1, 1-dicyano hydrazone compound and application thereof
阅读说明：本技术 一种1, 1-二氰基腙类化合物及其应用 (1, 1-dicyano hydrazone compound and application thereof ) 是由 张立新 张静 张力群 康卓 于 2020-02-19 设计创作，主要内容包括：本发明公开了一种结构新颖的1,1-二氰基腙类化合物,结构如通式I所示,式中各取代基的定义见说明书。<Image he="69" wi="175" file="100004_DEST_PATH_IMAGE002.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="174" wi="464" file="100004_DEST_PATH_IMAGE004.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>通式I化合物具有优异的杀细菌活性,可用于防治多种植物细菌性病害。(The invention discloses a1, 1-dicyano hydrazone compound with a novel structure, which has a structure shown as a general formula I, wherein the definition of each substituent group in the formula is shown in the specification。 The compound of the general formula I has excellent bactericidal activity and can be used for preventing and treating various plant bacterial diseases.)
1. A1, 1-dicyano hydrazone compound is shown as a general formula I:
in the formula:
w is selected from W1G is selected from hydrogen, X1、X2、X4、X5Selected from hydrogen, X3Is selected from C2-C6An alkyl group;
or, W is selected from W1G is selected from hydrogen, X1、X5Selected from hydrogen, X2、X3、X4Selected from chlorine;
or, W is selected from W1、W2Or W3And, in addition,
g is selected from C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkylcarbonyl group, C3-C6Cycloalkyl carbonyl or C1-C6An alkoxycarbonyl group, a carbonyl group,
X1、X2、X3、X4、X5each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C1-C6Alkylamino radical, C1-C6Dialkylamino radical, C1-C6Alkylcarbonyl or C1-C6An alkoxycarbonyl group, a carbonyl group,
X6、X7、X8、X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
however, when W is selected from W1When not selected from the following compounds:
X1、X2、X3、X4、X5selected from hydrogen, G is selected from methyl, ethyl or n-propoxycarbonyl; or G is selected from methyl, X1、X2、X4、X5Selected from hydrogen, X3Selected from nitro, carboxyl, chlorine, bromine, methyl, trifluoromethyl or methoxy; or G is selected from methyl, X1、X3、X4、X5Selected from hydrogen, X2Selected from nitro, chloro, methyl or trifluoromethyl; or, X2、X4Selected from trifluoromethyl, X1、X3、X5Selected from hydrogen, G is selected from ethyl, acetyl, n-propionyl, n-butyryl, methoxycarbonyl, ethoxycarbonyl, isobutoxycarbonyl, n-pentyloxycarbonyl or n-hexyloxycarbonyl; or, X2、X4Selected from chlorine, X1、X3、X5Selected from hydrogen, G is selected from methyl, methoxycarbonyl or ethoxycarbonyl; or, X2、X3、X4Selected from chlorine, X1、X5Selected from hydrogen, G is selected from acetyl, n-propionyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl or isobutoxycarbonyl; or, X1、X3、X4Selected from chlorine, X2、X5Selected from hydrogen, G is selected from acetyl, n-propionyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, isobutoxycarbonyl, n-pentoxycarbonyl or n-hexoxycarbonyl; or G is selected from ethyl, X1、X2、X4、X5Selected from hydrogen, X3Selected from chlorine; or G is selected from methyl, X1、X4、X5Selected from hydrogen, X2、X3Selected from chlorine; or G is selected from methyl, X2、X4Selected from hydrogen, X1、X3、X5Selected from chlorine; or G is selected from acetyl, X1、X3、X4、X5Selected from hydrogen, X2Selected from chloro or trifluoromethyl; or G is selected from ethoxycarbonyl, X1、X2、X4、X5Selected from hydrogen, X3Selected from fluorine; or G is selected from acetyl or ethoxycarbonyl, X2、X4Selected from hydrogen, X1、X5Selected from bromine, X3Selected from chlorine; or G is selected from n-propionyl, X1、X3、X4、X5Selected from hydrogen, X2Is selected from trifluoromethyl; or G is selected from isobutoxycarbonyl, X1、X2、X4、X5Selected from hydrogen, X3Selected from fluorine; or G is selected from ethoxycarbonyl, X1、X3、X4、X5Selected from hydrogen, X2Is selected from trifluoromethyl; or G is selected from n-propionyl, ethoxycarbonyl or isobutoxycarbonyl, X1Selected from chlorine, X4Selected from trifluoromethyl, X2、X3、X5Selected from hydrogen; or G is selected from ethoxycarbonyl or isobutoxycarbonyl, X1Selected from methoxy, X3Selected from nitro, X4Selected from methyl, X2、X5Selected from hydrogen; or G is selected from ethoxycarbonyl, X1、X4Selected from methoxy, X3Selected from chlorine, X2、X5Selected from hydrogen; or G is selected from ethoxycarbonyl, X1Selected from methoxy, X3Selected from chlorine, X4Selected from methyl, X2、X5Selected from hydrogen;
or tautomers of compounds of formula I;
or a salt of a compound of formula I.
