CN105777640B - Pyrazole cyclohexanediol ether compound and application thereof - Google Patents
Pyrazole cyclohexanediol ether compound and application thereof Download PDFInfo
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- CN105777640B CN105777640B CN201410804238.XA CN201410804238A CN105777640B CN 105777640 B CN105777640 B CN 105777640B CN 201410804238 A CN201410804238 A CN 201410804238A CN 105777640 B CN105777640 B CN 105777640B
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Abstract
The invention discloses a pyrazole cyclohexanediol ether compound, which has a structure shown as a general formula I:
Description
Technical Field
The present invention belongs to the field of agricultural bactericide. In particular to a pyrazole cyclohexanediol ether compound and application thereof as well as application thereof as a bactericide.
Background
United states Uniroyal company disclosed in US3179682 a highly effective, low toxicity, low residue, organosulfur acaricide Propargite (propagite) with dual action of contact and stomach toxicity.
Compounds of the general formula, having herbicidal activity, are disclosed in patent EP 2149556.
In order to find and discover novel pesticide varieties with higher efficiency, broad spectrum, low toxicity and low ecological risk, a series of pyrazole cyclohexanediol ether compounds with novel structures are designed and synthesized by combining a pyrazole ring and cyclohexanediol. The compound of the general formula I in the invention has a novel structure, and no related literature report exists.
Disclosure of Invention
The invention aims to provide a pyrazole cyclohexanediol ether compound which can control harmful bacteria. It can be used for preparing medicines for preventing and treating pathogenic bacteria in agriculture and other fields.
The technical scheme of the invention is as follows:
a pyrazole cyclohexanediol ether compound has a structure shown in a general formula I:
in the formula:
R1selected from hydrogen, C1-C8Alkyl, halo C1-C8Alkyl radical, C1-C8Alkoxy, halo C1-C8Alkoxy, cyano C1-C8Alkyl or C3-C6A cycloalkyl group;
R2selected from hydrogen, halogen, cyano, nitro, C1-C8Alkyl, halo C1-C8Alkyl radical, C1-C8Alkoxy, halo C1-C8Alkoxy radical, C1-C8Alkylthio or C1-C8An alkylsulfonyl group;
Q1selected from hydrogen, halogen, cyano, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy, cyano C1-C6Alkyl, cyano C1-C6Alkoxy, aryl, heteroaryl, aryloxy or heteroaryloxy which is unsubstituted or further substituted with 1 to 5 groups independently selected from: halogen, cyano, nitro, hydroxy, amino, mercapto, C1-C8Alkyl, halo C1-C8Alkyl radical, C1-C8Alkoxy, halo C1-C8Alkoxy radical, C3-C8Cycloalkyl radical, C2-C8Alkenyl, halo C2-C8Alkenyl radical, C2-C8Alkynyl, halo C2-C8Alkynyl, C2-C8Alkenyloxy, halogeno C2-C8Alkenyloxy radical, C2-C8Alkynyloxy, halo C2-C8Alkynyloxy, C1-C8Alkylthio, halo C1-C8Alkylthio radical, C1-C8Alkoxy radical C1-C8Alkyl, halo C1-C8Alkoxy radical C1-C8Alkyl radical, C1-C8Alkylthio group C1-C8Alkyl, halo C1-C8Alkylthio group C1-C8Alkyl radical, C1-C8Alkylsulfinyl, halogeno C1-C8Alkylsulfinyl radical, C1-C8Alkylsulfonyl, halo C1-C8Alkylsulfonyl radical, C1-C8Alkylamino, halogeno C1-C8Alkylamino or C2-C8A dialkylamino group.
Q2Selected from hydrogen, C1-C8Alkyl, halo C1-C8Alkyl radical, C1-C8Alkoxy, halo C1-C8Alkoxy radical, C3-C8Cycloalkyl radical, C2-C8Alkenyl radical, C2-C8Alkynyl, C2-C8Alkenyloxy, halogeno C2-C8Alkenyloxy radical, C2-C8Alkynyloxy, halo C2-C8Alkynyloxy, C1-C8Alkylthio, halo C1-C8Alkylthio radical, C1-C8Alkoxy radical C1-C8Alkyl, halo C1-C8Alkoxy radical C1-C8Alkyl radical, C1-C8Alkylthio group C1-C8Alkyl, halo C1-C8Alkylthio group C1-C8Alkyl radical, C1-C8Alkylsulfinyl, halogeno C1-C8Alkylsulfinyl radical, C1-C8Alkylsulfonyl, halo C1-C8Alkylsulfonyl radical, C1-C8Alkylamino, halogeno C1-C8Alkylamino radical, C2-C8Dialkylamino radical, C1-C8Alkylcarbonyl, halo C1-C8Alkylcarbonyl group, C1-C8Alkylcarbonyloxy, C1-C8Alkylcarbonylamino, C1-C8Alkoxycarbonyl group, C1-C8Alkylaminocarbonyl or Q3；
Q3Selected from aryl, aryl C unsubstituted or further substituted by 1-5 groups independently selected from1-C8Alkyl, aryl C1-C8Alkylcarbonyl, aryloxy C1-C8Alkyl, aryloxy C1-C8Alkylcarbonyl, heteroaryl C1-C8Alkyl, heteroaryl C1-C8Alkylcarbonyl, heteroaryloxy or heteroaryloxy C1-C8An alkylcarbonyl group: halogen, cyano, nitro, hydroxy, amino, mercapto, C1-C8Alkyl, halo C1-C8Alkyl radical, C1-C8Alkoxy, halo C1-C8Alkoxy radical, C3-C8Cycloalkyl radical, C2-C8Alkenyl, halo C2-C8Alkenyl radical, C2-C8Alkynyl, halo C2-C8Alkynyl, C2-C8Alkenyloxy, halogeno C2-C8Alkenyloxy radical, C2-C8Alkynyloxy, halo C2-C8Alkynyloxy, C1-C8Alkylthio, halo C1-C8Alkylthio radical, C1-C8Alkoxy radical C1-C8Alkyl, halo C1-C8Alkoxy radical C1-C8Alkyl radical, C1-C8Alkylthio group C1-C8Alkyl, halo C1-C8Alkylthio group C1-C8Alkyl radical, C1-C8Alkylsulfinyl, halogeno C1-C8Alkylsulfinyl radical, C1-C8Alkylsulfonyl, halo C1-C8Alkylsulfonyl radical, C1-C8Alkylamino, halogeno C1-C8Alkylamino or C2-C8A dialkylamino group.
