CN111484429B - Malononitrile compound and application thereof - Google Patents
Malononitrile compound and application thereof Download PDFInfo
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Abstract
The invention discloses a malononitrile compound with a novel structure, the structure is shown as a general formula I, and definition of each substituent group in the formula is shown in the specification.
Description
Technical Field
The present invention belongs to the field of agricultural bactericide. In particular to a malononitrile compound and application thereof.
Background
Bacterial diseases become the second most common diseases which are second to fungal diseases in agricultural production in China, and according to incomplete statistics, the current occurrence area of bacterial diseases in China is 1.2 hundred million mu, and the market capacity for preventing and controlling bacterial diseases exceeds 20 hundred million yuan. In the current agricultural production, the agents for preventing and treating bacterial diseases mainly comprise copper preparations (including organic or inorganic copper preparations) with larger dosage and antibiotic products; the copper preparation has low prevention effect and a large amount of heavy metals are sprayed into the environment, so that pollution is formed to soil, water and food, and the safety worry of the environment and the food is caused; on the other hand, the use of antibiotics in large amounts may cause the human pathogenic bacteria to develop resistance to medical antibiotics. The other agricultural bacteria can be used for the treatment of a small number of varieties, the actual production is doubly limited by resistance and prevention effect, and the popularization area is small. Therefore, the development of novel, efficient, low-toxic, and environmentally friendly bacterial disease control agents is very necessary and urgent.
In the prior art, the malononitrile compounds shown in the invention and the bactericidal activity thereof are not reported.
Disclosure of Invention
The invention aims to provide a malononitrile compound with a novel structure and application thereof as a bactericide in the fields of agriculture, forestry or sanitation.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a malononitrile compound, which is shown in a general formula I:
wherein:
X 1 、X 2 、X 3 、X 4 、X 5 each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio, halo C 1 -C 6 Alkylthio, C 1 -C 6 Alkylamino, C 1 -C 6 Dialkylamino, C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Alkoxycarbonyl, -nhch=c (CN) 2 or-CH 2 NHCH=C(CN) 2 ；
R 1 Selected from hydrogen, hydroxy, mercapto, amino, cyano、C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio, halo C 1 -C 6 Alkylthio, C 1 -C 6 Alkylamino or C 1 -C 6 A dialkylamino group;
R 2 selected from hydrogen, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, cyano C 1 -C 6 Alkyl, C 1 -C 6 Alkylcarbonyl, C 3 -C 6 Cycloalkyl carbonyl or C 1 -C 6 An alkoxycarbonyl group;
however, when R 1 、R 2 X is selected from hydrogen 1 、X 2 、X 3 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 、R 2 、X 1 、X 2 、X 4 、X 5 X is selected from hydrogen 3 Not selected from methyl, N-dimethylamino, methoxy, methylthio, or isopropoxy; alternatively, when R 1 、R 2 、X 2 、X 3 、X 4 、X 5 X is selected from hydrogen 1 Not selected from hydrogen; alternatively, when R 1 、R 2 、X 2 、X 4 、X 5 X is selected from hydrogen 1 、X 3 Not selected from chlorine; alternatively, when R 1 、R 2 Selected from hydrogen, X 2 Selected from methoxy, X 3 X is selected from n-propoxy 1 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 、R 2 Selected from hydrogen, X 2 Selected from methoxy, X 3 X is selected from n-butoxy 1 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 、R 2 Selected from hydrogen, X 2 Selected from methoxy, X 3 X is selected from isopentyloxy 1 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 、R 2 Selected from hydrogen, X 1 Selected from chlorine, X 3 、X 4 When selected from methoxy, X 2 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from the group consisting of armorThio, R 2 X is selected from hydrogen 1 、X 2 、X 3 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from methylthio radicals, R 2 、X 1 、X 2 、X 4 、X 5 X is selected from hydrogen 3 Not selected from amino, methoxy, fluoro or chloro; alternatively, when R 1 Selected from methylthio radicals, R 2 、X 1 、X 3 、X 4 、X 5 X is selected from hydrogen 2 Not selected from methyl or methoxy; alternatively, when R 1 Selected from methylthio radicals, R 2 Selected from hydrogen, X 1 、X 3 X is selected from chlorine 2 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from methylthio radicals, R 2 Selected from hydrogen, X 2 、X 3 When selected from methoxy, X 1 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from methylthio radicals, R 2 Selected from hydrogen, X 2 、X 4 X is selected from trifluoromethyl 1 、X 3 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from methylthio radicals, R 2 When selected from methyl, X 1 、X 2 、X 3 、X 4 、X 5 Not selected from hydrogen; or when X 1 、X 2 、X 3 、X 4 、X 5 、R 2 R is selected from hydrogen 1 Not selected from methyl, amino, cyano or mercapto; alternatively, when R 1 Selected from amino, R 2 Selected from hydrogen, X 3 When selected from methoxy, X 1 、X 2 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from amino, R 2 Selected from hydrogen, X 1 X is selected from chlorine 2 、X 3 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from amino, R 2 When selected from ethyl, X 1 、X 2 、X 3 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from methyl, R 2 Selected from hydrogen, X 3 X is selected from chlorine 1 、X 2 、X 4 、X 5 Not selected from hydrogen;or when X 1 、X 2 、X 3 、X 4 、X 5 、R 1 R is selected from hydrogen 2 Is not selected from cyanoethyl;
or salts of compounds of formula I.
