CN110894190B - Triazole compound and application thereof in agriculture - Google Patents

Triazole compound and application thereof in agriculture Download PDF

Info

Publication number
CN110894190B
CN110894190B CN201811065757.3A CN201811065757A CN110894190B CN 110894190 B CN110894190 B CN 110894190B CN 201811065757 A CN201811065757 A CN 201811065757A CN 110894190 B CN110894190 B CN 110894190B
Authority
CN
China
Prior art keywords
alkyl
radical
cycloalkyl
och
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811065757.3A
Other languages
Chinese (zh)
Other versions
CN110894190A (en
Inventor
李义涛
李法霖
林健
王传伟
伍阳
姚文强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Hec Pesticides R&d Co ltd
Original Assignee
Dongguan Hec Pesticides R&d Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan Hec Pesticides R&d Co ltd filed Critical Dongguan Hec Pesticides R&d Co ltd
Priority to CN201811065757.3A priority Critical patent/CN110894190B/en
Publication of CN110894190A publication Critical patent/CN110894190A/en
Application granted granted Critical
Publication of CN110894190B publication Critical patent/CN110894190B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention provides a triazole compound; specifically, the invention relates to a triazole compound shown in formula (I) or a stereoisomer, a nitrogen oxide and a salt of the triazole compound shown in formula (I), a preparation method of the triazole compound, application of the triazole compound as a fungicide, a form of a fungicide composition of the triazole compound, and a method for preventing and treating diseases by using the triazole compound or the triazole compound; wherein R is1、R2、X、n、R3And R4Have the meaning as described in the present invention.

