CN112638884A - Triazole sulfonamide derivative and preparation method and application thereof - Google Patents

Triazole sulfonamide derivative and preparation method and application thereof Download PDF

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CN112638884A
CN112638884A CN201980051311.1A CN201980051311A CN112638884A CN 112638884 A CN112638884 A CN 112638884A CN 201980051311 A CN201980051311 A CN 201980051311A CN 112638884 A CN112638884 A CN 112638884A
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alkyl
radical
halo
aryl
alkoxy
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CN112638884B (en
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李义涛
林健
高国良
姚文强
敬德旺
李法霖
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Dongguan Hec Pesticides R&d Co ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms

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Abstract

Provides a triazole sulfonamide derivative and a preparation method and application thereof; specifically, a triazole sulfonamide derivative represented by the formula (I) or a stereoisomer, a nitrogen oxide or a salt thereof, and a method for producing the triazole sulfonamide derivative, their use as fungicides in agriculture, a form of a fungicide composition thereof, and a method for controlling plant diseases using the compounds or the composition; wherein R is1、R2、R3、x、R4、R5And R6Have the meaning as described in the present invention.

Description

Triazole sulfonamide derivative and preparation method and application thereof Technical Field
The invention relates to the field of pesticides, in particular to a triazole sulfonamide derivative, a preparation method of the triazole sulfonamide derivative and application of the triazole sulfonamide derivative as a plant disease control agent in agriculture.
Background
The triazole sulfonamide derivative with biological activity is one of targets of development and research of new pesticides, wherein indazole flusulfamide developed by daily chemistry has high activity on phytophthora blight and downy mildew caused by oomycetes. Oomycetes diseases are common and seriously harmful diseases on fruit and vegetable crops, and the loss caused by the oomycetes diseases is not negligible. However, so far, there are not many agents effective for preventing oomycetes diseases, and triazole sulfonamide derivatives have considerable expansibility and structural modification potential (e.g., WO 2017143803, CN 106905251, etc.). The novel triazole sulfonamide derivatives disclosed in the present invention have not been reported.
Disclosure of Invention
The invention provides a novel triazole sulfonamide derivative which has good control effect on plant pathogenic fungi and can be further developed as a bactericide.
Specifically, in one aspect, the present invention provides a compound which is a compound having formula (I) or a stereoisomer, nitroxide, salt, (E) or (Z) isomer of the compound of formula (I) and mixtures thereof:
Figure PCTCN2019097704-APPB-000001
wherein the content of the first and second substances,
R 1and R2Each independently is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C6-10Aryl radical, C3-8cycloalkyl-C1-6Alkyl-or C6-10aryl-C1-6Alkyl-; wherein, said C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C6-10Aryl radical, C3-8cycloalkyl-C1-6Alkyl-or C6-10aryl-C1-6Alkyl-optionally substituted by 1,2, 3, 4 or 5 groups selected from halogen, hydroxy, cyano, nitro, amino, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6Substituent substitution of alkoxy;
or R1、R 2Together with the nitrogen atom to which they are attached form an optionally substituted 1,2, 3, 4 or 5 substituents selected from halogen, hydroxy, cyano, nitro, amino, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6An alkoxy-substituted 3-10 membered heterocyclyl or 5-10 membered heteroaryl;
R 3is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C1-6Alkyl, halo C2-6Alkenyl, halo C2-6Alkynyl, C6-10Aryl, halo C6-10Aryl radical, C6-10aryl-C1-6Alkyl-or halo-C6-10aryl-C1-6Alkyl-;
x is 0, 1 or 2;
R 4is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C 6-10Aryl radical, C3-8cycloalkyl-C1-6Alkyl-, C6-10aryl-C1-6Alkyl-, 5-6 membered heteroaryl, -C (═ O) OC1-6Alkyl radical, RmS(＝O) 2-or-C (═ O) Rn；
R mAnd RnEach independently is C1-6Alkyl or C6-10An aryl group;
wherein R is4Optionally substituted by 1,2, 3, 4 or 5 substituents selected from halogen, hydroxy, cyano, nitro, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl or halo C1-6Substituent substitution of alkoxy;
R 5is C6-10Aryl or 5-10 membered heteroaryl; wherein R is5Optionally substituted by 1,2, 3, 4 or 5 substituents selected from halogen, hydroxy, cyano, nitro, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl or halo C1-6Substituent substitution of alkoxy;
R 6is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl-, phenyl or phenyl-C1-6Alkyl-;
or R5、R 6And the carbon atom to which they are attached form C9-10Aryl or 9-10 membered heteroaryl; said C9-10Aryl and 9-10 membered heteroaryl optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, cyano, nitro, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl or halo C1-6Substituent of alkoxy.
In some embodiments, R1And R2Each independently is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C6-10Aryl radical, C3-6cycloalkyl-C1-3Alkyl-or C6-10aryl-C1-3An alkyl group-.
In still other embodiments, R1And R2Each independently is C1-4An alkyl group.
In still other embodiments, R1And R2Each independently is hydrogen, -CH3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH(CH 3)CH 2CH 3、-CH 2CH(CH 3) 2、-C(CH 3) 3、-CH＝CH 2、-CH 2CH＝CH 2、-CH＝CHCH 3、-CH 2CH 2CH＝CH 2、-CH 2CH＝CHCH 3、-CH＝CHCH 2CH 3、-C≡CH、-CH 2-C≡CH、-CH 2CH 2-C.ident.CH, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl.
Yet in some embodiments, R1And R2Each independently is-CH3。
In some embodiments, R3Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C1-4Alkyl, halo C2-4Alkenyl, halo C2-4Alkynyl, C6-10Aryl, halo C6-10Aryl radical, C6-10aryl-C1-3Alkyl-or halo-C6- 10aryl-C1-3An alkyl group-.
In still other embodiments, R3Is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, -CH3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-C(CH 3) 3、-CH 2Cl、-CHF 2or-CF3。
Yet in some embodiments, R3Is hydrogen.
In some embodiments, R4Is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl, phenyl, benzyl, C3-6cycloalkyl-C1-3Alkyl-, pyridyl, pyrazinyl, pyridazinyl, -C (═ O) OC1-4Alkyl radical, RmS(＝O) 2-or-C (═ O) Rn；
R mAnd RnEach independently is C1-4Alkyl or phenyl;
wherein R is4Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Substituent of alkoxy.
In still other embodiments, R4Is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl, phenyl, benzyl, C3-6cycloalkyl-C1-3Alkyl-, pyridyl, pyrazinyl, pyridazinyl, -C (═ O) OC1-4Alkyl radical, RmS(＝O) 2-or-C (═ O) Rn；
R mAnd RnEach independently is C1-4Alkyl or phenyl;
wherein R is4Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, cyano, nitro, CH3-or CF3-substituent substitution.
In still other embodiments, R4Is hydrogen, C1-4Alkyl, -C (═ O) OC1-4Alkyl, phenyl-S (═ O)2-or-C (═ O) Rn；
R nIs C1-4Alkyl or phenyl;
wherein R is4Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Substituent of alkoxy.