Preferred compounds of the invention are: in the general formula I, the components are shown in the specification,
X 1 、X 2 、X 3 、X 4 、X 5 each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy, C 1 -C 4 Alkylthio, halo C 1 -C 4 Alkylthio, C 1 -C 4 Alkylamino, C 1 -C 4 Dialkylamino, C 1 -C 4 Alkylcarbonyl, C 1 -C 4 Alkoxycarbonyl, -nhch=c (CN) 2 or-CH 2 NHCH=C(CN) 2 ；
R 1 Selected from hydrogen, hydroxy, mercapto, amino, cyano, C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy, C 1 -C 4 Alkylthio, halo C 1 -C 4 Alkylthio, C 1 -C 4 Alkylamino or C 1 -C 4 A dialkylamino group;
R 2 selected from hydrogen, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, cyano C 1 -C 4 Alkyl, C 1 -C 4 Alkylcarbonyl, C 3 -C 6 Cycloalkyl carbonyl or C 1 -C 4 An alkoxycarbonyl group;
or salts of compounds of the general formula I with 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, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
Further preferred compounds in the present invention are: in the general formula I, the components are shown in the specification,
X 1 、X 2 、X 3 、X 4 、X 5 each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, hydroxy, mercapto, amino, carboxy, methyl, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, trifluoromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2, 2-trifluoroethyl, heptafluoroisopropyl, methoxy, ethoxy, N-propoxy, isopropoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, trifluoromethylthio, 2,2, 2-trifluoroethylthio, methylamino, ethylamino, N-dimethylamino, -nhch=c (CN) 2 or-CH 2 NHCH=C(CN) 2 ；
R 1 Selected from hydrogen, hydroxy, mercapto, amino, cyano, methyl, ethyl, n-propyl, n-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, methylthio, ethylthio, n-propylthio, n-butylthio, methylamino, ethylamino, n-propylamino or n-butylamino;
R 2 selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyanomethyl, 2,2, 2-trifluoroethyl, acetyl, n-propionyl, cyclopropylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl;
or salts of compounds of the general formula I with 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, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
Still further preferred compounds of the present invention are: in the general formula I, the components are shown in the specification,
X 1 、X 2 、X 3 、X 4 、X 5 each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, hydroxy, mercapto, amino, carboxyl, methyl, ethyl, n-propylGroup, isopropyl group, N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, trifluoromethyl group, methoxy group, ethoxy group, trifluoromethoxy group, methylthio group, methylamino group, N-dimethylamino group, -nhch=c (CN) 2 or-CH 2 NHCH=C(CN) 2 ；
R 1 Selected from hydrogen, amino, methyl, methoxy, ethoxy, methylthio, ethylthio, methylamino or ethylamino;
R 2 selected from hydrogen, methyl, ethyl, 2,2, 2-trifluoroethyl, cyanomethyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl or ethoxycarbonyl;
or salts of compounds of the general formula I with 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, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
In the definitions of the compounds of the general formula given above, the terms used in the collection generally represent the following substituents:
halogen: refers to fluorine, chlorine, bromine or iodine.
Alkyl: straight or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl or different butyl, pentyl or hexyl isomers, etc.
Haloalkyl: straight or branched alkyl groups, the hydrogen atoms on these alkyl groups may be partially or fully substituted by halogen, such as monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2, 2-trifluoroethyl, heptafluoroisopropyl and the like.