Description

Triazole compound and application thereof in agriculture
Technical Field
The invention relates to the field of pesticides, in particular to triazole compounds and pesticides containing the compounds as active ingredients, especially plant harmful bacteria control agents.
Background
In modern agricultural production, various pesticides are required to be frequently used to ensure the healthy growth of crops, however, the pesticides are frequently used for a long time, so that part of diseases on the crops generate drug resistance to the existing pesticides, the prevention and treatment effect of the existing pesticides is reduced, the using dosage of the pesticides needs to be increased in order to achieve the purpose of preventing and treating the diseases, and the great burden is caused to the economy and the environment; in order to solve the problem of drug resistance, new compounds are required to be developed continuously in order to find new compounds for mode of action and to meet the requirement of modern pesticides for green environmental protection.
Disclosure of Invention
The invention provides a triazole compound and a composition containing the compound, wherein the triazole compound and the composition are used for preventing and treating plant diseases.
Specifically, the method comprises the following steps:
in one aspect, the invention provides compounds of formula (I) or stereoisomers, nitroxides and salts thereof:
Figure BDA0001798236080000011
wherein,
R1and 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-C1-6An alkyl group; or R1、R2And the N atom to which they are attached, form a 3-10 membered heterocyclic group or a 5-10 membered heteroaryl group; wherein, said C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C6-10Aryl radical, C3-8cycloalkyl-C1-6Alkyl radical, C6-10aryl-C1-6Alkyl, 3-10 membered heterocyclyl and 5-10 membered heteroaryl optionally substituted with 1,2, 3, 4 or 5RmSubstitution;
each RmIndependently is fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, oxo (═ O), C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6An alkoxy group;
x is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, 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-C1-6An alkyl group;
n is 0, 1 or 2;
R3is hydrogen, C1-8Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl radical, C3-8Cycloalkenyl radical, C3-8Cycloalkenyl radical-C1-6Alkyl radical3-8 membered heterocyclic group, 3-8 membered heterocyclic group-C1-6Alkyl, -S (═ O)2NR5R6、-C(＝O)NR7R8、C1-8Alkoxy radical, C2-6Alkenyloxy radical, C2-6Alkynyloxy, -C (═ O) -O-C1-8Alkyl, -S (═ O)y-C1-8Alkyl, -S (═ O)y-C3-8Cycloalkyl, -C (═ O) -C1-8Alkyl or-C (═ O) -C3-8A cycloalkyl group; wherein said C1-8Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl radical, C3-8Cycloalkenyl radical, C3-8Cycloalkenyl radical-C1-6Alkyl, 3-8 membered heterocyclyl and 3-8 membered heterocyclyl-C1-6Alkyl radical, C1-8Alkoxy radical, C2-6Alkenyloxy and C2-6Alkynyloxy optionally substituted by 1,2, 3, 4, 5 or 6RxSubstitution;
R4is hydrogen, C1-8Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl, 3-8 membered heterocyclyl or 3-8 membered heterocyclyl-C1-6An alkyl group; wherein said C1-8Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl, 3-8 membered heterocyclyl and 3-8 membered heterocyclyl-C1-6Alkyl is optionally substituted by 1,2, 3, 4, 5 or 6RySubstitution;
y is 0, 1 or 2;
R5、R6、R7and R8Each independently is hydrogen or C1-6An alkyl group;
wherein each R isxAnd RyIndependently is fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-8Alkyl radical, C1-8Alkoxy radical, C3-8Cycloalkyl, 3-8 membered heterocyclyl or 3-8 membered heterocyclyloxy;
wherein each R isxAnd RyOptionally substituted by fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo(＝O)、C1-8Alkyl radical, C1-8Alkoxy, halo C1-8Alkyl and halo C1-8Alkoxy substitution;
the conditions are as follows: the compounds of the invention of the formula (I) are not
Figure BDA0001798236080000021
Figure BDA0001798236080000022
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; or R1、R2And the N atom to which they are attached, form a 3-8 membered heterocyclyl or 5-10 membered heteroaryl; wherein, said C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C6-10Aryl radical, C3-6cycloalkyl-C1-3Alkyl radical, C6-10aryl-C1-3Alkyl, 3-8 membered heterocyclyl and 5-10 membered heteroaryl optionally substituted with 1,2, 3, 4 or 5RmSubstitution;
each RmIndependently is fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, oxo (═ O), C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4An alkoxy group;
x is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, 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 other embodiments, R1And R2Each independentlyIs 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; or R1、R2And the N atom to which they are attached, form a 3-6 membered heterocyclyl or 5-10 membered heteroaryl; wherein, said C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C6-10Aryl radical, C3-6cycloalkyl-C1-3Alkyl radical, C6-10aryl-C1-3Alkyl, 3-6 membered heterocyclyl and 5-10 membered heteroaryl optionally substituted with 1,2, 3, 4 or 5RmSubstitution;
each RmIndependently is fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, oxo (═ O), C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4An alkoxy group;
x is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C1-4Alkyl or halo C1-4An alkyl group.
In still other embodiments, R1And R2Each independently is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH＝CHCH2CH3、-C≡CH、-CH2-C≡CH、-CH2CH2-C ≡ CH, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl;
or R1、R2And the N atom to which it is attached form the following subformula:
Figure BDA0001798236080000031
x is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-C(CH3)3、-CH2Cl、-CHF2or-CF3。
In some embodiments, R3Is hydrogen, C1-8Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl, 3-8 membered heterocyclyl-C1-3Alkyl, -S (═ O)2NR5R6、-C(＝O)NR7R8、C1-6Alkoxy radical, C2-4Alkenyloxy radical, C2-4Alkynyloxy, -C (═ O) -O-C1-6Alkyl, -S (═ O)y-C1-6Alkyl, -C (═ O) -C1-6Alkyl or-C (═ O) -C3-6A cycloalkyl group; wherein said C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl, 3-8 membered heterocyclyl-C1-3Alkyl radical, C1-6Alkoxy radical, C2-4Alkenyloxy and C2-4Alkynyloxy optionally substituted by 1,2, 3, 4, 5 or 6RxSubstitution;
R4is hydrogen, C1-8Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl, 3-6 membered heterocyclyl or 3-6 membered heterocyclyl-C1-3An alkyl group; wherein said C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl, 3-6 membered heterocyclyl and 3-6 membered heterocyclyl-C1-3Alkyl is optionally substituted by 1,2, 3, 4, 5 or 6RySubstitution;
y is 0, 1 or 2;
R5、R6、R7and R8Each independently is hydrogen or C1-4An alkyl group;
wherein each R isxAnd RyIndependently is fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-6Alkyl radical, C1-6Alkoxy radical, C3-6Cycloalkyl, 3-8 membered heterocyclyl or 3-8 membered heterocyclyloxy;
wherein each R isxAnd RyOptionally substituted by fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl and halo C1-6Alkoxy substitution.
In other embodiments, R3Is hydrogen, C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl, -S (═ O)2NR5R6、-C(＝O)-O-C1-6Alkyl, -C (═ O) -C1-6Alkyl or-C (═ O) -C3-6A cycloalkyl group; wherein said C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl and C3-6cycloalkyl-C1-3Alkyl is optionally substituted by 1,2, 3, 4, 5 or 6RxSubstitution;
R4is hydrogen, C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl or C3-6A cycloalkyl group; wherein said C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl and C3-6Cycloalkyl is optionally substituted by 1,2, 3, 4, 5 or 6RySubstitution;
wherein R is5And R6Each independently is hydrogen or C1-4An alkyl group;
wherein each R isxAnd RyIndependently is fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-4Alkyl radical, C1-4Alkoxy radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl or 3-6 membered heterocyclyloxy;
wherein each R isxAnd RyOptionally substituted by fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl and halo C1-4Alkoxy substitution.
In still other embodiments, R3Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH＝CHCH2CH3、-C≡CH、-CH2-C≡CH、-CH2CH2-C ≡ CH, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
or R3Is of the sub-structure:
Figure BDA0001798236080000032
Figure BDA0001798236080000041
wherein R is3Optionally substituted by 1,2, 3, 4, 5 or 6RxSubstitution;
R4is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH＝CHCH2CH3、-C≡CH、-CH2-C≡CH、-CH2CH2-C ≡ CH, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
wherein R is4Optionally substituted by 1,2, 3, 4, 5 or 6RySubstitution;
each RxAnd RyIndependently fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH(CH3)CH2CH3、-OCH2CH(CH3)CH3、-OC(CH3)3Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
or each RxAnd RyIndependently the sub-formulae:
Figure BDA0001798236080000042
wherein each R isxAnd RyOptionally substituted by fluoro, chloro, bromo, iodo, cyano, amino, nitro, carboxy, hydroxy, oxo (═ O), -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH(CH3)CH2CH3、-OCH2CH(CH3)CH3、-OC(CH3)3、-CHF2、-CF3、CH2Cl、CCl3、-CF(CF3)2or-OCF3And (4) substitution.
In another aspect, the invention provides a composition comprising a compound of the invention and an agriculturally acceptable surfactant and/or carrier.
In yet another aspect, the present invention provides a use of the compound of the present invention or the composition of the present invention for controlling plant diseases.
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 found in the descriptions of "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and JerryMarch, 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-Hilldictionary 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-C6Alkyl "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)2CH3) N-propyl (n-Pr, -CH)2CH2CH3) Isopropyl group (i-Pr, -CH (CH)3)2) N-butyl (n-Bu, -CH)2CH2CH2CH3) Isobutyl (i-Bu, -CH)2CH(CH3)2) Sec-butyl (s-Bu, -CH (CH)3)CH2CH3) Tert-butyl (t-Bu, -C (CH)3)3) N-pentyl (-CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH)3)CH2CH2CH3) 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl (-CH (CH)3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3) 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)2CH3) 1-propoxy (n-PrO, n-propoxy, -OCH)2CH2CH3) 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＝CH2) 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、-CH2-C≡CCH3、-CH2CH2-C≡CH、-CH2-C≡CCH2CH3And 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 "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 atoms of the ring may optionally be oxidized toAn 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 "heterocyclylalkyl" means that a hydrogen atom in an alkyl group is replaced by one or more heterocyclyl groups, wherein the alkyl and heterocyclyl groups have the meanings as described herein.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
