WO2021244244A1 - Oxadiazole compound and application thereof - Google Patents

Abstract

Disclosed is an oxadiazole compound having a novel structure and as represented by general formula I: a compound of the general formula I has excellent bactericidal activity, and has a good prevention and control effect for plant bacterial diseases and fungal diseases. The present invention comprises uses of the compound of the general formula I as a bactericide in agriculture and other fields.

Description

An oxadiazole compound and its application Technical field

The invention belongs to the field of agricultural fungicides. Specifically, it relates to an oxadiazole compound and its application.

Background technique

WO2017081309A1, WO2017081310A1, WO2017081311A1, WO2017081312A1, WO2018015449A1, WO2018015458A1, WO2017055469A1, WO2017085098A1, WO2017085100A1, WO2017103219A1 and WO2017178245A1 and other patents related to 3-aryl (heteroaryl) plant derivatives and their derivatives in 3-aryl (heteroaryl) plant derivatives Use in pathogenic microorganisms.

In the prior art, the oxadiazole compound and its bactericidal activity as shown in the present invention have not been reported.

Summary of the invention

The purpose of the present invention is to provide an oxadiazole compound that can control a variety of plant bacterial diseases and fungal diseases, and its use in the preparation of medicines for preventing and controlling pathogens in agriculture and other fields.

In order to achieve the above objective, the technical solution of the present invention is as follows:

An oxadiazole compound, as shown in general formula I:

Where:

R _{1 is} selected from hydrogen, hydroxyl, mercapto, amino, cyano, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkane Oxy, C ₁ -C ₆ alkylthio, halogenated C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylamino or C ₁ -C ₆ dialkylamino;

R _{2 is} selected from hydrogen, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylcarbonyl, C ₃ -C ₆ cycloalkylcarbonyl, C ₃ -C ₆ cycloalkane C ₁ -C ₃ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkoxy C ₁ -C ₃ alkylcarbonyl, C ₁ -C ₆ alkylthio C ₁ -C ₃ Alkylcarbonyl, C ₁ -C ₆ alkylaminocarbonyl or C ₁ -C ₆ dialkylaminocarbonyl;

X ₁ and X ₂ are each independently selected from hydrogen, halogen or C ₁ -C ₆ alkyl;

n is selected from 0 or 1;

Or a salt of a compound of general formula I.

The more preferred compound in the present invention is: in general formula I

R _{1 is} selected from hydrogen, hydroxyl, mercapto, amino, cyano, C ₁ -C ₃ alkyl, halo C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halo C ₁ -C ₃ alkane Oxy, C ₁ -C ₃ alkylthio, halogenated C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylamino or C ₁ -C ₃ dialkylamino;

R _{2 is} selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₄ cycloalkylcarbonyl, C ₃ -C ₄ cycloalkane C ₁ -C ₂ alkylcarbonyl, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkoxy C ₁ -C ₂ alkylcarbonyl, C ₁ -C ₄ alkylthio C ₁ -C ₂ Alkylcarbonyl, C ₁ -C ₄ alkylaminocarbonyl or C ₁ -C ₄ dialkylaminocarbonyl;

X ₁ and X ₂ are each independently selected from hydrogen, fluorine or methyl;

n is selected from 0 or 1;

Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

A further preferred compound of the present invention is: in general formula I

R _{1 is} selected from hydrogen, hydroxyl, mercapto, amino, cyano, C ₁ -C ₃ alkyl, halo C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halo C ₁ -C ₃ alkane Oxy, C ₁ -C ₃ alkylthio, halogenated C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylamino or C ₁ -C ₃ dialkylamino;

R _{2 is} selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₄ cycloalkylcarbonyl, 2-(C ₃ -C ₄ cycloalkyl) acetyl, C ₁ -C ₄ alkoxycarbonyl, 2-(C ₁ -C ₄ alkoxy)acetyl, 2-(C ₁ -C ₄ alkylthio)acetyl, C ₁ -C ₄ alkylaminocarbonyl or C ₁ -C ₄ dialkylaminocarbonyl;

X ₁ and X _{2 are} selected from hydrogen, fluorine or methyl;

n is selected from 0 or 1;

Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

A further preferred compound of the present invention is: in the general formula I

R _{1 is} selected from hydrogen, amino, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or C ₁ -C ₃ alkylthio;

R _{2 is} selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₄ cycloalkylcarbonyl, 2-(C ₃ -C ₄ -cycloalkyl)acetyl, 2-(C ₁ -C ₄ alkoxy)acetyl or C ₁ -C ₄ dialkylaminocarbonyl;

X ₁ and X _{2 are} selected from hydrogen;

n is selected from 0 or 1;

Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

Alternatively, a further preferred compound of the present invention is: in general formula I

R _{1 is} selected from hydrogen, hydroxyl, mercapto, amino, cyano, methyl, ethyl, n-propyl, isopropyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoro Methoxy, methylthio, ethylthio, trifluoroethylthio, methylamino, ethylamino or N,N-dimethylamino;

R _{2 is} selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, trifluoromethyl, acetyl, propionyl, n-butyryl , Isobutyryl, n-valeryl, cyclopropylcarbonyl, 1-cyanocyclopropyl-1-carbonyl, cyclobutylcarbonyl, 2-cyclopropylacetyl, methoxycarbonyl, ethoxycarbonyl, 2 -Methoxyacetyl, 2-ethoxyacetyl, 2-n-propoxyacetyl, 2-isopropoxyacetyl, 2-n-butoxyacetyl, 2-sec-butoxyacetyl , 2-isobutoxyacetyl, 2-tert-butoxyacetyl, 2-methylthioacetyl, 2-ethylthioacetyl, N-methylaminocarbonyl, N-ethylaminocarbonyl or N ,N-Dimethylaminocarbonyl;

X ₁ and X _{2 are} selected from hydrogen, fluorine or methyl;

n is selected from 0 or 1;

Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

A further preferred compound of the present invention is: in general formula I

R _{1 is} selected from hydrogen;

R _{2 is} selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₄ cycloalkylcarbonyl, 2-(C ₃ -C ₄ -cycloalkyl)acetyl, 2-(C ₁ -C ₄ alkoxy)acetyl or C ₁ -C ₄ dialkylaminocarbonyl;

X ₁ and X _{2 are} selected from hydrogen;

n is selected from 0 or 1;

Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

Alternatively, a further preferred compound of the present invention is: in general formula I

R _{1 is} selected from hydrogen, amino, C ₁ -C ₃ alkyl or C ₁ -C ₃ alkylthio;

R _{2 is} selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₄ cycloalkylcarbonyl, 2-(C ₃ -C ₄ -cycloalkyl)acetyl, 2-(C ₁ -C ₄ alkoxy)acetyl or C ₁ -C ₄ dialkylaminocarbonyl;

X ₁ and X _{2 are} selected from hydrogen;

n is selected from 1;

Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

A further preferred compound of the present invention is: in general formula I

R _{1 is} selected from hydrogen;

R _{2 is} selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₄ cycloalkylcarbonyl, 2-(C ₃ -C ₄ -cycloalkyl)acetyl, 2-(C ₁ -C ₄ alkoxy)acetyl or C ₁ -C ₄ dialkylaminocarbonyl;

X ₁ and X _{2 are} selected from hydrogen;

n is selected from 0;

Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

In the definitions of compounds of the general formula given above, the terms used in pooling generally represent the following substituents:

Halogen: Refers to fluorine, chlorine, bromine or iodine.

Alkyl: straight or branched chain alkyl, such as methyl, ethyl, n-propyl, isopropyl or different butyl, pentyl or hexyl isomers.

Cycloalkyl: refers to a substituted or unsubstituted cyclic alkyl group, such as cyclopropyl, cyclopentyl or cyclohexyl; substituents such as methyl, halogen and the like.

Halogenated alkyl groups: straight or branched chain alkyl groups. The hydrogen atoms on these alkyl groups can be partially or completely replaced by halogens, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl Group, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, 1,1,2,2,2-pentafluoroethyl, etc.

Alkoxy: straight or branched chain alkyl, connected to the structure via an oxygen atom bond, such as methoxy, ethoxy, tert-butoxy, etc.

Haloalkoxy: The hydrogen atoms on the alkoxy group can be partially or completely replaced by halogen, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, tri Fluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like.

Alkylthio: straight or branched chain alkyl, connected to the structure via a sulfur atom bond, such as methylthio, ethylthio and the like.

Haloalkylthio: The hydrogen atoms on the alkylthio group can be partially or completely replaced by halogen, such as difluoromethylthio, trifluoroethylthio and the like.

Alkylamino: straight or branched chain alkyl, connected to the structure via a nitrogen atom bond, such as methylamino (CH ₃ NH-), ethylamino (CH ₃ CH ₂ NH-), n-propylamino (CH ₃ CH ₂ CH ₂ NH-), isopropylamino ((CH ₃ ) ₂ CHNH-) or isomeric butylamine.