Cyanoalkyl: straight-chain or branched alkyl groups, the hydrogen atoms on these alkyl groups may be partially or completely substituted by cyano groups,
for example cyanomethyl (CNCH) 2 (-), cyanoethyl (CNCH) 2 CH 2 -)、CNCH 2 CH 2 CH 2 -、CNCH 2 CH 2 CH 2 CH 2 -and the like.
An alkoxy group: a linear or branched alkyl group linked to the structure via an oxygen atom bond, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy and the like.
Haloalkoxy: straight-chain or branched alkoxy groups, the hydrogen atoms on these alkoxy groups may be partially or completely substituted by halogen, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, 2,2, 2-trifluoroethoxy and the like.
Alkylthio: a linear or branched alkyl group linked to the structure via a sulfur atom bond, such as methylthio, ethylthio, and the like.
Haloalkylthio: straight-chain or branched alkylthio groups, the hydrogen atoms on these alkylthio groups may be partially or wholly substituted with halogen, for example difluoromethylthio, trifluoromethylthio, 2,2, 2-trifluoroethylthio and the like.
Alkylamino: a linear or branched alkyl group linked to the structure via a nitrogen atom bond, such as methylamino, ethylamino, n-propylamino, isopropylamino or isomerised butylamine.
Dialkylamino group: two identical or different linear or branched alkyl groups are bonded to the structure via a nitrogen atom bond, such as N, N-dimethylamino, N-methyl-N-ethylamino, etc.
Alkylcarbonyl: the alkyl group is attached to the structure via a carbonyl group, such as acetyl (CH 3 CO-), n-propionyl (CH 3CH2 CO-), and the like.
Cycloalkyl carbonyl: cycloalkyl groups are attached to the structure via a carbonyl group, such as cyclopropylformyl.
Alkoxycarbonyl: alkyl-O-CO-, e.g. methoxycarbonyl (CH) 3 OCO-), ethoxycarbonyl (CH) 3 CH 2 OCO-), n-propoxycarbonyl (CH) 3 CH 2 CH 2 OCO-), n-butoxycarbonyl group (CH) 3 CH 2 CH 2 CH 2 OCO-) and the like.
Some of the compounds of the general formula I according to the invention are shown in Table 1, but the invention is by no means limited to these compounds.
TABLE 1
The physicochemical properties of the specific compounds listed in table 1 and their nuclear magnetic data and mass spectrum data are shown in table 2:
TABLE 2
The compounds of the general formula I according to the invention can be prepared in the following manner (in which the radicals are as defined above, unless otherwise indicated):
method 1: when R is 1 Is hydrogen or C 1 -C 6 In the case of alkyl groups, the compounds of the formula I can be prepared in the following manner (in the formula, alkoxyl represents C) 1 -C 6 Alkoxy groups such as methoxy, ethoxy, etc.):
the compound of the general formula II-1 reacts with the compound of the general formula III-1 in a proper solvent at the temperature of-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours to prepare the compound of the general formula I-1; the reaction may be carried out in the presence of a base.
The compound of the general formula I-1 is reacted with an alkylating reagent (such as methyl iodide, ethyl iodide, propyl iodide, dimethyl sulfate, diethyl sulfate, 2,2, 2-trifluoro-ethyl iodide, chloroacetonitrile, bromoacetonitrile and the like) or an acylating reagent (such as acetyl chloride, n-propionyl chloride, acetic anhydride, cyclopropylcarbonyl chloride, methyl chloroformate, ethyl chloroformate and the like) in a proper solvent at a temperature ranging from-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours to obtain the compound of the general formula I-2; the reaction may be carried out in the presence of a base.
Suitable solvents in the above reaction may be the same or different, and may 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, methylene chloride, 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-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc.), or a mixed solvent of the above solvents. The bases may be the same or different, and may be organic bases such as trimethylamine, triethylamine, pyridine, DBU, 4-dimethylaminopyridine (e.g., 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 (e.g., sodium carbonate, potassium carbonate, etc.), alkali metal bicarbonates (e.g., sodium bicarbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium t-butoxide, sodium t-butoxide, etc.).
