CN113429356B - Triazole sulfonamide derivative and application thereof in agriculture - Google Patents

Triazole sulfonamide derivative and application thereof in agriculture Download PDF

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CN113429356B
CN113429356B CN202010208211.XA CN202010208211A CN113429356B CN 113429356 B CN113429356 B CN 113429356B CN 202010208211 A CN202010208211 A CN 202010208211A CN 113429356 B CN113429356 B CN 113429356B
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alkyl
compound
alkoxy
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cycloalkyl
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CN113429356A (en
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李义涛
林健
李法霖
敬德旺
高国良
姚文强
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Dongguan Hec Pesticides R&d Co ltd
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    • 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

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  • 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)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention provides a novel triazole sulfonamide derivative and application thereof in agriculture; specifically, the invention relates to a triazole sulfonamide derivative shown in a formula (I) and a preparation method thereof; r in formula (I) 1 And R is 2 Each independently is hydrogen, C 1‑6 Alkyl, etc., R 3 Is C 3‑8 Cycloalkyl, R 4 is-SO 2 ‑NR a R b 、‑SO 2 ‑C 1‑6 Alkyl, -SO 2 ‑C 3‑8 Cycloalkyl, -SO 2 ‑C 1‑3 alkylene-C 3‑8 Cycloalkyl, -SO 2 ‑R c 、‑C 1‑3 alkylene-C (=o) O-C 1‑6 Alkyl or-C 1‑3 alkylene-C (=O) -NR d R e ，R a 、R b 、R c 、R d And R is e Having the meaning described in the present invention. The compound, the composition and/or the preparation containing the compound have better bactericidal activity and are applied as bactericides in agriculture.

Description

Triazole sulfonamide derivative and application thereof in agriculture
Technical Field
The invention belongs to the field of pesticides, and in particular provides a novel triazole sulfonamide derivative, a preparation method thereof and application of the triazole sulfonamide derivative as a plant disease control agent in agriculture.
Background
Plant diseases that damage ornamental, vegetable, field, cereal and fruit crops can result in significant yield loss, leading to increased consumption costs. In order to obtain high crop yields, it is extremely important to control plant diseases caused by phytopathogenic fungi. For this purpose, pesticidal products can be used during plant cultivation and growth, there are a number of products commercially available, but there is a continuing need for new compounds that are more efficient, more economical, less toxic, safer to the environment or have different sites of action.
The invention provides a novel triazole sulfonamide derivative with bactericidal activity.
Disclosure of Invention
The invention aims to provide a novel triazole sulfonamide derivative which is novel in structure, low in cost and excellent in prevention effect on cucumber downy mildew caused by pathogenic fungi.
In order to achieve the purpose of the invention, the following technical scheme is adopted:
in one aspect, the present invention provides a compound which is a compound having the formula (I) or a stereoisomer, oxynitride or salt thereof of a compound of the formula (I):
wherein:
R 1 and R is 2 Each independently is hydrogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-8 Cycloalkyl, C 3-8 cycloalkyl-C 1-3 Alkylene-,Phenyl optionally substituted with 1, 2, 3, 4 or 5 substituents selected from halogen or phenyl-C optionally substituted with 1, 2, 3, 4 or 5 substituents selected from halogen 1-3 An alkylene group; said R is 1 And R is 2 Each independently optionally substituted with 1, 2, 3, 4, 5 or 6 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, C 1-6 Alkyl, C 1-6 Alkoxy, halo C 1-6 Alkyl or halo C 1-6 Substitution of the substituent of the alkoxy group;
or R is 1 、R 2 And the N atom to which it is attached form a 3-8 membered heterocyclyl or a 5-10 membered heteroaryl; the 3-8 membered heterocyclyl or 5-10 membered heteroaryl is optionally substituted with fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino or C 1-6 Alkyl substitution.
R 3 Is C 3-8 Cycloalkyl; wherein R is 3 Optionally substituted with 1, 2, 3, 4, 5 or 6 groups selected from halogen, cyano, hydroxy, nitro, amino, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-8 Cycloalkyl, C 3-8 cycloalkyl-C 1-3 Alkylene-, halo C 1-6 Alkyl, C 1-6 Alkoxy or halo C 1-6 Alkoxy substitution;
R 4 is-SO 2 -NR a R b 、-SO 2 -C 1-6 Alkyl, -SO 2 -C 3-8 Cycloalkyl, -SO 2 -C 1-3 alkylene-C 3-8 Cycloalkyl, -SO 2 -R c 、-C 1-3 alkylene-C (=o) O-C 1-6 Alkyl or-C 1-3 alkylene-C (=O) -NR d R e ；
Wherein R is a And R is b Each independently is hydrogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-8 Cycloalkyl, C 3-8 cycloalkyl-C 1-3 Alkyl-, optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkylthio, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy, halo C 1-6 Alkylthio-substituted phenyl or phenyl optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkylthio, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy or halo C 1-6 Alkylthio substituted benzyl;
R c optionally 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Alkoxy, C 1-6 Alkylthio, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy, halo C 1-6 Alkylthio, C 1-6 alkoxy-C (=o) -, -NH-C 1-6 Alkyl or-N (C) 1-6 Alkyl group 2 A substituted phenyl group;
R d and R is e Each independently is hydrogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-8 Cycloalkyl, C 3-8 cycloalkyl-C 1-3 Alkylene-, optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkylthio, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy, halo C 1-6 Alkylthio, C 1-6 alkoxy-C (=o) -, -NH-C 1-6 Alkyl or-N (C) 1-6 Alkyl group 2 Substituted C 6-10 Aryl or optionally substituted with 1, 2, 3 or 4 groups selected from fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Alkylthio, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy, halo C 1-6 Alkylthio, C 1-6 alkoxy-C (=o) -, -NH-C 1-6 Alkyl or-N (C) 1-6 Alkyl group 2 Substituted 5-6 membered heteroaryl.
The 5-6 membered heteroaryl group comprises a 5 membered heteroaryl group and a 6 membered heteroaryl group, and the 5 membered heteroaryl group comprises thienyl, furyl, pyrrolyl, thiazole, thiadiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, imidazolyl, pyrazolyl, triazolyl and tetrazolyl; the 6 membered heteroaryl group includes pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl.
In some embodiments, R 1 And R is 2 Each independently is hydrogen, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl or C 3-6 cycloalkyl-C 1-3 An alkylene group; wherein R is 1 And R is 2 Each independently optionally substituted with 1, 2, 3, 4, 5 or 6 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, C 1-4 Alkyl, C 1-4 Alkoxy, halo C 1-4 Alkyl or halo C 1-4 The substituent of the alkoxy group is substituted.