Dialkylamino: Two identical or different linear or branched alkyl groups are connected to the structure via a nitrogen atom bond, such as dimethylamino ((CH ₃ ) ₂ N-), methylethylamino (( CH ₃ )(CH ₃ CH ₂ )N-) and so on.

Alkylcarbonyl: alkyl-CO-, such as acetyl (CH ₃ CO-), propionyl (CH ₃ CH ₂ CO-), n-butyryl (CH ₃ CH ₂ CH ₂ CO-), isobutyryl (( CH ₃ ) ₂ CHCO-), n-valeryl (CH ₃ CH ₂ CH ₂ CH ₂ CO-), etc.

Cycloalkylcarbonyl: cycloalkyl-CO-, such as cyclopropylcarbonyl

1-cyanocyclopropyl-1-carbonyl

Cyclobutyl carbonyl

Wait.

Cycloalkylalkyl-carbonyl group: a cycloalkyl group - CO- group, for example, 2- (C ₃ -C ₄ cycloalkyl) acetyl, more specifically, for example, 2-cyclopropyl-acetyl

Wait.

Alkoxycarbonyl: alkyl-O-CO-, such as methoxycarbonyl (CH ₃ OCO-), ethoxycarbonyl (CH ₃ CH ₂ OCO-) and the like.

Alkoxyalkylcarbonyl: alkoxy-alkyl-CO-, such as 2-(C ₁ -C ₄ alkoxy)acetyl, more specifically, such as 2-methoxyacetyl

2-ethoxyacetyl

2-n-propoxy acetyl

2-isopropoxyacetyl

2-n-butoxy acetyl

2-sec-butoxyacetyl

2-isobutoxyacetyl

2-tert-Butoxyacetyl

Wait.

Alkylthioalkylcarbonyl: alkylthio-alkyl-CO-, for example 2-(C ₁ -C ₄ alkylthio)acetyl, more specifically, for example 2-methylthioacetyl

2-Ethylthioacetyl

Wait.

Alkylaminocarbonyl: alkyl-NH-CO-, such as N-methylaminocarbonyl (CH ₃ NHCO-), N-ethylaminocarbonyl (CH3CH2NHCO-) and the like.

Dialkylaminocarbonyl: for example, N,N-dimethylaminocarbonyl ((CH3)2NCO-), N,N-diethylaminocarbonyl ((CH3CH2)2NCO-).

Some of the compounds of general formula I of the present invention are shown in Table 1, but the present invention is by no means limited to these compounds.

The compound of general formula I of the present invention can be prepared according to the following method (each group in the formula is defined as before unless otherwise specified): Method 1: When R ₁ is hydrogen, C ₁ -C ₆ alkyl or halogenated C _1- In the case of C ₆ alkyl, the compound of general formula I can be prepared as follows (L represents C ₁ -C ₆ alkoxy, such as methoxy, ethoxy, etc.):

A compound of general formula II-1 or a compound of general formula II-2 and a compound of general formula III-1 are reacted in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to prepare a compound of general formula I-1 ; The reaction can be carried out in the presence of a base.

Compounds of general formula I-1 and acylating reagents (such as acetyl chloride, propionyl chloride, n-butyryl chloride, isobutyryl chloride, n-valeryl chloride, cyclopropylformyl chloride, 1-cyanocyclopropyl-1-formyl chloride, ring Butylformyl chloride, 2-cyclopropylacetyl chloride, methyl chloroformate, ethyl chloroformate, 2-methoxyacetyl chloride, 2-ethoxyacetyl chloride, 2-n-propoxyacetyl chloride, 2-isopropyl Oxyacetyl chloride, 2-n-butoxy acetyl chloride, 2-sec-butoxy acetyl chloride, 2-isobutoxy acetyl chloride, 2-tert-butoxy acetyl chloride, 2-methylthio acetyl chloride, 2 -Ethylthioacetyl chloride, N-methylcarbamoyl chloride, N-ethylcarbamoyl chloride or N,N-dimethylcarbamoyl chloride, etc.) or alkylating reagents (such as methyl iodide, ethyl iodide, iodine) Propane, dimethyl sulfate, diethyl sulfate, 2,2,2-trifluoroiodoethane, etc.) can be prepared by reacting in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours. Compound of formula I-2; the reaction can be carried out in the presence of a base.

In the above reaction, suitable solvents can be the same or different, and can be alcohols (e.g., methanol, ethanol, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl Isobutyl ketone, etc.), halogenated hydrocarbons (e.g., chloroform, dichloromethane, etc.), esters (e.g., methyl acetate, ethyl acetate, etc.), ethers (e.g., tetrahydrofuran, dioxane, diethyl ether) , 1,2-dimethoxyethane, etc.), polar solvents (e.g., water, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone, dimethylmethylene Sulfone, etc.) or a mixed solvent of the above solvents. The bases can be the same or different, and can be organic bases such as trimethylamine, triethylamine, pyridine, DBU, 4-dimethylaminopyridine (eg, trimethylamine, triethylamine, pyridine, DBU, 4-dimethylaminopyridine, etc.) , Alkali metal hydrides (e.g., sodium hydride, potassium hydride, etc.), alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxides (e.g., calcium hydroxide, etc.), alkali Metal carbonates (such as sodium carbonate, potassium carbonate, etc.), alkali metal bicarbonates (such as sodium bicarbonate, etc.), metal alkoxides (such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, tertiary Sodium butoxide, etc.).

Method 2: When R ₁ is C ₁ -C ₆ alkylthio or halogenated C ₁ -C ₆ alkylthio, the compound of general formula I can be prepared according to the following method (A represents C ₁ -C ₆ alkyl or halogen Substitute C ₁ -C ₆ alkyl):

A compound of general formula II-1 or a compound of general formula II-2 and a compound of general formula III-2 are reacted in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to prepare a compound of general formula I-3 ; The reaction can be carried out in the presence of a base.

In the above reaction, suitable solvents can be the same or different, and can be alcohols (e.g., methanol, ethanol, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), and ketones (e.g., acetone, methyl ethyl ketone, methyl ethyl ketone, etc.). Isobutyl ketone, etc.), halogenated hydrocarbons (e.g., chloroform, dichloromethane, etc.), esters (e.g., methyl acetate, ethyl acetate, etc.), ethers (e.g., tetrahydrofuran, dioxane, diethyl ether) , 1,2-dimethoxyethane, etc.), polar solvents (e.g., water, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone, dimethylmethylene Sulfone, etc.) or a mixed solvent of the above solvents. The base can be the same or different, and can be trimethylamine, triethylamine, pyridine, DBU, 4-dimethylaminopyridine and other organic bases (eg, trimethylamine, triethylamine, pyridine, DBU, 4-dimethylaminopyridine, etc.) , Alkali metal hydrides (e.g., sodium hydride, potassium hydride, etc.), alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxides (e.g., calcium hydroxide, etc.), alkali Metal carbonates (such as sodium carbonate, potassium carbonate, etc.), alkali metal bicarbonates (such as sodium bicarbonate, etc.), metal alkoxides (such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, tertiary Sodium butoxide, etc.).

The method for preparing the compound of the general formula I-4 from the compound of the general formula I-3 is the same as the method for preparing the compound of the general formula I-2 from the compound of the general formula I-1.

Method 3: When R ₁ is a hydroxyl group, a mercapto group, an amino group or a C ₁ -C ₆ alkylamino group, the compound of general formula I can be prepared as follows:

Compounds of general formula I-3 and nucleophiles are reacted in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to prepare compounds of general formula I-5; compounds of general formula I-4 and nucleophiles The reagents are reacted in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to prepare a compound of general formula I-6.

In the above reaction, the nucleophile is sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrosulfide, sodium amide, ammonia, C ₁ -C ₆ alkyl ammonia (such as methylamine, ethylamine, etc.) or its hydrochloric acid Salt (such as methylamine hydrochloride, ethylamine hydrochloride, etc.).

In the above reaction, when the nucleophile is C ₁ -C ₆ alkyl ammonia hydrochloride, the reaction requires the participation of a suitable base to neutralize the hydrochloride. The suitable base is preferably trimethylamine, triethylamine, pyridine, and carbonic acid. Potassium, sodium carbonate, potassium bicarbonate, sodium bicarbonate, etc.

In the above reaction, suitable solvents can be the same or different, and can be alcohols (e.g., methanol, ethanol, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl Isobutyl ketone, etc.), halogenated hydrocarbons (e.g., chloroform, dichloromethane, etc.), esters (e.g., methyl acetate, ethyl acetate, etc.), ethers (e.g., tetrahydrofuran, dioxane, diethyl ether) , 1,2-Dimethoxyethane, etc.), polar solvents (e.g., water, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone, dimethylene Sulfone, etc.) or a mixed solvent of the above solvents.