Method 2: when R is 1 Is C 1 -C 6 Alkylthio or halogen C 1 -C 6 In the case of alkylthio groups, the compounds of the formula I can be prepared in the following manner (wherein A represents C 1 -C 6 Alkyl or halo C 1 -C 6 Alkyl):
the compound of the general formula II-2 reacts with the compound of the general formula III-1 in a proper solvent at the temperature of-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours to prepare the compound of the general formula I-3; in the reaction, the compound of the general formula II-2 is that of the general formula III-1 which is more than or equal to 1:1 (molar ratio); the reaction may be carried out in the presence of a base.
The process for preparing the compounds of the formula I-4 from the compounds of the formula I-3 is identical to the process for preparing the compounds of the formula I-2 from the compounds of the formula I-1.
Suitable solvents in the above reaction may be the same or different, and may 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, methylene chloride, 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-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc.), or a mixed solvent of the above solvents. The bases may be the same or different, and may be organic bases such as trimethylamine, triethylamine, pyridine, DBU, 4-dimethylaminopyridine (e.g., 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 (e.g., sodium carbonate, potassium carbonate, etc.), alkali metal bicarbonates (e.g., sodium bicarbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium t-butoxide, sodium t-butoxide, etc.).
Method 3: when R is 1 Is hydroxy, mercapto, amino or C 1 -C 6 In the case of alkylamino, the compounds of formula I can be prepared as follows:
reacting a compound of the general formula I-3 with a nucleophile in a suitable solvent at a temperature from-10 ℃ to the boiling point of the solvent for 0.5-48 hours to obtain a compound of the general formula I-5; the compound of formula I-4 is reacted with a nucleophile in a suitable solvent at a temperature from-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours to produce the compound of formula I-6.
In the above reaction, the nucleophilic reagent is sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrosulfide, sodium amide, ammonia water, C 1 -C 6 Alkyl ammonia (such as methylamine, ethylamine, etc.) or its hydrochloride (such as methylamine hydrochloride, ethylamine hydrochloride, etc.).
In the above reaction, when the nucleophilic reagent is C 1 -C 6 In the case of alkylaminohydrochlorides, the reaction requires a suitable base to neutralize the hydrochloride salt, preferably trimethylamine, triethylamine, pyridine, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and the like.
Suitable solvents in the above reaction may be the same or different, and may 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, methylene chloride, 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-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc.), or a mixed solvent of the above solvents.
Method 4: when R is 1 Is cyano, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy or C 1 -C 6 In the case of dialkylamino groups, the compounds of formula I can be prepared as follows:
reacting a compound of the general formula I-3 with a nucleophile in a suitable solvent at a temperature from-10 ℃ to the boiling point of the solvent for 0.5-48 hours to obtain a compound of the general formula I-7; the compound of formula I-4 is reacted with a nucleophile in a suitable solvent at a temperature from-10 ℃ to the boiling point of the solvent for 0.5 to 48 hours to produce the compound of formula I-8.
In the above reactionThe nucleophilic reagent is sodium cyanide, potassium cyanide, C 1 -C 6 Alkali metal salts of alkanols (e.g., sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc.), haloC 1 -C 6 Alkali metal salts of alkanols (e.g. sodium 2,2, 2-trifluoroethanol or potassium 2,2, 2-trifluoroethanol), C 1 -C 6 Dialkyl ammonia (e.g., N-dimethyl ammonia, N-methyl-N-ethyl ammonia, etc.) or its hydrochloride (e.g., N-dimethyl ammonia hydrochloride, N-methyl-N-ethyl ammonia hydrochloride, etc.).
In the above reaction, when the nucleophilic reagent is C 1 -C 6 In the case of the dialkylamine hydrochloride, a suitable base is required for the reaction to neutralize the hydrochloride, and suitable bases are preferably trimethylamine, triethylamine, pyridine, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate and the like.
Suitable solvents in the above reaction may be the same or different, and may 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, methylene chloride, 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-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc.), or a mixed solvent of the above solvents.
The process for preparing the compounds of the formula I-8 from the compounds of the formula I-7 is identical to the process for preparing the compounds of the formula I-2 from the compounds of the formula I-1.
Method 5: when R is 2 Is C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl or cyano C 1 -C 6 When alkyl, the compounds of formula I may be prepared as follows:
(1) When R is 1 Is hydrogen or C 1 -C 6 Alkyl group:
the compound of formula II-1 is reacted with the compound of formula III-2 to produce the compound of formula I-9.
The process for preparing the compounds of the formula I-9 from the compounds of the formula II-1 is identical to the process for preparing the compounds of the formula I-1 from the compounds of the formula II-1.