In other embodiments, R 1 And R is 2 Each independently is hydrogen, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 ) 2 、-CH(CH 3 )CH 2 CH 3 、-C(CH 3 ) 3 、-CH＝CH 2 、-CH 2 CH＝CH 2 、-CH≡CH、-CH 2 C.ident.CH, cyclopropyl-CH 2 -, cyclopropyl-CH 2 CH 2 -or cyclopropyl-CH 2 CH 2 CH 2 -。
In some embodiments, R 1 、R 2 And the N atom to which it is attached form a 3-6 membered heterocyclyl or a 5-10 membered heteroaryl; the 3-6 membered heterocyclyl or 5-10 membered heteroaryl is optionally substituted with fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino or C 1-4 Alkyl substitution.
In other embodiments, R 1 、R 2 And the N atom attached thereto form the following sub-structural formula:
in some embodiments, R 3 Is C 3-6 Cycloalkyl; wherein R is 3 Optionally substituted with 1, 2, 3, 4, 5 or 6 groups selected from halogen, cyano, hydroxy, nitro, amino, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl, C 3-6 cycloalkyl-C 1-3 Alkylene-, halo C 1-4 Alkyl, C 1-4 Alkoxy or halo C 1-4 Alkoxy substitution.
In other embodiments, R 3 Is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; wherein R is 3 Optionally substituted with 1, 2, 3, 4, 5 or 6 groups selected from halogen, cyano, hydroxy, nitro, amino, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl, C 3-6 cycloalkyl-C 1-3 Alkylene-, halo C 1-4 Alkyl, C 1-4 Alkoxy or halo C 1-4 Alkoxy substitution.
In still other embodiments, R 3 Is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; wherein R is 3 Optionally substituted with 1, 2, 3, 4, 5 or 6 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 ) 2 、-CH(CH 3 )CH 2 CH 3 、-C(CH 3 ) 3 Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclopropyl-CH 2 -substitution.
In some embodiments, R 4 is-SO 2 -NR a R b 、-SO 2 -C 1-4 Alkyl, -SO 2 -C 3-6 Cycloalkyl, -SO 2 -C 1-3 alkylene-C 3-6 Cycloalkyl, -SO 2 -R c 、-CH 2 -C(＝O)O-C 1-4 Alkyl or-CH 2 -C(＝O)-NR d R e ；
Wherein R is a And R is b Each independently is hydrogen, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl, C 3-6 cycloalkyl-C 1-3 Alkyl-, optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo C 1-4 Alkyl, halogenated C 1-4 Alkoxy, halo C 1-4 Alkylthio-substituted phenyl or phenyl optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo C 1-4 Alkyl, halogenated C 1-4 Alkoxy or halo C 1-4 Alkylthio substituted benzyl;
R c optionally 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo C 1-4 Alkyl, halogenated C 1-4 Alkoxy, halo C 1-4 Alkylthio, C 1-4 alkoxy-C (=o) -, -NH-C 1-4 Alkyl or-N (C) 1-4 Alkyl group 2 A substituted phenyl group;
R d and R is e Each independently is hydrogen, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl, C 3-6 cycloalkyl-C 1-3 Alkylene-, optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halo C 1-4 Alkyl, halogenated C 1-4 Alkoxy, halo C 1-4 Alkylthio, C 1-4 alkoxy-C (=o) -, -NH-C 1-4 Alkyl or-N (C) 1-4 Alkyl group 2 Substituted phenyl or optionally substituted with 1, 2, 3 or 4 groups selected from fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Alkylthio, halogenSubstitute C 1-4 Alkyl, halogenated C 1-4 Alkoxy, halo C 1-4 Alkylthio, C 1-4 alkoxy-C (=o) -, -NH-C 1-4 Alkyl or-N (C) 1-4 Alkyl group 2 Substituted pyridyl.
The pyridyl group includes pyridin-2-ylPyridin-3-yl->And pyridin-4-yl
In other embodiments, R 4 is-SO 2 -NR a R b 、-SO 2 -CH 3 、-SO 2 -CH 2 CH 3 、-SO 2 -CH 2 CH 2 CH 3 、-SO 2 -CH(CH 3 ) 2 、-SO 2 -CH 2 CH 2 CH 2 CH 3 、-SO 2 -CH 2 CH(CH 3 ) 2 、-SO 2 -CH(CH 3 )CH 2 CH 3 、-SO 2 -C(CH 3 ) 3 、-SO 2 -cyclopropyl, -SO 2 -cyclobutyl, -SO 2 -cyclopentyl, -SO 2 -cyclohexyl, -SO 2 -R c 、-CH 2 -C(＝O)O-C 1-4 Alkyl or-CH 2 -C(＝O)-NR d R e ；
Wherein R is a And R is b Each independently is hydrogen, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 ) 2 、-CH(CH 3 )CH 2 CH 3 or-C (CH) 3 ) 3 ；
R c To be optionally substituted by 1, 2, 3, 4 or 5 groups selected from fluorine, chlorineBromine, iodine, hydroxy, cyano, nitro, amino, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 ) 2 、-CH(CH 3 )CH 2 CH 3 、-C(CH 3 ) 3 、-OCH 3 、-OCH 2 CH 3 、-OCH 2 CH 2 CH 3 、-OCH(CH 3 ) 2 、-OCH 2 CH 2 CH 2 CH 3 、-OCH 2 CH(CH 3 ) 2 、-OCH(CH 3 )CH 2 CH 3 、-OC(CH 3 ) 3 、-SCH 3 、-SCH 2 CH 3 、-CF 3 、-OCF 3 、-SCF 3 、CH 3 OC(＝O)-、CH 3 CH 2 OC(＝O)-、-NHCH 3 、-NHCH 2 CH 3 、-N(CH 3 ) 2 or-N (CH) 2 CH 3 ) 2 A substituted phenyl group;
R d and R is e Each independently is hydrogen, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 ) 2 、-CH(CH 3 )CH 2 CH 3 、-C(CH 3 ) 3 Optionally substituted with 1, 2, 3, 4 or 5 groups selected from fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 ) 2 、-CH(CH 3 )CH 2 CH 3 、-C(CH 3 ) 3 、-OCH 3 、-OCH 2 CH 3 、-OCH 2 CH 2 CH 3 、-OCH(CH 3 ) 2 、-OCH 2 CH 2 CH 2 CH 3 、-OCH 2 CH(CH 3 ) 2 、-OCH(CH 3 )CH 2 CH 3 、-OC(CH 3 ) 3 、-SCH 3 、-SCH 2 CH 3 、-CF 3 、-OCF 3 、-SCF 3 、CH 3 OC(＝O)-、CH 3 CH 2 OC(＝O)-、-NHCH 3 、-NHCH 2 CH 3 、-N(CH 3 ) 2 or-N (CH) 2 CH 3 ) 2 Substituted phenyl or optionally substituted with 1, 2, 3 or 4 groups selected from fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 ) 2 、-CH(CH 3 )CH 2 CH 3 、-C(CH 3 ) 3 、-OCH 3 、-OCH 2 CH 3 、-OCH 2 CH 2 CH 3 、-OCH(CH 3 ) 2 、-OCH 2 CH 2 CH 2 CH 3 、-OCH 2 CH(CH 3 ) 2 、-OCH(CH 3 )CH 2 CH 3 、-OC(CH 3 ) 3 、-SCH 3 、-SCH 2 CH 3 、-CF 3 、-OCF 3 、-SCF 3 、CH 3 OC(＝O)-、CH 3 CH 2 OC(＝O)-、-NHCH 3 、-NHCH 2 CH 3 、-N(CH 3 ) 2 or-N (CH) 2 CH 3 ) 2 Substituted pyridin-3-yl.