In still other embodiments, R4Is hydrogen, C1-4Alkyl, -C (═ O) OC1-4Alkyl, phenyl-S (═ O)2-or-C (═ O) Rn；
R nIs C1-4Alkyl or phenyl;
wherein R is4Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, cyano, nitro, CH3-or CF3-substituent substitution.
In still other embodiments, R4Is hydrogen, -CH3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-C(＝O)CH 3or-C (═ O) OCH3；
Or R4Is of the sub-structure:
Figure PCTCN2019097704-APPB-000002
Figure PCTCN2019097704-APPB-000003
in some embodiments, R5Is C6-10Aryl or 5-10 membered heteroaryl; wherein R is5Optionally substituted by 1,2, 3, 4 or 5 substituents selected from halogen, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Substituent of alkoxy.
In still other embodiments, R5Is C6-10Aryl or 5-9 membered heteroaryl; wherein R is5Optionally substituted by 1,2, 3, 4 or 5 substituents selected from halogen, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Substituent of alkoxy.
In some embodiments, R5Is phenyl, naphthyl, pyridyl, pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, 1H-1,2, 4-triazolyl or 1H-indolyl;
wherein R is5Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Substituent of alkoxy.
Or R5、R 6And the carbon atom to which it is attached
Figure PCTCN2019097704-APPB-000004
In still other embodiments, R5Is phenyl, naphthalen-1-yl, pyridin-2-yl, pyridin-3-yl, 1H-pyrrol-2-yl, thiophen-3-yl, 1H-imidazol-1-yl, isoxazol-3-yl, 1H-indol-3-yl, or 1H-indol-4-yl;
wherein R is5Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Substituent of alkoxy.
In still other embodiments, R5Is phenyl, naphthalen-1-yl, pyridin-2-yl, pyridin-3-yl, 1H-pyrrol-2-yl, thiophen-3-yl, 1H-imidazol-1-yl, isoxazol-3-yl, 1H-indol-3-yl or 1H-indol-4-yl;
wherein R is5Optionally substituted by 1,2 or 3 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, -CH3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH(CH 3)CH 2CH 3、-CH 2CH(CH 3) 2、-C(CH 3) 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OCH 2CH 2CH 2CH 3、-OCH(CH 3)CH 2CH 3、-OCH 2CH(CH 3) 2、-OC(CH 3) 3、-CF 3or-OCF3Is substituted with the substituent(s).
In some embodiments, R6Is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl or phenyl.
In still other embodiments, R6Is hydrogen, C1-4Alkyl or phenyl.
In still other embodiments, R6Is hydrogen, -CH3Or a phenyl group.
In still other embodiments, the first and second electrodes are,
Figure PCTCN2019097704-APPB-000005
is of the sub-structure:
Figure PCTCN2019097704-APPB-000006
Figure PCTCN2019097704-APPB-000007
in some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, a salt, (E) or (Z) isomer of a compound having or represented by formula (II):
Figure PCTCN2019097704-APPB-000008
wherein R is4And R5Have the meaning as described in the present invention.
In some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, a salt, (E) or (Z) isomer of a compound having or represented by formula (II):
Figure PCTCN2019097704-APPB-000009
wherein the content of the first and second substances,
R 4is hydrogen, C1-4Alkyl, -C (═ O) OC1-4Alkyl radical, RmS(＝O) 2-or-C (═ O) Rn；
R mIs optionally substituted by 1 or 2 halogen, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Alkoxy-substituted phenyl;
R nis C1-4Alkyl or optionally substituted by halogen, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1- 4Alkoxy-substituted phenyl;
R 5is optionally substituted by 1,2 or 3 halogen, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Phenyl substituted by alkoxy, naphthyl, pyridin-2-yl or pyridin-3-yl optionally substituted by 1 or 2 halogens, optionally C1-4Alkyl-substituted 1H-pyrrol-2-yl or isoxazol-3-yl, thiophen-2-yl, 1H-imidazol-1-yl, 1H-indol-3-yl or 1H-indol-4-yl.
In still other embodiments, R4Is hydrogen, -CH3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-C(＝O)CH 3or-C (═ O) OCH3；
Or R4Is of the sub-structure:
Figure PCTCN2019097704-APPB-000010
in still other embodiments, R5Is optionally substituted by 1,2 or 3 fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, -CH3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH(CH 3)CH 2CH 3、-CH 2CH(CH 3) 2、-C(CH 3) 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-CF 3or-OCF3Substituted phenyl, naphthalen-1-yl, pyridin-2-yl or pyridin-3-yl optionally substituted with 1 or 2 fluoro, chloro, bromo or iodo, optionally substituted with-CH3、-CH 2CH 3、-CH 2CH 2CH 3or-CH (CH)3) 2Substituted 1H-pyrrol-2-yl or isoxazol-3-yl, thiophen-2-yl, 1H-imidazol-1-yl, 1H-indol-3-yl or 1H-indol-4-yl.
Yet in some embodiments, R5Is of the sub-structure:
Figure PCTCN2019097704-APPB-000011
Figure PCTCN2019097704-APPB-000012
in some embodiments, the present invention provides a compound that is a stereoisomer, a nitroxide, or a salt thereof, of a compound having or represented by formula (III):
Figure PCTCN2019097704-APPB-000013
wherein R is4And R5Have the meaning as described in the present invention.
In some embodiments, the present invention provides a compound that is a compound having one of the following structures or a stereoisomer, nitroxide, salt, (E) or (Z) isomer of a compound having one of the following structures and mixtures thereof:
Figure PCTCN2019097704-APPB-000014
Figure PCTCN2019097704-APPB-000015
Figure PCTCN2019097704-APPB-000016
Figure PCTCN2019097704-APPB-000017
in another aspect, the present invention provides a composition comprising at least one compound of the present invention.
Further, the composition of the present invention comprises an agriculturally pharmaceutically acceptable surfactant and/or carrier.
In still another aspect, the present invention provides use of the compound of the present invention or the composition of the present invention as a plant disease control agent in agriculture.
In yet another aspect, the present invention provides a method of controlling plant diseases by a compound of the present invention or a composition of the present invention.
Further, the present invention provides a method of applying the compound of the present invention or the composition of the present invention to a plant or a plant growing locus before or after germination of a plant disease.
Detailed description of the invention
Definitions and general terms
Reference will now be made in detail to certain embodiments of the invention, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. One skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ or contradict this application (including but not limited to defined terminology, application of terminology, described techniques, and the like), this application controls.
It will be further appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.
The following definitions, as used herein, should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of the elements, and the handbook of chemistry and Physics, 75 th edition, 1994. In addition, general principles of Organic Chemistry can be referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and Jerry March, John Wiley & Sons, New York:2007, the entire contents of which are incorporated herein by reference.
The articles "a," "an," and "the" as used herein are intended to include "at least one" or "one or more" unless otherwise indicated or clearly contradicted by context. Thus, as used herein, the articles refer to one or to more than one (i.e., to at least one) of the objects. For example, "a component" refers to one or more components, i.e., there may be more than one component contemplated for use or use in embodiments of the described embodiments.
The term "comprising" is open-ended, i.e. includes the elements indicated in the present invention, but does not exclude other elements.