(2) When R is 1 Not hydrogen or C 1 -C 6 In the case of alkyl groups (where K represents hydroxy, mercapto, amino, cyano, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy, C 1 -C 6 Alkylamino or C 1 -C 6 Dialkylamino group):
the compound of formula II-2 is reacted with the compound of formula III-2 to produce the compound of formula I-10.
The method for preparing the compound of formula I-10 from the compound of formula II-2 is the same as the method for preparing the compound of formula I-3 from the compound of formula II-2.
The compounds of formula I-10 are reacted with nucleophiles to produce compounds of formula I-11.
The preparation of the compounds of the formula I-11 from the compounds of the formula I-10 is identical to the preparation of the compounds of the formula I-6 from the compounds of the formula I-4 or the preparation of the compounds of the formula I-8 from the compounds of the formula I-4.
Compounds of the general formula II-1 may be prepared by means of the methods described commercially or according to known methods (e.g.U.S. Pat. No. 3, 2503524, RSC Advances, 6 (29), 24491-24500; 2016, huaxue Shiji, 35 (9), 849-850; 2013, WO2010019637, WO2014139326, WO2004009602, WO2005117909, WO 2010086118).
Compounds of formula II-2 may be prepared by commercial or well-known methods (e.g. Organic Process Research & Development, 15 (3), 556-564; 2011, CN102001977, WO2018089786, journal of Enzyme Inhibition and Medicinal Chemistry, 28 (1), 163-171; 2013).
The compounds of formula III-1, compounds of formula III-2 and other starting materials and reagents may be prepared by purchase or by conventional methods.
The compounds of the general formula I according to the invention are used as bactericides in the agricultural, forestry or hygiene sector. Further, the compound can be used for controlling various plant bacterial diseases, such as fruit blotch (such as melon and fruit blotch, etc.), leaf blotch (such as tomato bacterial leaf blotch, etc.), bacterial wilt (such as tomato bacterial wilt, potato wilt, etc.), bacterial blight, ulcer disease (such as citrus canker, kiwi canker, etc.), soft rot (such as celery cabbage soft rot, etc.), bacterial angular blotch (such as cucumber bacterial angular blotch, etc.), bacterial leaf streak (such as rice bacterial leaf blotch, etc.), leaf blight, bacterial leaf blight (such as rice bacterial leaf blight, etc.), wildfire and bacterial scab, etc.
Detailed Description
The following specific examples serve to further illustrate the invention, but the invention is by no means limited to these examples. (the raw materials used are commercially available unless otherwise noted)
Synthetic examples
According to the synthetic route, the compounds shown in the general formula I of the invention can be prepared and obtained respectively by adopting different raw material compounds, and the following is further specifically described:
example 1: preparation of Compound 15
To a 50 ml reaction flask were added 3, 4-dichlorobenzylamine (0.30 g, 1.71 mmol), ethoxymethylenemalononitrile (0.22 g, 1.80 mmol) and 20 ml ethanol, and the reaction was stirred at room temperature, after completion of the TLC monitoring reaction, most of the ethanol was distilled off under reduced pressure, cooled, filtered to give a white solid of 0.42 g.
Example 2: preparation of Compound 19
To a 100 ml reaction flask were added 3, 4-dichlorobenzylamine (1.00 g, 5.71 mmol), 2- (1-ethoxyethylene) malononitrile (0.78 g, 5.73 mmol) and 50 ml ethanol, and after completion of the reaction, which was monitored by TLC, the reaction was refluxed at 80 c, most of the ethanol was distilled off under reduced pressure, cooled, filtered to give 1.36 g of a white solid.
Example 3: preparation of Compound 20
To a 50 ml reaction flask were added 2-methylbenzylamine (0.50 g, 4.13 mmol), 2- (bis (methylthio) methylene) malononitrile (0.71 g, 4.18 mmol) and 25 ml methanol, and after completion of the reaction, which was monitored by TLC under reflux at 65 c, most of the methanol was distilled off under reduced pressure, cooled, filtered to give a white solid of 0.90 g.
Raw material 2- (bis (methylthio) methylene) malononitrile may be prepared in a known manner, for example, as reported in reference to Organic Process Research & Development, 15 (3), 556-564, 2011.
Example 4: preparation of Compound 23
Compound 20 (0.50 g, 2.06 mmol), ammonia water (0.72 g, 20.55 mmol) and 100 ml ethanol were weighed into a 250 ml reaction flask, and after the reaction was monitored by TLC, the reaction was refluxed at 80 ℃, and after the reaction was completed, the solution was removed under reduced pressure, and column chromatography was performed to obtain 0.40 g of white solid.