2. The compound of claim 1, wherein in formula I,
w is selected from W1G is selected from hydrogen, X1、X2、X4、X5Selected from hydrogen, X3Is selected from C2-C4An alkyl group;
or, W is selected from W1G is selected from hydrogen, X1、X5Selected from hydrogen, X2、X3、X4Selected from chlorine;
or, W is selected from W1、W2Or W3And, in addition,
g is selected from C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkylcarbonyl group, C3-C6Cycloalkyl carbonyl or C1-C4An alkoxycarbonyl group, a carbonyl group,
X1、X2、X3、X4、X5each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C1-C4Alkylthio, halo C1-C4Alkylthio radical, C1-C4Alkylamino radical, C1-C4Dialkylamino radical, C1-C4Alkylcarbonyl or C1-C4An alkoxycarbonyl group, a carbonyl group,
X6、X7、X8、X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C4An alkoxy group;
or tautomers of compounds of formula I;
or a salt of a compound of formula I.
3. The compound of claim 2, wherein in formula I,
w is selected from W1G is selected from hydrogen, X1、X2、X4、X5Selected from hydrogen, X3Selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl;
or, W is selected from W1G is selected from hydrogen, X1、X5Selected from hydrogen, X2、X3、X4Selected from chlorine;
or, W is selected from W1、W2Or W3And, in addition,
g is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, chloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2, 2, 2-trifluoroethyl, heptafluoroisopropyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl,
X1、X2、X3、X4、X5each 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, chloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, 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, methoxycarbonyl or ethoxycarbonyl,
X6、X7、X8、X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19selected from hydrogen;
or tautomers of compounds of formula I;
or salts of the compounds of the general formula I with hydrochloric acid, hydrobromic acid, sulphuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulphonic acid, 4-toluenesulphonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
4. A compound according to any one of claims 1 to 3, characterized in that, in formula I,
w is selected from W1G is selected from hydrogen, X1、X2、X4、X5Selected from hydrogen, X3Selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl;
or, W is selected from W1G is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl or n-butyl, X1、X5Selected from hydrogen, X2、X3、X4Selected from chlorine;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X1Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, X2、X3、X4、X5Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X1、X5Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, X2、X3、X4Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X2、X4Selected from methyl, X1、X3、X5Selected from hydrogen;
or, W is selected from W1G is selected from methyl, X2、X4Selected from trifluoromethyl, X1、X3、X5Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X1、X2Selected from chlorine, X3、X4、X5Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X1、X3Selected from chlorine, X2、X4、X5Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X1、X4Selected from chlorine, X2、X3、X5Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X1、X5Selected from chlorine, X2、X3、X4Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X2、X3Selected from chlorine, X1、X4、X5Selected from hydrogen;
or, W is selected from W2G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X6、X7、X8、X9、X10、X11、X12Selected from hydrogen;
or, W is selected from W3G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonylAlkyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X13、X14、X15、X16、X17、X18、X19Selected from hydrogen;
or tautomers of compounds of formula I;
or salts of the compounds of the general formula I with hydrochloric acid, hydrobromic acid, sulphuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulphonic acid, 4-toluenesulphonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
5. Use of a compound of the general formula I according to claim 1 as bactericide in agriculture, forestry or hygiene.
6. Use of compounds of the general formula I according to claim 5 as agents for controlling bacterial diseases in plants.
Technical Field
The present invention belongs to the field of agricultural bactericide. In particular to a1, 1-dicyan hydrazone compound and application thereof.
Background
Bacterial diseases become the second most common diseases next to fungal diseases in agricultural production in China, according to incomplete statistics, the bacterial diseases of China currently occur in an area of 1.2 hundred million acres, and the bacterial disease control market capacity exceeds 20 hundred million yuan. In the current agricultural production, the medicaments for preventing and treating bacterial diseases mainly comprise copper preparations (including organic or inorganic copper preparations) with large use amount and antibiotic products; wherein, the copper preparation has low control effect and a large amount of heavy metals are sprayed into the environment to pollute soil, water and food, thus causing the safety worry of the environment and the food; on the other hand, the use of a large amount of antibiotics may cause human pathogenic bacteria to develop resistance to medical antibiotics. Other varieties which can be used for agricultural bacterial treatment are only a few, and are limited by resistance and prevention effect in actual production, so that the popularization area is small. Therefore, the development of novel, highly effective, low-toxicity, environmentally friendly bacterial disease control agents is very necessary and urgent.