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.
The term "haloalkyl" denotes an alkyl group substituted with one or more halogen atoms, examples of which include, but are not limited to, -CF3，-CHF2，-CH2Cl，-CH2CF3，-CH2CHF2，-CH2CH2CF3And the like.
The term "haloalkoxy" denotes an alkoxy group substituted with one or more halogen atoms, examples of which include, but are not limited to, -OCF3，-OCHF2，-OCHCl2，-OCH2CHF2，-OCH2CHCl2，-OCH(CH3)CHF2And 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 "alkenyloxy" means an alkenyl group attached to the rest of the molecule through an oxygen atom, wherein the alkenyl group has the meaning as described herein.
The term "alkynyloxy" denotes an alkynyl group attached to the rest of the molecule through an oxygen atom, wherein the alkynyl group has the meaning as described herein.
The term "haloaryl" denotes an aryl group substituted with one or more halogen atoms, examples of which include, but are not limited to, 4-fluorophenyl, 2, 4-difluorophenyl and the like.
The term "haloarylalkyl" denotes an arylalkyl group substituted with one or more halogen atoms.
The term "cycloalkenyl" denotes mono-, bi-or tricyclic ring systems containing 3 to 12 carbon atoms, mono-or polyvalent, comprising at least one carbon-carbon double bond, said ring systems being non-aromatic. In one embodiment, cycloalkenyl groups contain 3 to 10 carbon atoms; in another embodiment, cycloalkenyl groups contain 3 to 8 carbon atoms; in yet another embodiment, cycloalkenyl groups contain 3 to 6 carbon atoms. The cycloalkenyl group is optionally substituted with one or more substituents described herein. Examples include, but are not limited to, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, and the like.
The term "cycloalkenylalkyl" denotes an alkyl group wherein the hydrogen atom is replaced by one or more cycloalkenyl groups, wherein alkyl and cycloalkenyl groups have the meaning as described herein.
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+(R31R32R33R34) Ammonium cation of (2), wherein R is31、R32、R33And R34Independently selected from hydrogen, C1-C6Alkyl and C1-C6A hydroxyalkyl group. Salts of compounds of formula (I) or (II) may be prepared by treating a compound of formula (I) or (II) with a metal hydroxide, such as sodium hydroxide, or an amine, such as 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.
Detailed description of the Compounds of the invention
The present invention aims to provide a compound having a remarkable effect of controlling plant diseases, a composition and a preparation containing the compound, and an application thereof as a fungicide.
In one aspect, the invention provides compounds of formula (I) or stereoisomers, nitroxides and salts thereof:
Figure BDA0001798236080000081
wherein,
R1and R2Each independently is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, cycloalkyl-alkyl, or aryl-alkyl; or R1、R2And the N atom to which they are attached, together form a heterocyclic or heteroaryl group; wherein said alkyl, alkenyl, alkynyl, cycloalkyl, aryl, cycloalkyl-alkyl, aryl-alkyl, heterocyclyl and heteroaryl are optionally substituted with 1,2, 3, 4 or 5RmSubstitution;
each RmIndependently fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, carboxy, oxo (═ O), alkyl, haloalkyl, alkoxy, or haloalkoxy;
x is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aryl-alkyl or haloaryl-alkyl;
n is 0, 1 or 2;
R3is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl-alkyl, cycloalkenyl-alkyl, heterocyclyl-alkyl, -S (═ O)2NR5R6、-C(＝O)NR7R8Alkoxy, alkenyloxy, alkynyloxy, -C (═ O) -O-alkyl, -S (═ O)y-alkyl, -S (═ O)y-cycloalkyl, -C (═ O) -alkyl or-C (═ O) -cycloalkyl; wherein said alkyl, alkenyl, alkynyl, cycloalkyl-alkyl, cycloalkenyl-alkyl, heterocyclyl and heterocyclyl-alkyl, alkoxy, alkenyloxy and alkynyloxy are optionally substituted with 1,2, 3, 4, 5 or 6RxSubstitution;
R4is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl-alkyl, heterocyclyl or heterocyclyl-alkyl; wherein said alkyl, alkenyl, alkynyl, cycloalkyl-alkyl, heterocyclyl and heterocyclyl-alkyl are optionally substitutedBy 1,2, 3, 4, 5 or 6RySubstitution;
y is 0, 1 or 2;
R5、R6、R7and R8Each independently is hydrogen or alkyl;
wherein each R isxAnd RyIndependently fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), alkyl, alkoxy, cycloalkyl, heterocyclyl or heterocyclyloxy;
wherein each R isxAnd RyOptionally substituted with fluoro, chloro, bromo, iodo, cyano, amino, nitro, carboxy, hydroxy, oxo (═ O), alkyl, alkoxy, haloalkyl, and haloalkoxy;
the conditions are as follows: the compounds of the invention of the formula (I) are not
Figure BDA0001798236080000091
Figure BDA0001798236080000092
In some embodiments, R1And 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-C1-6An alkyl group; wherein, said C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C6-10Aryl radical, C3-8cycloalkyl-C1-6Alkyl and C6-10aryl-C1-6Alkyl is optionally substituted by 1,2, 3, 4 or 5RmSubstitution;
each RmIndependently is fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, oxo (═ O), C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6An alkoxy group.
In other embodiments, R1And R2Each independently isHydrogen, 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; wherein, said C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C6-10Aryl radical, C3-6cycloalkyl-C1-3Alkyl and C6-10aryl-C1-3Alkyl is optionally substituted by 1,2, 3, 4 or 5RmSubstitution;
each RmIndependently is fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, oxo (═ O), C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4An alkoxy group.
In still other 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; wherein, said C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C6-10Aryl radical, C3-6cycloalkyl-C1-3Alkyl and C6-10aryl-C1-3Alkyl is optionally substituted by 1,2, 3, 4 or 5RmSubstitution;
each RmIndependently is fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, oxo (═ O), C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4An alkoxy group.
In still other embodiments, R1And R2Each independently is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH＝CHCH2CH3、-C≡CH、-CH2-C≡CH、-CH2CH2-C.ident.CH, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl.
In still other embodiments, R1And R2Optionally substituted with 1,2, 3, 4 or 5 Rm;
wherein each R ismIndependently fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, oxo (═ O), -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CHF2、CF3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH(CH3)CH2CH3、-OCH2CH(CH3)CH3、-OC(CH3)3or-OCF3。
In other embodiments, R1、R2And the N atom to which they are attached, form a 3-10 membered heterocyclic group or a 5-10 membered heteroaryl group; wherein said 3-10 membered heterocyclyl and 5-10 membered heteroaryl are optionally substituted with 1,2, 3, 4 or 5RmSubstitution;
each RmIndependently is fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, oxo (═ O), C1-6Alkyl, halo C1-6Alkyl radical, C1-6Alkoxy or halo C1-6An alkoxy group.
In other embodiments, R1、R2And the N atom to which they are attached, form a 3-8 membered heterocyclyl or 5-10 membered heteroaryl; wherein said 3-8 membered heterocyclyl and 5-10 membered heteroaryl are optionally substituted with 1,2, 3, 4 or 5RmSubstitution;
each RmIndependently is fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, oxo (═ O), C1-4Alkyl, halo C1-4Alkyl radical, C1-4Alkoxy or halo C1-4An alkoxy group.
In still other embodiments, R1、R2And the N atom to which they are attached, form a 3-6 membered heterocyclyl or 5-10 membered heteroaryl; wherein said 3-6 membered heterocyclyl and 5-10 membered heteroaryl are optionally substituted with 1,2, 3, 4 or 5RmSubstitution;
each RmIndependently fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, oxo (═ O), -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CHF2、CF3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH(CH3)CH2CH3、-OCH2CH(CH3)CH3、-OC(CH3)3or-OCF3。
In still other embodiments, R1、R2And the N atom to which it is attached form the following subformula:
Figure BDA0001798236080000101
in some embodiments, X is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, carboxyl, cyano, nitro, amino, carboxyl, or a salt thereof,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-C1-6An alkyl group.
In other embodiments, X is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, 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, X is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, C1-4Alkyl or halo C1-4An alkyl group.
In still other embodiments, X is hydrogen, fluoro, chloro, bromo, iodo, hydroxy, cyano, nitro, amino, carboxy, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-C(CH3)3、-CH2Cl、-CHF2or-CF3。
In some embodiments, R3Is hydrogen, C1-8Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl radical, C3-8Cycloalkenyl radical, C3-8Cycloalkenyl radical-C1-6Alkyl, 3-8 membered heterocyclyl-C1-6Alkyl, -S (═ O)2NR5R6、-C(＝O)NR7R8、C1-8Alkoxy radical, C2-6Alkenyloxy radical, C2-6Alkynyloxy, -C (═ O) -O-C1-8Alkyl, -S (═ O)y-C1-8Alkyl, -S (═ O)y-C3-8Cycloalkyl, -C (═ O) -C1-8Alkyl or-C(＝O)-C3-8A cycloalkyl group; wherein said C1-8Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl radical, C3-8Cycloalkenyl radical, C3-8Cycloalkenyl radical-C1-6Alkyl, 3-8 membered heterocyclyl and 3-8 membered heterocyclyl-C1-6Alkyl radical, C1-8Alkoxy radical, C2-6Alkenyloxy and C2-6Alkynyloxy optionally substituted by 1,2, 3, 4, 5 or 6RxSubstitution;
y is 0, 1 or 2;
R5、R6、R7and R8Each independently is hydrogen or C1-6An alkyl group;
wherein each R isxIndependently is fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-8Alkyl radical, C1-8Alkoxy radical, C3-8Cycloalkyl, 3-8 membered heterocyclyl or 3-8 membered heterocyclyloxy.
In still other embodiments, each R isxOptionally substituted by fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-8Alkyl radical, C1-8Alkoxy, halo C1-8Alkyl and halo C1-8Alkoxy substitution.