Example 5: preparation of Compound 25
Compound 20 (0.50 g, 2.06 mmol), methylamine hydrochloride (0.69 g, 10.22 mmol), triethylamine 5 ml and 40 ml ethanol were weighed and placed in a 100 ml reaction flask, and after the reaction was monitored by TLC, reflux reaction was performed at 80 ℃, and after the reaction was completed, the solution was removed under reduced pressure and column chromatography was performed to obtain 0.47 g of white solid.
Example 6: preparation of Compound 28
Compound 20 (0.50 g, 2.06 mmol), sodium methoxide (0.56 g, 10.37 mmol), triethylamine 5 ml and 25 ml ethanol were weighed and placed in a 50 ml reaction flask, reflux reaction was performed at 80 ℃, after TLC monitoring, decompression desolventizing was performed, and column chromatography was performed to obtain 0.47 g of white solid.
Example 7: preparation of Compound 31
N-methylbenzylamine (1.00 g, 8.26 mmol), ethoxymethylenemalononitrile (1.01 g, 8.28 mmol) and 30 ml ethanol were added to a 50 ml reaction flask, and after the completion of the reaction, which was monitored by TLC under reflux at 80℃most of the ethanol was distilled off under reduced pressure, cooled, filtered to give 1.75 g of a white solid.
Example 8: preparation of Compound 32
Compound 15 (0.29 g, 1.16 mmol), bromoacetonitrile (0.14 g, 1.18 mmol), sodium hydride (0.04 g, 1.00 mmol) and 25 ml tetrahydrofuran were weighed into a 50 ml single-port bottle, stirred at room temperature for reaction, after TLC monitoring, the reaction was completed, desolventized under reduced pressure, and column chromatography gave a white solid of 0.13 g.
Example 9: preparation of Compound 33
Compound 15 (0.38 g, 1.51 mmol), cyclopropylcarbonyl chloride (0.16 g, 1.54 mmol) and 30 ml toluene were weighed into a 50 ml single vial and reacted at 110 ℃ under reflux, after TLC monitoring the reaction, the reaction was removed under reduced pressure and column chromatography to give 0.17 g of yellow solid.
Example 10: preparation of Compound 34
Compound 15 (0.45 g, 1.79 mmol), ethyl chloroformate (0.20 g, 1.89 mmol), sodium hydride (0.068 g, 1.70 mmol) and 25 ml tetrahydrofuran were weighed into a 50 ml single-port bottle, stirred at room temperature and reacted, after TLC monitoring the reaction, the reaction was performed under reduced pressure to remove the solvent, and column chromatography was performed to obtain 0.18 g of yellow solid.
Biological Activity assay
Example 11: determination of control Effect on plant bacterial diseases
The compound of the invention is used for controlling and measuring various plant bacterial diseases, and the test procedures are as follows:
the compound to be tested is dissolved with a small amount of N, N-dimethylformamide and diluted with water to the required concentration. Uniformly mixing pathogenic bacteria cultured to a stationary growth period with a quantitative compound solution, putting melon seeds subjected to germination acceleration into a mixed solution of a bacterial solution and the compound, soaking for half an hour, sowing the seeds into an earthworm soil culture cup, putting the earthworm soil culture cup into a greenhouse for moisture preservation and culture, generally culturing for two weeks, and carrying out control effect investigation after the seeds are fully developed by contrast.
Cutting 2 cm square leaf of Chinese cabbage, and placing into glass culture dish with double layers of filter paper. Dissolving with N, N dimethylformamide, diluting with water to desired concentration, spraying on the surface of leaf of Chinese cabbage, air drying the liquid medicine on the surface of leaf in a fume hood, needling to form wound on the surface of leaf with inoculating needle, inoculating 5 microliter of soft rot fungus of Chinese cabbage cultured to stationary growth phase into the wound, and inoculating. Finally, the test materials are placed into an incubator for light-shielding cultivation for 48 hours, and the control effect investigation is carried out after the contrast is fully developed.
The compound to be tested is dissolved by a small amount of N, N-dimethylformamide and diluted to the required concentration by water. Spraying the compound on the surface of a plant test material, air-drying the surface liquid medicine at a shade place, spraying and inoculating pathogenic bacteria bacterial liquid cultured to a stable growth period on the surface of the plant test material, and then placing the plant test material in a greenhouse for moisture preservation and culture. Usually, the culture is carried out for about ten days, and after the control is fully ill, the control effect investigation is carried out.