Disclosure of Invention
The invention aims to provide a1, 1-dicyano hydrazone compound and application thereof as a bactericide in the fields of agriculture, forestry or sanitation.
The technical scheme of the invention is as follows:
a1, 1-dicyano hydrazone compound is shown as a general formula I:
in the formula:
w is selected from W1G is selected from hydrogen, X1、X2、X4、X5Selected from hydrogen, X3Is selected from C2-C6An alkyl group;
or, W is selected from W1G is selected from hydrogen, X1、X5Selected from hydrogen, X2、X3、X4Selected from chlorine;
or, W is selected from W1、W2Or W3And, in addition,
g is selected from C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkylcarbonyl group, C3-C6Cycloalkyl carbonyl or C1-C6An alkoxycarbonyl group, a carbonyl group,
X1、X2、X3、X4、X5each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C1-C6Alkylamino radical, C1-C6Dialkylamino radical, C1-C6Alkylcarbonyl or C1-C6An alkoxycarbonyl group, a carbonyl group,
X6、X7、X8、X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
however, when W is selected from W1When not selected from the following compounds:
X1、X2、X3、X4、X5selected from hydrogen, G is selected from methyl, ethyl or n-propoxycarbonyl; or G is selected from methyl, X1、X2、X4、X5Selected from hydrogen, X3Selected from nitro, carboxyl, chlorine, bromine, methyl, trifluoromethyl or methoxy; or G is selected from methyl, X1、X3、X4、X5Selected from hydrogen, X2Selected from nitro, chloro, methyl or trifluoromethyl; or, X2、X4Selected from trifluoromethyl, X1、X3、X5Selected from hydrogen, G is selected from ethyl, acetyl, n-propionyl, n-butyryl, methoxycarbonyl, ethoxycarbonyl, isobutoxycarbonyl, n-pentyloxycarbonyl or n-hexyloxycarbonyl; or, X2、X4Selected from chlorine, X1、X3、X5Selected from hydrogen, G is selected from methyl, methoxycarbonyl or ethoxycarbonyl; or, X2、X3、X4Selected from chlorine, X1、X5Selected from hydrogen, G is selected from acetyl, n-propionyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl or isobutoxycarbonyl; or, X1、X3、X4Selected from chlorine, X2、X5Selected from hydrogen, G is selected from acetyl, n-propionyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, isobutoxycarbonyl, n-pentoxycarbonyl or n-hexoxycarbonyl; or G is selected from ethyl, X1、X2、X4、X5Selected from hydrogen, X3Selected from chlorine; or G is selected from methyl, X1、X4、X5Selected from hydrogen, X2、X3Selected from chlorine; or G is selected from methyl, X2、X4Selected from hydrogen, X1、X3、X5Selected from chlorine; or G is selected from acetyl, X1、X3、X4、X5Selected from hydrogen, X2Selected from chloro or trifluoromethyl; or G is selected from ethoxycarbonyl, X1、X2、X4、X5Selected from hydrogen, X3Selected from fluorine; or G is selected from acetyl or ethoxycarbonyl, X2、X4Selected from hydrogen, X1、X5Selected from bromine, X3Selected from chlorine; or G is selected from n-propionyl, X1、X3、X4、X5Selected from hydrogen, X2Is selected from trifluoromethyl; or G is selected from isobutoxycarbonyl, X1、X2、X4、X5Selected from hydrogen, X3Selected from fluorine; or G is selected from ethoxycarbonyl, X1、X3、X4、X5Selected from hydrogen, X2Is selected from trifluoromethyl; or G is selected from n-propionyl, ethoxycarbonyl or isobutoxycarbonyl, X1Selected from chlorine, X4Selected from trifluoromethyl, X2、X3、X5Selected from hydrogen; or G is selected from ethoxycarbonyl or isobutoxycarbonyl, X1Selected from methoxy, X3Selected from nitro, X4Selected from methyl, X2、X5Selected from hydrogen; or G is selected from ethoxycarbonyl, X1、X4Selected from methoxy, X3Selected from chlorine, X2、X5Selected from hydrogen; or G is selected from ethoxycarbonyl, X1Selected from methoxy, X3Selected from chlorine, X4Selected from methyl, X2、X5Selected from hydrogen;
or tautomers of compounds of formula I;
or a salt of a compound of formula I.