The preferable technical scheme of the invention is as follows: in the general formula I
R1Selected from hydrogen, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C3Alkyl, cyano C1-C6Alkyl or C3-C6A cycloalkyl group;
R2selected from hydrogen, halogen, cyano, nitro, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C1-C6Alkylthio or C1-C6An alkylsulfonyl group;
Q1selected from hydrogen, halogen, cyano, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy, cyano C1-C6Alkyl, cyano C1-C6Alkoxy, phenyl which is unsubstituted or further substituted with 1 to 5 groups independently selected from: halogen, cyano, nitro, hydroxy, amino, mercapto, or a salt thereof,C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
Q2selected from hydrogen, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C8Cycloalkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyloxy, halogeno C2-C6Alkenyloxy radical, C2-C6Alkynyloxy, halo C2-C6Alkynyloxy, C1-C6Alkoxy radical C1-C6Alkyl, halo C1-C6Alkoxy radical C1-C6Alkyl radical, C1-C6Alkylamino, halogeno C1-C6Alkylamino radical, C2-C6Dialkylamino radical, C1-C6Alkylcarbonyl, halo C1-C6Alkylcarbonyl group, C1-C6Alkylcarbonyloxy, C1-C6Alkylcarbonylamino, C1-C6Alkoxycarbonyl group, C1-C6Alkylaminocarbonyl or Q3；
Q3Selected from aryl, aryl C unsubstituted or further substituted by 1-5 groups independently selected from1-C6Alkyl, aryl C1-C6Alkylcarbonyl, aryloxy C1-C6Alkyl, aryloxy C1-C6Alkylcarbonyl, heteroaryl C1-C6Alkyl, heteroaryl C1-C6Alkylcarbonyl, heteroaryloxy or heteroaryloxy C1-C6An alkylcarbonyl group: halogen, cyano, nitro, hydroxy, amino, mercapto, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C8Cycloalkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C2-C6Alkynyl or halo C2-C6Alkynyl.
The further preferable technical scheme of the invention is as follows: in the general formula I
R1Selected from hydrogen, C1-C4Alkyl or C3-C6A cycloalkyl group;
R2selected from hydrogen, halogen, cyano, nitro, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C4An alkoxy group;
Q1selected from hydrogen, halogen, cyano, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy, cyano C1-C4Alkyl, cyano C1-C4Alkoxy, phenyl which is unsubstituted or further substituted with 1 to 3 groups independently selected from: halogen, cyano, nitro, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C4An alkoxy group;
Q2selected from hydrogen, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy, halo C1-C4Alkoxy radical, C2-C4Alkenyl radical, C2-C4Alkynyl, C1-C4Alkylcarbonyl, halo C1-C4Alkylcarbonyl group, C1-C4Alkylcarbonyloxy or Q3；
Q3Selected from aryl, aryl C unsubstituted or further substituted by 1-5 groups independently selected from1-C4Alkyl, aryl C1-C4Alkylcarbonyl, aryloxy C1-C4Alkyl, aryloxy C1-C4Alkylcarbonyl, heteroaryl C1-C4Alkyl, heteroaryl C1-C4Alkylcarbonyl, heteroaryloxy or heteroaryloxy C1-C4An alkylcarbonyl group: halogen, cyano, nitro, hydroxy, amino, mercapto, C1-C4Alkyl, halo C1-C4Alkyl radical, C1-C4Alkoxy or halo C1-C4An alkoxy group.
The invention further preferably adopts the technical scheme that: in the general formula I
R1Selected from hydrogen, methyl, ethyl, cyclopropyl or cyclohexyl;
R2selected from hydrogen, chlorine, bromine or methyl;
Q1selected from hydrogen, chloro, bromo, methyl, ethyl, chloromethyl, difluoromethyl, trifluoromethyl, methoxymethyl, methoxy, ethoxy, monofluoromethoxy, trifluoromethoxy, trifluoroethoxy, cyanomethyl, cyanomethoxy, phenyl, p-chlorophenyl, p-fluorophenyl, p-methylphenyl, p-trifluoromethylphenyl, p-methoxyphenyl, p-trifluoromethoxyphenyl, 2, 4-dichlorophenyl, or 2, 4-dimethylphenyl;
Q2selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, n-butyl, chloromethyl, difluoromethyl, trifluoromethyl, methoxymethyl, methoxy, ethoxy, monofluoromethoxy, trifluoromethoxy, trifluoroethoxy, vinyl, propenyl, allyl, ethynyl, 1-propynyl, propargyl, acetyl, propionyl, chloroacetyl, 2-chloropropionyl, 3-chloropropionyl, acetoxy, propionyloxy or Q3；
Q3Selected from the group consisting of phenyl, 4-chlorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, 4-trifluoromethoxyphenyl, 4-cyanophenyl, 2, 4-dichlorophenyl, 2, 4-difluorophenyl, 2,3, 5-trichloro-4, 6-dicyanophenyl, pyridyl, 4-cyanopyridin-2-yl, 6-chloropyridin-2-yl, 4-chlorophenylmethyl, 4-fluorophenylmethyl, 4-trifluoromethylbenzyl, 4-nitrobenzyl, 4-tert-butylbenzyl, 2-chloro-6-fluorophenylmethyl, 2, 6-difluorobenzyl, 6-chloropyridin-3-ylmethyl, 2-chloropyridin-5-ylmethyl, methyl, benzyl, 6-chloropyridazin-3-yl, 3-chloropyridazin-5-yl, benzoyl, 4-chlorobenzoyl4-fluorobenzoyl, 2, 6-difluorobenzoyl, 4-chlorophenylacetyl, 4-tert-butylacetylyl, pyridine-2-formyl, pyridine-3-formyl, 2-chloropyridine-3-formyl, 1-methyl-pyrazole-5-formyl, 1, 3-dimethyl-pyrazole-5-formyl, phenoxyacetyl, 4-chlorophenoxyacetyl, 4-fluorophenoxyacetyl, 4-trifluoromethylphenoxyacetyl, 2-chloro-4-trifluoromethylphenoxyacetyl, 4-methoxyphenoxyacetyl, 2, 4-dichlorophenoxyacetyl, 2, 4-difluorophenoxyacetyl, 2, 6-difluorophenoxyacetyl or 2,4, 5-trichlorophenoxyacetyl.