The test results were as follows:
600 At mg/L, the control effect of the compounds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33 and 34 on melon fruit blotches is 100%.
400 At mg/L, the control effect of the compounds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33 and 34 on bacterial angular leaf spot of cucumber, bacterial leaf streak of rice and bacterial leaf blight of rice is 100%.
400 At mg/L, the control effect of the compounds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33 and 34 on the cabbage soft rot and tomato bacterial leaf spot is 100%.
Claims (7)
1. A malononitrile compound, characterized in that: the compound is shown in a general formula I:
wherein:
X 1 、X 2 、X 3 、X 4 、X 5 each independently of the otherSelected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio, halo C 1 -C 6 Alkylthio, C 1 -C 6 Alkylamino, C 1 -C 6 Dialkylamino, C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Alkoxycarbonyl, -nhch=c (CN) 2 or-CH 2 NHCH＝C(CN) 2 ；
R 1 Selected from hydrogen, hydroxy, mercapto, amino, cyano, C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio, halo C 1 -C 6 Alkylthio, C 1 -C 6 Alkylamino or C 1 -C 6 A dialkylamino group;
R 2 selected from hydrogen, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl, cyano C 1 -C 6 Alkyl, C 1 -C 6 Alkylcarbonyl, C 1 -C 6 Cycloalkyl carbonyl or C 1 -C 6 An alkoxycarbonyl group;
however, when R 1 、R 2 X is selected from hydrogen 1 、X 2 、X 3 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 、R 2 、X 1 、X 2 、X 4 、X 5 X is selected from hydrogen 3 Not selected from methyl, N-dimethylamino, methoxy, methylthio, or isopropoxy; alternatively, when R 1 、R 2 、X 2 、X 3 、X 4 、X 5 X is selected from hydrogen 1 Not selected from hydrogen; alternatively, when R 1 、R 2 、X 2 、X 4 、X 5 X is selected from hydrogen 1 、X 3 Not selected from chlorine; alternatively, when R 1 、R 2 Selected from hydrogen, X 2 Selected from methoxy, X 3 X is selected from n-propoxy 1 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 、R 2 Selected from hydrogen, X 2 Selected from methoxy, X 3 X is selected from n-butoxy 1 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 、R 2 Selected from hydrogen, X 2 Selected from methoxy, X 3 X is selected from isopentyloxy 1 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 、R 2 Selected from hydrogen, X 1 Selected from chlorine, X 3 、X 4 When selected from methoxy, X 2 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from methylthio radicals, R 2 X is selected from hydrogen 1 、X 2 、X 3 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from methylthio radicals, R 2 、X 1 、X 2 、X 4 、X 5 X is selected from hydrogen 3 Not selected from amino, methoxy, fluoro or chloro; alternatively, when R 1 Selected from methylthio radicals, R 2 、X 1 、X 3 、X 4 、X 5 X is selected from hydrogen 2 Not selected from methyl or methoxy; alternatively, when R 1 Selected from methylthio radicals, R 2 Selected from hydrogen, X 1 、X 3 X is selected from chlorine 2 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from methylthio radicals, R 2 Selected from hydrogen, X 2 、X 3 When selected from methoxy, X 1 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from methylthio radicals, R 2 Selected from hydrogen, X 2 、X 4 X is selected from trifluoromethyl 1 、X 3 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from methylthio radicals, R 2 When selected from methyl, X 1 、X 2 、X 3 、X 4 、X 5 Not selected from hydrogen; or when X 1 、X 2 、X 3 、X 4 、X 5 、R 2 R is selected from hydrogen 1 Not selected from methyl, amino, cyano or mercapto; alternatively, when R 1 Selected from amino, R 2 Selected from hydrogen, X 3 When selected from methoxy, X 1 、X 2 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from amino, R 2 Selected from hydrogen, X 1 X is selected from chlorine 2 、X 3 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from amino, R 2 When selected from ethyl, X 1 、X 2 、X 3 、X 4 、X 5 Not selected from hydrogen; alternatively, when R 1 Selected from methyl, R 2 Selected from hydrogen, X 3 X is selected from chlorine 1 、X 2 、X 4 、X 5 Not selected from hydrogen; or when X 1 、X 2 、X 3 、X 4 、X 5 、R 1 R is selected from hydrogen 2 Is not selected from cyanoethyl;