Preferably, in some embodiments, R 4 is-SO 2 -NR a R b 、-SO 2 -C 1-6 Alkyl, -SO 2 -C 3-8 Cycloalkyl, -SO 2 -C 1-3 alkylene-C 3-8 Cycloalkyl, -SO 2 -R c 、-C 1-3 alkylene-C (=o) O-C 1-6 Alkyl or-C 1-3 alkylene-C (=o) -NHR e ；
R a 、R b 、R c And R is e Having the meaning described in the present invention.
More preferably, and in some embodiments, R 4 is-SO 2 -NR a R b 、-SO 2 -C 1-4 Alkyl, -SO 2 -C 3-6 Cycloalkyl, -SO 2 -C 1-3 alkylene-C 3-6 Cycloalkyl, -SO 2 -R c 、-CH 2 -C(＝O)O-C 1-4 Alkyl or-CH 2 -C(＝O)-NHR e ；
R a 、R b 、R c And R is e Having the meaning described in the present invention.
In still other embodiments, R 4 The following sub-structural formula is shown as follows:
in some embodiments, the present invention provides a compound that is a compound having one of the following structures or stereoisomers, nitroxides, and salts of a compound having one of the following structures:
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 invention comprises an agropharmaceutically acceptable adjuvant.
In yet another aspect, the present invention provides the use of a compound of the present invention and/or a composition of the present invention for controlling plant diseases.
Further, the plant diseases according to the present invention are caused by plant pathogenic fungi.
The compound and/or the composition disclosed by the invention have excellent control effects on diseases caused by pathogenic fungi, especially on cucumber downy mildew; under the condition of lower effective dose concentration, the control effect on cucumber downy mildew can still reach more than 80 percent.
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 in the accompanying structural and chemical formulas. The invention is intended to cover all alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. Those 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 of one or more of the incorporated references, patents and similar materials differing from or contradictory to the present application (including but not limited to defined terms, term application, described techniques, etc.), the present application controls.
It should further be 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 sub-combination.
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, chemical elements are in accordance with CAS version of the periodic Table of the elements, and handbook of chemistry and physics, 75 th edition, 1994. In addition, general principles of organic chemistry may be referenced to the descriptions in "Organic Chemistry", thomas Sorrell, university Science Books, sausalato:1999, and "March's Advanced Organic Chemistry" by Michael b.smith and Jerry March, john Wiley & Sons, new york:2007, the entire contents of which are incorporated herein by reference.
The articles "a," "an," and "the" are intended to include "at least one" or "one or more" unless the context clearly dictates otherwise or otherwise. Thus, as used herein, the articles refer to articles of manufacture that include one or more than one (i.e., at least one) object. For example, "a component" refers to one or more components, i.e., more than one component is contemplated as being employed or used in embodiments of the described embodiments.
The term "comprising" is an open-ended expression, i.e., including what is indicated by the invention, but not excluding other aspects.
"stereoisomers" refer to compounds having the same chemical structure but different arrangements of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.
"enantiomer" refers to two isomers of a compound that do not overlap but are in mirror image relationship to each other.
"diastereoisomers" refers to stereoisomers which have two or more chiralities and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting point, boiling point, spectral properties, and reactivity. The diastereomeric mixture 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 S.P. Parker, ed., mcGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, new York; and Eliel, e.and Wilen, s., "Stereochemistry of Organic Compounds", john Wiley & Sons, inc., new York, 1994.
Many organic compounds exist in 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 represent the absolute configuration of the molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are symbols for specifying the rotation of plane polarized light by a compound, where (-) or l indicates that the compound is left-handed. The compound prefixed with (+) or d is dextrorotatory. One 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 can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.
Any asymmetric atom (e.g., carbon, etc.) of the disclosed compounds may exist in racemic or enantiomerically enriched form, such as in 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 be present in the form of one of the possible isomers or mixtures thereof, for example racemates and non-corresponding isomer mixtures, 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 substituent 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.
The resulting mixture of any stereoisomers may be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers, e.g., by chromatography and/or fractional crystallization, depending on the differences in the physicochemical properties of the components.
Any of the resulting racemates of the end products or intermediates can be resolved into the optical enantiomers by methods familiar to those skilled in the art, e.g., by separation of the diastereoisomeric salts thereof obtained, using known methods. The racemic product can also be separated by chiral chromatography, e.g., high Performance Liquid Chromatography (HPLC) using chiral adsorbents. In particular, enantiomers may be prepared by asymmetric synthesis.
The compounds of the invention may be optionally substituted with one or more substituents, as described in the present invention, such as the compounds of the general formula above, or as specific examples within the examples, subclasses, and classes of compounds encompassed by the invention. It is to be 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 specific substituent. An optional substituent group may be substituted at each substitutable position of the group unless otherwise indicated. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, then the substituents may be the same or different at each position. Specifically, examples of "one or more" refer to 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. Wherein the substituents may be, but are 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 alkyl, alkylamino, 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, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl, and the like.
In addition, unless explicitly indicated otherwise, the descriptions used in this disclosure of the manner in which each … is independently "and" … is independently "and" … is independently "are to be construed broadly as meaning that particular items expressed between the same symbols in different groups do not affect each other, or that particular items expressed between the same symbols in the same groups do not affect each other.
In the various parts of the present specification, substituents of the presently disclosed compounds are disclosed in terms of the type or scope of groups. It is specifically noted that the present invention includes each individual subcombination of the individual members of these group classes and ranges. For example, the term "C 1 -C 6 Alkyl "or" C 1-6 Alkyl "means in particular methyl, ethyl, C independently disclosed 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 An alkyl group.
The term "alkyl" or "alkyl group" as used herein, means a saturated straight or branched monovalent hydrocarbon group containing 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 to 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 (Et, -CH) 2 CH 3 ) N-propyl (n-Pr, -CH) 2 CH 2 CH 3 ) Isopropyl (i-Pr, -CH (CH) 3 ) 2 ) N-butyl (n-Bu, -CH) 2 CH 2 CH 2 CH 3 )，Isobutyl (i-Bu, -CH) 2 CH(CH 3 ) 2 ) Sec-butyl (s-Bu, -CH (CH) 3 )CH 2 CH 3 ) Tert-butyl (t-Bu, -C (CH) 3 ) 3 ) N-pentyl (-CH) 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH) 3 )CH 2 CH 2 CH 3 ) 3-pentyl (-CH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) And so on.