In other embodiments, R3Is hydrogen, C1-8Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl, 3-8 membered heterocyclyl-C1-3Alkyl, -S (═ O)2NR5R6、-C(＝O)NR7R8、C1-6Alkoxy radical, C2-4Alkenyloxy radical, C2-4Alkynyloxy, -C (═ O) -O-C1-6Alkyl, -S (═ O)y-C1-6Alkyl, -C (═ O) -C1-6 alkyl or-C (═ O) -C3-6A cycloalkyl group; wherein said C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl, 3-8 membered heterocyclic group-C1-3Alkyl radical, C1-6Alkoxy radical, C2-4Alkenyloxy and C2-4Alkynyloxy optionally substituted by 1,2, 3, 4, 5 or 6RxSubstitution;
y is 0, 1 or 2;
R5、R6、R7and R8Each independently is hydrogen or C1-4An alkyl group;
wherein each R isxIndependently is fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-6Alkyl radical, C1-6Alkoxy radical, C3-6Cycloalkyl, 3-8 membered heterocyclyl or 3-8 membered heterocyclyloxy.
In still other embodiments, each R isxOptionally substituted by fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl and halo C1-6Alkoxy substitution.
In still other embodiments, R3Is hydrogen, C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl, -S (═ O)2NR5R6、-C(＝O)-O-C1-6Alkyl, -C (═ O) -C1-6Alkyl or-C (═ O) -C3-6A cycloalkyl group; wherein said C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl and C3-6cycloalkyl-C1-3Alkyl is optionally substituted by 1,2, 3, 4, 5 or 6RxSubstitution;
R5and R6Each independently is hydrogen or C1-4An alkyl group;
wherein each R isxIndependently is fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-4Alkyl radical, C1-4Alkoxy radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl or 3-6 membered heterocyclyloxy.
Yet in some embodiments, each R isxOptionally substituted by fluorine, chlorine, bromine, iodine,Cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl and halo C1-4Alkoxy substitution.
In some embodiments, R3Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH＝CHCH2CH3、-C≡CH、-CH2-C≡CH、-CH2CH2-C ≡ CH, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
In other embodiments, R3Is of the sub-structure:
Figure BDA0001798236080000111
in still other embodiments, R3Optionally substituted by 1,2, 3, 4, 5 or 6RxSubstitution;
wherein each R isxIndependently fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH(CH3)CH2CH3、-OCH2CH(CH3)CH3、-OC(CH3)3Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
In still other embodiments, R3Optionally substituted by 1,2, 3, 4, 5 or 6RxSubstitution;
wherein each R isxIndependently the sub-formulae:
Figure BDA0001798236080000112
in still other embodiments, each R isxOptionally substituted by fluoro, chloro, bromo, iodo, cyano, amino, nitro, carboxy, hydroxy, oxo (═ O), -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH(CH3)CH2CH3、-OCH2CH(CH3)CH3、-OC(CH3)3、-CHF2、-CF3、CH2Cl、CCl3、-CF(CF3)2or-OCF3And (4) substitution.
In some embodiments, R4Is hydrogen, C1-8Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl, 3-8 membered heterocyclyl or 3-8 membered heterocyclyl-C1-6An alkyl group; wherein said C1-8Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-8Cycloalkyl radical, C3-8cycloalkyl-C1-6Alkyl, 3-8 membered heterocyclyl and 3-8 membered heterocyclyl-C1-6Alkyl is optionally substituted by 1,2,3. 4, 5 or 6RySubstitution;
wherein each R isyIndependently is fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-8Alkyl radical, C1-8Alkoxy radical, C3-8Cycloalkyl, 3-8 membered heterocyclyl or 3-8 membered heterocyclyloxy;
wherein each R isyOptionally substituted by fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-8Alkyl radical, C1-8Alkoxy, halo C1-8Alkyl and halo C1-8Alkoxy substitution.
In other embodiments, R4Is hydrogen, C1-8Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl, 3-6 membered heterocyclyl or 3-6 membered heterocyclyl-C1-3An alkyl group; wherein said C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl, 3-6 membered heterocyclyl and 3-6 membered heterocyclyl-C1-3Alkyl is optionally substituted by 1,2, 3, 4, 5 or 6RySubstitution;
wherein each R isyIndependently is fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-6Alkyl radical, C1-6Alkoxy radical, C3-6Cycloalkyl, 3-8 membered heterocyclyl or 3-8 membered heterocyclyloxy;
wherein each R isyOptionally substituted by fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl and halo C1-6Alkoxy substitution.
In still other embodiments, R4Is hydrogen, C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl or C3-6A cycloalkyl group; wherein said C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl or C3-6Cycloalkyl is optionally substituted by 1,2, 3, 4, 5 or 6RySubstitution;
wherein each R isyIndependently is fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-4Alkyl radical, C1-4Alkoxy radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl or 3-6 membered heterocyclyloxy;
wherein each R isyOptionally substituted by fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl and halo C1-4Alkoxy substitution.
In still other embodiments, R4Is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH＝CHCH2CH3、-C≡CH、-CH2-C≡CH、-CH2CH2-C ≡ CH, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
In still other embodiments, R4Optionally substituted by 1,2, 3, 4, 5 or 6RySubstitution;
wherein each R isyIndependently fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH(CH3)CH2CH3、-OCH2CH(CH3)CH3、-OC(CH3)3Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
In still other embodiments, R4Optionally substituted by 1,2, 3, 4, 5 or 6RySubstitution;
wherein each R isyIndependently the sub-formulae:
Figure BDA0001798236080000121
in still other embodiments, each R isyOptionally substituted by fluoro, chloro, bromo, iodo, cyano, amino, nitro, carboxy, hydroxy, oxo (═ O), -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH(CH3)CH2CH3、-OCH2CH(CH3)CH3、-OC(CH3)3、-CHF2、-CF3、CH2Cl、CCl3、-CF(CF3)2or-OCF3And (4) substitution.
In some embodiments, the present invention provides compounds of formula (II) or stereoisomers, nitroxides, and salts thereof, of compounds of formula (II):
Figure BDA0001798236080000131
wherein,
R3is C1-8Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl, 3-8 membered heterocyclyl-C1-3Alkyl, -S (═ O)2NR5R6、-C(＝O)NR7R8、C1-6Alkoxy radical, C2-4Alkenyloxy radical, C2-4Alkynyloxy, -C (═ O) -O-C1-6Alkyl, -S (═ O)y-C1-6Alkyl, -C (═ O) -C1-6Alkyl or-C (═ O) -C3-6A cycloalkyl group; wherein said C1-6Alkyl radical, C2-4Alkenyl radical, C2-4 alkynyl, C3-6 cycloalkyl, C3-6cycloalkyl-C1-3Alkyl, 3-8 membered heterocyclyl-C1-3Alkyl radical, C1-6Alkoxy radical, C2-4Alkenyloxy and C2-4Alkynyloxy optionally substituted by 1,2, 3, 4, 5 or 6RxSubstitution;
y is 0, 1 or 2;
R5、R6、R7and R8Each independently is hydrogen or C1-4An alkyl group;
wherein each R isxIndependently is fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-6Alkyl radical, C1-6Alkoxy radical, C3-6Cycloalkyl, 3-8 membered heterocyclyl or 3-8 membered heterocyclyloxy;
wherein each R isxOptionally substituted by fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl and halo C1-6Alkoxy substitution.
In still other embodiments, R3Is C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl radical, C3-6cycloalkyl-C1-3Alkyl, -S (═ O)2NR5R6、-C(＝O)-O-C1-6Alkyl, -C (═ O) -C1-6Alkyl or-C (═ O) -C3-6A cycloalkyl group; wherein said C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-6Cycloalkyl and C3-6cycloalkyl-C1-3Alkyl is optionally substituted by 1,2, 3, 4, 5 or 6RxSubstitution;
R5and R6Each independently is hydrogen or C1-4An alkyl group;
wherein each R isxIndependently is fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-4Alkyl radical, C1-4Alkoxy radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl or 3-6 membered heterocyclyloxy;
wherein each R isxOptionally substituted by fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-4Alkyl radical, C1-4Alkoxy, halo C1-4Alkyl and halo C1-4Alkoxy substitution.
In still other embodiments, R3is-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH＝CHCH2CH3、-C≡CH、-CH2-C≡CH、-CH2CH2-C ≡ CH, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
or R3Is of the sub-structure:
Figure BDA0001798236080000132
wherein R is3Optionally substituted by 1,2, 3, 4, 5 or 6RxSubstitution;
each RxIndependently fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH(CH3)CH2CH3、-OCH2CH(CH3)CH3、-OC(CH3)3Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
or each RxIndependently the sub-formulae:
Figure BDA0001798236080000141
wherein each R isxOptionally substituted by fluoro, chloro, bromo, iodo, cyano, amino, nitro, carboxy, hydroxy, oxo (═ O), -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH(CH3)CH2CH3、-OCH2CH(CH3)CH3、-OC(CH3)3、-CHF2、-CF3、CH2Cl、CCl3、-CF(CF3)2or-OCF3And (4) substitution.
And also in someIn embodiments, R3Is of the sub-structure:
Figure BDA0001798236080000142
in some embodiments, the present invention provides a compound having one of the following structures or stereoisomers, nitroxides, and salts thereof of a compound having one of the following structures:
Figure BDA0001798236080000143
Figure BDA0001798236080000151
in another aspect, the present invention provides a composition comprising at least one compound of the present invention as an active ingredient.
Further, the composition of the present invention comprises an agriculturally pharmaceutically acceptable surfactant and/or carrier.
In another aspect, the invention provides the use of a compound of the invention or a composition of the invention in agriculture.
Further, the present invention provides a use of the compound of the present invention or the composition of the present invention for controlling plant diseases.
In another aspect, the invention provides a method of using a compound of the invention or a composition of the invention in agriculture.
Further, the present invention provides a method for controlling plant diseases by using the compound of the present invention or the composition of the present invention.
Compositions and formulations of the compounds of the invention
The compounds of the present invention are generally useful as fungicide active ingredients in compositions, i.e., formulations, typically further 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 ammonium type 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 sulfate, aluminum 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 compounds or compositions according to the invention are useful as plant disease control agents, in crop protection and in the protection of materials for controlling unwanted fungal and bacterial diseases, for example:
diseases caused by powdery mildew pathogens, e.g., the genus Blumeria, such as Blumeria graminis (Blumeria graminis); the genus aphelenchoides (podosphaea), such as the aphelenchoides leucotricha (podosphaea leucotricha); genus mono-vesicular shell (Sphaerotheca), such as balsamine mono-vesicular shell (Sphaerotheca fuliginea); devil's claw (Uncinula) genera, such as grapevine's claw (Uncinula necator);