"stereoisomers" refers to compounds having the same chemical structure but differing in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.
"enantiomer" refers to two isomers of a compound that are not overlapping but are in mirror image relationship to each other.
"diastereomer" refers to a stereoisomer that has two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivities. Mixtures of diastereomers may be separated by high resolution analytical procedures such as electrophoresis and chromatography, e.g., HPLC.
The stereochemical definitions and rules used in the present invention generally follow the general definitions of S.P. Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; and Eliel, E.and Wilen, S., "Stereochemistry of Organic Compounds", John Wiley & Sons, Inc., New York, 1994.
Many organic compounds exist in an optically active form, i.e., they have the ability to rotate the plane of plane polarized light. In describing optically active compounds, the prefixes D and L or R and S are used to denote the absolute configuration of a molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are the symbols used to specify the rotation of plane polarized light by the compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are dextrorotatory. A particular stereoisomer is an enantiomer and a mixture of such isomers is referred to as an enantiomeric mixture. A50: 50 mixture of enantiomers is referred to as a racemic mixture or racemate, which may occur when there is no stereoselectivity or stereospecificity in the chemical reaction or process.
Any asymmetric atom (e.g., carbon, etc.) of a compound disclosed herein can exist in racemic or enantiomerically enriched forms, such as the (R) -, (S) -or (R, S) -configuration. In certain embodiments, each asymmetric atom has at least 50% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in the (R) -or (S) -configuration.
Depending on the choice of starting materials and methods, the compounds of the invention may exist as one of the possible isomers or as mixtures thereof, for example as racemates and mixtures of non-corresponding isomers (depending on the number of asymmetric carbon atoms). Optically active (R) -or (S) -isomers can be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. If the compound contains a double bond, the substituents may be in the E or Z configuration; if the compound contains a disubstituted cycloalkyl group, the substituents of the cycloalkyl group may have cis or trans configuration.
Any resulting mixture of stereoisomers may be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers, depending on differences in the physicochemical properties of the components, for example, by chromatography and/or fractional crystallization.
The racemates of any of the resulting end products or intermediates can be resolved into the optical enantiomers by known methods using methods familiar to those skilled in the art, e.g., by separation of the diastereomeric salts obtained. The racemic product can also be separated by chiral chromatography, e.g., High Performance Liquid Chromatography (HPLC) using a chiral adsorbent. In particular, enantiomers can be prepared by asymmetric synthesis.
The compounds of the invention may be optionally substituted with one or more substituents, as described herein, in compounds of the general formula above, or as specifically exemplified, sub-classes, and classes of compounds encompassed by the invention. It is understood that the term "optionally substituted" may be used interchangeably with the term "substituted or unsubstituted". In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced with a particular substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substitutable position of the group. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, the substituents may be substituted at each position, identically or differently. Specifically, examples of "one or more" refer to 1,2, 3, 4, 5, 6, 7, 8, 9, or 10. Wherein said substituent may be, but is not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxyl-substituted alkyl, hydroxyl-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkanoyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl, and the like.
In addition, unless otherwise explicitly indicated, the descriptions of the terms "… independently" and "… independently" and "… independently" used in the present invention are interchangeable and should be understood in a broad sense to mean that the specific items expressed between the same symbols do not affect each other in different groups or that the specific items expressed between the same symbols in the same groups do not affect each other.
In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C1-C 6Alkyl "or" C1-6Alkyl "means in particular independently disclosed methyl, ethyl, C3Alkyl radical, C4Alkyl radical, C5Alkyl and C6An alkyl group.
The term "alkyl" or "alkyl group" as used herein, denotes a saturated, straight or branched chain, monovalent hydrocarbon group containing from 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in one embodiment, the alkyl group contains 1 to 8 carbon atoms; in another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 4 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.
Examples of alkyl groups include, but are not limited to, methyl (Me, -CH)3) Ethyl group (Et, -CH)2CH 3) N-propyl (n-Pr, -CH)2CH 2CH 3) Isopropyl group (i-Pr, -CH (CH)3) 2) N-butyl (n-Bu, -CH)2CH 2CH 2CH 3) Isobutyl (i-Bu, -CH)2CH(CH 3) 2) Sec-butyl (s-Bu, -CH (CH)3)CH 2CH 3) Tert-butyl (t-Bu, -C (CH)3) 3) N-pentyl (-CH)2CH 2CH 2CH 2CH 3) 2-pentyl (-CH (CH)3)CH 2CH 2CH 3) 3-pentyl (-CH (CH)2CH 3) 2) 2-methyl-2-butyl (-C (CH)3) 2CH 2CH 3) 3-methyl-2-butyl (-CH (CH)3)CH(CH 3) 2) 3-methyl-1-butyl (-CH)2CH 2CH(CH 3) 2) 2-methyl-1-butyl (-CH)2CH(CH 3)CH 2CH 3) And so on.
The term "alkoxy" means an alkyl group attached to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH)3) Ethoxy (EtO, -OCH)2CH 3) 1-propoxy (n-PrO, n-propoxy, -OCH)2CH 2CH 3) 2-propoxy (i-PrO, i-propoxy, -OCH (CH)3) 2) And so on.
The term "alkenyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one site of unsaturation, i.e. one carbon-carbon sp2A double bond, wherein the alkenyl group may be optionally substituted with one or more substituents described herein, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". In one embodiment, the alkenyl group contains 2 to 8 carbon atoms; in another embodiment, the alkenyl group contains 2 to 6 carbon atoms; in yet another embodiment, the alkenyl group contains 2 to 4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH ═ CH)2) Allyl (-CH)2CH＝CH 2) Allyl (CH)3-CH ═ CH-), oxo butenyl (CH)3-C (═ O) -CH ═ CH-) and the like.
The term "alkynyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond. In one embodiment, alkynyl groups contain 2-8 carbon atoms; in another embodiment, alkynyl groups contain 2-6 carbon atoms; in yet another embodiment, alkynyl groups contain 2-4 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C.ident.CH, -CH2-C≡CH、-CH 2-C≡CCH 3、-CH 2CH 2-C≡CH、-CH 2-C≡CCH 2CH 3And so on.
The term "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing from 3 to 12 carbon atoms. In one embodiment, the cycloalkyl group contains 3 to 10 carbon atoms; in another embodiment, cycloalkyl contains 3 to 8 carbon atoms; in yet another embodiment, the cycloalkyl group contains 3 to 6 carbon atoms. The cycloalkyl group is optionally substituted with one or more substituents described herein. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and the like.
The term "cycloalkylalkyl" denotes an alkyl group wherein the hydrogen atom is replaced by one or more cycloalkyl groups, wherein alkyl and cycloalkyl groups have the meaning as described herein.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The term "haloalkyl" denotes an alkyl group substituted with one or more halogen atoms, examples of which include, but are not limited to, -CF3，-CHF 2，-CH 2Cl，-CH 2CF 3，-CH 2CHF 2，-CH 2CH 2CF 3And so on.