The term "alkylene" refers to a saturated divalent hydrocarbon group resulting from the removal of two hydrogen atoms from an alkyl group. Unless otherwise specified, alkylene groups contain 1 to 12 carbon atoms. In one embodiment, the alkylene group contains 1 to 6 carbon atoms; in another embodiment, the alkylene group contains 1 to 4 carbon atoms; in yet another embodiment, the alkylene group contains 1 to 3 carbon atoms; in yet another embodiment, the alkylene group contains 1 to 2 carbon atoms. Examples of this include methylene (-CH) 2 (-), ethylene (-CH) 2 CH 2 (-), etc.
The term "haloalkyl" means an alkyl group substituted with one or more halogen atoms, examples of which include, but are not limited to, fluoromethyl (-CH) 2 F) Difluoromethyl (-CHF) 2 ) Trifluoromethyl (-CF) 3 ) Etc.
The term "alkenyl" denotes a straight-chain or branched monovalent hydrocarbon radical containing 2 to 12 carbon atoms, in which there is at least one site of unsaturation, i.e. one carbon-carbon sp 2 A 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 comprises 2 to 6A carbon atom; 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) 2 CH＝CH 2 ) Propenyl (CH) 3 -ch=ch-), oxo-butenyl (CH 3 -C (=o) -ch=ch-), and so on.
The term "alkynyl" denotes a straight or branched monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond. Examples of alkynyl groups include, but are not limited to, ethynyl (-CH≡CH), propargyl (-CH) 2 C≡ch), and the like.
The term "alkoxy" means that the alkyl group is attached to the remainder 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) 2 CH 3 ) 1-propoxy (n-PrO, n-propoxy, -OCH) 2 CH 2 CH 3 ) 2-propoxy (i-PrO, i-propoxy, -OCH (CH) 3 ) 2 ) Etc.
The term "haloalkoxy" means that the alkoxy group is substituted with one or more halogen atoms, examples of which include, but are not limited to, difluoromethoxy (-OCHF) 2 ) Trifluoromethoxy (-OCF) 3 ) Etc.
The term "alkylthio" means that the alkyl group is attached to the remainder of the molecule through a sulfur atom, wherein the alkyl group has the meaning as described herein. Examples of alkylthio groups include, but are not limited to, -SCH 3 、-SCH 2 CH 3 、-SCH 2 CH 2 CH 3 、-SCH(CH 3 ) 2 Etc.
The term "haloalkylthio" means that the alkylthio group is substituted with one or more halogen atoms, examples of which include, but are not limited to, difluoromethylthio (-SCHF) 2 ) Trifluoromethylthio (-SCF) 3 ) Etc.
The term "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing 3 to 12 carbon atoms. In one embodiment, cycloalkyl groups contain 3 to 10 carbon atoms; in another embodiment, cycloalkyl groups contain 3 to 8 carbon atoms; in yet another embodiment, cycloalkyl groups contain 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 "cycloalkylalkylene" means that the cycloalkyl group is attached to the remainder of the molecule through an alkylene group, wherein the cycloalkyl group and alkylene group have the meanings described herein; examples include, but are not limited to, cyclopropylmethylene (cyclopropyl-CH 2 (-), cyclopropylethylene (cyclopropyl-CH) 2 CH 2 (-), etc.
The terms "heterocyclyl" and "heterocycle" are used interchangeably herein to refer to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing 3 to 15 ring atoms, wherein the monocyclic, bicyclic or tricyclic ring contains no aromatic rings and at least one ring atom is selected from the group consisting of nitrogen, sulfur and oxygen atoms. Unless otherwise indicated, a heterocyclic group may be a carbon or nitrogen group, and-CH 2 The group may optionally be replaced by-C (=o) -. The sulfur atom of the ring may optionally be oxidized to an S-oxide. The nitrogen atom of the ring may optionally be oxidized to an N-oxide. Examples of heterocyclyl groups include, but are not limited to, oxiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (e.g., 2-pyrrolidinyl), 2-pyrrolinyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, 1, 3-dioxacyclopentyl, dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidinyl, 4-piperidinyl), morpholinyl, thiomorpholinyl, (1-oxo) -thiomorpholinyl, (1, 1-dioxo) -thiomorpholinyl, piperazinyl, dioxanyl, dithianyl, thiazanyl, homopiperazinyl, homopiperidinyl, oxepinyl, thietanyl, 2-oxo Hetero-5-azabicyclo [2.2.1]Hept-5-yl, tetrahydropyridinyl. In heterocyclic groups-CH 2 Examples of the substitution of the-group by-C (=o) -include, but are not limited to, 2-oxopyrrolidinyl, oxo-1, 3-thiazolidinyl, 2-piperidonyl, 3, 5-dioxopiperidyl. Examples of sulfur atoms in the heterocyclic group that are oxidized include, but are not limited to, sulfolane, 1-dioxothiomorpholino. The heterocyclyl group is optionally substituted with one or more substituents described herein.
The term "unsaturated" as used in the present invention means that the group contains one or more unsaturations.
The term "heteroatom" refers to O, S, N, P and Si, including N, S and any oxidation state forms of P; primary, secondary, tertiary and quaternary ammonium salt forms; or a form in which the hydrogen on the nitrogen atom in the heterocycle is substituted, for example, N (like N in 3, 4-dihydro-2H-pyrrolyl), NH (like NH in pyrrolidinyl) or NR (like NR in N-substituted pyrrolidinyl).
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The term "aryl" means a monocyclic, bicyclic and tricyclic carbocyclic ring system 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 contains a ring of 3 to 7 atoms, and wherein one or more attachment points are attached to the remainder of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring". Examples of aryl groups may include phenyl, indenyl, naphthyl and anthracenyl. The aryl group is optionally substituted with one or more substituents described herein.
The term "arylalkylene" means that the aryl group is attached to the remainder of the molecule through an alkylene group, wherein the aryl group and alkylene group have the meaning as described herein; examples include, but are not limited to, phenylmethylene (i.e., benzyl), phenylethylene, and the like.
The term "heteroaryl" means 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 and has one or more attachment points attached to the remainder of the molecule. The term "heteroaryl" may be used interchangeably with the term "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein. In one embodiment, the heteroaryl group of 5 to 10 atoms comprises 1,2,3 or 4 heteroatoms independently selected from O, S and N.
