1 Hz, 1H), 6.73 (dd, J =6.3, 2.8 Hz, 1H), 6.64 (ddd, J = 9.0, 4.0, 2.8 Hz, 1H), 4.43 (s, 2H), 4.01 (t, J = 6.5 Hz, 2H), 3.42 (t, J = 6.6 Hz, 2H), 1.66–1.15 (m, 8H). Example 26, chemical name N′-(2-naphthyl)hydrazinohexyl carboxylate (denoted as compound C26): yellow solid, yield 67%. mp 48–50 °C. 1 H NMR (400 MHz, DMSO- d 6) δ 9.17 (s, 1H), 7.97 (s, 1H),7.70 (dd, J = 8.6, 3.3 Hz, 2H), 7.62 (d, J = 8.2 Hz, 1H), 7.38–7.24 (m, 6H), 7.19(t, J = 7.5 Hz, 1H), 7.04 (dd, J = 8.8, 2.3 Hz, 1H), 6.91 (d, J = 2.2 Hz, 1H), 4.44(s, 2H), 4.04 (t, J = 6.6 Hz, 2H), 3.43 (t, J = 6.6 Hz, 2H), 1.69–1.13 (m, 8H). 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 (CL, Curvularia lunate ), wheat scab (XC, Fusarium gramineae ), Fusarium wilt of watermelon (XK, Fusarium oxysporum f. sp. Snow ), 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. Vasoinfection 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 40 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.

[0051] Table 2: Inhibition rate (%) of example compounds against plant pathogenic fungi at 40 mg / L

[0052] Pot experiment on resistance to downy mildew: Preparation of the 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 500 times to obtain a test solution of 300 mg / L.

[0053] 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. Spores of the test fungus were prepared into a suspension with a concentration of 10⁵ spores / mL and inoculated onto the underside of grapevine leaves using a spray method. 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 after the surface moisture of the leaves had naturally evaporated, infected leaves were removed from the plants and sprayed with the test solution. After the leaf surface moisture had naturally evaporated, the petioles were immersed in water, and then incubated in a high-humidity environment for 72 hours. The experimental effect was evaluated by comparing the percentage of spore-covered area on the leaf surface of the experimental group and the control group.

[0054] Pot experiment on resistance to powdery mildew: Preparation of the 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 500 times to obtain a test solution of 300 mg / L.

[0055] 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.

[0056] Table 3 shows the control indices of compounds C4, C6, C8, C13–C17, C20–C22, and C25 against grape downy mildew and melon powdery mildew.

[0057] Table 3: Control index of example compounds against grape downy mildew and melon powdery mildew*

[0058] 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%.

[0059] As shown in Tables 2 and 3, at a concentration of 40 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 exceeding 80% against powdery mildew of melon and downy mildew of grape at a concentration of 300 ppm, demonstrating potential applications in the preparation of plant antimicrobial agents and serving as active or synergistic components for such agents.

[0060] 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.

[0061] 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.

[0062] 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 formula (II), 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） (II) in, Each R 1 Each is independently selected from halogens, C1-C6 alkyl groups, and C1-C6 haloalkyl groups; Each R 2 Each is independently selected from halogens, C1-C6 alkyl groups, C1-C6 haloalkyl groups, C1-C3 alkoxy groups, or C1-C3 haloalkoxy groups; and n and m are each independently selected from any integer between 0 and 5.

2. The hydrazine carbamate compound according to claim 1, wherein, The halogen is selected from fluorine, chlorine, bromine or iodine; The C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, or isopropyl; The C1-C6 haloalkyl group is selected from trifluoromethyl, trichloromethyl, trifluoroethyl or heptafluoroisopropyl; The C1-C3 alkoxy group is selected from methoxy or ethoxy; and / or The C1-C3 haloalkoxy groups are selected from trifluoromethoxy groups.

3. The hydrazine carbamate compound according to claim 1, wherein, Each R 1 Each is independently selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, methoxy, or trifluoromethyl; and each R 2 Each is independently selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, methoxy, trifluoromethyl, or trifluoromethoxy.

4. The hydrazine carbamate compound according to claim 1, wherein, n is 1, R 1 Selected from 4-fluoro or 4-chloro.

5. 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-trifluoromethoxy, 4-methyl, or 4-ethyl; or m is 2, R 2 Selected from 2,4-difluoro, 3,4-difluoro, or 3-chloro-4-fluoro.

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 (III) is condensed with a substituted phenylhydrazine or naphthylhydrazine, or the corresponding hydrochloride, sulfate or acetate, to give the compound of formula (I) or the compound of formula (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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