The term "haloBy "alkoxy" is meant an alkoxy group substituted with one or more halogen atoms, examples of which include, but are not limited to, -OCF3，-OCHF 2，-OCHCl 2，-OCH 2CHF 2，-OCH 2CHCl 2，-OCH(CH 3)CHF 2And so on.
The term "heterocyclyl" the terms "heterocyclyl" and "heterocycle" are used interchangeably herein and refer to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing 3 to 15 ring atoms, wherein no aromatic ring is included in the monocyclic, bicyclic or tricyclic ring, and at least one ring atom is selected from the group consisting of nitrogen, sulfur and oxygen atoms. Unless otherwise specified, heterocyclyl may be carbon-or nitrogen-based, and-CH2-the group may optionally be replaced by-C (═ O) -. The sulfur atom of the ring may optionally be oxidized to the S-oxide. The nitrogen atom of the ring may optionally be oxidized to an N-oxygen compound.
The terms "3-12 membered heterocyclyl", "3-10 membered heterocyclyl", "3-8 membered heterocyclyl" or "3-6 membered heterocyclyl", wherein "3-12 membered", "3-10 membered", "3-8 membered" or "3-6 membered" typically describe the number of ring-forming atoms in the molecule. For example, piperidinyl is 6-membered heterocyclyl.
The term "aryl" denotes monocyclic, bicyclic and tricyclic carbon ring systems containing 6 to 14 ring atoms, or 6 to 12 ring atoms, or 6 to 10 ring atoms, wherein at least one ring system is aromatic, wherein each ring system comprises a ring of 3 to 7 atoms with one or more attachment points to the rest of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring". Examples of the aryl group may include phenyl, indenyl, naphthyl and anthryl. The aryl group is optionally substituted with one or more substituents described herein.
The term "arylalkyl" means that the hydrogen atoms in the alkyl group are replaced by one or more aryl groups, wherein the alkyl and aryl groups have the meaning as described herein. Examples include, but are not limited to, benzyl, phenethyl, and the like.
The term "heteroaryl" denotes monocyclic, bicyclic and tricyclic ring systems containing 5 to 12 ring atoms, or 5 to 10 ring atoms, or 5 to 6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring of 5 to 7 atoms with one or more attachment points to the rest of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein. In one embodiment, a heteroaryl group of 5-10 atoms contains 1,2, 3, or 4 heteroatoms independently selected from O, S, and N. Examples of heteroaryl groups may include pyridyl, pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, 1,2, 4-triazolyl, indolyl and the like.
The terms "5-9 membered heteroaryl", "5-10 membered heteroaryl", "9-10 membered heteroaryl", or "5-6 membered heteroaryl", wherein "5-9 membered", "5-10 membered", "9-10 membered", "5-6 membered" typically describe the number of ring-forming atoms in the molecule. For example, pyridinyl is 6 membered heteroaryl.
In the various parts of this specification, linking substituents are described. Where the structure clearly requires a linking group, the markush variables listed for that group are understood to be linking groups. For example, if the structure requires a linking group and the markush group definition for that variable recites "alkyl" or "aryl," it is understood that the "alkyl" or "aryl" represents an attached alkylene group or arylene group, respectively.
The term "alkylene" refers to a saturated divalent hydrocarbon radical resulting from the removal of two hydrogen atoms from a saturated hydrocarbon radical. Unless otherwise specified, the alkylene group contains 1 to 12 carbon atoms, in other embodiments 1 to 6 carbon atoms, in other embodiments 1 to 4 carbon atoms, and in other embodiments 1 to 2 carbon atoms. Examples of this include methylene (-CH)2-, ethylene (-CH)2CH 2-, isopropylidene (-CH (CH)3)CH 2-) and the like.
The term "haloalkenyl" denotes an alkenyl group substituted with one or more halogen atoms.
The term "haloalkynyl" denotes an alkynyl group substituted by one or more halogen atoms.
The term "haloaryl" denotes an aryl group substituted with one or more halogen atoms.
The term "haloarylalkyl" means that the "arylalkyl" group is substituted with one or more halogen atoms.
Wherein R is5And R6At a different time,
Figure PCTCN2019097704-APPB-000018
can be expressed as (E) isomer, (Z) isomer or a mixture of (E) isomer and (Z) isomer; wherein said (E) isomer corresponds to
Figure PCTCN2019097704-APPB-000019
Corresponding to the isomer
Figure PCTCN2019097704-APPB-000020
The isomer, (E) isomer or a mixture of the (Z) isomer and the (E) isomer can be separated and identified by a conventional method such as high performance liquid chromatography, nuclear magnetic resonance hydrogen spectroscopy and/or single crystal diffraction.
Salts of the compounds of the present invention include those derived from alkali or alkaline earth metals as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and those of formula N+(R AR BR CR D) Ammonium cation of (2), wherein R isA、R B、R CAnd RDIs independently selected fromHydrogen, C1-C 6Alkyl and C1-C 6A hydroxyalkyl group. Salts of compounds having formula (I), formula (II) or formula (III) may be prepared by treating a compound having formula (I), formula (II) or formula (III) with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine).
When a compound of the invention comprises a base moiety, acceptable salts can be formed from organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, napthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids.
Compositions and formulations of the compounds of the invention
The compounds of the invention are generally useful as fungicide active ingredients in compositions or formulations, typically also comprising an agriculturally acceptable surfactant and/or carrier.
The surfactant may be any of various surfactants known in the art of pesticide formulation, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants may be used as emulsifiers, dispersants, wetting agents, penetration enhancers or adjuvants.
Suitable anionic surfactants are alkali metal, alkaline earth metal or ammonium salts of sulfonic acids, sulfuric acids, phosphoric acids, carboxylic acids and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignosulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl-and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols or sulfates of fatty acid esters. An example of a phosphate is a phosphate ester. Examples of carboxylates are alkyl carboxylates and also carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated by 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be used for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate.
Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds having 1 or 2 hydrophobic groups, or salts of long chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyoxyethylene and polyoxypropylene, or block polymers of the A-B-C type comprising alkanols, polyoxyethylene and polyoxypropylene. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali metal salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamine or polyvinylamine.
The carrier may be any of various carriers known in the field of agricultural chemical preparations, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: white carbon black, kaolin, diatomite, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, an amine fertilizer, a mixture of urea and an amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, a mixture of anhydrous potassium carbonate and anhydrous potassium bicarbonate, and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.
The fungicide composition according to the present invention may further contain various formulation auxiliaries commonly used in the field of pesticide formulation, and specifically, the formulation auxiliaries may be one or more of a solvent, a cosolvent, a thickener, an antifreeze, a capsule material, a protectant, an antifoaming agent, a disintegrant, a stabilizer, a preservative, a binder, and a chelating agent.
Suitable solvents are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, such as toluene, paraffins, tetrahydronaphthalene, alkylated naphthalenes; alcohols, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, such as cyclohexanone; esters, such as lactate, carbonate, fatty acid ester, γ -butyrolactone; a fatty acid; a phosphonate ester; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof.
The solvents mentioned above can also be used as cosolvents.
Suitable thickeners are selected from polysaccharides (e.g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates.
Suitable antifreeze agents are selected from the group consisting of ethylene glycol, propylene glycol, glycerol, urea, glycerol and mixtures thereof.