or a salt of a compound of formula I;
with the proviso that the compounds of formula I do not include
2. A compound according to claim 1, wherein in formula I,
X 1 、X 2 、X 3 、X 4 、X 5 each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy, C 1 -C 4 Alkylthio, halo C 1 -C 4 Alkylthio, C 1 -C 4 Alkylamino, C 1 -C 4 Dialkylamino, C 1 -C 4 Alkylcarbonyl, C 1 -C 4 Alkoxycarbonyl, -nhch=c (CN) 2 or-CH 2 NHCH＝C(CN) 2 ；
R 1 Selected from hydrogen, hydroxy, mercapto, amino, cyano, C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkoxy, C 1 -C 4 Alkylthio, halo C 1 -C 4 Alkylthio, C 1 -C 4 Alkylamino or C 1 -C 4 A dialkylamino group;
R 2 selected from hydrogen, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl, cyano C 1 -C 4 Alkyl, C 1 -C 4 Alkylcarbonyl, C 3 -C 6 Cycloalkyl carbonyl or C 1 -C 4 An alkoxycarbonyl group;
or salts of compounds of the general formula I with 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, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
3. A compound according to claim 2, wherein in formula I,
X 1 、X 2 、X 3 、X 4 、X 5 each independently selected from the group consisting of hydrogen, fluoro, chloro, bromo, cyano, nitro, hydroxy, mercapto, amino, carboxy, methyl, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-trifluoroethyl, heptafluoroisopropyl, methoxy, ethoxy, N-propoxy, isopropoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, trifluoromethylthio, 2-trifluoroethylthio, methylamino, ethylamino, N-dimethylamino, -nhch=c (CN) 2 or-CH 2 NHCH＝C(CN) 2 ；
R 1 Selected from the group consisting of hydrogen, hydroxy, mercapto, amino, cyano, methyl, ethyl, n-propyl, n-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, methylthio, ethylthio, n-propylthio, n-butylthioMethylamino, ethylamino, n-propylamino or n-butylamino;
R 2 selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyanomethyl, 2-trifluoroethyl, acetyl, n-propionyl, cyclopropylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl;
or salts of compounds of the general formula I with 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, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
4. A compound according to claim 3, wherein in formula I,
X 1 、X 2 、X 3 、X 4 、X 5 each independently selected from hydrogen, fluoro, chloro, bromo, cyano, nitro, hydroxy, mercapto, amino, carboxy, methyl, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, sec-butyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, methylthio, methylamino, N-dimethylamino, -nhch=c (CN) 2 or-CH 2 NHCH＝C(CN) 2 ；
R 1 Selected from hydrogen, amino, methyl, methoxy, ethoxy, methylthio, ethylthio, methylamino or ethylamino;
R 2 selected from hydrogen, methyl, ethyl, 2-trifluoroethyl, cyanomethyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl or ethoxycarbonyl;
or salts of compounds of the general formula I with 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, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
5. The compound according to claim 1, wherein the compound of formula I is selected from the group consisting of:
6. use of a compound of the general formula I according to claim 1 as bactericide in the agricultural, forestry field.
7. Use of a compound of the general formula I according to claim 5 as a medicament for controlling bacterial plant diseases.
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| US3309396A (en) * | 1961-07-13 | 1967-03-14 | Dow Chemical Co | 1, 1, 3, 3-tetramethyl butylamino-methylenemalonitrile |
| JPS57146705A (en) * | 1981-03-09 | 1982-09-10 | Hokkai Sankyo Kk | Antibacterial for agricultural and horticultural purposes |
| CN106916084A (en) * | 2015-12-25 | 2017-07-04 | 沈阳中化农药化工研发有限公司 | A kind of malononitrile oximido ether compound and application thereof |
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| US3309396A (en) * | 1961-07-13 | 1967-03-14 | Dow Chemical Co | 1, 1, 3, 3-tetramethyl butylamino-methylenemalonitrile |
| JPS57146705A (en) * | 1981-03-09 | 1982-09-10 | Hokkai Sankyo Kk | Antibacterial for agricultural and horticultural purposes |
| CN106916084A (en) * | 2015-12-25 | 2017-07-04 | 沈阳中化农药化工研发有限公司 | A kind of malononitrile oximido ether compound and application thereof |
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