The invention further adopts the following preferable technical scheme: in the general formula I
R1Is selected from methyl;
R2selected from hydrogen;
Q1is selected from p-chlorophenyl;
Q2selected from hydrogen, methyl, n-propyl, n-butyl, allyl, propargyl, acetyl, chloroacetyl or Q3；
Q3Selected from the group consisting of 4-trifluoromethylphenyl, 2,3, 5-trichloro-4, 6-dicyanophenyl, 4-chlorobenzyl, 2-chloro-6-fluorobenzyl, 4-tert-butylbenzyl, 4-cyanopyridin-2-yl, 6-chloropyridin-3-ylmethyl, 6-chloropyridazin-3-yl, 2-chloropyridine-3-formyl, 2, 6-difluorobenzoyl, 1, 3-dimethyl-pyrazole-5-formyl, 4-trifluoromethylphenoxyacetyl, 2-chloro-4-trifluoromethylphenoxyacetyl, 4-methoxyphenoxyacetyl, 2, 4-dichlorophenoxyacetyl, or 2,4, 5-trichlorophenoxyacetyl.
The most preferable technical scheme of the invention is as follows: in the general formula I
R1Is selected from methyl;
R2selected from hydrogen;
Q1is selected from p-chlorophenyl;
Q2selected from methyl, allyl or propargyl;
Q3selected from 4-cyano-2-pyridyl, 6-chloropyridin-3-ylmethyl, 6-chloropyridazin-3-yl, 2-chloropyridin-3-yl, 2, 6-difluorobenzoyl or 2-chloro-4-trifluoromethylA phenoxyacetyl group.
In the definition of the compounds (I) 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 groups, such as methyl, ethyl, propyl, isopropyl, n-butyl or tert-butyl. Cycloalkyl groups: substituted or unsubstituted cyclic alkyl groups, such as cyclopropyl, cyclopentyl or cyclohexyl. Substituents such as methyl, halogen, and the like. Halogenated alkyl groups: straight-chain or branched alkyl groups in which the hydrogen atoms may be partially or completely substituted with halogen atoms, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like. Alkoxy groups: straight or branched chain alkyl groups attached to the structure via oxygen atom linkages. Alkoxyalkyl groups: the alkoxy group is attached to the structure via an alkyl group. Such as CH3OCH2-，CH3CH2OCH2-. Haloalkoxyalkyl groups: the hydrogen atoms on the alkyl group of the alkoxyalkyl group may be partially or fully substituted with halogen atoms. Such as ClCH2CH2OCH2-. Haloalkoxy groups: straight-chain or branched alkoxy groups in which the hydrogen atoms may be partially or completely replaced by halogen atoms. For example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like. Alkylthio group: straight or branched chain alkyl groups attached to the structure via a sulfur atom. Alkylthioalkyl: alkylthio groups are attached to the structure through alkyl groups. Such as CH3SCH2-. Haloalkylthio: straight-chain or branched alkylthio groups in which the hydrogen atoms may be partially or wholly replaced by halogen atoms. For example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like. Alkylthioalkyl: alkylthio radicals attached to the structure via alkyl radicals, e.g. CH2SCH2-. Haloalkylthioalkyl: the haloalkylthio group being attached to the structure via an alkyl group, e.g. ClCH2SCH2-. Alkylamino group: straight or branched chain alkyl, linked to the structure via a nitrogen atom. Haloalkylamino group: straight-chain or branched alkylamino radicals in which the alkyl radical is presentThe hydrogen atoms in (A) may be partially or completely substituted with halogen atoms. Alkenyl: straight-chain or branched alkenes, for example ethenyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl and hexenyl isomers. Alkenyl also includes polyenes such as 1, 2-allenyl and 2, 4-hexadienyl. Halogenated alkenyl groups: straight-chain or branched alkenes in which the hydrogen atoms may be partially or completely replaced by halogen atoms. Alkynyl: straight-chain or branched alkynes, such as ethynyl, 1-propynyl, propargyl and the different butynyl, pentynyl and hexynyl isomers. Alkynyl also includes groups consisting of multiple triple bonds, such as 2, 5-hexadiynyl. Halogenated alkynyl group: straight-chain or branched alkynes, in which the hydrogen atoms may be partially or completely replaced by halogen atoms. Alkenyloxy: linear or branched alkenes linked to the structure via oxygen atoms. Haloalkenyloxy: straight-chain or branched alkenyloxy groups in which the hydrogen atoms may be partially or completely replaced by halogen atoms. Alkynyloxy: straight or branched alkynes, linked to the structure via oxygen atom bonds. Haloalkynyloxy: straight-chain or branched alkynyloxy, in which the hydrogen atoms may be partially or completely substituted by halogen atoms. Alkylsulfinyl group: straight or branched chain alkyl groups are attached to the structure via a sulfinyl (-SO-) group, such as methylsulfinyl. Haloalkylsulfinyl group: straight-chain or branched alkylsulfinyl groups in which the hydrogen atoms of the alkyl group may be partially or fully substituted by halogen atoms. An alkylsulfonyl group: straight or branched chain alkyl via sulfonyl (-SO)2-) is attached to a structure, such as a methylsulfonyl group. Haloalkylsulfonyl group: straight-chain or branched alkylsulfonyl wherein the hydrogen atoms of the alkyl group may be partially or wholly substituted by halogen atoms. An alkylcarbonyl group: the alkyl radical being bound to the structure via a carbonyl group, e.g. CH3CO-，CH3CH2CO-. Halogenated alkylcarbonyl group: the hydrogen atoms of the alkyl group of the alkylcarbonyl group may be partially or fully substituted by halogen atoms, e.g. CF3CO-. Alkyl amino carbonyl: such as CH3NHCO-，CH3CH2NHCO-. Alkoxycarbonyl group: the alkoxy group is attached to the structure via a carbonyl group. Such as CH3OCO-，CH3CH2OCO-. Alkylcarbonyloxy group: such as CH3COO-，CH3CH2NHCOO-. Alkylcarbonylamino group: such as CH3CONH-，CH3CH2NHCONH-. Aryl groups and aryl moieties of arylmethyl, aryloxy, aryloxymethyl groups include phenyl or naphthyl groups and the like. Arylmethyl: aryl-CH2-, such as benzyl: PhCH2-. Aryloxy group: aryl-O-, such as: phenoxy, pyridyloxy. Aryloxymethyl group: aryloxy-CH2-, such as: PhOCH2-。
Heteroaryl group: the heteroaryl group referred to in the present invention is a five-membered or six-membered ring aryl group containing 1 or more heteroatoms of N, O, S. For example, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thiazolyl, quinolinyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, pyrazolyl, pyranyl, triazolyl, tetrazolyl, benzothiazolyl, benzofuryl and the like. Heteroaryloxy group: the heteroaromatic ring is attached to the structure via an oxygen, such as pyridyloxy, pyrimidyloxy, and the like.