The more preferred compounds of the present invention are: in the general formula I, the compound is shown in the specification,
w is selected from W1G is selected from hydrogen, X1、X2、X4、X5Selected from hydrogen, X3Is selected from C2-C4An alkyl group;
or, W is selected from W1G is selected from hydrogen, X1、X5Selected from hydrogen, X2、X3、X4Selected from chlorine;
or, W is selected from W1、W2Or W3And, in addition,
g is selected from C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkylcarbonyl group, C3-C6Cycloalkyl carbonyl or C1-C4An alkoxycarbonyl group, a carbonyl group,
X1、X2、X3、X4、X5each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C1-C4Alkylthio, halo C1-C4Alkylthio radical, C1-C4Alkylamino radical, C1-C4Dialkylamino radical, C1-C4Alkylcarbonyl or C1-C4An alkoxycarbonyl group, a carbonyl group,
X6、X7、X8、X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C4An alkoxy group;
or tautomers of compounds of formula I;
or a salt of a compound of formula I.
Further preferred compounds of the invention are: in the general formula I, the compound is shown in the specification,
w is selected from W1G is selected from hydrogen, X1、X2、X4、X5Selected from hydrogen, X3Selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl;
or, W is selected from W1G is selected from hydrogen, X1、X5Selected from hydrogen, X2、X3、X4Selected from chlorine;
or, W is selected from W1、W2Or W3And, in addition,
g is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, chloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2, 2, 2-trifluoroethyl, heptafluoroisopropyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl,
X1、X2、X3、X4、X5each 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, chloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, 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, methoxycarbonyl or ethoxycarbonyl,
X6、X7、X8、X9、X10、X11、X12、X13、X14、X15、X16、X17、X18、X19selected from hydrogen;
or tautomers of compounds of formula I;
or salts of the compounds of the general formula I with hydrochloric acid, hydrobromic acid, sulphuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulphonic acid, 4-toluenesulphonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
Further preferred compounds of the invention are: in the general formula I, the compound is shown in the specification,
w is selected from W1G is selected from hydrogen, X1、X2、X4、X5Selected from hydrogen, X3Selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl;
or, W is selected from W1G is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl or n-butyl, X1、X5Selected from hydrogen, X2、X3、X4Selected from chlorine;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X1Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, X2、X3、X4、X5Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X1、X5Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, X2、X3、X4Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X2、X4Selected from methyl, X1、X3、X5Selected from hydrogen;
or, W is selected from W1G is selected fromMethyl group, X2、X4Selected from trifluoromethyl, X1、X3、X5Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X1、X2Selected from chlorine, X3、X4、X5Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X1、X3Selected from chlorine, X2、X4、X5Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X1、X4Selected from chlorine, X2、X3、X5Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X1、X5Selected from chlorine, X2、X3、X4Selected from hydrogen;
or, W is selected from W1G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X2、X3Selected from chlorine, X1、X4、X5Selected from hydrogen;
or, W is selected from W2G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylmethylAcyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X6、X7、X8、X9、X10、X11、X12Selected from hydrogen;
or, W is selected from W3G is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl, X13、X14、X15、X16、X17、X18、X19Selected from hydrogen;
or tautomers of compounds of formula I;
or salts of the compounds of the general formula I with hydrochloric acid, hydrobromic acid, sulphuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulphonic acid, 4-toluenesulphonic 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 groups: straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl or the different butyl, pentyl or hexyl isomers, etc.
Halogenated alkyl groups: straight-chain or branched alkyl groups, the hydrogen atoms on which may be partially or totally substituted by halogen, such as, for example, chloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2, 2, 2-trifluoroethyl, heptafluoroisopropyl, and the like.
Alkoxy groups: straight or branched chain alkyl groups bonded to the structure via an oxygen atom, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and the like.
Haloalkoxy groups: straight-chain or branched alkoxy groups in which the hydrogen atoms may be partially or completely replaced by halogen, for example chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, 2, 2, 2-trifluoroethoxy and the like.
Alkylthio group: straight or branched chain alkyl groups attached to the structure via a sulfur atom, such as methylthio, ethylthio, and the like.
Haloalkylthio: straight-chain or branched alkylthio groups in which the hydrogen atoms may be partially or fully substituted by halogen, such as difluoromethylthio, trifluoromethylthio, 2, 2, 2-trifluoroethylthio and the like.
Alkylamino group: straight or branched chain alkyl groups attached to the structure via a nitrogen atom, such as methylamino, ethylamino, n-propylamino, isopropylamino or the isomeric butylamines.
Dialkylamino group: two identical or different straight-chain or branched alkyl groups are bonded to the structure via a nitrogen atom, such as N, N-dimethylamino, N-methyl-N-ethylamino, etc.
An alkylcarbonyl group: the alkyl group is bonded to the structure via a carbonyl group, such as acetyl (CH3CO-), propionyl (CH3CH2CO-), and the like.
Cycloalkyl carbonyl group: the cycloalkyl group is attached to the structure via a carbonyl group, such as cyclopropylformyl.
Alkoxycarbonyl group: alkyl-O-CO-, e.g. methoxycarbonyl (CH)3OCO-), ethoxycarbonyl (CH)3CH2OCO-), n-propoxycarbonyl (CH)3CH2CH2OCO-), n-butoxycarbonyl (CH)3CH2CH2CH2OCO-), etc.
In the general formula I shown in the invention, when G is a hydrogen atom, the compounds in the general formula I have the following tautomerism, and the compounds in the general formula I also comprise all the tautomerism in the condition.
Some of the compounds of general formula I of the present invention are shown in tables 1 to 3, but the present invention is by no means limited to these compounds.
In the general formula I, when W = W1When, formula I can be represented by formula I-W1Represents; substituent X1、X2、X3、X4、X5G is shown in Table 1.
TABLE 1
In the general formula I, when W = W2And X6=X7=X8=X9=X10=X11=X12When H, formula I may be represented by formula I-W2Represents; the substituents G are shown in Table 2.
TABLE 2
In the general formula I, when W = W3And X13=X14=X15=X16=X17=X18=X19When H, formula I may be represented by formula I-W3Represents; the substituents G are shown in Table 3.
The physicochemical properties, nuclear magnetic data, and mass spectrum data of some of the compounds listed in tables 1 to 3 are shown in table 4:
TABLE 4
The compounds of the general formula I according to the invention can be prepared by the following process (where the radicals are as defined above unless otherwise stated):
in the compounds of the general formula I, when G is H, the compounds are shown by a general formula I-1, and when G is other substituent groups, the compounds are shown by a general formula I-2:
the compound in the general formula II can be prepared into a corresponding diazonium salt product, namely the compound in the general formula III, through conventional diazotization reaction.
The compound of the general formula III and malononitrile react in a proper solvent in the presence of a proper base at a temperature from-10 ℃ to the boiling point of the solvent for 0.5-48 hours to prepare the compound of the general formula I-1. Suitable bases are sodium acetate, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or sodium tert-butoxide, etc. Suitable solvents may be water, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, methanol, ethanol, ethyl acetate, acetonitrile, dioxane, THF, DMF, DMSO or a mixture thereof.
Reacting a compound of formula I-1 with a compound of formula G-LG in a suitable solvent in the absence or presence of a base at a temperature of from-10 ℃ to the boiling point of the solvent for a period of from 0.5 to 48 hoursThen the compound of the general formula I-2 can be prepared. Suitable bases are sodium acetate, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or sodium tert-butoxide, etc. Suitable solvents may be water, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, methanol, ethanol, ethyl acetate, acetonitrile, dioxane, THF, DMF, DMSO or a mixture thereof. In the compounds of formula G-LG represents a leaving group which suitably may be a halogen or other conventional nucleofugic group, e.g. C1-C4Alkoxy or C1-C4Alkylthio groups, such as specifically methoxy, ethoxy, methylthio or ethylthio, and the like.
The compounds of the formula II, the compounds of the formula G-LG and other starting materials and reagents are generally commercially available or can be prepared by conventional methods.
The compounds of the invention may also be prepared according to the methods disclosed in US3755598A, US3660462A, US3202698, US3157569, US3062635, JP07206800A, WO9735863A1, US4115104A, JP48087020A, JP48087019A, US3213124, US3135736 or European Journal of Biochemistry, 33(2), 247-52, 1973 etc., or by reference to other known methods.
The compound shown in the general formula I can be used for controlling various plant bacterial diseases, such as fruit blotch (such as muskmelon fruit blotch) and leaf blotch (such as tomato bacterial leaf blotch), bacterial wilt (such as tomato bacterial leaf blotch and potato bacterial wilt), bacterial blight, canker (such as citrus canker and kiwi canker), soft rot (such as Chinese cabbage soft rot), bacterial angular leaf spot (such as cucumber bacterial angular leaf spot), bacterial streak (such as rice bacterial streak), leaf blight, bacterial leaf blight (such as rice bacterial leaf blight), wildfire, bacterial scab and the like.
Detailed Description
The following specific examples are intended to further illustrate the invention, but the invention is by no means limited to these examples. (all materials are commercially available unless otherwise noted)
Synthetic examples
The compounds of formula I of the present invention can be prepared according to the synthetic routes described above, using different starting compounds, and are further described in detail below:
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