Suitable capsule materials are selected from the group consisting of polyurethanes, polyureas, urea-formaldehyde resins and mixtures thereof.
Suitable protective agents are selected from polyvinyl alcohol and/or polyethylene glycol.
Suitable antifoaming agents are selected from the group consisting of polysiloxanes, silicone emulsions, long chain alcohols, fatty acids and salts thereof, and fluoro-organics and mixtures thereof.
Suitable disintegrants are selected from bentonite, urea, ammonium sulphate, aluminium chloride, citric acid, succinic acid, sodium bicarbonate and mixtures thereof.
Suitable stabilizers are selected from the group consisting of triphenyl phosphite, epichlorohydrin, acetic anhydride and mixtures thereof.
Suitable preservatives are selected from benzoic acid, sodium benzoate, 1, 2-benzisothiazolin-3-one (BIT for short), carbazone, potassium sorbate and mixtures thereof.
Suitable binders are selected from polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological or synthetic waxes and cellulose ethers.
The fungicides according to the invention can be applied in their formulated form or in the use forms prepared therefrom, such as aerosols, capsule suspensions, cold-fogging concentrates, hot-fogging concentrates, encapsulated granules, fine granules, flowable concentrates for seed treatment (flowable concentrates), ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogranules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, gas agents (under pressure), gas-generating products, foams, pastes, suspension concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granules, water-soluble and water-dispersible granules or tablets, water-soluble or water-dispersible powders for seed treatment, wettable powders, natural and synthetic substances impregnated with active substances, and microcapsules in polymers and seed coatings, and ULV (ultra low volume) cold and hot fog formulations. The above forms of use can be prepared by conventional means in the art.
Application of the inventive compounds and compositions
The compound of the present invention is useful as a plant disease control agent, i.e., as a bactericide. The present invention therefore also comprises a method for controlling plant diseases caused by phytopathogenic fungi, which comprises applying to the plants to be protected or to parts thereof or to the seeds of the plants to be protected an effective amount of a compound according to the invention or of a fungicidal composition comprising said compound. The compounds and/or compositions of the present invention provide control of diseases caused by a broad spectrum of phytopathogenic fungi of the classes Basidiomycetes, Ascomycetes, Oomycetes and Deuteromycetes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, turf, vegetable, field, cereal and fruit crops. These pathogens include: oomycetes, including Phytophthora (Phytophthora) diseases such as Phytophthora infestans, Phytophthora sojae (Phytophthora megasporum), Phytophthora citri (Phytophthora parasitica), Phytophthora citrullus (Phytophthora parasiti), Phytophthora cinnamomi (Phytophthora cinnamomi) and Phytophthora cucurbitae (Phytophthora capsici), Pythium graminum (Pythium) species diseases such as Pythium turtium (Pythium aphanidermatum) diseases, and Peronosporaceae (Peronospora) species diseases such as Plasmopara viticola (Plasmopara viticola), Peronospora (Peronospora spp.) (including P. nicotianae (Peronospora tabacina) and P. parasitica (Pseudoperonospora Pseudoperonospora), including P. nicotianae (Pseudoperonospora cinerea) and P. Pseudoperonospora (Pseudoperonospora Pseudoperonospora) diseases including P); ascomycetes (including Alternaria (Alternaria) such as Alternaria solani and Phytophthora brassicae (Alternaria solani), Mycoporia globosa (Guignardia) diseases such as Staphylococcus viticola (Guignardia bidwell), Venturia (Venturia) diseases such as Venturia mali (Venturia inaequalis), Sphaerotheca (Sepia) diseases such as Microphyllum nodosum (Septorium nodorum) and Phytophthora parasitica (Septorii), Powderzia (Powdery) diseases such as Erysiphe graminis (Erysiphe spp.) and Sphaerotheca (Septoria oryzae), Powder Erysiphe (Erysiphe) diseases such as Microphyllum graminis (Erysiphe sp.) and Pseudoperonospora cinerea (Ostericola), Staphylococcus viticola (Uncinula necator), Pseudoperonospora cucumerina (Sphaerothecoides) and Pseudoperonospora cinerea (Botrytis), Scleroti cinerea) diseases such as Microphyllum cinerea (Botrytium cinerea), Scleroti cinerea) diseases such as Microphyllum cinerea (Botrytum cinerea), Scleroti cinerea (Potentilla) diseases such as Microphyllum cinerea (Botrytum cinerea), Scleroti cinerea) diseases such as Microphyllum cinerea (Potentilla cinerea), Scleroti cinerea (Potentilla cinerea), Scleroti cinerea) diseases such, Pyricularia oryzae (Magnaporthe grisea), Rhizoctonia solani (Phomopsis viticola), Helminthosporium (Helminthosporium) diseases such as northern leaf blight (Helminthosporium tritici reptilis), Moss reticulata (Pyrenophora teres), anthrax bacteria such as Hedychium nigrum (Glomerella) or Anthrax (Colletochium spp.) diseases (such as Colletotrichum graminicum (Colestochium graminicum) and watermelon anthrax (Colletochium orbiculosum)), and wheat holothrix graminis (Gaeumannomyces graminis); basidiomycetes, including rust diseases caused by the genus Puccinia (Puccinia spp.), such as Puccinia recondita (Puccinia recondita), Puccinia striiformis (Puccinia striiformis), Puccinia purpurea (Puccinia hordei), Puccinia graminis (Puccinia graminis) and Puccinia arachidis (Puccinia arachidis), coffee rust (hemix) and soybean rust (Phakopsora pachyrhizi); other pathogens include Rhizoctonia species (Rhizoctonia spp.) (such as Rhizoctonia solani); fusarium species diseases such as Fusarium roseum (Fusarium roseum), Fusarium graminearum (Fusarium graminearum), and Fusarium oxysporum (Fusarium oxysporum); verticillium dahliae (Verticillium dahliae); sclerotium rolfsii (sclerotiotium rolfsii); physalospora piricola (Rynchosporium secalis); black acerola (Cercosporium personatum), Episra nigrella (Cercospora arachidicola), and Episra fuscospora (Cercospora betacola); and other classes and species closely related to these pathogens. In addition to their fungicidal activity, the compositions or combinations also have a resistant activity against bacteria such as Erwinia amylovora (Erwinia amylovora), Xanthomonas campestris (Xanthomonas campestris), Pseudomonas syringae (Pseudomonas syringae) and other species.
The bactericide composition of the invention is simple in use method, and can be applied to crops and places where the crops grow by a conventional method such as soil mixing, spraying, pouring and the like before or after the germination of plant diseases, wherein the application amount is determined according to climatic conditions or crop states, generally 10-5000g is applied per mu, and the diluted application amount is 10-400mg/L (preferably 100-300 mg/L). The diluent is preferably water.
The bactericidal effect of the bactericide composition of the present invention is generally related to external factors such as climate, but the influence of climate can be alleviated by using appropriate dosage forms.
The compositions of the present invention may also be used in admixture with other compounds having fungicidal, insecticidal or herbicidal properties, as well as with nematicides, acaricides, protectants, herbicidal safeners, growth regulators, plant nutrients or soil conditioners, and the like.