Examples of heteroaryl groups include, but are not limited to, 2-furyl, 3-furyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (e.g., 3-pyridazinyl), 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (e.g., 5-tetrazolyl), triazolyl (e.g., 2-triazolyl and 5-triazolyl), 2-thienyl, 3-thienyl, pyrazolyl, isothiazolyl, 1,2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 4-oxadiazolyl, 1, 2-triazolyl, 3-triazolyl, 1, 3-triazolyl, 3-thiotriazinyl, 1, 2-thiotriazinyl, 1-thiotriazinyl; the following bicyclic rings are also included, but are in no way limited to: benzimidazolyl, benzofuranyl, benzothienyl, indolyl (e.g., 2-indolyl), benzopiperidinyl, and the like.
Salts of the compounds of the present invention include those derived from alkali metals or alkaline earth metals, as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and have the formula N + (R 19 R 20 R 21 R 22 ) Wherein R is an ammonium cation of 19 、R 20 、R 21 And R is 22 Independently selected from hydrogen, C 1 -C 6 Alkyl and C 1 -C 6 A hydroxyalkyl group. Salts of the compounds of formula (I) may be prepared by reacting a metal hydroxide (e.g. sodium hydroxide) Or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecamine or benzylamine) to treat the compound of formula (I).
When the compounds of the present invention contain a base moiety, acceptable salts may be formed with organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids.
Compositions and formulations of the compounds of the invention
The compounds of the present invention are generally useful as bacterially active ingredients in compositions or formulations, typically also including agropharmaceutically acceptable adjuvants; the agropharmaceutically acceptable auxiliary agent comprises a surfactant and/or a carrier.
The surfactant may be any of various surfactants known in the art of agricultural chemical formulation, and the present invention is preferably one or more of an emulsifier, a dispersant and a wetting agent.
Other carriers besides the above surfactants may be various carriers well known in the art of agricultural chemical formulation, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, synthetic carriers. Specifically, for example: white carbon black, kaolin, diatomaceous earth, 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 emulsifier may be various emulsifiers known in the field of pesticide formulation, and specifically, the emulsifier may be one or more of calcium dodecyl benzene sulfonate, triphenyl ethyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide adduct of fatty amide, fatty acid polyoxyethylene ester, rosin acid ethylene oxide adduct, polyol fatty acid ester and ethylene oxide adduct thereof, styrylphenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether.
The dispersing agent can be various dispersing agents known in the pesticide formulation field, and specifically, the dispersing agent is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid formaldehyde condensate sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenyl ethyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignin sulfonic acid sodium salt.
The wetting agent can be various wetting agents known in the pesticide formulation field, and concretely, the wetting agent can be one or more of sodium dodecyl sulfate, secondary sodium alkyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl naphthalene sulfonate and alkylphenol polyoxyethylene ether sulfate.
The bactericidal composition according to the present invention may further contain various adjuvants for formulation commonly used in the field of agricultural chemical formulation, and specifically, the adjuvants for formulation may be one or more of solvents, co-solvents, thickeners, antifreezes, encapsulating materials, protectants, antifoaming agents, disintegrants, stabilizers, preservatives and binders.
The above solvent may be various solvents well known in the field of agricultural chemical formulation, and specifically, the solvent may be one or more of organic solvents, vegetable oils, mineral oils, solvent oils and water.
Wherein the organic solvent comprises one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N-dimethyl capramide, N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, octane, heptane, methanol, isopropanol, N-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1, 4-dioxane and cyclohexanone.
The vegetable oil comprises one or more of methylated vegetable oil, turpentine-based vegetable oil, turpentine, epoxidized soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine seed oil.
The mineral oil includes one or more of liquid wax, engine oil, kerosene, and lubricating oil.
Meanwhile, the solvent can also be used as a cosolvent.
The above antifreezing agent may be various antifreezing agents known in the field of agricultural chemical formulation, and the present invention is preferably one or more of ethylene glycol, propylene glycol, glycerin and urea.
The thickener may be various thickeners known in the field of pesticide dosage forms, and specifically, the thickener may be one or more of xanthan gum, polyvinyl alcohol, polyacrylate alcohol, polyethylene glycol, white carbon black, diatomaceous earth, kaolin, clay, sodium alginate, aluminum magnesium silicate, aluminum sodium silicate, carboxymethyl cellulose, hydroxypropyl cellulose sodium, and organic bentonite.
The capsule wall material can be various capsule wall materials known in the pesticide formulation field, and the invention is preferably one or more of polyurethane, polyurea and urea-formaldehyde resin.
The protective agent may be any of various protective agents known in the field of agricultural chemical formulations, and the present invention is preferably polyvinyl alcohol and/or polyethylene glycol.
The above defoamer may be various defoamers known in the field of pesticide formulation, and the present invention is preferably one or more of organosiloxane, tributyl phosphate and silicone.
The stabilizer is one or more selected from triphenyl phosphite, epichlorohydrin and acetic anhydride.
The preservative is selected from one or more of benzoic acid, sodium benzoate, 1, 2-benzisothiazolin-3-one (BIT for short), pinocembrane and potassium sorbate.
The invention also provides a preparation prepared from the bactericidal composition, and the preparation formulation of the preparation is emulsifiable concentrate, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension, suspension emulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water spreading oil, wettable powder, water dispersible granules, dry suspension, soluble powder, soluble granules, emulsifiable powder, emulsifiable granules, solid microcapsule preparation, effervescent tablets, effervescent granules, water floating dispersible granules or seed coating. The above dosage forms can be prepared by methods conventional in the art.
The preparation method of the emulsifiable concentrate preparation can comprise, for example, mixing and stirring the active components, the solvent, the cosolvent and the emulsifier to form a uniform transparent oil phase, thus obtaining the emulsifiable concentrate preparation.
The above aqueous emulsion preparation method may include, for example, mixing the active ingredient, the emulsifier, the cosolvent and the solvent to form a homogeneous oil phase; water, thickener, antifreeze, etc. are mixed to make it into a uniform aqueous phase. Under high-speed shearing, adding the water phase into the oil phase or adding the oil phase into the water phase to form the aqueous emulsion with good dispersibility.
The microemulsion may be prepared by mixing and stirring the active ingredient, the emulsifier and the solvent into a uniform transparent oil phase. Under stirring, water was gradually added to form a uniform transparent microemulsion.
The preparation method of the water/oil suspending agent comprises the following steps: for example, water or oil is used as a medium, and additives such as active components, surfactants and the like are added into a sanding kettle, ground to a certain particle size, and filtered. And adding the metered thickener into the ground mother solution, and shearing and dispersing uniformly. Making into oil suspension or water suspension.
The preparation method of the water-dispersible granule and the soluble granule comprises the following steps: for example, the water-dispersible granule or soluble granule can be obtained by uniformly mixing the active components, the dispersing agent, the wetting agent, the carrier and the like, then crushing the mixture to a certain particle size by air flow, adding water for kneading, finally adding the mixture into a granulator for granulating, and drying the mixture.
The preparation method of the soluble powder and the wettable powder comprises the following steps: for example, the active ingredients, various auxiliary agents, and other fillers such as carriers may be thoroughly mixed and pulverized by a pulverizer.