Method 4: When R ₁ is a cyano group, a C ₁ -C ₆ alkoxy group, a halogenated C ₁ -C ₆ alkoxy group or a C ₁ -C ₆ dialkylamino group, the compound of general formula I can be carried out as follows preparation:

The compound of the general formula I-3 and the nucleophile are reacted in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to obtain the compound of the general formula I-7; the compound of the general formula I-4 and the nucleophilic The reagents are reacted in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to prepare a compound of general formula I-8.

In the above reaction, the nucleophile is sodium cyanide, potassium cyanide, _{alkali metal salts of C 1} -C ₆ alkanols (such as sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc.), halogenated C ₁ -C ₆ Alkali metal salts of alkanols (such as sodium 2,2,2-trifluoroethoxide or potassium 2,2,2-trifluoroethoxide, etc.), C ₁ -C ₆ dialkyl ammonia (such as N,N-dimethyl Ammonia, N-methyl-N-ethylamine, etc.) or its hydrochloride (such as N,N-dimethylammonium hydrochloride, N-methyl-N-ethylammonium hydrochloride, etc.).

In the above reaction, when the nucleophile is C ₁ -C ₆ dialkylamine hydrochloride, the reaction requires the participation of a suitable base to neutralize the hydrochloride. Suitable bases are preferably trimethylamine, triethylamine, pyridine, Potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, etc.

In the above reaction, suitable solvents can be the same or different, and can be alcohols (e.g., methanol, ethanol, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl Isobutyl ketone, etc.), halogenated hydrocarbons (e.g., chloroform, dichloromethane, etc.), esters (e.g., methyl acetate, ethyl acetate, etc.), ethers (e.g., tetrahydrofuran, dioxane, diethyl ether) , 1,2-dimethoxyethane, etc.), polar solvents (e.g., water, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone, dimethylmethylene Sulfone, etc.) or a mixed solvent of the above solvents.

The method for preparing the compound of the general formula I-8 from the compound of the general formula I-7 is the same as the method for preparing the compound of the general formula I-2 from the compound of the general formula I-1.

Method 5: When R ₂ is a C ₁ -C ₆ alkyl group or a halogenated C ₁ -C ₆ alkyl group, the compound of general formula I can also be prepared as follows:

(1) When R ₁ is hydrogen, C ₁ -C ₆ alkyl or halo C ₁ -C ₆ alkyl (L represents C ₁ -C ₆ alkoxy, such as methoxy, ethoxy, etc.):

The compound of the general formula II-3 can be reacted with the compound of the general formula III-1 to obtain the compound of the general formula I-9. The method for preparing the compound of the general formula I-9 from the compound of the general formula II-3 is the same as the method for preparing the compound of the general formula I-1 from the compound of the general formula II-1 or the compound of the general formula II-2.

(2) When R _{1 is} not hydrogen, C ₁ -C ₆ alkyl or halo C ₁ -C ₆ alkyl (A represents C ₁ -C ₆ alkyl or halo C ₁ -C ₆ alkyl; K Represents a hydroxyl group, a mercapto group, an amino group, a cyano group, a C ₁ -C ₆ alkoxy group, a halogenated C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ alkylamino group or a C ₁ -C ₆ dialkylamino group):

The compound of the general formula II-3 can be reacted with the compound of the general formula III-2 to obtain the compound of the general formula I-10. The method for preparing the compound of the general formula I-10 from the compound of the general formula II-3 is the same as the method for preparing the compound of the general formula I-3 from the compound of the general formula II-1 or the compound of the general formula II-2.

The compound of the general formula I-10 can be prepared by reacting the compound of the general formula I-10 with a nucleophile. The method for preparing the compound of the general formula I-11 from the compound of the general formula I-10 is the same as the method for preparing the compound of the general formula I-6 from the compound of the general formula I-4 or preparing the compound of the general formula I-8 from the compound of the general formula I-4.

The sources of raw materials and intermediates involved in the above preparation methods are as follows:

Compounds of general formula II-1 can be prepared according to known methods, for example with reference to the methods reported in WO2019171234, WO2018005192, WO2007111212, WO2017081309, WO2018015449 or WO2018015458; compounds of general formula II-2 can be prepared according to known methods, for example, with reference to WO2017018803, WO2018177880, Prepared by the methods reported in WO2017103219, WO2017109044, WO2017103223, WO2017055469, WO2018185013, WO2018184984 or WO2018184987;

Compounds of general formula II-3 can be prepared according to known methods, for example, referring to the methods reported in WO2016031815, WO2018185013, WO2018177894, WO2017055473, WO2017178245 or WO2018184988; compounds of general formula III-1 can be prepared by purchase or by known methods, for example, refer to CN105384725 , CN108727377, US2503524, WO2004009602, WO2012151525, WO2010060589, WO2005117909, WO2003070729, WO2016196071, WO2016196417, WO2010019637, Bioorganic&Medicinal Chemistry Letters, 22(6), 2283-2286, ACS Medicinal Chemistry Letters, 2019, 10(11) Journal of Medicinal Chemistry, 47(24), 5894-5911; 2004 or Journal of Medicinal Chemistry, 60(13), 5673-5698; Prepared by the methods reported in 2017;

The compound of general formula III-2 can be prepared by purchasing according to known methods, for example, refer to Organic Process Research & Development, 15(3), 556-564; 2011, Molecules, 17, 12187-12196; 2012, Chemical Communications (Cambridge, United Kingdom), 53(59), 8356-8359; 2017, Journal of Enzyme Inhibition and Medicinal Chemistry, 28(1), 163-171; Prepared by methods reported in 2013 or WO2018089786; acylation reagent, alkylation reagent and other conventional raw materials Reagents and reagents are usually commercially available, but can also be self-made according to conventional methods.

The compound represented by the general formula I of the present invention is used to control plant bacterial diseases, and can be used to prevent and control a variety of plant bacterial diseases, such as fruit spot disease (such as melon fruit spot, etc.), leaf spot disease (such as tomato bacteria). Leaf spot disease, etc.), bacterial wilt (such as tomato bacterial wilt, potato bacterial wilt, etc.), bacterial blight, canker disease (such as citrus canker, kiwi fruit canker, etc.), soft rot (such as soft Chinese cabbage) Rot, etc.), bacterial angular leaf spot (e.g. cucumber bacterial angular leaf spot, etc.), bacterial leaf streak (e.g. rice bacterial leaf streak, etc.), leaf blight, bacterial leaf blight (e.g. rice white leaf Blight, etc.), wildfire and bacterial scab.

The compounds of the present invention can also be used to prevent and control diseases caused by various fungi such as Oomycetes, Basidiomycetes, Ascomycetes and Deuteromycetes on various crops. Gray mold, cucumber anthracnose, cucumber powdery mildew, tomato early blight, tomato late blight, pepper blight, grape downy mildew, grape white rot, apple ring leaf disease, apple spot leaf disease, rice sheath blight, rice paddy Diseases such as blast, wheat rust, wheat leaf spot, wheat powdery mildew, rape sclerotium, and corn spot disease have good control effects.

Due to its positive properties, the above-mentioned compounds can be advantageously used to protect important crops, livestock and breeding animals in agriculture and horticulture, and the environment frequently visited by humans from harmful bacteria.

In order to obtain the desired effect, the dosage of the compound varies due to various factors, such as the compound used, the crop to be protected, the type of pest, the degree of infection, climatic conditions, the method of application, the dosage form used, and so on.

A compound dose of 5 g-5 kg per hectare can provide adequate control.

The present invention also includes a bactericide with the compound of general formula I as the active ingredient. The weight percentage of the active components in the bactericide is between 0.1-99%. The fungicide also includes agricultural, forestry, and sanitary acceptable carriers and auxiliary agents.

The bactericide of the present invention can be applied in the form of a formulation. The compound of general formula I is used as an active component to be dissolved or dispersed in a carrier and/or adjuvant or formulated into a preparation so as to be easier to disperse when used as a bactericidal agent.

In the present invention, the compound of general formula I is used as the active component, and the compound of general formula I can be prepared into a variety of formulation types in a manner well known in the art, including water, soluble liquid, emulsifiable concentrate, microemulsion, water emulsion, and suspension. , Suspended seed coating agent, dispersible oil suspension agent, ultra-low volume agent, powder, wettable powder, soluble powder, emulsifiable powder, granule, water dispersible granule, soluble granule, emulsifiable granule, dry suspension agent , Effervescent granules, floating granules, tablets, soluble tablets, effervescent tablets, microcapsule powders, microcapsule suspensions, in any case, the choice of formulation type depends on the physics and chemistry of the compound of general formula I And biological characteristics.