General synthetic procedure
In this specification, a structure is dominant if there is any difference between the chemical name and the chemical structure. In general, the compounds of the invention may be prepared by the methods described herein, unless otherwise indicated, wherein the substituents are as defined herein.
Those skilled in the art will recognize that: the chemical reactions described herein may be used to suitably prepare a number of other compounds of the invention, and other methods for preparing the compounds of the invention are considered to be within the scope of the invention. For example, the synthesis of those non-exemplified compounds according to the present invention can be successfully accomplished by those skilled in the art by modification, such as appropriate protection of interfering groups, by the use of other known reagents (other than those described herein), or by some routine modification of reaction conditions. In addition, the reactions disclosed herein or known reaction conditions are also recognized as being applicable to the preparation of other compounds of the present invention. In addition, in some embodiments, unless otherwise specified, the reaction of the present invention is carried out at room temperature, wherein the room temperature is 0 to 35 ℃.
The test conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: brookfield (Bruker) nuclear magnetic instrument at 400MHz or 600MHz in CDC1 at room temperature3，d 6-DMSO，CD 3OD or d6Acetone as solvent (reported in ppm) with TMS (0ppm) or chloroform (7.26ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (singleton), d (doublet), t (triplet), q (quatet, quartet), d (singlet), d (doublet, triplet), d (doublet, triplet, or triplet, and) M (multiplet ), br (broad), dd (duublet of doublets), dt (duublet of triplets, double triplets). Coupling constants are expressed in hertz (Hz).
The mass spectrum test conditions used in the invention are as follows: the conditions for low resolution Mass Spectrometry (MS) data determination were: agilent 6120 Quadrupole HPLC-MS (column model: Zorbax SB-C18,2.1X 30mm,3.5 μm,6min, flow rate 0.6mL/min, mobile phase 5% -95% (CH with 0.1% formic acid)3CN) in (H containing 0.1% formic acid)2Proportion in O)), at 210/254nm with UV detection, using electrospray ionization mode (ESI).
The following synthetic schemes describe the steps for preparing the compounds disclosed herein.
Synthetic schemes
Synthesis scheme I
Figure PCTCN2019097704-APPB-000021
The target compound of formula (I-1) can be prepared by the first synthesis scheme. Carrying out condensation reaction on the compound of the formula (a) and the compound of the formula (b) to obtain a compound of a formula (c); carrying out nucleophilic substitution reaction on the compound in the formula (c) and an intermediate O to obtain a target compound in a formula (I-1);
wherein R is4、R 5And R6Have the meaning as described in the present invention.
Examples
Intermediate O: synthesis of 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride
Figure PCTCN2019097704-APPB-000022
Step A: synthesis of 1, 2-di (1H-1,2, 4-triazole-3-yl) dithioane
Figure PCTCN2019097704-APPB-000023
3-mercapto-1, 2, 4-triazole (101.0g,1.00mol) is dissolved in dichloromethane (500mL), pyridine (79.0g,1.00mol) is added, benzenesulfonyl chloride (88.30g,0.50mol) is slowly added dropwise at 0 ℃, and after the dropwise addition is finished for 2h, the mixture is stirred at room temperature for 18 h. The dichloromethane was evaporated under reduced pressure using a rotary evaporator, the residue was stirred for 1 hour with water (500mL) under mechanical stirring, filtered, and the residue was washed with water (800mL) and ethyl acetate (300mL), respectively, and air-dried to give 95.2g of a yellow powder with a yield of 95.2%.
LC-MS:(M+1)m/z＝201.1。
And B: synthesis of 3,3' -disulfanediylbis (N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide)
Figure PCTCN2019097704-APPB-000024
Under the protection of nitrogen, 1, 2-bis (1H-1,2, 4-triazole-3-yl) disulfane (60.0g,0.30mol) is dissolved in N, N-dimethylformamide (300mL), potassium carbonate (69.0g,0.50mol) is added, N-dimethylaminosulfonyl chloride (93.34g,0.65mol) is slowly dropped at 0 ℃, the reaction is continued for 6 hours after the dropping is finished for 2 hours. After the reaction was completed, the reaction solution was slowly poured into water, stirred for 1 hour, filtered, and the solid was air-dried to obtain 107.2g of a white powder with a yield of 86.3%.
LC-MS:(M+1)m/z＝415.0。
And C: synthesis of 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride
Figure PCTCN2019097704-APPB-000025
3,3' -disulfanediylbis (N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide) (41.40g,0.10mol) was dissolved in 1, 2-dichloroethane (300mL), water (300mL) was added, cooling to 0 deg.C, acetic acid (100mL) was added, the temperature was controlled at 10 deg.C to 25 deg.C, chlorine (35.50g,0.50mol) was continuously fed over 2 hours, and the reaction was continued for half an hour. After completion of the reaction, the solution was transferred to a separatory funnel, allowed to stand for separation, the organic phase was washed three times with water (30mL), and the solvent was evaporated under reduced pressure using a rotary evaporator to obtain 48.11g of a white powder with a yield of 87.8%.
LC-MS:(M+1)m/z＝274.8。
Intermediate O1: (E) synthesis of (E) -1-benzylidene-2-methylhydrazine
Figure PCTCN2019097704-APPB-000026
Methylhydrazine (1.26g,11.0mmol) having a content of 40% was added to a 100mL single-neck flask, and tetrahydrofuran (30mL) was added, and stirred at 0 ℃ for 10 minutes, and benzaldehyde (1.06g,10.0mmol) was dissolved in tetrahydrofuran (10mL) and slowly added dropwise to the reaction system, and reacted at room temperature for 3 hours. TLC monitored the progress of the reaction, after the reaction was complete, quenched with water (20mL), extracted with ethyl acetate (20mL x 3), the organic phase was dried over anhydrous sodium sulfate and filtered, the filtrate was removed the solvent under reduced pressure using a rotary evaporator, and the residue was separated by column chromatography [ ethyl acetate/petroleum ether (v/v) ═ 1/3] to give 1.26g of a white solid, yield: 94 percent.
1H NMR(400MHz,CDCl 3)δ(ppm):7.74(s,1H),7.52(dd,J＝7.1,2.1Hz,2H),7.34(dd,J＝6.4,2.3Hz,2H),5.62(s,1H),4.58(s,1H),3.53(s,3H)；
LC-MS:(M+1)m/z＝135.1。
Referring to the preparation method of intermediate O1((E) -1-benzylidene-2-methylhydrazine), the intermediate compounds in table 1 can be obtained by reacting the corresponding hydrazine with formaldehyde derivatives.