Tables 1 to 3 respectively list R in the general formula I1、R2、Q1The moiety (c) is not limited to these substituents.
TABLE 1R1Substituent group
TABLE 2R2Substituent group
TABLE 3Q1Substituent group
Some of the compounds of formula I of the present invention can be illustrated in tables 4 to 19 but are not intended to limit the present invention.
When R in the formula I1＝CH3，R2＝H，Q1When H, Q2The substituents are different, and are shown in Table 4, and represent the compound numbers of 4-1-4-275.
TABLE 4
Table 5: in the general formula I, R1＝CH3，R2＝H，Q1＝4-Cl-C6H4When is, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 5-1 to 5-275.
Table 6: in the general formula I, R1＝CH3，R2＝H，Q1＝C6H5When is, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 6-1 to 6-275.
Table 7: in the general formula I, R1＝CH3，R2＝H，Q1When Pyridin-2-yl, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 7-1 to 7-275.
Table 8: in the general formula I, R1＝CH3，R2＝Cl，Q1When H, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 8-1 to 8-275.
Table 9: in the general formula I, R1＝CH3，R2＝Cl，Q1＝C6H5When is, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 9-1 to 9-275.
Table 10: in the general formula I, R1＝CH3，R2＝Cl，Q1＝4-Cl-C6H4When is, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 10-1 to 10-275.
Table 11: in the general formula I, R1＝CH3，R2＝Cl，Q1When Pyridin-2-yl, Q2The selection of the substituents is consistent with that in Table 4, the substituents sequentially correspond to 4-1 to 4-275, and the compounds are numbered from 11-1 to 11-275.
TABLE 12R in formula I1＝C2H5，R2＝H，Q1When H, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 12-1 to 12-275.
Table 13: in the general formula I, R1＝C2H5，R2＝H，Q1＝4-Cl-C6H4When is, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 13-1 to 13-275.
Table 14: in the general formula I, R1＝C2H5，R2＝H，Q1＝C6H5When is, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 14-1 to 14-275.
Table 15: in the general formula I, R1＝C2H5，R2＝H，Q1When Pyridin-2-yl, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 15-1 to 15-275.
Table 16: in the general formula I, R1＝C2H5，R2＝Cl，Q1When H, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 16-1 to 16-275.
Table 17: in the general formula I, R1＝C2H5，R2＝Cl，Q1＝C6H5When is, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 17-1 to 17-275.
Table 18: in the general formula I, R1＝C2H5，R2＝Cl，Q1＝4-Cl-C6H4When is, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 18-1 to 18-275.
Table 19: in the general formula I, R1＝C2H5，R2＝Cl，Q1When Pyridin-2-yl, Q2The selection of the substituent groups is consistent with that in Table 4, the substituent groups sequentially correspond to 4-1 to 4-275, and the compound numbers are 18-1 to 18-275.
The compounds of the general formula I according to the invention can be prepared by the following processes, in which the radicals are as defined above, unless otherwise indicated.
The compound of the general formula I is prepared from an intermediate II and a compound III under the alkaline condition:
in compound III, L is a leaving group and is halogen, methyl sulfonate or p-toluene sulfonate. The other groups are as defined above.
Suitable solvents may be selected from, for example, tetrahydrofuran, diethyl ether, acetonitrile, dichloromethane, chloroform, dioxane, toluene, xylene, benzene, N-dimethylformamide, dimethyl sulfoxide, acetone or butanone.
Suitable bases may be selected from, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide, sodium tert-butoxide, etc.
The suitable temperature is from room temperature to the boiling point of the solvent, and is usually 20 to 100 ℃.
The reaction time is 30 minutes to 20 hours, usually 1 to 10 hours.
The intermediate II can be prepared by the addition reaction of the intermediate IV and the compound V under the alkaline condition:
in the formula, each group is as defined above.
Suitable solvents may be selected from, for example, tetrahydrofuran, diethyl ether, acetonitrile, dichloromethane, chloroform, dioxane, toluene, xylene, benzene, N-dimethylformamide, dimethyl sulfoxide, acetone or butanone. .
Suitable bases may be selected from, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide, sodium tert-butoxide, etc.
The suitable temperature is from room temperature to the boiling point of the solvent, and is usually 20 to 100 ℃.
The reaction time is 30 minutes to 20 hours, usually 1 to 10 hours.
Intermediate IV can be prepared by condensation of intermediate VI with (substituted) hydrazine according to known methods, see in particular WO2006018715, intermediate VI is commercially available or can be prepared by known methods, see in particular US3781438, CN1257490 and WO9615115, etc. (substituted) hydrazines are all commercially available.