The bactericidal composition of the invention can be provided in the form of a finished preparation, i.e. the materials in the composition are already mixed; or in the form of separate preparations which are self-mixed in a tank or can before use and optionally diluted with water depending on the desired concentration of active substance.
Use of the compounds and compositions of the invention
The compounds of the present invention are useful as plant disease controlling agents. Thus, the present invention may also include a method for controlling plant diseases caused by phytopathogenic fungi, said method comprising applying to the plant to be protected or to a part thereof or to the seed of the plant to be protected an effective amount of a compound of the invention or a fungicidal composition comprising an effective amount of said compound. The compounds and/or compositions of the present invention provide control of diseases caused by broad-spectrum plant pathogenic fungi of basidiomycetes, ascomycetes, oomycetes and deuteromycetes. They are effective against a broad spectrum of plant diseases, especially foliar pathogens of ornamental, lawn, vegetable, field, cereal and fruit crops. These pathogens include: oomycetes, including Phytophthora (Phytophthora) diseases such as Phytophthora infestans (Phytophthora infestans), phytophthora sojae (Phytophthora megasperma), citrus foot rot (Phytophthora parasitica), phytophthora camphorata (Phytophthora cinnamomi) and Phytophthora cucurbitae (Phytophthora capsici), pythium (Pythium) species diseases such as Pythium triclopyr (Pythium aphanidermatum), and Peronospora species diseases such as downy mildew (Plasmopara viticola), peronospora diseases (Peronospora spp.) (including Peronospora tabacia (Peronospora tabacina) and Peronospora parasitica (Peronospora parasitica)), pseudoperonospora (Pseudoperonospora spp.) (including Peronospora cucumeria (Pseudoperonospora cubensis) and scentis discriminan (bria tucae)); ascomycetes (including Alternaria (Alternaria) pathogens such as Alternaria solani (Alternaria solani) and Brassica oleracea (Alternaria brassicae), fabry (Guignardia) pathogens such as Botrytis cinerea (Guignardia bidwell), venturia (Venturia) pathogens such as Botrytis cinerea (Venturia inaequalis), septoria (Septoria) pathogens such as Lesion mould (Septoria nodorum) and leaf blight (Septoria tritica), powdery mildew (powdery) pathogens such as Leuconostoc (Erysiphe spp) (including wheat mildew (Erysiphe graminis) and Asclepiaum (Erysiphe polygoni)), grape powdery mildew (Uncinula neccatur), cucumber powdery mildew (Sphaerotheca fuligena) and apple (Podosphaera leucotricha), wheat middlingia (Pseudocercosporella herpotrichoides), gray mold (Botrytis) pathogens such as Botrytis cinerea (Botrytis cinerea) and Sclerotinia (Monilinia fructicola), powdery mildew (such as Sclerotinia cinerea) and Sclerotinia (37), powdery mildew (37) pathogens (such as Sclerotinia Colletotrichum) and Sclerotina (35), and Sclerotinia (35) pathogens (such as Sclerotinia Colletotrichum) and Sclerotinia (35) and Sclerotina (35) and Sclerotinia (35), including rust diseases caused by rust (Puccinia spp.) (such as Puccinia recondita (Puccinia recondita), puccinia striolata (Puccinia striiformis), puccinia phyllanthus (Puccinia hordei), puccinia striolata (Puccinia graminis) and Puccinia pedunculata (Puccinia arachidis)), puccinia caffei (Hemileia vastatrix) and soybean rust (Phakopsora pachyrhizi); other pathogens include Rhizoctonia species (Rhizoctonia spp.) (e.g., rhizoctonia solani (Rhizoctonia solani)); fusarium (Fusarium) species diseases such as Fusarium roseum, fusarium graminearum (Fusarium graminearum), and Fusarium oxysporum (Fusarium oxysporum); verticillium dahliae (Verticillium dahliae); southern blight (Sclerotium rolfsii); the fungus (Rynchosporium secalis); black spot bacteria (Cercosporidium personatum), black spot bacteria (Cercospora arachidicola) and brown spot bacteria (Cercospora beticola); and other classes and species closely related to these pathogens. In addition to their fungicidal activity, the compositions or combinations also have resistant activity against bacteria such as Pyricularia pyrifolia (Erwinia amylovora), xanthomonas campestris (Xanthomonas campestris), pseudomonas syringae (Pseudomonas syringae), and other species.
The bactericidal compound and/or the bactericidal composition of the invention is simple in application method, is applied to crops and the sites where the crops grow before or after the germination of plant diseases according to the conventional method, such as soil mixing, spraying, pouring and the like, and the application amount of the bactericidal compound and/or the bactericidal composition is generally 10-5000g (effective amount) per mu according to the climatic conditions or the state of the crops, and is diluted to 10-400mg/L (preferably 100-300 mg/L). The diluent is preferably water.
The bactericidal effect of the compounds or compositions of the present invention is generally related to external factors such as climate, but the effect of climate can be slowed down by the use of suitable dosage forms.
The compounds or compositions of the present invention may also be used in combination with other compounds having fungicidal, insecticidal or herbicidal properties, and may also be used in combination with nematicides, acaricides, protectants, herbicide safeners, growth regulators, plant nutrients or soil conditioners and the like.
General synthetic procedure
The following schemes describe the preparation of the compounds of the present invention which, unless otherwise indicated, may be prepared by the methods described herein. The starting materials, reagents, and the like used in preparing the compounds of the invention are all commercially available; or the starting materials, reagents, etc. used in the preparation of the compounds of the present invention may be prepared by methods conventional in the art. In this specification, a structure is dominant if there is any difference between a chemical name and a chemical structure.
The testing conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: nuclear magnetic instrument of 400MHz or 600MHz of Bruker (Bruker) under room temperature condition, CDC1 3 ，d 6 -DMSO，CD 3 OD or d 6 Acetone as solvent (reported in ppm) with TMS (0 ppm) or chloroform (7.26 ppm) as referenceStandard-meeting. When multiple peaks occur, the following abbreviations will be used: s (single, singlet), d (doublet ), t (triplet, quartet), q (quartet), m (multiplet ), br (broadened, broad), dd (doublet of doublets, doublet), dt (doublet of triplets, doublet). Coupling constants are expressed in hertz (Hz).
The conditions for measuring the low-resolution Mass Spectrum (MS) data of the invention are as follows: agilent 6120 Quadragole HPLC-MS (column model: zorbax SB-C18,2.1X30mm,3.5 μm,6min, flow rate 0.6mL/min, mobile phase 5% -95% (CH containing 0.1% formic acid) 3 CN) in (H containing 0.1% formic acid) 2 Ratio in O)) was detected with UV at 210/254nm using electrospray ionization mode (ESI).