TABLE 1
Figure PCTCN2019097704-APPB-000027
Figure PCTCN2019097704-APPB-000028
Figure PCTCN2019097704-APPB-000029
Figure PCTCN2019097704-APPB-000030
Example 1: (E) synthesis of (E) -3- ((2-benzylidene-1-methylhydrazino) sulfonyl) -N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide
Figure PCTCN2019097704-APPB-000031
Adding the intermediate (E) -1-benzylidene-2-methylhydrazine (0.52g,4.0mmol), pyridine (0.64g,8.0mmol) and tetrahydrofuran (30mL) into a 100mL single-neck bottle, stirring uniformly at room temperature, slowly adding 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride (1.64g,6.0mmol) into the reaction system, and stirring for reaction at room temperature for 12 hours. Quenching with water (20mL), extraction with ethyl acetate (15mL × 3), drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure using a rotary evaporator, and column chromatography of the residue [ ethyl acetate/petroleum ether (v/v) ═ 1/3] afforded 0.65g of a white solid in yield: 44 percent.
1H NMR(400MHz,CDCl 3)δ(ppm):8.58(s,1H),7.74(s,1H),7.62(dd,J＝7.1,2.1Hz,2H),7.37-7.32(m,3H),3.53(s,3H),2.95(s,6H)；
LC-MS:(M+1)m/z＝373.1。
Referring to a similar synthesis method of example 1, the intermediate O (1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride) is reacted with the corresponding intermediate compounds in table 1 respectively to obtain the target compounds in table 2.
TABLE 2
Figure PCTCN2019097704-APPB-000032
Figure PCTCN2019097704-APPB-000033
Figure PCTCN2019097704-APPB-000034
Figure PCTCN2019097704-APPB-000035
Figure PCTCN2019097704-APPB-000036
Figure PCTCN2019097704-APPB-000037
Figure PCTCN2019097704-APPB-000038
Figure PCTCN2019097704-APPB-000039
Figure PCTCN2019097704-APPB-000040
Figure PCTCN2019097704-APPB-000041
Figure PCTCN2019097704-APPB-000042
Examples of Activity test
Test targets: cucumber downy mildew and cucumber powdery mildew
And (3) test treatment: the compound was dissolved in DMF to 1% EC for use. The bactericidal activity of these compounds at 200ppm, 100ppm, 50ppm, 25ppm against the test targets was evaluated by the in vivo pot method.
1) Pseudoperonospora cubensis test (Pseudoperonospora cubensis)
Selecting 1 potted cucumber seedling with consistent growth vigor in true leaf period (removing growing point), spraying, air drying, inoculating 24 hr later, taking fresh cucumber downy mildew diseased leaf, washing off sporocyst on back of diseased leaf with distilled water, and making into sporangium suspension (2-3X 10)5one/mL). Uniformly spraying and inoculating on cucumber seedlings by using an inoculation sprayer (the pressure is 0.1MPa), transferring inoculated test materials to an artificial climate chamber, keeping the relative humidity at 100% and the temperature at about 21 ℃, keeping the temperature at about 21 ℃ after 24 hours, keeping the relative humidity at about 95% for moisture induction, carrying out grading investigation according to blank control disease occurrence conditions after 5 days, and calculating the control effect according to disease indexes.
2) Cucumber powdery mildew test (Sphaerothecafeuliginea)
Selecting a cucumber seedling with a true leaf period and consistent growth vigor, and drying in the shade for 24 hours after spraying treatment. Washing fresh powdery mildew spores on cucumber leaves, filtering the fresh powdery mildew spores by using double-layer gauze to prepare suspension with the spore concentration of about 10 ten thousand/mL, and spraying for inoculation. And (3) transferring the inoculated test material into an artificial climate, keeping the relative humidity between 60 and 70 percent, keeping the temperature between 21 and 23 ℃, carrying out grading investigation according to blank control disease occurrence conditions after about 10 days, and calculating the control effect according to disease indexes.
The test results are shown in tables 3-4.
TABLE 3 controlling effect of the compounds according to the invention on cucumber downy mildew at a concentration of 200ppm
Compound (I) Control effect (%) Compound (I) Control effect (%)
Example 2 90 Example 3 80
Example 4 80 Example 5 100
Example 7 80 Example 8 100
Example 9 90 Example 17 80
Example 18 90 Example 20 90
Example 21 100 Example 22 100
Example 23 80 Example 24 80
Example 25 90 Example 26 80
Example 27 100 Example 28 100
Example 29 100 Example 30 100
Example 31 100 Example 32 100
Example 33 100 Example 34 100
Example 35 100 Example 36 100
Example 37 80 Example 38 90
Compound (I) Control effect (%) Compound (I) Control effect (%)
Example 39 95 Example 40 100
EXAMPLE 41 100 Example 42 100
Example 43 100 Example 44 100
Example 45 80 Example 46 100
Example 47 80 Example 51 80
TABLE 4 controlling effect of the compounds according to the invention against cucumber downy mildew at a concentration of 100ppm
Compound (I) Control effect (%) Compound (I) Control effect (%)
Example 8 80 Example 21 80
Example 27 100 Example 28 80
Example 29 100 Example 30 90
Example 31 100 Example 32 100
Example 33 80 Example 36 90
Example 40 80 EXAMPLE 41 85
Example 42 90 Example 43 90
Example 44 90 Example 46 90
In addition, at a concentration of 50ppm, the control effect of the compounds of the invention of example 27, example 29, example 31, example 32, example 36, example 42, example 43 and example 44 on cucumber downy mildew is still above 80%; at a concentration of 200ppm, the compounds of the invention, examples 27 and 32, also have an 80% control effect on cucumber powdery mildew.
The above test results show that the compound of the present invention has a good control effect on phytopathogenic fungi, especially on cucumber downy mildew, wherein the control effect of some of the compounds (example 32) on cucumber downy mildew is still over 80% at lower concentrations (e.g. 25 ppm); has better development prospect.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

Claims (10)

  1. A compound having the formula (I) or a stereoisomer, nitroxide, salt, (E) or (Z) isomer of the compound of formula (I) and mixtures thereof:
    Figure PCTCN2019097704-APPB-100001
    wherein the content of the first and second substances,
    R 1and R2Each independently is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C6-10Aryl radical, C3-8cycloalkyl-C1-6Alkyl-or C6-10aryl-C1-6Alkyl-; wherein, said C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C6-10Aryl radical, C3-8cycloalkyl-C1-6Alkyl-or C6-10aryl-C1-6Alkyl-optionally substituted by 1,2, 3, 4 or 5 groups selected from halogen, hydroxy, cyano, nitro, amino, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6Substitution of alkoxy groupsSubstituted by radicals;
    or R1、R 2Together with the nitrogen atom to which they are attached form an optionally substituted 1,2, 3, 4 or 5 substituents selected from halogen, hydroxy, cyano, nitro, amino, C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6An alkoxy-substituted 3-10 membered heterocyclyl or 5-10 membered heteroaryl;
    R 3is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C1-6Alkyl, halo C2-6Alkenyl, halo C2-6Alkynyl, C6-10Aryl, halo C6-10Aryl radical, C6-10aryl-C1-6Alkyl-or halo-C6-10aryl-C1-6Alkyl-;
    x is 0, 1 or 2;
    R 4is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C6-10Aryl radical, C3-8cycloalkyl-C1-6Alkyl-, C6-10aryl-C1-6Alkyl-, 5-6 membered heteroaryl, -C (═ O) OC1-6Alkyl radical, RmS(＝O) 2-or-C (═ O) Rn；
    R mAnd RnEach independently is C1-6Alkyl or C6-10An aryl group;
    wherein R is4Optionally substituted by 1,2, 3, 4 or 5 substituents selected from halogen, hydroxy, cyano, nitro, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl or halo C1-6Substituent substitution of alkoxy;
    R 5is C 6-10Aryl or 5-10 membered heteroaryl; wherein R is5Optionally substituted by 1,2, 3, 4 or 5 substituents selected from halogen, hydroxy, cyano, nitro, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl or halo C1-6Substituent substitution of alkoxy;
    R 6is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl-, phenyl or phenyl-C1-6Alkyl-;
    or R5、R 6And the carbon atom to which they are attached form C9-10Aryl or 9-10 membered heteroaryl; said C9-10Aryl and 9-10 membered heteroaryl optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, cyano, nitro, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl or halo C1-6Substituent of alkoxy.
  2. The compound of claim 1, wherein,
    R 1and R2Each independently is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C6-10Aryl radical, C3-6cycloalkyl-C1-3Alkyl-or C6-10aryl-C1-3Alkyl-;
    R 3is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C1-4Alkyl, halo C2-4Alkenyl, halo C2-4Alkynyl, C6-10Aryl, halo C6-10Aryl radical, C6-10aryl-C1-3Alkyl-or halo-C6-10aryl-C1-3An alkyl group-.
  3. The compound of claim 2, wherein,
    R 1and R2Each independently is hydrogen, -CH3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH(CH 3)CH 2CH 3、-CH 2CH(CH 3) 2、-C(CH 3) 3、-CH＝CH 2、-CH 2CH＝CH 2、-CH＝CHCH 3、-CH 2CH 2CH＝CH 2、-CH 2CH＝CHCH 3、-CH＝CHCH 2CH 3、-C≡CH、-CH 2-C≡CH、-CH 2CH 2-C ≡ CH, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl;
    R 3is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, -CH3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-C(CH 3) 3、-CH 2Cl、-CHF 2or-CF3。
  4. The compound of claim 1, wherein,
    R 4is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl, phenyl, benzyl, C3-6cycloalkyl-C1-3Alkyl-, pyridyl, pyrazinyl, pyridazinyl, -C (═ O) OC1-4Alkyl radical, RmS(＝O) 2-or-C (═ O) Rn；
    R mAnd RnEach independently is C1-4Alkyl or phenyl;
    wherein R is4Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Substituent substitution of alkoxy;
    or R4Optionally substituted with 1,2 or 3 substituents selected from halogen, hydroxy, cyano, nitro, methyl or trifluoromethyl.
  5. The compound of claim 4, wherein,
    R 4is hydrogen, -CH3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-C(＝O)CH 3or-C (═ O) OCH3；
    Or R4Is of the sub-structure:
    Figure PCTCN2019097704-APPB-100002
  6. the compound of claim 1, wherein,
    R 5is phenyl, naphthyl, pyridyl, pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, 1H-1,2, 4-triazolylOr 1H-indolyl;
    wherein R is5Optionally substituted by 1,2 or 3 substituents selected from halogen, hydroxy, cyano, nitro, C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl or halo C1-4Substituent substitution of alkoxy;
    R 6is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl or phenyl;
    or R5、R 6And the carbon atom to which it is attached
    Figure PCTCN2019097704-APPB-100003
  7. The compound of claim 6, wherein,
    R 5is phenyl, naphthalen-1-yl, pyridin-2-yl, pyridin-3-yl, 1H-pyrrol-2-yl, thiophen-3-yl, 1H-imidazol-1-yl, isoxazol-3-yl, 1H-indol-3-yl or 1H-indol-4-yl;
    wherein R is5Optionally substituted by 1,2 or 3 substituents selected from fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, -CH3、-CH 2CH 3、-CH 2CH 2CH 3、-CH(CH 3) 2、-CH 2CH 2CH 2CH 3、-CH(CH 3)CH 2CH 3、-CH 2CH(CH 3) 2、-C(CH 3) 3、-OCH 3、-OCH 2CH 3、-OCH 2CH 2CH 3、-OCH(CH 3) 2、-OCH 2CH 2CH 2CH 3、-OCH(CH 3)CH 2CH 3、-OCH 2CH(CH 3) 2、-OC(CH 3) 3、-CF 3or-OCF3Substituted with the substituent(s);
    R 6is hydrogen, -CH3Or a phenyl group.
  8. The compound according to any one of claims 1 to 7, which is a compound having one of the following structures or a stereoisomer, nitroxide, salt, (E) or (Z) isomer of a compound having one of the following structures and mixtures thereof:
    Figure PCTCN2019097704-APPB-100004
    Figure PCTCN2019097704-APPB-100005
    Figure PCTCN2019097704-APPB-100006
    Figure PCTCN2019097704-APPB-100007
  9. a composition comprising a compound of any one of claims 1-8.
  10. Use of the compound according to any one of claims 1 to 8 or the composition according to claim 9 as a plant disease control agent.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113429356A (en) * 2020-03-23 2021-09-24 东莞市东阳光农药研发有限公司 Triazole sulfonamide derivative and application thereof in agriculture

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022030107A1 (en) * 2020-08-06 2022-02-10
CN115232081B (en) * 2021-04-25 2023-06-13 武汉智汇农耀科技有限公司 Triazolesulfonamide derivative containing mutant alkene fragment, preparation method and application thereof, bactericide and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997041113A1 (en) * 1996-04-26 1997-11-06 Nissan Chemical Industries, Ltd. Sulfamoyltriazole derivatives and agricultural and horticultural bactericides
CN105669576A (en) * 2016-02-22 2016-06-15 华中师范大学 Germicidal compound, germicide composition and preparation and application of germicide composition and preparation
CN108689951A (en) * 2017-04-05 2018-10-23 东莞东阳光科研发有限公司 3-triazole compounds and its application in agricultural

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997041113A1 (en) * 1996-04-26 1997-11-06 Nissan Chemical Industries, Ltd. Sulfamoyltriazole derivatives and agricultural and horticultural bactericides
CN105669576A (en) * 2016-02-22 2016-06-15 华中师范大学 Germicidal compound, germicide composition and preparation and application of germicide composition and preparation
CN108689951A (en) * 2017-04-05 2018-10-23 东莞东阳光科研发有限公司 3-triazole compounds and its application in agricultural

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HUA CHENG ET AL.: "Discovery of 1,2,4-triazole-1,3-disulfonamides as dual inhibitors of mitochondrial complex II and complex III", 《NEW JOURNAL OF CHEMISTRY》 *
YITAO LI ET AL.: "Design, Synthesis, and Biological Activity of Novel Triazole Sulfonamide Derivatives Containing a Benzylamine Moiety", 《JOURNAL OF HETEROCYCLIC CHEMISTRY》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113429356A (en) * 2020-03-23 2021-09-24 东莞市东阳光农药研发有限公司 Triazole sulfonamide derivative and application thereof in agriculture
CN113429356B (en) * 2020-03-23 2024-01-16 东莞市东阳光农药研发有限公司 Triazole sulfonamide derivative and application thereof in agriculture

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