diseases caused by rust pathogens, for example, the genus, e.g., brown rust (Gymnosphaerella sabinae); camelina rust (hemieia) genus, such as camelina coffea (hemiaviastatrix); phakopsora (Phakopsora) genera, such as Phakopsora pachyrhizi (Phakopsora purpurizi) and Phakopsora meibomiae (Phakopsora meibomiae); puccinia (Puccinia) genera, such as Puccinia recondite (Puccinia recondite), Puccinia triticina (P.triticina), Puccinia graminis (Puccinia graminis) or Puccinia striiformis (Puccinia striiformis); genus unicellular rust (Uromyces), such as, for example, Ruscus verrucosa (Uromyces apendiculus);
diseases caused by Oomycete (oomycin) pathogens, e.g. white rust (Albugo) genera, such as white rust (Albugo Candida); peronospora species (Bremia), for example, Peronospora lactucae (Bremia lactucae); peronospora species, for example Peronospora pisi (Peronospora pisi) or Peronospora cruciferae (Peronospora brassicae); phytophthora (Phytophthora) species, such as Phytophthora infestans; plasmopara species, such as Plasmopara viticola (Plasmopara viticola); pseudoperonospora (Pseudoperonospora), for example Pseudoperonospora praecox (Pseudoperonospora humuli) or Pseudoperonospora cubensis; pythium (Pythium) genera, such as Pythium ultimum;
leaf blight (Leaf patch) and Leaf wilting (Leaf wilt) diseases caused by the following pathogens: for example, the genus Alternaria (Alternaria), such as Alternaria alternata (Alternaria solani); a genus of Asperula beta (Cercospora), for example, Asperuma beta (Cercospora beta); cladosporium species, such as Cladosporium cucumerinum; the genus Cochliobolus (Cochliobolus) such as Cochliobolus graminis (Cochliobolus sativus) (conidia form: Helminthosporium (Drechslera), Syn: Helminthosporium (Helminthosporium)), and Thielavia gondii (Cochliobolus miyabenus); anthrax (Colletotrichum) genus, such as Phaseolus vulgaris (Colletotrichum lindemuthanum); the genus Puccinia (Cycloconium), such as malachite leaf spot (Cycloconium oleginum); intercalary shell (Diaporthe) genera, such as citrus intercalary shell (Diaporthe citri); elsinoe spp (Elsinoe) such as Elsinoe citroideus (Elsinoefawcettii); discodermospora (Gloeosporium), e.g. discodermospora roseticolor; plexi-shell (glomeriella) genus, such as plexi-shell (glomeriella cingulata); the genus of coccobacillus (Guignardia), such as coccobacillus viticola (Guignardia bidwelli); the genus Leptosphaeria (Leptosphaeria), such as Leptosphaeria maculans (Leptosphaeria maculans), Leptosphaeria nodorum (Leptosphaeria nodorum); large destructed shells (Magnaporthe) genera, such as gray large destructed shells (Magnaporthe grisea); aschersonia (Microdochium), e.g.Aschersonia (Microdochium nivale); the genus sphacelella (Mycosphaerella), such as Mycosphaerella graminicola (Mycosphaerella graminicola), Mycosphaerella arachidicola (m.arachidacola), and Mycosphaerella fijiensis (m.fijiensis); septoria (phaesperaria) genus, such as septoria nodorum (phaesperaria nodorum); pyrenophora (Pyrenophora) genus, such as Pyrenophora teres (Pyrenophora teres), Pyrenophora tritici-repentis (Pyrenophora tritici-epentais); the genus Bectona (Ramularia), for example, Ramularia sincalifornica (Ramularia collo-cygni), Ramularia leucotricha (Ramularia areola); rhynchophorium genus, such as Rhynchophorium secalii (Rhynchophorium secalis); conidia (Septoria) genera, such as Septoria apiacea (Septoria apiacea), Septoria lycopersici (Septoria lycopersici); corallina (Typhula) genus, such as Corallina carnea (Typhulaincarnata); genus Venturia (Venturia), such as apple scab (Venturia inaqualis);
root and stem diseases caused by the following pathogens: for example, the genus of the species of the genus of the species of; fusarium (Fusarium) genus, such as Fusarium oxysporum (Fusarium oxysporum); the genus Gaeumannomyces, such as Gaeumannomyces graminis (Gaeumannomyces graminis); rhizoctonia (Rhizoctonia) genus, such as Rhizoctonia solani (Rhizoctonia solani); for example, diseases of the genus cladosporium (Sarocladium) caused by cladosporium oryzae (Sarocladium oryzae); sclerotium (Sclerotium) disease caused by Sclerotium rot (Sclerotium oryzae); tapesia species, such as Tapesia acuformis; genus Rhinocerotis (Thielavirosis), such as Rhinocerotis (Thielavirosis basicola);
panicle or panicle diseases (including corn cobs) caused by the following pathogens: for example, the genus Alternaria (Alternaria), such as the genus Alternaria (Alternaria spp.); aspergillus (Aspergillus) genus, such as Aspergillus flavus; cladosporium (Cladosporium), such as Cladosporium cladosporioides (Cladosporium cladosporioides); claviceps (Claviceps) genus, such as Claviceps (Claviceps purpurea); fusarium (Fusarium) genus, such as Fusarium flavum (Fusarium culmorum); gibberella species, such as Gibberella zeae (Gibberella zeae); small picture shells (monograms) belong to the genus, e.g., snow rot small picture shells (monograms); genus chitin (Stagonospora), such as chitin glumae (Stagonosporanodosum);
diseases caused by smut, for example, of the genus leptospirillum (Sphacelotheca), such as leptospirillum seriana (Sphacelotheca reiliana); tilletia species (Tilletia), such as Tilletia grisea (Tilletia), Tilletia controversa (T.contrivarsa); ustilago virens (Urocystis) genus, such as Ustilago virens (Urocystis occulta); smut (Ustilago) genera, such as, for example, Ustilago nuda (Ustilago nuda), Ustilago tritici (U.nuda tritici);
fruit decay caused by the following pathogens: for example, Aspergillus (Aspergillus) genus, such as Aspergillus flavus (Aspergillus flavus); botrytis (Botrytis) genera, such as Botrytis cinerea (Botrytis cinerea); penicillium (Penicillium) genera, such as Penicillium expansum (Penicillium expansum) and Penicillium purpurogenum (p.purpurogenum); sclerotinia species, such as Sclerotinia sclerotiorum (Sclerotinia sclerotiorum); verticillium species, such as Verticillium alboatrum (Verticillium alboatrum);
rotting and soil-borne rot, mildew, wilting, rot and damping-off of seeds caused by the following pathogens: for example, the genus Alternaria (Alternaria), such as Alternaria brassicae (Alternaria brassicola); the genus Saccharomycosis (Aphanomyces), such as, for example, Rhizoctonia solani (Aphanomyces euteiches); ascochyta (Ascochyta) genus, such as, for example, Bisporum lentinus (Ascochyta lentis); aspergillus (Aspergillus) such as Aspergillus flavus; cladosporium (Cladosporium) genus, such as Cladosporium herbarum (Cladosporium herbarum); the genus Cochliobolus (Cochliobolus) such as Cochliobolus graminis (Cochliobolus sativus) (conidia form: Helminthosporium endocordalis, Helminthosporium (Bipolaris) Syn: Helminthosporium); anthrax (Colletotrichum) genus, such as Colletotrichum fuliginosum (Colletotrichum coccodes); fusarium (Fusarium) genus, such as Fusarium flavum (Fusarium culmorum); gibberella species, such as Gibberella zeae (Gibberella zeae); the genus ascochyta (macrophostoma), such as ascochyta phaseoloides (macrophostoma phaseolina); small picture shells (monograms) belong to the genus, e.g., snow rot small picture shells (monograms nivalis); penicillium (Penicillium) genus, such as Penicillium expansum (Penicillium expandasum); phoma (Phoma) genus, such as Phoma nigricans (Phomalignam); phomopsis species, such as Phomopsis sojae; phytophthora (Phytophtora) species, such as Phytophthora infestans (Phytophtora cacorum); pyrenophora (Pyrenophora) genus, such as Pyrenophora graminea (Pyrenophora graminea); pyricularia (Pyricularia) genus, such as Pyricularia oryzae (Pyricularia oryzae); pythium (Pythium) genera, such as Pythium ultimum; rhizoctonia (Rhizoctonia) genus, such as Rhizoctonia solani (Rhizoctonia solani); rhizopus (Rhizopus) genus, such as Rhizopus oryzae (Rhizopus oryzae); sclerotinia species (Sclerotium), such as Sclerotinia sclerotiorum (Sclerotium rolfsii); septoria (Septoria) genus, such as Septoria nodorum (Septoria nodorum); corallina (Typhula) genus, such as Corallina carnea (Typhula incarnata); verticillium species, such as Verticillium dahliae (Verticillium dahliae);
cancerous diseases, galls and broom diseases (witches' brooms) caused by the following pathogens: for example, genus Haematoloma (Nectria), such as Haematoloma manshuriensis (Nectria galligena);
atrophy diseases caused by the following pathogens: for example, the genus Sclerotinia (Monilinia), such as Sclerotinia drus (Monilinia laxa);
leaf wheal or leaf curl caused by the following pathogens: for example, the genus Exobasidium (Exobasidium), such as the genus Exobasidium putida (Exobasidium vexans); exocystis (Taphrina), such as exocystis malformation (taphridaeformans);
degenerative diseases of woody plants caused by the following pathogens: for example, diseases according to the discipline (Esca) caused by, for example, Rhizopus oryzae (Phaeomoniella chlamydospora), Phaeoacremonium aleophilum and Histoplasma geotrichum (Fomitipidia media); such as grape blight disease (Eutypa dieback) caused by grape vine blight (Eutypa latica); diseases of the genus Ganoderma (Ganoderma), for example, caused by Ganoderma boninense (Ganoderma boninense); for example, a scleroderma (Rigidoporus) disease caused by scleroderma (Rigidoporus lignosus);
flower and seed diseases caused by the following pathogens: for example, the genus Botrytis (Botrytis), such as Botrytis cinerea (Botrytis cinerea);
diseases of plant tubers caused by the following pathogens: for example, the genus Rhizoctonia (Rhizoctonia), such as Rhizoctonia solani (Rhizoctonia solani); helminthosporium species, such as Helminthosporium solani (Helminthosporium solani);
clubroot diseases caused by the following pathogens: for example, Plasmodiophora, such as Plasmodiophora yunnanensis (Plasmodiophora brassicae);
diseases caused by the following bacterial pathogens: for example, the genus Xanthomonas (Xanthomonas), such as Xanthomonas oryzae var alba (Xanthomonas campestris pv. oryzae); pseudomonas, such as Pseudomonas syringae Cucumaria var syringae (Pseudomonas syringae pv. lachrymans); erwinia (Erwinia) genus, such as Erwinia amylovora (Erwinia amylovora).
In addition, they are suitable for combating fungi which infect wood or plant roots.
Fungicides can be used in crop protection for controlling Pseudomonas (Pseudomonas), Rhizobiaceae (Rhizobiaceae), Enterobacter (Enterobacteriaceae), Corynebacterium (Corynebacterium), and Streptomyces (Streptomyces).