Synthesis scheme one
The target compound represented by the formula (I) can be prepared by a method of synthesis scheme one. The compound shown in the formula (a) and the compound shown in the formula (b) undergo nucleophilic substitution reaction under alkaline conditions (such as pyridine, sodium hydride, potassium carbonate and the like) to obtain a target compound shown in the formula (I);
Wherein R is 1 、R 2 、R 3 And R is 4 Having the meaning described in the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Intermediate a: n (N) 3 -cyclopropyl-N 1 ,N 1 Synthesis of-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide
The first step: synthesis of 1, 2-bis (1H-1, 2, 4-triazol-3-yl) disulfane
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3-mercapto-1, 2, 4-triazole (101.0 g,1.00 mol) was dissolved in dichloromethane (500 mL), pyridine (79.0 g,1.00 mol) was added, and the mixture was stirred at 0℃and p-toluenesulfonyl chloride (95.3 g,0.50 mol) was slowly added dropwise over 2 hours. After the addition was completed, the mixture was stirred at 25℃for 18 hours. The methylene chloride was distilled off under reduced pressure by a rotary evaporator, and water (500 mL) was added to the residue under mechanical stirring, followed by stirring for 1 hour. Filtration, washing the filter residue with water (800 mL) and ethyl acetate (300 mL), air drying, gave 95.2g of yellow powder with the following yield: 95.2%.
LC-MS:(M+1)m/z＝201.1。
And a second step of: synthesis of 3- ((1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazol-3-yl) disulfanyl) -N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide
1, 2-bis (1H-1, 2, 4-triazol-3-yl) dithiolane (60.0 g,0.30 mol) was dissolved in N, N-dimethylformamide (300 mL) under nitrogen, and potassium carbonate (69.0 g,0.50 mol) was added thereto and mixed under stirring at 0 ℃. N, N-dimethylaminosulfonyl chloride (93.3 g,0.65 mol) was slowly added dropwise thereto, and the reaction was continued for 6 hours after the completion of the addition for 2 hours. After the reaction was completed, the reaction solution was slowly poured into water and stirred for 1 hour. The solid was filtered and air-dried to give 107.2g of white powder in the following yield: 86.3%.
LC-MS:(M+1)m/z＝415.0。
And a third step of: synthesis of 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride
3- ((1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazol-3-yl) disulphanyl) -N, N-dimethyl-1H-1, 2, 4-triazole-1-sulfonamide (41.40 g,0.10 mol) was dissolved in 1, 2-dichloroethane (150 mL), water (300 mL) was added, cooled to 0℃and acetic acid (100 mL) was added, the temperature was controlled at 10℃to 25℃and after 2 hours chlorine (35.50 g,0.50 mol) was introduced and the reaction was continued for half an hour. After the completion of the reaction, the solution was transferred to a separating funnel, left to stand for separation, the organic phase was washed three times with water (30 mL), and the solvent was distilled off under reduced pressure using a rotary evaporator to give 48.11g of white powder with the following yield: 87.8%.
LC-MS:(M+1)m/z＝274.8。
Fourth step: n (N) 3 -cyclopropyl-N 1 ,N 1 Synthesis of-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide
Cyclopropylamine (1.14 g,0.02 mol), triethylamine (2.22 g,0.022 mol) and tetrahydrofuran (30 mL) were added to a 100mL three-necked flask under nitrogen protection, stirred at 0℃and a solution of 1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole-3-sulfonyl chloride (6.04 g,0.02 mol) in tetrahydrofuran (20 mL) was added dropwise over 10 minutes and reacted at 25℃for 2 hours after the addition was completed. The solid was removed by filtration, and the solvent was removed from the filtrate under reduced pressure using a rotary evaporator to give a pale yellow solid, which was recrystallized [ ethyl acetate/petroleum ether (v/v) =5/1 ], to give 4.42g of a white solid in the following yield: 75.0%.
1 H NMR(400MHz,DMSO-d 6 )δ(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。
Intermediate B: synthesis of 2-chloro-N- (4-isopropylphenyl) acetamide
4-isopropylaniline (0.67 g,5.0 mmol), triethylamine (0.51 g,5.0 mol) and methylene chloride (30 mL) were added to a 100mL single-necked flask, stirred in an ice bath, chloroacetyl chloride (0.68 g,6.0 mmol) was slowly added to the reaction system, and after the addition was completed, the reaction was stirred at room temperature for 2 hours, water quenching (50 mL) was added, extraction (20 mL. Times.3) with methylene chloride, drying over anhydrous magnesium sulfate, filtration and removal of the solvent under reduced pressure of the filtrate by a rotary evaporator gave 0.72g as a yellow oily liquid, yield 68%.
LC-MS:(M+1)m/z＝212.2。
The intermediate compounds in table 1 were prepared from the corresponding aniline derivatives and chloroacetyl chloride as starting materials, with reference to the preparation of intermediate B, or with reference to the preparation of the prior art.
TABLE 1
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Example 1: n (N) 3 -cyclopropyl-N 3 - (N, N-dimethylaminosulfonyl) -N 1 ,N 1 Synthesis of-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide
Will N 3 -cyclopropyl-N 1 ,N 1 dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.30 g,1.0 mmol), 60% sodium hydride (0.08 g,2.0 mmol) and tetrahydrofuran (10 mL) were added to a 50mL single-necked flask, and N, N-dimethylaminosulfonyl chloride (0.29 g,2.0 mmol) was slowly added to the reaction system and reacted at room temperature of 25℃for 8 hours. After the reaction was completed, water was added to quench (20 mL), extracted with ethyl acetate (15 ml×3), and the organic phases were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the solvent was removed from the filtrate under reduced pressure by a rotary evaporator, and the residue was purified by column chromatography (ethyl acetate/petroleum ether (v/v) =1/3), to give 0.30g of a white solid, yield: 77.0%.
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.67(s,1H),3.22(s,6H),3.08(s,6H),2.90-2.84(m,1H),1.24-1.20(m,2H),1.10-1.05(m,2H)；
LC-MS:(M+23)m/z＝403.0。
Example 2: n (N) 3 -cyclopropyl-N 3 - ((4-methoxyphenyl) sulfonyl) -N 1 ,N 1 Synthesis of-dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide
Will N 3 -cyclopropyl-N 1 ,N 1 dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.30 g,1.0 mmol), 60% sodium hydride (0.08 g,2.0 mmol) and tetrahydrofuran (10 mL) were added to a 50mL single-port flask, 4-methoxybenzenesulfonyl chloride (0.41 g,2.0 mmol) was slowly added to the reaction system, reacted at room temperature 25 ℃ for 8 hours, after completion of the reaction, quenched with water (20 mL), extracted with ethyl acetate (15 mL x 3), the organic phases were combined, the organic phases were washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the solvent was removed from the filtrate under reduced pressure by a rotary evaporator, and the residue was purified by column chromatography (ethyl acetate/petroleum ether (v/v) =1/3) to give a white solid, 0.33g, yield: 71%.