When Q is2Selected from aryloxy C1-C8Alkylcarbonyl and heteroaryloxy C1-C8In the case of alkylcarbonyl, it can be produced by the following method (as Q) in addition to the above production method2For phenoxymethylcarbonyl as an example):
the compound of the general formula I is prepared from an intermediate VII and phenol under alkaline conditions:
in formula VII, X is a leaving group selected from chlorine or bromine, and the other groups are as defined above.
Suitable solvents may be selected from, for example, tetrahydrofuran, diethyl ether, acetonitrile, dichloromethane, chloroform, dioxane, toluene, xylene, benzene, N-dimethylformamide, dimethyl sulfoxide, acetone or butanone.
Suitable bases may be selected from, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide, sodium tert-butoxide, etc.
The suitable temperature is from room temperature to the boiling point of the solvent, and is usually 20 to 100 ℃.
The reaction time is 30 minutes to 20 hours, usually 1 to 10 hours.
Intermediate VII can be prepared from intermediate II and compound VIII under alkaline conditions:
the definitions of the groups in the formula and the definition of X are the same as above.
Suitable solvents may be selected from, for example, tetrahydrofuran, diethyl ether, acetonitrile, dichloromethane, chloroform, dioxane, toluene, xylene, benzene, N-dimethylformamide, dimethyl sulfoxide, acetone or butanone.
Suitable bases may be selected from, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide, sodium tert-butoxide, etc.
The suitable temperature is from room temperature to the boiling point of the solvent, and is usually 20 to 100 ℃.
The reaction time is 30 minutes to 20 hours, usually 1 to 10 hours.
The compounds III, V and VIII are all available or prepared according to the conventional method.
The compounds of the general formula I show bactericidal activity against harmful germs in the agricultural, civil and animal technical fields. Therefore, another technical scheme of the invention relates to the application of the compound shown in the general formula I as a bactericide, namely the application of the compound shown in the general formula I in preparing medicines for preventing and treating germs in agriculture or other fields. In particular, the compound of the general formula I has good activity on diseases such as cucumber downy mildew, corn rust, rice blast and the like.
The compounds of the general formula I show a controlling effect on weeds which are harmful in the field of agricultural technology. Therefore, another embodiment of the present invention relates to the use of the compounds of the general formula I as herbicides, i.e. the use of the compounds of the general formula I for the preparation of a herbicide for controlling weeds in agriculture or in other fields.
The invention also provides a sterilization and weeding composition, which contains the compound shown in the general formula I and an agriculturally acceptable carrier, wherein the weight percentage of active components in the composition is 0.1-99%. Therefore, the technical scheme of the invention also comprises the application of the bactericidal composition in preventing and controlling germs in the agricultural or horticultural field.
The present invention also provides a process for the preparation of a composition as defined above: the compound of formula I is admixed with a carrier. The active ingredient in such compositions may comprise a single compound or a mixture of several compounds according to the invention.
The compositions of the present invention may be administered in the form of a formulation. The compounds of formula I are dissolved or dispersed as active ingredients in carriers or formulated so as to be more easily dispersed when used as fungicides. For example: these chemical formulations can be formulated as wettable powders, suspensions, water dispersible granules or emulsifiable concentrates. In these compositions, at least one liquid or solid carrier is added, and when necessary, a suitable surfactant may be added.
The carrier in the composition of the present invention is a substance satisfying the following conditions: it is formulated with the active ingredient so as to be conveniently applied to the locus to be treated, which may be, for example, a plant, seed or soil; or to facilitate storage, transport or handling. The carrier may be a solid or a liquid, including materials which are normally gaseous but which have been compressed to form a liquid, and carriers which are normally used in formulating germicidal compositions may be used.
The technical scheme of the invention also comprises a method for preventing and controlling germs and weeds, which comprises the following steps: the bactericidal composition of the present invention is applied to weeds or their growth media to be controlled. Preferably, an effective amount of 10 to 1000 grams per hectare is generally selected, with an effective amount of 20 to 500 grams per hectare being preferred.
For certain applications, for example in agriculture, one or more other fungicides, insecticides, herbicides, plant growth regulators or fertilizers and the like may be added to the fungicidal compositions of the present invention, thereby providing additional advantages and effects.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
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
Example 1: preparation of Compound 5-1
(1) Preparation of intermediate 3- (4-chlorophenyl) -1-methyl-5-pyrazolol
10.60 g of methyl p-chlorobenzoylacetate solution in 50ml of methanol are heated under reflux. A small excess of methylhydrazine was added dropwise and refluxed for 3 hours. After the reaction was monitored by TLC, the mixture was concentrated and cooled to precipitate crystals. Filter and rinse the crystals with a small amount of methanol. Drying to obtain 7.5 g of crystal 3- (4-chlorphenyl) -1-methyl-5-pyrazole alcohol.
(2) Preparation of Compound 5-1
In a 500mL three-necked flask, 23.05g (0.10mol) of intermediate 3- (4-chlorophenyl) -1-methyl-5-pyrazole alcohol and 10.78g (0.11mol) of cyclohexene oxide were added, and then 0.4g (0.01mol) of NaOH was added as a catalyst, toluene was used as a solvent, and the mixture was heated to 105 to 108 ℃ to react for 8 hours. Cooling to room temperature, adding water, layering, concentrating, cooling, and recrystallizing to obtain 29.20g of white solid with yield of 95% and melting point of 150-152 ℃.
Example 2: preparation of Compounds 5-99
In a 100mL flask, 0.66g (2mmol) of intermediate 2- (3- (4-chlorophenyl) -1-methyl-1H-pyrazol-5-yloxy) cyclohexanol (5-1) and 0.10g (60%, 2.4mmol) NaH were added, 20mL of DMF was added as a solvent, and after stirring at room temperature for 30min, a solution of 0.29g (2.4mmol) of allyl bromide in DMF was added dropwise, and the temperature was raised to about 80 ℃ to perform reaction. After completion of the reaction monitored by TLC, it was cooled to room temperature, the reaction mixture was poured into 20mL of water, extracted with 200mL of ethyl acetate, and the residue after desolventization was separated by column chromatography to give 0.37g of a colorless oil in 53.6% yield.