The fungicide composition of the invention is simple in use method, and can be applied to crops and places where crops grow by conventional methods such as soil mixing, spraying, pouring and the like before or after germination of plant diseases, wherein the application amount is determined according to climatic conditions or crop conditions, 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 fungicidal compositions of the present invention have a fungicidal effect which is usually associated with external factors such as climate, but the effect of climate can be alleviated by using appropriate formulations.
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, wherein the substituents are as defined in formula (I) or formula (II), unless otherwise indicated.
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.
Synthetic schemes
The following synthetic schemes describe the steps for preparing the compounds disclosed herein. Wherein R is1、R2、X、R3And R4Have the meaning described in the present invention.
Synthesis scheme I
Figure BDA0001798236080000201
The target compound I-1 can be prepared by the first synthesis scheme. The compound A and the compound B react under the alkaline condition to obtain the target compound I-1.
Synthesis scheme two
Figure BDA0001798236080000202
The target compound I-2 can be prepared by the second synthesis scheme. Reacting the compound A with the compound C to obtain a compound D; reacting the compound D with the compound E under an alkaline condition to obtain a target compound I-2;
wherein Y is fluorine, chlorine, bromine or iodine.
Synthesis scheme three
Figure BDA0001798236080000203
The target compound I-3 can be prepared by the third synthesis scheme. And reacting the compound D with the compound F under an alkaline condition to obtain a target compound I-3.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Examples
Intermediate T1: synthesis of 1, 2-di (1H-1,2, 4-triazole-3-yl) dithioane
Figure BDA0001798236080000204
3-mercapto-1, 2, 4-triazole (101.0g,1.00mol) is dissolved in dichloromethane (500mL), pyridine (79.0g,1.00mol) is added, stirring is carried out at 0 ℃, benzenesulfonyl chloride (88.3g,0.50mol) is slowly added dropwise, and the dropwise addition is completed within 2 hours. After the addition was complete, the mixture was stirred at 25 ℃ for 18 hours. The methylene chloride was evaporated under reduced pressure using a rotary evaporator, and the residue was stirred for 1 hour with water (500mL) added under mechanical stirring. Filtration and washing of the residue with water (800mL) and ethyl acetate (300mL) respectively followed by air drying gave 95.2g of a yellow powder in the following yield: 95.2 percent.
LC-MS:(M+1)m/z＝201.1。
Intermediate T2: synthesis of 3, 3' -disulfanediylbis (N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide)
Figure BDA0001798236080000211
1, 2-bis (1H-1,2, 4-triazol-3-yl) disulfane (60.0g,0.30mol) was dissolved in N, N-dimethylformamide (300mL) under nitrogen, potassium carbonate (69.0g,0.50mol) was added, and the mixture was stirred and mixed at 0 ℃. N, N-dimethylaminosulfonyl chloride (93.3g,0.65mol) was slowly added dropwise over 2 hours, and the reaction was continued for 6 hours. After the reaction was completed, the reaction solution was slowly poured into water and stirred for 1 hour. Filtration and air drying of the solid gave 107.2g of white powder in the following yield: 86.3 percent.
LC-MS:(M+1)m/z＝415.0。
Intermediate T3: synthesis of 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride
Figure BDA0001798236080000212
3, 3' -disulfanediylbis (N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide) (41.40g,0.10mol) is dissolved in 1, 2-dichloroethane (150mL), water (300mL) is added, the mixture is cooled to 0 ℃, acetic acid (150mL) is added, the temperature is controlled between 10 ℃ and 25 ℃, chlorine (35.50g,0.50mol) is introduced after 2 hours, and the reaction is 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 percent.
LC-MS:(M+1)m/z＝274.8。
Intermediate T4: n is a radical of3-cyclopropyl-N1,N1Synthesis of (dimethyl) -1H-1,2, 4-triazole-1, 3-disulfonamide
Figure BDA0001798236080000213
Under the protection of nitrogen, cyclopropylamine (1.14g,0.02mol), triethylamine (2.22g,0.022mol) and tetrahydrofuran (30mL) were added to a 100mL three-necked flask, stirred at 0 ℃ and a solution of 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride (6.04g,0.02mol) in tetrahydrofuran (20mL) was added dropwise over 10 minutes, and then reacted at 25 ℃ for 2 hours. The solid was removed by filtration, and the filtrate was freed of the solvent under reduced pressure using a rotary evaporator to give a pale yellow solid, which was recrystallized [ EtOAc/PE (v/v) ═ 5/1] to give 4.42g of a white solid in the following yield: 75.0 percent.
1H NMR(400MHz,DMSO-d6)(ppm):9.30(s,1H),7.49(s,1H),2.96(s,6H),2.48(m,1H),0.63-0.56(m,2H),0.50-0.43(m,2H)；
LC-MS:(M+1)m/z＝296.3。
Example 1: n is a radical of3-cyclopropyl-N3- (N, N-dimethylaminosulfonyl) -N1,N1Synthesis of (E) -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide
Figure BDA0001798236080000214
Will N3-cyclopropyl-N1,N1-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.30g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and N, N-dimethylformamide (10mL) were added to a 50mL single-neck flask, and N, N-dimethylaminosulfonyl chloride (0.29g,2.0mmol) was slowly added to the reaction system and reacted at 25 ℃ for 8 hours. Quench with water (20mL), extract with ethyl acetate (15mL x 3), wash the organic phase with saturated brine, dry over anhydrous magnesium sulfate, filter, remove the solvent from the filtrate under reduced pressure using a rotary evaporator, and purify by column chromatography [ EtOAc/PE (v/v) ═ 1/3]To obtain 0.32g of white solid, yield: 80 percent.
1H-NMR(400MHz,DMSO-d6)(ppm):9.43(s,1H),2.99(s,12H),2.46(m,1H),0.68-0.54(m,2H),0.51-0.38(m,2H)；
LC-MS:(M+1)m/z＝403.4。
The preparation of example 1 was carried out using the corresponding materials and intermediate N3-cyclopropyl-N1,N1And (3) reacting the (E) -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide to obtain the target compound shown in the table 1.
TABLE 1
Figure BDA0001798236080000221
Figure BDA0001798236080000231
Figure BDA0001798236080000241
Figure BDA0001798236080000251
Example 23: n is a radical of3-ethyl-N3-isopropyl-N1,N1Synthesis of (E) -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide
Figure BDA0001798236080000252
1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride (0.28g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and N, N-dimethylformamide (10mL) are added into a 50mL single-neck bottle, and N-ethyl isopropylamine (0.17g,2.0mmol) is slowly added into the reaction system to react for 8 hours at room temperature of 25 ℃. Quenched with water (20mL), extracted with ethyl acetate (15mL × 3), the organic phase washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was purified by rotary evaporator under reduced pressure to remove the solvent and column chromatography [ EtOAc/PE (v/v) ═ 1/3] afforded 0.12g of white solid, yield: 38 percent.
1H NMR(400MHz,CDCl3)(ppm):8.61(s,1H),4.31(dt,J＝13.6,6.8Hz,1H),3.38(d,J＝7.1Hz,2H),3.07(s,6H),1.31(t,J＝7.1Hz,3H),1.20(d,J＝6.8Hz,6H)；
LC-MS:(M+1)m/z＝326.1。
Activity assay
In the following test examples, the inventors examined the control efficacy of the compounds of the present invention against harmful fungi by taking some of the compounds of the present invention as examples.
Test targets: rhizoctonia solani, botrytis cinerea, peronospora cubensis and erysiphe necator
And (3) test treatment: the compound was dissolved in DMF to 1% EC for use. The bactericidal activity of these compounds at different doses against 4 test targets was evaluated using the in vivo potting method.
1) Pseudoperonospora cubensis test (Pseudoperonospora cubensis)
Selecting 1 potted cucumber seedling with consistent growth vigor in the true leaf period (removing growing points), spraying, air drying, inoculating 24 hr later, taking fresh cucumber downy mildew diseased leaves, washing the back of the diseased leaves with distilled waterSporangia, preparing sporangia 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.
3) Cucumber gray mold (Botrytis cinerea)
The method adopts a leaf inoculation method. Two potted cucumber seedlings with the same growth vigor of the true leaf period are selected, and after the agent is sprayed and dried, a fungus cake is inoculated on the leaves. And (3) after 24-26 ℃ dark light moisture preservation is carried out for 24 hours, natural illumination moisture preservation culture is carried out for about 3 days. After the contrast is fully developed, the diameter of the lesion spot of each inoculation point is measured by a caliper, and the control effect is calculated.
4) Rhizoctonia solani (Rhizoctonia)
Selecting potted corn seedlings with two leaves and one heart and consistent growth vigor, naturally drying after spraying treatment, inoculating for about 24 hours, and inoculating a fungus cake on leaves after the medicament is sprayed and dried. And (3) after the dark light is moisturized for 24 hours at the temperature of 25-26 ℃, natural illumination is recovered for moisturizing and culturing for about 3 days. After the disease is sufficiently distributed in contrast, the length of the lesion spot of each inoculation point is measured by a caliper, and the control effect is calculated.
And (3) test results: the test results are shown in tables 2 to 4.
TABLE 2200 mg/L dosage partial compound test results of the present invention
Figure BDA0001798236080000261
Figure BDA0001798236080000271
TABLE 3100 mg/L dose partial compound test results of this invention
Figure BDA0001798236080000272
TABLE 450 mg/L dosage partial compound test results of the invention
Figure BDA0001798236080000273
Figure BDA0001798236080000281
From the above test results, it is understood that the compounds of the present invention have excellent controlling effects on diseases on plants, particularly cucumber downy mildew. In addition, the partial compound of the invention still shows activity to cucumber downy mildew under the dosage of 25mg/L, 12.5mg/L and 6.25mg/L, such as the control effect to cucumber downy mildew under the dosage of 25mg/L of example 13, example 16, example 19, example 20 and example 21 is more than 40 percent; and partial compounds of the invention also have certain control effect on rice sheath blight disease, cucumber powdery mildew and cucumber gray mold under the dosage of 200 mg/L.