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.67(s,1H),8.00(d,J＝8.9Hz,2H),7.03(d,J＝8.9Hz,2H),3.92(s,3H),3.08(s,6H),2.90-2.84(m,1H),1.24-1.20(m,2H),1.10-1.05(m,2H)；
LC-MS:(M+23)m/z＝466.0。
Respectively 4-fluorobenzenesulfonyl chloride, 4-methylbenzenesulfonyl chloride, 3-chloro-4-fluorobenzenesulfonyl chloride, benzenesulfonyl chloride, 3, 5-difluorobenzenesulfonyl chloride, methyl 2-bromoacetate, ethyl 2-bromoacetate and intermediate A (chemical name: N) 3 -cyclopropyl-N 1 ,N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide of the formula:) For raw materials, refer to the preparation of example 1 or example 2The target compounds in Table 2 were obtained by the method.
TABLE 2
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Example 10: synthesis of 2- ((N-cyclopropyl-1- (N, N-dimethylaminosulfonyl) -1H-1,2, 4-triazole) -3-sulfonylamino) -N- (4-isopropylphenyl) acetamide
Will N 3 -cyclopropyl-N 1 ,N 1 dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.30 g,1.0 mmol), 60% sodium hydride (0.08 g,2.0 mmol) and tetrahydrofuran (10 mL) were added to a 50mL three-port flask, 2-chloro-N- (4-isopropylphenyl) acetamide (0.42 g,2 mmol) was slowly added to the reaction system, reacted at room temperature for 8 hours at 25 ℃, quenched with water (20 mL) after completion of the reaction, extracted with ethyl acetate (15 mL x 3), the organic phases were combined, the organic phases were washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (N-hexane/ethyl acetate (v/v) =3/1) and the eluent was concentrated under reduced pressure with a rotary evaporator to give a white solid of 0.30g, yield: 63.0%.
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.72(s,1H),8.56(s,1H),7.47(d,J＝8.3Hz,2H),7.39(d,J＝8.1Hz,2H),4.25(s,2H),3.87(d,J＝6.3Hz,6H),3.10(s,6H),2.86–2.78(m,1H),1.96–1.88(m,1H),0.91-0.86(m,2H),0.88–0.84(m,2H)；
LC-MS:(M+1)m/z＝471.1。
Respectively by the intermediate compound and the intermediate A (chemical name: N 3 -cyclopropyl-N 1 ,N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide of the formula:) The starting materials were prepared according to the preparation method of example 10, and the target compounds shown in table 3 were obtained.
TABLE 3 Table 3
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Biological activity test:
Test target: cucumber downy mildew fungus
Test treatment: the compound was dissolved with N, N-dimethylformamide to 1% ec (emulsifiable concentrate) for use. The bactericidal activity of the compounds of the invention, the comparative compound A, the comparative compound B, the comparative compound C and the comparative compound D on test targets at different doses (200 mg/L, 100mg/L, 50mg/L and 25 mg/L) was evaluated by a living potting method.
Selecting 1 pot cucumber seedling with consistent growth condition in true leaf period (removing growing point), spraying, naturally drying, inoculating 24 hr after treatment, collecting fresh cucumber downy mildew disease leaf, dipping with brush pen, washing sporangium on the back of the disease leaf with distilled water, and preparing into sporangium suspension (2-3 x 10) 5 and/mL). Uniformly spraying and inoculating on cucumber seedling with an inoculating sprayer (pressure of 0.1 MPa), transferring the inoculated sample to a climatic chamber, maintaining relative humidity at about 120deg.C, maintaining temperature at about 21deg.C after 24 hr, and inducing humidity at about 95deg.CGrading investigation is carried out after 5 days according to the disease condition of the blank control, and the control effect is calculated according to the disease index.
Wherein, the structural formulas corresponding to the comparative compound A, the comparative compound B, the comparative compound C and the comparative compound D are shown in the table a:
table a
The test results show that:
at a dose of 200mg/L, the control effect of example 1, example 2, example 3, example 4, example 5, example 6, example 7, example 8, example 9, example 10, example 11, example 12, example 13, example 14, example 15, example 16, example 17, example 18, example 19, example 20, example 21, example 22 on cucumber downy mildew is more than 80%;
at a dose of 100mg/L, the control effect of the compositions of the examples 2, 3, 5, 6, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 and 22 on cucumber downy mildew is more than 80%;
at 50mg/L dose, the control effect of the examples 10, 11, 14, 15, 16, 17, 18, 19, 20, 21 and 22 on cucumber downy mildew is above 80%; in addition, the control effect of the comparative compound A, the comparative compound B, the comparative compound C and the comparative compound D on cucumber downy mildew is below 70% at a dose of 50 mg/L;
the control effect of the compounds of the invention and the comparative compounds on cucumber downy mildew at a dose of 25mg/L is shown in Table b:
Table b
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The test results show that the compound has good control effect on plant pathogenic fungi, especially cucumber downy mildew, has good application prospect and has further development value.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.

Claims (5)

1. A compound which is a compound having the formula (I):
wherein:
R 1 and R is 2 Each independently is CH 3 ；
R 3 Is cyclopropyl;
R 4 is-SO 2 -R c or-CH 2 -C(＝O)-NR d R e ；
Wherein R is c To be optionally substituted with 1 or 2 groups selected from fluorine, chlorine, bromine, iodine or C 1-4 An alkyl-substituted phenyl group;
R d and R is e Each independently is hydrogen, optionally substituted with 1 or 2 groups selected from fluorine, chlorine, bromine, iodine, C 1-4 Alkyl, C 1-4 Alkoxy, halo C 1-4 Alkoxy or C 1-4 alkoxy-C (=o) -substituted phenyl or pyridinyl optionally substituted with 1 selected from fluoro, chloro, bromo or iodo;
the conditions are as follows: r is R d And R is e One of them is H, but not both.
2. A compound according to claim 1, wherein:
Wherein R is c To be optionally substituted with 1 or 2 groups selected from fluorine, chlorine, bromine, iodine or-CH 3 A substituted phenyl group;
R d and R is e Each independently is hydrogen, optionally substituted with 1 or 2 groups selected from fluorine, chlorine, bromine, iodine, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 ) 2 、-CH(CH 3 )CH 2 CH 3 、-C(CH 3 ) 3 、-OCH 3 、-OCH 2 CH 3 、-OC(CH 3 ) 3 、-OCF 3 、CH 3 OC (=o) -or CH 3 CH 2 OC (=o) -substituted phenyl or pyridin-3-yl optionally substituted with 1 selected from fluorine, chlorine, bromine or iodine.
3. The compound according to any one of claims 1-2, which is a compound or salt having one of the following structures:
4. a composition comprising a compound of any one of claims 1-3.
5. Use of a compound according to any one of claims 1 to 3 or a composition according to claim 4 for controlling plant diseases, wherein the plant diseases are cucumber downy mildew.
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