Example 3: preparation of Compounds 5-206
In a 250mL flask, 6.57g (20.0mmol) of intermediate 2- (3- (4-chlorophenyl) -1-methyl-1H-pyrazol-5-yloxy) cyclohexanol and 3.03g (30.0mmol) of triethylamine were added, then 100mL of dichloromethane was added as a solvent, a solution of 2.71g (24mmol) of chloroacetyl chloride in dichloromethane was added dropwise to the flask with stirring at room temperature, and then the reaction was continued to be stirred at room temperature. After the completion of the TLC monitoring reaction, the solvent was dried by spinning, the mixture was poured into 50mL of water, and 200mL of ethyl acetate was added to conduct extraction, and the organic layer was separated, washed with 10mL of saturated saline, dried over anhydrous magnesium sulfate, and desolventized under reduced pressure, and the residue was separated by column chromatography to obtain 6.89g of a brown oily substance with a yield of 85.1%.
Example 4: preparation of Compounds 5-141
A100 mL flask was charged with 0.33g (1.0mmol) of intermediate 2- (3- (4-chlorophenyl) -1-methyl-1H-pyrazol-5-yloxy) cyclohexanol and 0.08g (60%, 2.0mmol) of NaH, and then 20mL of DMF was added as a solvent, and after reaction at room temperature for 30min with stirring, a solution of 0.18g (1.0mmol) of 2-chloro-3-trifluoromethylpyridine in DMF was added dropwise, and the temperature was raised to about 80 ℃ to effect reaction. After completion of the TLC monitoring reaction, the reaction mixture was cooled to room temperature, poured into 20mL of water, extracted with 200mL of ethyl acetate, and the residue after desolventization was separated by column chromatography to give 0.20g of a pale green oil in 42.5% yield.
Example 5: preparation of Compounds 5-60
A100 mL flask was charged with 0.49g (1.5mmol) of intermediate 2- (3- (4-chlorophenyl) -1-methyl-1H-pyrazol-5-yloxy) cyclohexanol and 0.12g (60%, 3.0mmol) of NaH, and then 20mL of DMF was added as a solvent, and after reaction at room temperature for 30min with stirring, a solution of 0.24g (1.5mmol) of p-chlorobenzyl chloride in DMF was added dropwise to the flask, and the temperature was raised to about 80 ℃ to carry out reaction. After completion of the TLC monitoring reaction, it was cooled to room temperature, and the reaction mixture was poured into 20mL of water, extracted with 200mL of ethyl acetate, and the residue after desolventization was separated by column chromatography to give 0.41g of a colorless oil with a yield of 64.1%.
Example 6: preparation of Compounds 5-80
In a 100mL flask, 0.33g (1.0mmol) of intermediate 2- (3- (4-chlorophenyl) -1-methyl-1H-pyrazol-5-yloxy) cyclohexanol and 0.20g (2.0mmol) of triethylamine were added, and then 20mL of dichloromethane was added as a solvent, and a solution of 0.24g (1.5mmol) of 2-chloronicotinoyl chloride in dichloromethane was added dropwise to the flask with stirring at room temperature, followed by continuing the reaction with stirring at room temperature. After the completion of the TLC monitoring reaction, the solvent was dried by spinning, the mixture was poured into 20mL of water, and 50mL of ethyl acetate was added to conduct extraction, the organic layer was separated, washed with 10mL of saturated saline, dried over anhydrous magnesium sulfate, and desolventized under reduced pressure, and the residue was separated by column chromatography to give 0.34g of a reddish brown oil with a yield of 75.5%.
Example 6: preparation of Compounds 5-272
A100 mL flask was charged with 0.16g (1.0mmol) of 4-trifluoromethylphenol and 0.21g (1.5mmol) of K2CO3Then, 30mL of DMF was added as a solvent, and the mixture was stirred at room temperature for reaction for 30min, and then a DMF solution of 0.40g (1.0mmol) of intermediate 2- (3- (4-chlorophenyl) -1-methyl-1H-pyrazol-5-yloxy) cyclohexyl 2-chloroacetate was added dropwise to the flask, followed by heating to 50 ℃ for reaction. After completion of the TLC monitoring reaction, the mixture was poured into 40mL of water, and extracted with 50mL of ethyl acetate, and the organic layer was separated, washed with 10mL of saturated brine, dried over anhydrous magnesium sulfate, and desolventized under reduced pressure, and the residue was separated by column chromatography to obtain 0.36g of a colorless oil with a yield of 67.9%.
Other compounds of formula I may be prepared by the preparation methods provided by the present invention.
Melting point and nuclear magnetic data of some of the compounds: (1HNMR, 300MHz, internal standard TMS, solvent CDCl3) The following were used:
compound 5-1: melting point 150-. δ ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.71(s, 3H), 3.76(m, 1H), 3.95(m, 1H), 5.85(s, 1H), 7.33(d, 2H), 7.66(d, 2H).
Compounds 5-2 δ ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 2.14(s, 3H), 3.64(s, 3H), 4.13(m, 1H), 5.05(m, 1H), 5.86(s, 1H), 7.34(d, 2H), 7.66(d, 2H).
Compounds 5-6 δ ppm 0.87(t, 3H), 1.34(m, 4H), 1.45(m, 2H), 1.46(m, 2H), 1.78(m, 2H), 2.12(m, 2H), 3.41(m, 1H), 3.37(m, 2H), 3.69(s, 3H), 4.07(m, 1H), 5.84(s, 1H).
Compounds 5-48 δ ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.56(s, 3H), 4.39(m, 1H), 5.56(m, 1H), 5.97(s, 1H), 6.97(t, 1H), 7.34(d, 2H), 7.66(d, 2H), 7.85(d, 1H), 8.31(d, 1H).
Compounds 5-46. delta. ppm 1.36(m, 4H), 1.65(m, 2H), 2.22(m, 2H), 3.42(s, 3H), 4.42(m, 1H), 4.81(m, 1H), 5.85(s, 1H), 7.33(d, 2H), 7.66(d, 2H).
Compounds 5-60 δ ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.52(m, 1H), 3.66(s, 3H), 4.11(m, 1H), 4.60(s, 2H), 5.81(s, 1H), 7.21(d, 2H), 7.28(d, 2H), 7.34(d, 2H), 7.64(d, 2H).
Compounds 5-72 δ ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.53(m, 1H), 3.67(s, 3H), 4.12(m, 1H), 4.66(s, 2H), 5.83(s, 1H), 7.26(d, 1H), 7.34(d, 2H), 7.55(d, 1H), 7.65(d, 2H), 8.31(s, 1H).
Compounds 5-75 δ ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.61(s, 3H), 4.26(m, 1H), 5.33(m, 1H), 5.84(s, 1H), 6.99(t, 2H), 7.33(d, 2H), 7.48(m, 1H), 7.66(d, 2H).
Compounds 5-80 δ ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.62(s, 3H), 4.31(m, 1H), 5.39(m, 1H), 5.86(s, 1H), 7.17(t, 1H), 7.32(d, 2H), 7.62(d, 2H), 7.92(d, 1H), 8.49(m, 1H).
Compounds 5-90 δ ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.61(s, 3H), 4.18(m, 1H), 4.64(s, 2H), 5.20(m, 1H), 5.84(s, 1H), 7.07(d, 2H), 7.34(d, 1H), 7.43(d, 1H), 7.61(s, 1H), 7.66(d, 2H).
Compounds 5-99.. delta.ppm 1.32(m, 4H), 1.73(m, 2H), 2.07(m, 2H), 3.48(m, 1H), 3.69(s, 3H), 4.04(t, 2H), 4.11(m, 1H), 5.18(d, 1H), 5.27(d, 1H), 5.90(s, 1H), 5.93(s, 1H), 7.34(d, 2H), 7.67(d, 2H).
Compounds 5-100 δ ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.66(s, 1H), 3.67(d, 1H), 3.70(s, 3H), 4.08(m, 1H), 4.29(s, 2H), 5.85(s, 1H), 7.33(d, 2H), 7.66(d, 2H).
Compounds 5-139. delta.ppm 1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.51(s, 3H), 4.32(m, 1H), 5.40(m, 1H), 5.92(s, 1H), 6.91(s, 1H), 7.06(d, 1H), 7.34(d, 2H), 7.67(d, 2H), 8.29(d, 1H).
Compounds 5-162 δ ppm1.32(s, 9H), 1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.57(m, 1H), 3.67(s, 3H), 4.15(m, 1H), 4.61(s, 2H), 5.84(s, 1H), 7.22(d, 2H), 7.322(m, 4H), 7.64(m, 2H).
Compounds 5-180. delta. ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.62(s, 3H), 4.18(m, 1H), 4.57(s, 2H), 5.20(m, 1H), 5.81(s, 1H), 6.82(s, 1H), 7.34(d, 2H), 7.38(s, 1H), 7.66(d, 2H).
Compounds 5-204 δ ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.60(s, 3H), 3.70(s, 3H), 4.18(m, 1H), 4.49(s, 2H), 5.20(m, 1H), 5.84(s, 1H), 6.73(m, 4H), 7.33(d, 2H), 7.66(d, 2H).
Compounds 5-206. delta. ppm1.32(s, 9H), 1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.48(s, 3H), 4.23(m, 1H), 4.34(s, 2H), 4.41(m, 1H), 6.81(s, 1H), 7.33(d, 2H), 7.66(d, 2H).
Compounds 5-235. delta. ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.51(s, 3H), 4.32(m, 1H), 5.58(m, 1H), 5.92(s, 1H), 6.82(d, 1H), 7.31(d, 1H), 7.34(d, 2H), 7.67(d, 2H).
Compounds 5-245 δ ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.56(m, 1H), 3.62(s, 3H), 4.08(m, 1H), 4.79(s, 2H), 5.78(s, 1H), 6.96(t, 1H), 7.16(d, 2H), 7.26(d, 2H), 7.64(d, 2H).
Compounds 5-265. delta. ppm1.34(m, 4H), 1.78(m, 2H), 2.20(s, 3H), 2.12(m, 2H), 3.59(s, 3H), 4.07(s, 3H), 4.24(m, 1H), 5.16(m, 1H), 5.88(s, 1H), 6.45(s, 1H), 7.33(d, 2H), 7.64(d, 2H).
Compounds 5-271. delta. ppm1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.76(s, 3H), 4.19(m, 1H), 4.72(s, 2H), 3.95(m, 1H), 5.14(m, 1H), 5.85(s, 1H), 6.58(d, 1H), 7.04(d, 2H), 7.31(s, 1H), 7.39(d, 2H), 7.81(d, 2H).
Compounds 5-272,. delta.ppm 1.34(m, 4H), 1.78(m, 2H), 2.12(m, 2H), 3.61(s, 3H), 4.18(m, 1H), 4.64(s, 2H), 5.20(m, 1H), 5.84(s, 1H), 7.07(d, 2H), 7.34(d, 2H), 7.43(d, 2H), 7.66(d, 2H).
Examples of measurement of biological Activity
The compounds of the present invention were tested for various fungal diseases of plants. The method of testing is as follows:
(1) living body protecting Activity assay
The test was performed using potted seedling assay. Selecting potted cucumber seedlings with consistent growth in two leaf stages as a cucumber downy mildew test material; selecting potted corn seedlings with consistent growth in two leaf stages as corn rust test materials; and selecting potted wheat seedlings with consistent growth in two leaf periods as wheat powdery mildew test materials. The compound of the invention is used for carrying out foliar spray treatment according to the designed concentration, a blank control for spraying clear water is additionally arranged, the treatment is repeated for 3 times, and the disease inoculation is carried out the next day after the treatment. After inoculation, the plants are put in a climatic chamber (the temperature is 25 ℃ in the day, the temperature is 20 ℃ in the night, and the relative humidity is 95-99%) for moisture preservation and culture, after 24 hours, the plant test materials are transferred into a greenhouse for culture, and the plants which do not need the moisture preservation and culture are directly inoculated and cultured in the greenhouse. The compound disease control effect evaluation is carried out after the control is sufficiently ill (usually, one week). Disease grading refers to the national standard of the people's republic of China, namely the pesticide field efficacy test criterion, and the prevention and treatment effect is calculated according to the disease index.
Some of the test results are as follows:
controlling effect of cucumber downy mildew:
when the concentration of the liquid medicine is 400ppm, the control effect of the compounds 5-139 and 5-235 is 100 percent; the control effect of the compounds 5-72 and 5-80 is more than 80 percent;
when the concentration of the liquid medicine is 100ppm, the control effect of the compound 5-235 is 100 percent; the control effect of the compound 5-235 is 60 percent;
prevention effect of corn rust:
when the concentration of the liquid medicine is 400ppm, the control effect of the compounds 5-139 and 5-235 is 100 percent; the control effect of the compounds 5-100 and 5-72 is more than 60 percent;
when the concentration of the liquid medicine is 100ppm, the control effect of the compound 5-235 is 80 percent; the control effect of the compound 5-139 is 60%.
(2) In vitro determination of bacteriostatic activity
The measurement method is as follows: the high-throughput screening method is adopted, i.e. a compound sample to be detected is dissolved by using a proper solvent (the type of the solvent is acetone, methanol, DMF, and the like, and is selected according to the dissolving capacity of the solvent on the sample), and a liquid to be detected with the required concentration is prepared. Under an ultraclean working environment, adding the solution to be tested into micropores of a 96-hole culture plate, adding the pathogen propagule suspension into the micropore, placing the treated culture plate in a constant-temperature incubator for culture, and investigating after 24 hours. During investigation, the germination or growth condition of the pathogen propagules is visually observed, and the bacteriostatic activity of the compound is evaluated according to the germination or growth condition of the control treatment.
The results of the in vitro bacteriostatic activity (expressed as inhibition) test of some compounds are as follows:
the prevention effect of rice blast is as follows:
when the concentration of the liquid medicine is 400ppm, the control effect of the compound 5-2 and the like is 100 percent; the control effect of the compounds 5-99, 5-235 and 5-90 is 80 percent.
Claims (6)
1. A pyrazole cyclohexanediol ether compound is characterized in that: the structure of the compound is shown as the general formula I:
in the formula:
in the general formula I
R1Selected from hydrogen, methyl, ethyl, cyclopropyl or cyclohexyl;
R2selected from hydrogen, chlorine, bromine or methyl;
Q1selected from phenyl, p-chlorophenyl, p-fluorophenyl, p-methylphenyl, p-trifluoromethylphenyl, p-methoxyphenyl, p-trifluoromethoxyphenyl, 2, 4-dichlorophenyl or 2, 4-dimethylphenyl;
Q2selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, chloromethyl, difluoromethyl, trifluoromethyl or Q3；
Q3Selected from the group consisting of phenyl, 4-chlorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, 4-trifluoromethoxyphenyl, 4-cyanophenyl, 2, 4-dichlorophenyl, 2, 4-difluorophenyl, 2,3, 5-trichloro-4, 6-dicyanophenyl, pyridyl, 4-cyanopyridin-2-yl, 6-chloropyridin-2-yl, 4-chlorophenylmethyl, 4-fluorophenylmethyl, 4-trifluoromethylbenzyl, 4-nitrobenzyl, 4-tert-butylbenzyl, 2-chloro-6-fluorophenylmethyl, 2, 6-difluorobenzyl, 6-chloropyridin-3-ylmethyl, 2-chloropyridin-5-ylmethyl, methyl, benzyl, 6-chloropyridazin-3-yl, 3-chloropyridazin-5-yl, phenoxyacetyl, 4-chlorophenoxyacetyl, 4-fluorophenoxyacetyl, 4-trifluoromethylphenoxyacetyl, 2-chloro-4-trifluoromethylphenoxyacetyl, 4-methoxyphenoxyacetyl, 2, 4-dichlorophenoxyacetyl, 2, 4-difluorophenoxyacetyl, 2, 6-difluorophenoxyacetyl or 2,4, 5-trichlorophenoxyacetyl.
2. The compound of claim 1, wherein: in the general formula I
R1Is selected from methyl;
R2selected from hydrogen;
Q1is selected from p-chlorophenyl;
Q2selected from hydrogen, methyl, n-propyl, n-butyl or Q3；
Q3Selected from 4-trifluoromethylphenyl, 2,3, 5-trichloro-4, 6-dicyanophenyl, 4-chlorophenylmethyl, 2-chloro-6-fluorophenylmethyl, 4-tert-butylbenzyl, 4-cyanopyridine-2-yl, 6-chloropyridin-3-ylmethyl, 6-chloropyridazin-3-yl, 4-trifluoromethylphenoxyacetyl, 2-chloro-4-trifluoromethylphenoxyacetyl, 4-methoxyphenoxyacetyl, 2, 4-dichlorophenoxyacetyl or 2,4, 5-trichlorophenoxyacetyl.
3. The compound of claim 2, wherein: in the general formula I
R1Is selected from methyl;
R2selected from hydrogen;
Q1is selected from p-chlorophenyl;
Q2selected from methyl or Q3；
Q3Selected from 4-cyano-2-pyridyl, 6-chloropyridin-3-ylmethyl, 6-chloropyridazin-3-yl or 2-chloro-4-trifluoromethylphenoxyacetyl.
4. Use of a compound of the general formula I according to claim 1 for controlling germs in the agricultural or horticultural field.
5. A germicidal composition, characterized by: comprising as active ingredient a compound of the general formula I according to claim 1 and an agriculturally acceptable carrier, the composition containing from 0.5 to 90% by weight of the active ingredient.
6. Use of the fungicidal composition according to claim 5 for controlling germs in the agricultural or horticultural field.
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