Claims (6)

1. A compound having formula (I) or a salt of a compound of formula (I):
Figure FDA0002576986220000011
wherein,
R1and R2Each independently is C1-4An alkyl group;
x is hydrogen;
n is 2;
R3is C1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, -C (═ O) -O-C1-6Alkyl, -C (═ O) -C1-6Alkyl or-C (═ O) -C3-6A cycloalkyl group; wherein said C1-6Alkyl is optionally substituted by 1,2 or 3RxSubstitution;
R4is cyclopropyl;
wherein each R isxIndependently is fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, 3-6 membered heterocyclyl or 3-6 membered heterocyclyloxy;
wherein each R isxOptionally substituted by fluorine, chlorine, bromine, iodine, cyano, amino, nitro, carboxyl, hydroxyl, oxo (═ O), C1-4Alkyl or C1-4Alkoxy substitution.
2. The compound of claim 1, wherein,
R1and R2Each independently is-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3or-C (CH)3)3。
3. The compound of claim 1, wherein,
R3is-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH(CH3)CH2CH3、-CH2CH(CH3)CH3、-C(CH3)3、-CH＝CH2、-CH2CH＝CH2、-CH＝CHCH3、-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH＝CHCH2CH3、-C≡CH、-CH2-C ≡ CH or-CH2CH2-C≡CH；
Or R3Is of the sub-structure:
Figure FDA0002576986220000012
4. a compound according to claims 1-3, which is a compound having one of the following structures or a salt of a compound having one of the following structures:
Figure FDA0002576986220000021
5. a composition comprising a compound according to any one of claims 1 to 4 and an agriculturally pharmaceutically acceptable surfactant and/or carrier.
6. Use of a compound according to any one of claims 1 to 4 or a composition according to claim 5 for controlling plant diseases.
CN201811065757.3A 2018-09-13 2018-09-13 Triazole compound and application thereof in agriculture Active CN110894190B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811065757.3A CN110894190B (en) 2018-09-13 2018-09-13 Triazole compound and application thereof in agriculture