The bactericidal preparation of the compound of general formula I of the present invention can be prepared by the usual processing method, that is, after the active substance is mixed with a liquid carrier or a solid carrier, one or more surface active agents such as emulsifiers, dispersants, wetting agents, and thickening agents are added. Agents, stabilizers and defoamers, etc. Usually the composition contains at least one carrier and at least one surfactant. In all cases, it should be ensured that the active ingredient of the composition of the present invention is evenly distributed.

Aqueous agent is to mix the compound of general formula I, surfactant, and water uniformly to form a uniform and transparent liquid. It usually contains 5-50% of active ingredients, 5-20% of emulsifiers, 0-10% of other additives such as penetrants, and the balance of water.

The soluble liquid agent mixes the compound of general formula I, the surfactant, and the non-aqueous polar solvent uniformly to form a uniform transparent liquid. The soluble liquid usually contains 5-60% of active ingredients, 5-20% of emulsifiers, 0-10% of other additives such as penetrants, and the balance of the liquid carrier.

The emulsifiable concentrate mixes the compound of general formula I, the surfactant, and the organic solvent uniformly to form a homogeneous oily liquid. Emulsifiable concentrates usually contain 1 to 70% of active ingredients, 5 to 20% of emulsifiers, 0 to 10% of other additives such as penetrants, stabilizers, and the balance of the liquid carrier.

The microemulsion mixes the compound of general formula I, surfactant, water, and organic solvent uniformly to form a uniform transparent liquid. Microemulsions usually contain 1-50% of active ingredients, 5-30% of emulsifiers, 2-10% of antifreeze, 0-10% of other additives such as penetrants, stabilizers, and the balance of the liquid carrier.

In the water emulsion, the compound of general formula I, the surfactant, and the organic solvent are uniformly mixed to form the oil phase; the water and the antifreeze are mixed together to form the water phase. Use a high-shear emulsifier to shear the oil phase at high speed while slowly adding the water phase to the oil phase to obtain a uniformly dispersed water emulsion. It usually contains 5-50% active ingredient, 5-20% emulsifier, 2-5% antifreeze, and the balance of liquid carrier.

The suspending agent mixes the compound of general formula I, dispersant, wetting agent, antifreeze, and water uniformly, and is sanded by a sand mill to obtain a stable, non-deposition, flowable liquid. Suspending agents usually contain 5-50% active ingredients, 2-10% dispersant, 2-5% wetting agent, 2-5% antifreeze, 0-10% other additives such as defoamers, thickeners, Preservative, and the balance of the liquid carrier.

The suspension seed coating agent is uniformly mixed with the compound of general formula I, dispersant, wetting agent, film-forming agent, and water, and then sanded by a sand mill to obtain a stable, non-deposition, flowable liquid. Suspended seed coatings usually contain 1-50% active ingredient, 2-10% dispersant, 2-5% wetting agent, 2-5% antifreeze, 2-10% film former, 0-10% others Additives such as defoamers, thickeners, preservatives, warning colors, and liquid carrier balance.

The dispersible oil suspension agent mixes the compound of general formula I, the surfactant, and the oil-based carrier uniformly, and is sanded by a sand mill to obtain a stable, non-deposition, flowable liquid. The dispersible oil suspension usually contains 5-50% of active ingredients, 5-30% of surfactants, 0-10% of other additives such as thickeners, stabilizers, and the balance of the liquid carrier.

The ultra-low volume agent mixes the compound of general formula I, the surfactant, and the organic solvent uniformly, and processes it into a uniform transparent oil phase. It usually contains 1-30% of active ingredients, 5-30% of emulsifiers, 0-10% of other additives such as stabilizers, and the balance of the liquid carrier.

The powder mixes the compound of general formula I, the auxiliary agent, and the carrier, and is pulverized to obtain a powder. The powder usually contains 5-85% of active ingredient, 5-10% of dispersant, 0-10% of other additives such as stabilizer, and the balance of solid carrier.

The wettable powder is mixed with a compound of general formula I, a dispersant, a wetting agent, and a carrier, and pulverized to obtain a powder. Wettable powders usually contain 5-85% of active ingredients, 5-10% of dispersants, 1-10% of wetting agents, 0-10% of other additives such as stabilizers, and the balance of solid carriers.

The soluble powder is mixed with a compound of general formula I, a dispersant, a wetting agent, and a carrier, and then pulverized to obtain a powder. The soluble powder usually contains 5 to 80% of active ingredients, 5 to 10% of dispersant, 1 to 10% of wetting agent, 0 to 10% of other additives such as stabilizers, and the balance of solid carrier.

The emulsifiable powder is mixed with a compound of general formula I, a surfactant, and an organic solvent to prepare a uniform transparent oil phase, and then the above-mentioned oil phase is uniformly sprayed on the pre-pulverized carrier. The emulsifiable powder usually contains 5-50% active ingredient, 5-30% emulsifier, 5-10% wetting and dispersing agent, 0-15% organic solvent, and the balance of solid carrier.

The granule is mixed with the compound of general formula I, auxiliary agent and carrier, then kneaded, granulated, dried and coated. Granules usually contain 0.5-20% active ingredient, 0.1-10% binder, 0-10% other additives such as stabilizers, and the balance of solid carrier.

The water dispersible granules are mixed with the compound of general formula I, dispersant, wetting agent, disintegrant and carrier, then kneaded, granulated and dried. Water dispersible granules usually contain 5-85% active ingredient, 1-10% dispersant, 1-10% wetting agent, 0.1-10% binder, and 0-10% other additives such as disintegrant, stabilizer Agent, and the balance of the solid carrier.

The soluble granules are mixed with the compound of general formula I, dispersant, wetting agent, disintegrant and carrier, then kneaded, granulated and dried. Soluble granules usually contain 5-85% active ingredient, 1-10% dispersant, 1-10% wetting agent, 0.1-10% binder, and 0-10% other additives such as disintegrant and stabilizer , And the balance of the solid carrier.

The emulsifiable granule mixes the compound of general formula I, the surfactant, and the organic solvent to form a uniform transparent oil phase, and then the oil phase is uniformly sprayed on the pre-pulverized carrier, kneaded, granulated, and dried. Emulsifiable granules usually contain 5-50% active ingredients, 5-30% emulsifiers, 5-10% wetting and dispersing agents, 0-15% organic solvents, and 0-10% other additives such as disintegrants, Stabilizer, binder, and the balance of solid carrier.

The dry suspending agent is uniformly mixed with the compound of general formula I, dispersant, wetting agent, carrier, and water, then sanded by a sand mill, and spray dried after sanding. Dry suspensions usually contain 5 to 80% of active ingredients, 2 to 20% of dispersing agents, 2 to 10% of wetting agents, and 0 to 10% of other additives such as defoamers, thickeners, and the balance of solid carriers.

Effervescent granules: The compound of general formula I, wetting and dispersing agent, effervescent disintegrating agent, and carrier are mixed, then kneaded and granulated. Effervescent granules usually contain 0.5-30% active ingredient, 2-20% wetting and dispersing agent, 2-20% effervescent disintegrant, and 0-10% other additives such as stabilizers, binders, and solids. Carrier margin.

Floating granules are mixed with the compound of general formula I, wetting and dispersing agent, floating beads, and carrier, then kneaded and granulated. Floating granules usually contain 0.5-30% active ingredients, 2-20% wetting and dispersing agents, 5-20% floating beads, and 0-10% other additives such as stabilizers, binders, disintegrants, and solids. Carrier margin.

The tablet is mixed with the compound of formula I, dispersant, wetting agent, disintegrant, and carrier, then kneaded, compressed, and dried. Tablets usually contain 5-50% active ingredient, 1-10% dispersant, 1-10% wetting agent, 0.1-10% binder, 0-10% other additives such as disintegrant, stabilizer, And the balance of the solid carrier.

In the soluble tablet, the compound of general formula I, a dispersant, a wetting agent, a disintegrant, and a carrier are mixed, then kneaded, compressed, and dried. Soluble tablets usually contain 5-50% active ingredient, 1-10% dispersant, 1-10% wetting agent, 0.1-10% binder, and 0-10% other additives such as disintegrant and stabilizer , And the balance of the solid carrier.

An effervescent tablet is mixed with the compound of general formula I, a wetting and dispersing agent, an effervescent disintegrant, and a carrier, then kneaded and compressed. Effervescent tablets usually contain 0.5-30% active ingredients, 2-20% wetting and dispersing agents, 2-20% effervescent disintegrants, and 0-10% other additives such as stabilizers, binders, and solids. Carrier margin.

Microcapsule powder dissolve the compound of general formula I in a solvent, add emulsifier and wall materials to it, stir evenly to obtain an oil phase; add a dispersant to the water to obtain an aqueous phase; under high-speed stirring, add the oil phase to the water phase, An oil-in-water emulsion is formed; under agitation, a curing agent is added to the emulsion, heated and kept to form a capsule, and then filtered and dried. Microcapsule powders usually contain 0.5-30% active ingredients, 2-10% emulsifiers, 2-10% wetting and dispersing agents, and 5-30% other additives such as wall materials, defoamers, curing agents, stabilizers, And the balance of the solid carrier.

Microcapsule suspending agent dissolve the compound of general formula I in a solvent, add emulsifier and wall materials to it, stir evenly to obtain an oil phase; add a dispersant to the water to obtain an aqueous phase; under high-speed stirring, add the oil phase to the water phase , To form an oil-in-water emulsion; under agitation, add a curing agent to the emulsion, heat and keep it to form a capsule to form a microcapsule suspension. Microcapsule suspensions usually contain 0.5-30% active ingredients, 2-10% emulsifiers, 2-10% wetting and dispersing agents, and 5-30% other additives such as wall materials, defoamers, preservatives, thickening Agent, curing agent, stabilizer, and the balance of the liquid carrier.

The preparation of the bactericidal preparation of the compound of the general formula I of the present invention can adopt the well-known (liquid or solid) carriers and various auxiliary agents by those skilled in the art. Examples include but are not limited to the following types of substances.

The suitable surfactant in the bactericidal preparation of the compound of general formula I of the present invention can be an emulsifier, a dispersant or a wetting agent; it can be one or more of non-ionic or ionic. The ionic surfactant is selected from sulfonates, sulfates, carboxylates, phosphate salts, succinate salts, lignosulfonates, acrylamide acrylic copolymers and the like. Nonionic surfactants are selected from fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty amine polyoxyethylene ethers, fatty acid polyoxyethylene ethers, acid alcohol esters and their polyoxyethylene ethers, alkyl polyethylene glycols Alcohol ether, alkyl phenyl polyglycol ether, fatty amide and its polyoxyethylene ether, alkanolamide and its polyoxyethylene ether, polyoxyethylene polyoxypropylene ether block copolymer, sodium alkyl naphthalene sulfonate Fatty alcohol polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, etc.

The above-mentioned surfactants can be selected from one or more of the surfactants shown, such as: sodium or calcium lignosulfonate, polyoxyethylene (n20) phenethyl phenol ether oleate, alkyl Aryl polyoxyethylene polyoxypropylene ether, tristyryl phenol polyoxyethylene (n20) ether phosphorylated triethanolamine salt, agricultural milk 0201B, agricultural milk 0203B, agricultural milk 100#, agricultural milk 600#, agricultural milk 700# , Nong Milk 1601#, Nong Milk AEO-3, Nong Milk AEO-5, Nong Milk AEO-7, Nong Milk T-20, Nong Milk T-80, Nong Milk T-85, Nong Milk S-80, Nong Milk S-85, agricultural milk NP-7, agricultural milk NP-10, agricultural milk NP-15, agricultural milk OX-2681, agricultural milk OX-8686, agricultural milk OX-690, agricultural milk 2201#, polycarboxylate dispersion GY-D800, polycarboxylate dispersant GY-D04, polycarboxylate dispersant GY-D02, alkyl naphthalene sulfonate formaldehyde condensate (NNO), naphthol sulfonate formaldehyde condensate sodium salt, alkyl Phenol polyoxyethylene polyoxypropylene ether, styrene maleic anhydride, methyl naphthalenesulfonic acid formaldehyde condensate, castor oil ethylene oxide adduct, alkylphenol polyoxyethylene polyoxypropylene ether, alkyl-diethyl Glycol ether-sodium sulfonate, N-methyl-oleoyl-sodium taurate, detergent LS, sodium methylene naphthalene sulfonate, sodium oleic acid methyl amino ethyl sulfonate, dispersant SP-28F , Dispersant SP-SC3, Darun dispersant D909S, alkyl aryl polyoxyethylene ether, dodecyl polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether formaldehyde condensate, dibutyl naphthalene sulfonic acid Sodium (pulverized powder BX), dibutyl naphthalenesulfonic acid formaldehyde condensate, dispersant SD-811, dispersant SD815, dispersant SK-24, dispersant SK-20TX, dispersant SK-5218, dispersant SK- 33H, dispersant SK-10LX, dispersant SK-551, dispersant Atlox 4913, dispersant EL-20, dispersant EL-40, dispersant EL-90, dispersant YUS-NV1203, dispersant YUS-NV1420, dispersant Dispersant YUS-WG4, dispersant YUS-TG285, dispersant YUS-WP1, dispersant YUS-110, dispersant YUS-EP60P, dispersant YUS-CH1100, dispersant SP-OF3468, dispersant SP-OF3472, dispersant SP -2728, dispersant SP-SC29, dispersant Supragil MNS/90, dispersant Soprophor FD, dispersant YUS-FS1, dispersant YUS-PQ100, dispersant YUS-WG5, YUS-D935, octylphenol polyoxyethylene Ether sulfate, Morwet EFW, wetting agent Igepal BC/10, wetting agent GEROPONL-WET/P, wetting agent Rhodasurf 860/p, wetting agent SP-SC3266, wetting agent PICO-SW2, wetting agent PICO -SW3, Wetting agent YUS-LXC, wetting agent YUS-204, sodium alkyl alcohol polyoxyethylene ether sulfate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkyl succinic acid sulfonate, twelve Sodium alkyl benzene sulfonate, sodium dodecyl sulfate, calcium dodecyl benzene sulfonate, etc.

The suitable liquid carrier in the bactericidal preparation of the compound of general formula I of the present invention can be one or more of water, organic solvent, and oily medium. Suitable organic solvents are selected from aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, alcohols and their ethers and esters, ketones, etc., such as benzene, xylene, toluene, alkylbenzene, alkylnaphthalene , Chlorobenzene, vinyl chloride, trichloroethane, dichloromethane, chloroform, carbon tetrachloride, polychloroethane, petroleum fractions, cyclohexane, methanol, ethanol, isopropanol, butanol, ethylene glycol , Propylene glycol, glycerol, sorbitol, benzyl alcohol, furfuryl alcohol, cyclohexanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-pyrrolidone, tributyl phosphate, dimethyl methyl Amide and dimethyl sulfoxide, etc. Suitable oily medium is selected from soybean oil, methyl oleate, light mineral oil, liquid paraffin, kerosene, turpentine and the like.

Suitable solid carriers in the bactericidal preparation of the compound of general formula I of the present invention include natural or synthetic ones. Can be selected from but not limited to clay, rock powder, chalk, quartz, clay, montmorillonite, sodium sulfate, silica, diatomaceous earth, pumice, gypsum, talc, bentonite, kaolin, attapulgite, light calcium carbonate , Clay, montmorillonite, magnesium aluminum silicate, activated clay, white carbon black, ammonium sulfate, benzofuran resin, superphosphate, alumina, calcite, marble, pumice, etc. Suitable particle carriers include crushed and classified Natural rocks such as sepiolite and dolomite and synthetic particles made of organic and inorganic powders.

Suitable binders and thickeners include synthetic or natural water-soluble polymers. Can be selected from but not limited to carbonyl methyl alcohol, polyvinyl alcohol, polyvinyl acetate, xanthan gum, gelatin, gum arabic, polyvinylpyrrolidone, magnesium aluminum silicate, polyvinyl alcohol, polyethylene glycol, phenolic resin, Shellac, methyl cellulose, soluble starch, carboxymethyl cellulose and sodium alginate, etc., are added to the preparation in the form of powder, granules or latex.

Suitable defoamers can be selected from, but not limited to, defoamers SAG1522, silicones, C8-10 fatty alcohols, phosphate esters, C10-20 saturated fatty acids (such as capric acid), amides, and the like.

Suitable antifreeze can be selected from but not limited to ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, ethylene glycol butyl ether, propylene glycol butyl ether, ethylene glycol butyl ether acetate, urea Wait.

Suitable penetrants can be selected from, but not limited to, silicone, penetrant T, penetrant JFC, and the like.

Suitable film-forming agents include natural products and their modifications and synthetic polymers. Can be selected from but not limited to sodium carboxymethyl starch, soluble starch, phosphorylated starch, oxidized starch, chitosan and its derivatives, polypropylene graft copolymer, xanthan gum, sodium alginate, agar, gelatin, arabic Glue, polyethylene glycol, polyvinyl alcohol, polyvinyl acetate, polyacrylamide, polyvinylpyrrolidone, polyacrylic acid, etc.

Suitable preservatives can be selected from, but not limited to, sodium benzoate, cassone, potassium sorbate and the like.

Suitable disintegrants can be selected from but not limited to sodium carboxymethyl starch, croscarmellose sodium, croscarmellose sodium, modified starch, cross-linked polyvinylpyrrolidone, ammonium sulfate, sodium sulfate, Sodium chloride, ammonium chloride, etc.

The effervescent disintegrant can be an acidic component and/or an alkaline component, wherein the acidic component can be selected from organic acids and inorganic acids, such as tartaric acid, citric acid, salicylic acid, phosphoric acid, etc.; the alkaline component can be It is selected from basic carbonates and carbonates, for example: sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate and the like.

Suitable warning colors can be selected from, but not limited to, inorganic pigments, such as iron oxide, titanium oxide or Prussian blue; organic dyes, such as alizarine, acid scarlet G, basic rose spirit, azo dyes, metal phthalocyanines, and the like.

Suitable wall materials include one or more of natural polymer materials, semi-synthetic polymer materials and fully synthetic polymer materials. The natural polymer material can be selected from but not limited to gelatin, acacia, agar, alginate, chitosan, fibrin, zein, etc.; the semi-synthetic polymer material can be selected from but not limited to methyl (ethyl) cellulose , Carboxymethyl cellulose (sodium), cellulose acetate and its esters and partial glycerides, etc.; fully synthetic polymer materials can be selected from but not limited to polyacrylic resin, urea resin, polyamide, polyester, polymethyl Methyl acrylate, polyurea, polyurethane, etc.

Suitable curing agents include one or more of polyols and polyamines. The polyol can be selected from but not limited to ethylene glycol, glycerol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol Alcohol 600, etc.; polyamines can be selected from but not limited to ethylene diamine, propylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, ethanolamine, diethanolamine, triethanolamine, hexamethylenetetramine, iso Folone diamine and so on.

The bactericidal preparation of the compound of general formula I of the present invention can be diluted or sprayed directly with water by the user before use, or it can be used directly.

The technical scheme of the present invention also includes a method for preventing and curing pathogens: applying the fungicidal agent of the present invention to the pathogens or their growth medium. Generally, the more suitable effective amount is selected to be 10 g to 1000 g per hectare, and the effective amount is preferably 10 to 500 g per hectare.

It should be clear that various changes and modifications can be made within the scope defined by the claims of the present invention.

detailed description

The following specific examples are used to further illustrate the present invention, but the present invention is by no means limited to these examples. (Unless otherwise noted, all raw materials used are commercially available)

Synthesis Example

According to the synthetic route described above, using different raw material compounds, the compounds represented by the general formula I of the present invention can be prepared separately, which are further described in detail as follows:

Example 1: Preparation of Compound 1

1.00g (3.58mmol) (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)methanamine hydrochloride (referring to the method reported in WO2018184984) ) Put it into a 50ml single-necked flask, add 20ml ethanol and shake it until fully mixed, add 0.37g (3.66mmol) triethylamine, 0.44g (3.61mmol) ethoxymethylenemalononitrile, and stir to react at room temperature. After the reaction was monitored by TLC, the solvent was removed under reduced pressure, and the residue was column chromatographed to obtain 0.93 g of the target product as a white solid. ^{The 1} H NMR and liquid quality data of compound 1 are as follows:

¹ H NMR(600MHz, Chloroform-d)δ8.19(d,2H), 7.48--7.37(m,3H), 6.87(br s,1H), 4.58(d,2H).LC-MS(m/z ,ESI): 320.1(M+H).

Example 2: Preparation of compound 12

Add 0.25g (0.78mmol) N-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)carbonyl dicyandiamide, 15ml to a 25ml single-mouth bottle Toluene, 0.08g (0.87mmol) propionyl chloride, heated and refluxed for reaction. After the reaction was monitored by TLC, the solvent was removed under reduced pressure, and the residue was column chromatographed to obtain 0.24 g of the target product as a brown solid. ^{The 1} H NMR data of compound 12 are as follows:

¹ H NMR (600MHz, Chloroform-d) δ 8.28 (s, 1H), 8.17 (d, 2H), 7.30 (d, 2H), 5.40 (s, 2H), 2.67 (q, 2H), 1.27 (d ,3H).

Example 3: Preparation of Compound 13

According to the synthesis method of Example 2, compound 13 (yellow solid) was prepared. ^{The 1} H NMR data of compound 13 are as follows:

¹ H NMR (600MHz, Chloroform-d) δ 8.27 (s, 1H), 8.17 (d, 2H), 7.30 (d, 2H), 5.40 (s, 2H), 2.61 (t, 2H), 1.82-1.72 (m,2H),0.99(t,3H).

Example 4: Preparation of compound 14

According to the synthesis method of Example 2, compound 14 (brown solid) was prepared. ^{The 1} H NMR and liquid quality data of compound 14 are ^{as follows: 1} H NMR (600MHz, Chloroform-d) δ 8.22(s, 1H), 8.17(d, 2H), 7.29(d, 2H), 5.41(s, 2H) ),3.07--2.98(m,1H),1.55(s,6H).LC-MS(m/z,ESI): 388.4(MH).

Example 5: Preparation of Compound 15

Referring to the synthesis method of Example 2, compound 15 (brown oil) was prepared. ^{The 1} H NMR data of compound 15 are as follows:

¹ H NMR (600MHz, Chloroform-d) δ 8.26 (s, 1H), 8.17 (d, 2H), 7.30 (d, 2H), 5.40 (s, 2H), 2.63 (t, 2H), 1.77-1.67 (m,2H),1.42-1.32(m,2H),0.93(t,3H).

Example 6: Preparation of compound 16

According to the synthesis method of Example 2, compound 16 (yellow oil) was prepared. ^{The 1} H NMR data of compound 16 are as follows:

¹ H NMR(600MHz, Chloroform-d) δ8.46(s,1H), 8.17(d,2H), 7.35(d,2H), 5.49(s,2H), 1.90-1.83(m,1H), 1.31 –1.26(m,2H),1.16–1.10(m,2H).

Example 7: Preparation of Compound 19

(1) Synthesis of intermediate 2-cyclopropyl acetyl chloride

0.11 g (1.1 mmol) of cyclopropyl acetic acid was put into a 25 ml single-necked flask, 15 ml of thionyl chloride was added, and the reaction was heated and refluxed for 3 hours. After cooling to room temperature, it was directly used in the next reaction after desolving under reduced pressure.

(2) Synthesis of compound 19

In a 25ml reaction flask, add 2-cyclopropylacetyl chloride prepared in the previous step, 15ml dichloromethane, 0.30g (0.94mmol) N-(4-(5-(trifluoromethyl)-1,2,4 -Oxadiazol-3-yl)phenyl)carbonyldicyanamide, 0.19g (1.88mmol) of triethylamine, stirred and reacted at room temperature. After the reaction was monitored by TLC, the solvent was removed under reduced pressure, and the residue was column chromatographed to obtain 0.31 g of the target product as a yellow oil. ^{The 1} H NMR data of compound 19 are as follows:

¹ H NMR(600MHz,DMSO-d ₆ )δ9.31(s,1H),8.00(d,2H),7.44(d,2H),4.86(s,2H),2.81(d,2H),1.07-- 0.97 (m, 1H), 0.52-0.46 (m, 2H), 0.17-0.11 (m, 2H).

Example 8: Preparation of Compound 22

According to the synthesis method of Example 2, compound 22 (yellow solid) was prepared. ^{The 1} H NMR and liquid quality data of compound 22 are ^{as follows: 1} H NMR (600MHz, DMSO-d ₆ )δ8.39(s,1H), 8.06(d,2H),7.46(d,2H),5.31(s, 2H), 4.74(s, 2H), 3.34(s, 3H). LC-MS(m/z, ESI): 390.4(MH).

Example 9: Preparation of Compound 34

Refer to the synthesis method of Example 2 to prepare compound 34 (white solid). ^{The 1} H NMR and liquid quality data of compound 34 are ^{as follows: 1} H NMR (600MHz, DMSO-d ₆ ) δ 8.20 (s, 1H), 8.09 (d, 2H), 7.63 (d, 2H), 4.95 (s, 2H), 2.81(s, 6H).LC-MS(m/z,ESI): 389.2(MH).

Example 10: Preparation of Compound 35

Put 1g (3.58mmol) (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)methylamine hydrochloride into a 50ml single-necked flask, add 20ml Dichloromethane and shake until well mixed, add 0.37g (3.66mmol) triethylamine, 0.61g (3.59mmol) 2-(bis(methylthio)methylene)malononitrile (refer to Organic Process Research&Development, 15 (3), 556-564; prepared by the method reported in 2011), the reaction was stirred at room temperature. After the reaction was monitored by TLC, the solvent was removed under reduced pressure, and the residue was subjected to column chromatography to obtain 1.09 g of the target product as a yellow solid. ^{The 1} H NMR data of compound 35 are as follows:

¹ H NMR (600MHz, DMSO-d ₆ ) δ9.31 (s, 1H), 8.09 (d, 2H), 7.56 (d, 2H), 4.84 (s, 2H), 2.63 (s, 3H).

Example 11: Preparation of Compound 50

According to the synthesis method of Example 7, compound 50 (yellow oil) was prepared. ^{The 1} H NMR and liquid quality data of compound 50 are as follows:

¹ H NMR(600MHz,DMSO-d ₆ )δ8.06(d,2H), 7.62(d,2H), 4.97(s,2H), 2.57(s,3H), 2.03-1.95(m,1H), 1.03-0.94(m,4H).LC-MS(m/z,ESI): 434.1(M+H).

Example 12: Preparation of Compound 53

According to the synthesis method of Example 7, compound 53 (yellow oil) was prepared. ^{The 1} H NMR and liquid quality data of compound 53 are as follows:

¹ H NMR(600MHz,DMSO-d ₆ )δ8.07(d,2H), 7.64(d,2H), 4.94(s,2H), 2.53(s,3H), 2.48(d,2H), 1.09-- 1.00(m,1H),0.54-0.46(m,2H),0.22-0.16(m,2H).LC-MS(m/z,ESI): 448.2(M+H).

Example 13: Preparation of Compound 56

According to the synthesis method of Example 7, compound 56 (yellow oil) was prepared. ^{The 1} H NMR and liquid quality data of compound 56 are as follows:

¹ H NMR(600MHz,DMSO-d ₆ )δ8.07(d,2H), 7.64(d,2H), 4.93(s,2H), 4.30(s,2H), 3.34(s,3H), 2.56( s,3H).LC-MS(m/z,ESI): 438.1(M+H).

Example 14: Preparation of Compound 69

(1) Synthesis of intermediate 2-(1-methoxyethylene)malononitrile

Put 1g (0.015mol) of malononitrile into a 50ml single-necked flask, add 1.91g (0.016mol) of trimethyl orthoacetate, raise the temperature to 95°C and stir the reaction, and stop the reaction after 1.5 hours. After cooling to room temperature, it was directly used in the next reaction after desolving under reduced pressure.

(2) Synthesis of compound 69

Add 1g (3.58mmol) (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)methylamine hydrochloride, 30ml ethanol and 0.44g (4.36mmol) of triethylamine was added to the 2-(1-methoxyethylene)malononitrile (0.52g, 4.26mmol) prepared in the previous step, and the reaction was stirred at a temperature of 40°C. After the reaction was monitored by TLC, the solvent was removed under reduced pressure, and the residue was column chromatographed to obtain 0.97 g of the target product as a white solid. ^{The 1} H NMR and liquid quality data of compound 69 are as follows:

¹ H NMR (600MHz, Chloroform-d) δ 8.18 (d, 2H), 7.41 (d, 2H), 6.92 (s, 1H), 4.61 (d, 2H), 2.28 (s, 3H).LC-MS (m/z, ESI): 332.1(MH).

Example 15: Preparation of Compound 103

Add 0.1g (0.27mmol) 2-((methylthio)((4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl) into a 25ml single-mouth bottle Amino)methylene)malononitrile, 15ml of ethanol, 0.4g (2.86mmol) of ammonia (25% solution), heated and refluxed for reaction. After the reaction was monitored by TLC, the solvent was removed under reduced pressure, and the residue was subjected to column chromatography to obtain 0.07 g of the target product as a white solid. ^{The 1} H NMR and liquid quality data of compound 103 are as follows:

¹ H NMR (600MHz, Chloroform-d) δ 8.20 (d, 2H), 7.48 (d, 2H), 6.03 (s, 1H), 5.15 (br s, 2H), 4.57 (d, 2H).LC- MS(m/z, ESI): 333.2(MH).

Example 16: Preparation of Compound 137

Add 0.5g (2.18mmol) 4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)aniline, 0.32g (2.62mmol) ethoxymethylenemalononitrile (Prepared with reference to the method reported in WO2018005192) and 20ml of ethanol, heated and refluxed and stirred for reaction. After the reaction was monitored by TLC, the solvent was removed under reduced pressure, and the residue was column chromatographed to obtain 0.12 g of the target product as a white solid. ^{The 1} H NMR data of compound 137 are as follows:

¹ H NMR (600MHz, DMSO-d ₆ ) δ 10.58 (s, 1H), 8.37 (d, 1H), 8.03 (d, 2H), 7.82 (d, 2H).

Example 17: Preparation of Compound 171

Add 0.1g (0.44mmol) 4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)aniline, 0.11g (0.65mmol) 2-(bis(methylthio) Methylene) malononitrile and 15 ml of ethanol are heated and refluxed for reaction. After the reaction was monitored by TLC, the solvent was removed under reduced pressure, and 0.12 g of the target yellow oily substance was obtained after column chromatography of the residue. ^{The 1} H NMR data of compound 171 are as follows:

¹ H NMR (600MHz, DMSO-d ₆ ) δ 10.80 (s, 1H), 8.11 (d, 2H), 7.52 (d, 2H), 2.57 (s, 3H).

Biological activity determination

Example 18: Determination of the control effect on plant bacterial diseases

The compound of the present invention has been used for the prevention and control of various plant bacterial diseases. For different bacterial diseases, the test procedure is as follows:

Melon fruit spot disease: Dissolve the test compound with a small amount of N,N dimethylformamide and dilute with water to the required concentration. The pathogenic bacteria cultivated to the stable growth stage are mixed with the quantitative compound solution uniformly, the melon seeds that have been germinated are soaked in the mixture of the bacterial solution and the compound for half an hour, and then the seeds are sown in the earthworm soil culture cup and placed in the greenhouse Medium moisturizing culture, usually culture for two weeks, after the control has fully developed the disease, the control effect investigation will be carried out.

Chinese cabbage soft rot: Cut 2 cm square cabbage leaves and put them in a glass petri dish lined with double-layer filter paper. The compound dissolved in N,N dimethylformamide and diluted with water to the required concentration is sprayed on the surface of the cabbage leaves. After drying the liquid on the surface of the cabbage leaves in a fume hood, the inoculation needle is used to acupuncture the surface of the cabbage leaves. For the wound, 5 microliters of soft rot fungus of Chinese cabbage cultivated to a stable growth period is added to the wound for inoculation. Finally, the test materials were placed in an incubator for 48 hours in the dark, and the control effect was investigated after the control had fully developed disease.

Cucumber bacterial angular leaf spot, tomato bacterial leaf spot, rice bacterial leaf spot, rice bacterial leaf blight: dissolve the test compound with a small amount of N,N dimethylformamide and dilute with water to the required concentration . The compound is sprayed on the surface of the plant test material, and after the surface drug solution is air-dried in a cool place, the pathogenic bacteria liquid cultured to a stable growth stage is sprayed on the surface of the plant test material, and then the plant test material is placed in a greenhouse for moisturizing culture. It is usually cultivated for about ten days, and after the control has fully developed the disease, the control effect investigation will be carried out.

Citrus canker disease: The experiment was set up with treatments and controls. Each treatment was repeated 10 times, and each repeated 1 leaf. The inoculation needle was used to create 8-10 acupuncture points on the detached citrus leaf; (I.e., dissolve the test compound with a small amount of N,N dimethylformamide) after diluting to the required concentration, apply foliar spray to the detached citrus leaves, and then inoculate the pathogenic bacteria. After the treatment is completed, place it in a 90mm petri dish (use an appropriate amount) Sterile water-moistened absorbent paper, placed on the bottom of the petri dish for moisturizing), cultured in a thermostat at 28°C, 7 days later, observed and recorded the in vitro incidence of citrus canker, and investigated the prevention effect. Control effect (%)=(control acupuncture incidence points-treatment acupuncture incidence points)/control acupuncture incidence points×100%.

The test results are as follows:

At 600mg/L, compounds 1, 12, 13, 14, 15, 16, 19, 22, 34, 35, 50, 53, 56, 69, 103, 137, and 171 are not ineffective against melon fruit spot disease Less than 90%.

At 400 mg/L, compounds 1, 12, 13, 14, 15, 16, 19, 22, 34, 35, 50, 53, 56, 69, 103, 137, and 171 have an effect on cucumber bacterial angular leaf spot and rice bacterial The control effect of leaf spot, rice bacterial leaf blight, soft rot of Chinese cabbage and tomato bacterial leaf spot is not less than 90%.

At 100mg/L, compound 1, 12, 13, 14, 15, 16, 19, 22, 34, 35, 50, 53, 56, 69, 103, 137, and 171 have no less than 90 preventive effects against citrus canker. %.

Example 19: Determination of bactericidal activity against soybean rust

Protective activity test method: The method of in vivo potting is adopted, that is, a small amount of solvent is used for the sample of the compound to be tested (the type of solvent is acetone, methanol, DMF, etc., and it is selected according to its ability to dissolve the sample. The volume of the solvent and the spray volume The ratio is equal to or less than 0.05) to dissolve, dilute with water containing 0.1% Tween 80 to prepare the test solution of the required concentration, and set a solvent clear water solution as a blank control. On a crop sprayer, spray the test solution on the diseased host plants (the host plants are standard potted seedlings cultivated in the greenhouse), and then inoculate the disease 24 hours later. According to the characteristics of the disease, the diseased plants that need temperature control and moisturizing culture are inoculated and cultured in an artificial climate room. After the disease is infested, they are moved to the greenhouse for cultivation; the diseased plants that do not need moisturizing culture are directly inoculated and cultivated in the greenhouse. After the control is fully onset (usually one week), the compound's disease prevention effect will be evaluated.

The in vivo protective activities against soybean rust are as follows:

When the concentration of the drug solution is 100 mg/L, the effects of compounds 1, 12, 13, 14, 15, 16, 19, 22, 34, 35, 50, 53, 56, 69, 103, 137, and 171 on soybean rust Not less than 90%;

When the concentration of the drug solution is 25 mg/L, the control effect of compound 1, 12, 13, 14, 15, 16, 19, 22, 34, 35, 50, 56, 69, 103, 171 against soybean rust is not less than 90 %;

When the concentration of the drug solution is 6.25 mg/L, the control effect of compounds 1, 12, 13, 14, 16, 22, 34, 35, 50, 56, 69 on soybean rust is not less than 90%;

When the concentration of the liquid medicine is 3.125 mg/L, the control effect of compound 1, 16, 22, 34 on soybean rust is not less than 90%;

When the concentration of the drug solution is 0.39 mg/L, the control effect of compounds 16 and 22 on soybean rust is not less than 90%.

Claims (13)

1. An oxadiazole compound, characterized in that: the compound is represented by general formula I:

   

   Where:

   R _{1 is} selected from hydrogen, hydroxyl, mercapto, amino, cyano, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkane Oxy, C ₁ -C ₆ alkylthio, halogenated C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylamino or C ₁ -C ₆ dialkylamino;

   R _{2 is} selected from hydrogen, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylcarbonyl, C ₃ -C ₆ cycloalkylcarbonyl, C ₃ -C ₆ cycloalkane C ₁ -C ₃ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkoxy C ₁ -C ₃ alkylcarbonyl, C ₁ -C ₆ alkylthio C ₁ -C ₃ Alkylcarbonyl, C ₁ -C ₆ alkylaminocarbonyl or C ₁ -C ₆ dialkylaminocarbonyl;

   X ₁ and X ₂ are each independently selected from hydrogen, halogen or C ₁ -C ₆ alkyl;

   n is selected from 0 or 1;

   Or a salt of a compound of general formula I.
2. The compound according to claim 1, characterized in that: in the general formula I

   R _{1 is} selected from hydrogen, hydroxyl, mercapto, amino, cyano, C ₁ -C ₃ alkyl, halo C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halo C ₁ -C ₃ alkane Oxy, C ₁ -C ₃ alkylthio, halogenated C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylamino or C ₁ -C ₃ dialkylamino;

   R _{2 is} selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₄ cycloalkylcarbonyl, C ₃ -C ₄ cycloalkane C ₁ -C ₂ alkylcarbonyl, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkoxy C ₁ -C ₂ alkylcarbonyl, C ₁ -C ₄ alkylthio C ₁ -C ₂ Alkylcarbonyl, C ₁ -C ₄ alkylaminocarbonyl or C ₁ -C ₄ dialkylaminocarbonyl;

   X ₁ and X ₂ are each independently selected from hydrogen, fluorine or methyl;

   n is selected from 0 or 1;

   Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
3. The compound according to claim 2, characterized in that: in the general formula I

   R _{1 is} selected from hydrogen, hydroxyl, mercapto, amino, cyano, C ₁ -C ₃ alkyl, halo C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halo C ₁ -C ₃ alkane Oxy, C ₁ -C ₃ alkylthio, halogenated C ₁ -C ₃ alkylthio, C ₁ -C ₃ alkylamino or C ₁ -C ₃ dialkylamino;

   R _{2 is} selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₄ cycloalkylcarbonyl, 2-(C ₃ -C ₄ cycloalkyl) acetyl, C ₁ -C ₄ alkoxycarbonyl, 2-(C ₁ -C ₄ alkoxy)acetyl, 2-(C ₁ -C ₄ alkylthio)acetyl, C ₁ -C ₄ alkylaminocarbonyl or C ₁ -C ₄ dialkylaminocarbonyl;

   X ₁ and X _{2 are} selected from hydrogen, fluorine or methyl;

   n is selected from 0 or 1;

   Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
4. The compound according to claim 3, characterized in that: in the general formula I

   R _{1 is} selected from hydrogen, amino, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy or C ₁ -C ₃ alkylthio;

   R _{2 is} selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₄ cycloalkylcarbonyl, 2-(C ₃ -C ₄ -cycloalkyl)acetyl, 2-(C ₁ -C ₄ alkoxy)acetyl or C ₁ -C ₄ dialkylaminocarbonyl;

   X ₁ and X _{2 are} selected from hydrogen;

   n is selected from 0 or 1;

   Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
5. The compound according to claim 4, characterized in that: in the general formula I

   R _{1 is} selected from hydrogen;

   R _{2 is} selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₄ cycloalkylcarbonyl, 2-(C ₃ -C ₄ -cycloalkyl)acetyl, 2-(C ₁ -C ₄ alkoxy)acetyl or C ₁ -C ₄ dialkylaminocarbonyl;

   X ₁ and X _{2 are} selected from hydrogen;

   n is selected from 0 or 1;

   Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
6. The compound according to claim 5, characterized in that: in the general formula I

   R _{1 is} selected from hydrogen;

   R _{2 is} selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₄ cycloalkylcarbonyl, 2-(C ₃ -C ₄ -cycloalkyl)acetyl, 2-(C ₁ -C ₄ alkoxy)acetyl or C ₁ -C ₄ dialkylaminocarbonyl;

   X ₁ and X _{2 are} selected from hydrogen;

   n is selected from 0;

   Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
7. The compound according to claim 4, characterized in that: in the general formula I

   R _{1 is} selected from hydrogen, amino, C ₁ -C ₃ alkyl or C ₁ -C ₃ alkylthio;

   R _{2 is} selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₄ cycloalkylcarbonyl, 2-(C ₃ -C ₄ -cycloalkyl)acetyl, 2-(C ₁ -C ₄ alkoxy)acetyl or C ₁ -C ₄ dialkylaminocarbonyl;

   X ₁ and X _{2 are} selected from hydrogen;

   n is selected from 1;

   Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
8. The compound according to claim 3, characterized in that: in the general formula I

   R _{1 is} selected from hydrogen, hydroxyl, mercapto, amino, cyano, methyl, ethyl, n-propyl, isopropyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoro Methoxy, methylthio, ethylthio, trifluoroethylthio, methylamino, ethylamino or N,N-dimethylamino;

   R _{2 is} selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, trifluoromethyl, acetyl, propionyl, n-butyryl , Isobutyryl, n-valeryl, cyclopropylcarbonyl, 1-cyanocyclopropyl-1-carbonyl, cyclobutylcarbonyl, 2-cyclopropylacetyl, methoxycarbonyl, ethoxycarbonyl, 2 -Methoxyacetyl, 2-ethoxyacetyl, 2-n-propoxyacetyl, 2-isopropoxyacetyl, 2-n-butoxyacetyl, 2-sec-butoxyacetyl , 2-isobutoxyacetyl, 2-tert-butoxyacetyl, 2-methylthioacetyl, 2-ethylthioacetyl, N-methylaminocarbonyl, N-ethylaminocarbonyl or N ,N-Dimethylaminocarbonyl;

   X ₁ and X _{2 are} selected from hydrogen, fluorine or methyl;

   n is selected from 0 or 1;

   Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
9. A use of the compound of general formula I according to claim 1 as a bactericide in the fields of agriculture, forestry or sanitation.
10. The use of the compound of general formula I according to claim 9 for controlling plant bacterial diseases, characterized in that: the plant bacterial diseases are fruit spot, leaf spot, bacterial wilt, bacterial blight, ulcer disease , Soft rot, bacterial angular leaf spot, bacterial leaf streak, leaf blight, bacterial leaf blight, wildfire or bacterial scab.
11. A use of the compound of general formula I according to claim 1 as a fungicide in the fields of agriculture, forestry or sanitation.
12. A bactericidal composition, characterized in that the composition contains the compound of general formula I according to claim 1 and an agriculturally acceptable carrier, and the weight percentage of the active component in the composition is 0.1-99%.
13. A method for preventing and controlling pathogens, which is characterized in that: applying a bactericidal effective dose of the bactericidal composition according to claim 12 to the crop or the growth medium or location of the crop.