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811065757.3A CN110894190B (en) 2018-09-13 2018-09-13 Triazole compound and application thereof in agriculture

Publications (2)

Publication Number Publication Date
CN110894190A CN110894190A (en) 2020-03-20
CN110894190B true CN110894190B (en) 2020-09-11

Family

ID=69785350

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811065757.3A Active CN110894190B (en) 2018-09-13 2018-09-13 Triazole compound and application thereof in agriculture

Country Status (1)

Country Link
CN (1) CN110894190B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN115667229A (en) * 2020-05-30 2023-01-31 东莞市东阳光农药研发有限公司 Triazole sulfonamide derivative and preparation method and application thereof
CN113929665A (en) * 2020-06-29 2022-01-14 东莞市东阳光农药研发有限公司 Aryl-substituted triazole sulfonamide derivative and preparation method and application thereof
CN114105959A (en) * 2020-08-28 2022-03-01 东莞市东阳光农药研发有限公司 Triazole sulfonamide derivative and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN88101622A (en) * 1987-03-21 1988-10-05 先灵农业化学品公司 Fungicidal agents
JPH02174758A (en) * 1988-12-27 1990-07-06 Ishihara Sangyo Kaisha Ltd Nitrogen-containing 5-membered ring compound, production thereof and noxious organism controlling agent containing the same
CN1024316C (en) * 1989-11-15 1994-04-27 先灵农业化学品公司 Imidazole fungicides
WO1997041113A1 (en) * 1996-04-26 1997-11-06 Nissan Chemical Industries, Ltd. Sulfamoyltriazole derivatives and agricultural and horticultural bactericides
JP2005082479A (en) * 2003-09-04 2005-03-31 Nissan Chem Ind Ltd Method for controlling plasmodiophora brassicae using sulfamoyl compound
CN1949970A (en) * 2004-04-30 2007-04-18 巴斯福股份公司 Fungicidal mixtures

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN88101622A (en) * 1987-03-21 1988-10-05 先灵农业化学品公司 Fungicidal agents
JPH02174758A (en) * 1988-12-27 1990-07-06 Ishihara Sangyo Kaisha Ltd Nitrogen-containing 5-membered ring compound, production thereof and noxious organism controlling agent containing the same
CN1024316C (en) * 1989-11-15 1994-04-27 先灵农业化学品公司 Imidazole fungicides
WO1997041113A1 (en) * 1996-04-26 1997-11-06 Nissan Chemical Industries, Ltd. Sulfamoyltriazole derivatives and agricultural and horticultural bactericides
JP2005082479A (en) * 2003-09-04 2005-03-31 Nissan Chem Ind Ltd Method for controlling plasmodiophora brassicae using sulfamoyl compound
CN1949970A (en) * 2004-04-30 2007-04-18 巴斯福股份公司 Fungicidal mixtures

Also Published As

Publication number Publication date
CN110894190A (en) 2020-03-20

Similar Documents

Publication Publication Date Title
CN110894190B (en) Triazole compound and application thereof in agriculture
CN108689951B (en) Triazole compound and application thereof in agriculture
CN110950812B (en) Triazole compound and application thereof in agriculture
CN110734433B (en) Triazole compound and application thereof in agriculture
JP2764265B2 (en) Microbicide composition
EP3953341B1 (en) Novel oxadiazole compounds for controlling or preventing phytopathogenic fungi
CN112638884B (en) Triazole sulfonamide derivative and preparation method and application thereof
KR20160072134A (en) Novel crystalline form of 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1h-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenylmethane sulfonate
CN112624987A (en) Cyclopentyl-substituted disulfonamide compound and application thereof in agriculture
CN112624988A (en) Novel triazole compound and application thereof in agriculture
CN110577498B (en) Triazole compound and application thereof in agriculture
CN115667229A (en) Triazole sulfonamide derivative and preparation method and application thereof
CN110938034B (en) Quinoline derivatives and their use in agriculture
CN108947964B (en) Fungicide hydroximoyl-tetrazole derivatives
CN111630044A (en) Oximino-tetrazole derivatives and application thereof in agriculture
CN109305964B (en) Fungicide hydroximoyl-tetrazole derivatives
CN109574990B (en) Fungicide hydroximoyl-tetrazole derivatives
CN112110894B (en) Phenyl oxime derivative and preparation method and application thereof
CN107428706A (en) As agricultural chemicals and the triazole derivative of plant growth regulator
CN110914261B (en) Oxadiazole oxime derivative and application thereof in agriculture
CN110452220B (en) Oxime derivatives and their use in agriculture
CN112110911B (en) 1,3, 4-Oxadiazole oxime derivative and preparation method and application thereof
CN112442018B (en) Triazole-1, 3-disulfonamide derivative and application thereof in agriculture
CN112047895B (en) Triazole compound, and preparation method and application thereof
CN112979633B (en) Novel oxime derivative, preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant