Thioester compound as well as preparation method and application thereof

Abstract

The invention provides a thioester compound as well as a preparation method and application thereof, and particularly provides a compound as shown in a formula I, a geometric isomer, a stereoisomer or a pharmaceutically acceptable salt of the compound, and application of the compound in killing and / or preventing and treating phytopathogen or plant diseases caused by the phytopathogen. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of pesticides, and specifically relates to a thioester compound and a preparation method and application thereof. Background Art

[0002] Crop pathogens often cause significant losses to major crops such as grains, fruits and vegetables. Using chemical fungicides to prevent and control them is crucial to increasing production, ensuring food production safety, and improving people's living standards. However, due to the irrational use of existing pesticides, pathogens have developed serious resistance to existing agricultural protective agents, and the ecological and environmental safety issues of pesticides have become increasingly prominent. As a major pesticide producer, my country has a huge amount of chemical fungicides, a broad market prospect, and a strong demand for new products.

[0003] In summary, there is an urgent need in the art to develop a new class of compounds with excellent fungicidal activity. Summary of the invention

[0004] The present invention aims to provide a thioester compound with excellent fungicidal activity, novel chemical structure, excellent control effect on various plant pathogens, safe for the environment and ecology, and less toxic and side effects.

[0005] 1. A compound of formula I, its geometric isomers, stereoisomers, or pesticide-acceptable salts thereof,

[0006]

[0007] In the formula,

[0008] A is selected from substituted or unsubstituted C 6-10 aryl, unsubstituted or substituted 5-10 membered heteroaryl, substituted or unsubstituted saturated or partially saturated 5-10 membered heterocyclic group; wherein the substitution means that one or more (such as 2, 3, 4 or 5) hydrogen atoms on the group are independently replaced by a group selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6 Alkenyl, halogenated C 2-6 Alkynyl, C 1-6 Alkyl-S-, C 3-6 Cycloalkyloxy, C 3-6 Cycloalkylthio, -CN, -NO2, oxo, C 3-7 Cycloalkyl, 3-6 membered heterocyclic group, C 6-10 Aryl, 5-6 membered heteroaryl, -N=N-phenyl, benzyl, SO2R 3 、-COR3 、-COOR 3 、-CONR 3 R 4 and -SO2NR 3 R 4 wherein the phenyl group in -N=N-phenyl may be substituted by one or more groups selected from the group consisting of halogen, -CN, -NO2, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy;

[0009] B is substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted 5-10 membered heteroaryl (such as -benzo 5-6 membered heteroaryl or benzo 5-6 membered heteroaryl-), substituted or unsubstituted (phenyl or 5-10 membered heteroaryl)-L-(phenyl or 5-6 membered heteroaryl), substituted or unsubstituted -C 5-6 Heteroarylphenyl-phenyl, substituted or unsubstituted-phenyl 5-6 heteroaryl-phenyl, substituted or unsubstituted phenyl-phenyl-N=N-phenyl or substituted or unsubstituted benzo(C 3-6 wherein the substitution refers to one or more (such as 2, 3, 4 or 5) hydrogen atoms on the group being independently replaced by a group selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6 Alkenyl, halogenated C 2-6 Alkynyl, C 1-6 Alkyl-S-, halo-C 1-6 Alkyl-S-, -Si(C 1-6 Alkyl)3, -C(CH3)=NOC 1-3 Alkyl, C 3-6 Cycloalkyloxy, C 3-6 Cycloalkylthio, -CN, -NO2, oxo, C 3-7 Cycloalkyl, C 3-6 Cycloalkyl-C 3-6 Cycloalkyl, 3-6 membered heterocyclic group, C 6-10 Aryl, 5-6 membered heteroaryl, -N=N-phenyl, benzyl, SO2R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and -SO2NR3 R 4 wherein the phenyl group in -N=N-phenyl may be substituted by one or more groups selected from the group consisting of halogen, -CN, -NO2, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy;

[0010] n is 0, 1, 2 or 3;

[0011] L is none, O, -C1-C3 alkyl-, ethynyl, halogen-substituted or unsubstituted vinyl, NH, CONH or -C(CH3)=NO-CH2-;

[0012] R 3 and R 4 are each independently selected from hydrogen, C 1-6 Alkyl, C 1-6 Haloalkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclic group.

[0013] In another preferred embodiment, A is selected from substituted or unsubstituted phenyl or substituted or unsubstituted 5-6 membered heteroaryl having 1, 2, 3 or 4 heteroatoms selected from O, N, S, SO and SO2. Preferably, the substitution means that 1 or more (such as 2, 3, 4 or 5) hydrogen atoms on the group are independently replaced by groups selected from the following groups: halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl and halogenated C 1-6 Alkoxy.

[0014] In another preferred embodiment, A is selected from the following substituted or unsubstituted groups: phenyl, naphthyl, thiazolyl, thiadiazolyl, isothiazolyl, tetrazolyl, pyridyl, thiomorpholine-S-oxide, thiomorpholine-S,S-oxide, pyrimidinyl, indole, quinoline, isoquinoline, pyridazinyl, pyrazinyl, triazinyl, thienyl, oxazolyl, oxadiazolyl, isoxazolyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl; wherein the substitution means that one or more (such as 2, 3, 4 or 5) hydrogens on the group are independently replaced by groups selected from the following group: halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6 Alkenyl, halogenated C 2-6 Alkynyl, C 1-6 Alkyl-S-, C 3-6Cycloalkyloxy, C 3-6 Cycloalkylthio, -CN, -NO2, oxo, C 3-7 Cycloalkyl, 3-6 membered heterocyclic group, C 6-10 Aryl, 5-6 membered heteroaryl, -N=N-phenyl, benzyl, SO2R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and -SO2NR 3 R 4 ; R 3 and R 4 are each independently selected from hydrogen, C 1-6 Alkyl, C 1-6 Haloalkyl, C 3-6 Preferably, the substitution refers to that one or more (such as 2, 3, 4 or 5) hydrogen atoms on the group are independently replaced by a group selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl and halogenated C 1-6 Alkoxy.

[0015] In another preferred embodiment, A is selected from the following group:

[0016]

[0017] In various

[0018] Each g is independently 0, 1, 2, 3, 4 or 5;

[0019] Each R' is independently selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6 Alkenyl, halogenated C 2-6 Alkynyl, C 1-6 Alkyl-S-, C 3-6 Cycloalkyloxy, C 3-6 Cycloalkylthio, -CN, -NO2, oxo, C 3-7 Cycloalkyl, 3-6 membered heterocyclic group, C 6-10 Aryl, 5-6 membered heteroaryl, -N=N-phenyl, benzyl, SO2R 3 、-COR 3 、-COOR 3 、-CONR 3 R4 and -SO2NR 3 R 4 ; R 3 and R 4 are each independently selected from hydrogen, C 1-6 Alkyl, C 1-6 Haloalkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclic group.

[0020] Preferably, each R' is independently selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl and halogenated C 1-6 Alkoxy.

[0021] In another preferred embodiment, A is selected from the following structures A1-A88:

[0022]

[0023] In another preferred embodiment, B is substituted or unsubstituted phenyl or naphthyl, substituted or unsubstituted phenyl-phenyl, substituted or unsubstituted phenyl-O-phenyl, substituted or unsubstituted-phenyl-O-5-6-membered heteroaryl, substituted or unsubstituted-phenyl-5-6-membered heteroaryl, substituted or unsubstituted-5-6-membered heteroaryl-phenyl, substituted or unsubstituted-5-6-membered heteroaryl-5-6-membered heteroaryl, substituted or unsubstituted-5-6-membered heteroaryl and phenyl-phenyl, substituted or unsubstituted-phenyl-CF=CH-phenyl, substituted or unsubstituted-phenyl-ethynyl-phenyl, substituted or unsubstituted-phenyl The present invention relates to phenyl-C(CH3)=NO-CH2-phenyl, substituted or unsubstituted-phenyl-NH-phenyl, substituted or unsubstituted-phenyl-CONH-phenyl, substituted or unsubstituted-phenyl-phenyl-N=N-phenyl, substituted or unsubstituted-phenyl and C5-C6 cycloalkyl, substituted or unsubstituted-phenyl and 5-6 membered heterocyclic group, substituted or unsubstituted-phenyl and 5-6 membered heteroaryl, substituted or unsubstituted-phenyl-cyclopropyl-cyclopropyl, wherein the substitution refers to that one or more (such as 2, 3, 4 or 5) hydrogens on the group are independently replaced by a group selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6 Alkenyl, halogenated C 2-6 Alkynyl, C 1-6 Alkyl-S-, halo-C 1-6 Alkyl-S-, -Si(C 1-6alkyl)3, -C(CH3)=NO-CH3, C 3-6 Cycloalkyloxy, C 3-6 Cycloalkylthio, -CN, -NO2, oxo, C 3-7 Cycloalkyl, C 3-6 Cycloalkyl-C 3-6 Cycloalkyl, 3-6 membered heterocyclic group, C 6-10 Aryl, 5-6 membered heteroaryl, benzyl, SO2R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and -SO2NR 3 R 4 ; R 3 and R 4 are each independently selected from hydrogen, C 1-6 Alkyl, C 1-6 Haloalkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclic group;

[0024] Preferably, the substitution refers to that one or more (such as 2, 3, 4 or 5) hydrogen atoms on the group are independently replaced by a group selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 1-6 Alkyl-S-, halo-C 1-6 Alkyl-S-, -Si(C 1-6 alkyl)3, -C(CH3)=NO-CH3, -CN.

[0025] In another preferred embodiment, B is a substituted or unsubstituted phenyl group. Preferably, the substitution means that one or more (such as 2, 3, 4 or 5) hydrogen atoms on the group are independently replaced by groups selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 1-6 Alkyl-S-, halo-C 1-6 Alkyl-S-, -Si(C 1-6 More preferably, the substitution refers to one or more hydrogen atoms on the group being independently replaced by a group selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6Alkoxy, more preferably the substitution means that one or more hydrogens on the group are independently replaced by a group selected from the group consisting of halogen and C 1-6 Alkoxy.

[0026] In another preferred embodiment, the B group is selected from any B group in Table a, preferably, B is

[0027] In another preferred embodiment, n=0.

[0028] In another preferred embodiment, B and n have the definitions shown in Table a:

[0029] Table a

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046] In another preferred embodiment, the compound is selected from the compounds shown in the examples.

[0047] In a second aspect, the present invention provides a pesticide composition comprising (i) as an active ingredient a compound of the first aspect, its geometric isomers, stereoisomers, or pesticide-acceptable salts thereof; and (ii) a pesticide-acceptable carrier.

[0048] In another preferred embodiment, in the composition, the content of the compound is 0.001-99.999 wt %.

[0049] In another preferred embodiment, the pesticide is a fungicide composition.

[0050] The third aspect of the present invention provides a use of the compound as described in the first aspect, its geometric isomers, stereoisomers, or its pesticide acceptable salts, or the pesticide composition of the second aspect of the present invention in the preparation of pesticides for killing and / or controlling plant pathogens or plant diseases caused by them.

[0051] In another preferred embodiment, the pathogen is selected from: Rhizoctonia, Sporocolonis, Pseudocorhinus, Puccinia, Puccinia, Pseudocorhinus, Pythium, Oomycetes, or a combination thereof.

[0052] In another preferred embodiment, the plant disease is selected from anthracnose, leaf spot, rust, powdery mildew, sheath blight, leaf blight, gray mold, white rot, damping-off, fusarium head blight, take-all, target spot, downy mildew, phytophthora, or a combination thereof.

[0053] In another preferred embodiment, examples of plants with plant diseases include soybean, corn, wheat, melon, rice, strawberry, peanut, and cotton; examples of plant diseases include soybean rust, corn rust, wheat powdery mildew, melon powdery mildew, rice sheath blight, wheat sheath blight, strawberry gray mold, peanut white rot, cotton damping-off, wheat head blight, wheat take-all, and cucumber target spot, wherein the melon powdery mildew includes cucumber powdery mildew, etc.; the pathogens include Phakopsora pachyrhizi syd., Puccinia sorghi Schw, Blumeria graminis, Erysiphe cucurbitacearum, Sphaerotheca cucurbitae, Thanatephorus cucurbitus, etc. cucumeris), Rhizoctonia cerealis, and Rhizoctonia solani, Botrytis cinerea Pers., Fusarium graminearum schw., Fusariuma venaceum, Fusarium moniliforme sheld., Uromyces, Phytophthora, Pythium. Preferably, the plant disease is caused by Uromyces fabae, Phytophthora capsici, Pythium, etc.

[0054] In a fourth aspect, the present invention provides a method for killing and / or controlling plant pathogens, comprising the steps of contacting the compound as described in the first aspect, its geometric isomers, stereoisomers, or its pesticide-acceptable salts, or the pesticide composition as described in the second aspect with plant pathogens, thereby killing and / or controlling the plant pathogens.

[0055] In another preferred embodiment, the method comprises applying the compound, its geometric isomers, stereoisomers, or its pesticide acceptable salts or pesticide compositions to plants in need or to the environment in which they grow, such as agriculture, pastures, lawns, flower beds and / or indoors.

[0056] In a fifth aspect, the present invention provides a method for preparing the compound described in the first aspect, its geometric isomers, stereoisomers, or its pesticide acceptable salts, the method comprising the steps of:

[0057]

[0058] Wherein, A, B, n are as described above;

[0059] (s1) reacting compound II-1 with an acylating agent in an inert solvent to obtain compound II-2; and

[0060] (s2) II-2 is reacted with II-3 or II-4 in an inert solvent in the presence of a base to obtain a compound of formula I.

[0061] Preferably, step (s1) is: in an inert solvent (preferably, the solvent is selected from: benzene, toluene, ethyl acetate, acetonitrile, dichloromethane, dichloroethane, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1,4-dioxane, PEG400, n-heptane, n-hexane, cyclohexane, petroleum ether, dimethylformamide, dimethyl sulfoxide, or a combination thereof), compound II-1 reacts with an acylating agent (thionyl chloride, oxalyl chloride, triphosgene, sulfonyl chloride, or a combination thereof) to obtain compound II-2;

[0062] Preferably, step (s2) is: in an inert solvent (preferably, the solvent is selected from: benzene, toluene, ethyl acetate, acetonitrile, dichloromethane, dichloroethane, tetrahydrofuran, ether, methyl tert-butyl ether, 1,4-dioxane, PEG400, n-heptane, n-hexane, cyclohexane, petroleum ether, dimethylformamide, dimethyl sulfoxide, or a combination thereof), in a base (preferably, the base is selected from: sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride, sodium methoxide, sodium ethoxide, triethylamine, dimethylaminopyridine, sodium tert-butoxide, potassium tert-butoxide, lithium diisopropylamide, diisopropylethylamine, pyridine, or a combination thereof), II-2 reacts with II-3 or II-4 (such as at 0-25°C or at 0°C to reflux temperature) to obtain a compound of formula I.

[0063] It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described below (such as embodiments) can be combined with each other to form a new or preferred technical solution. Due to space limitations, they will not be described one by one here. DETAILED DESCRIPTION

[0064] After extensive and in-depth research, a large number of screenings and tests, the inventors have provided a class of thioester compounds with novel structures and excellent fungicidal activity, as well as preparation methods and applications thereof, and completed the present invention on this basis.

[0065] the term

[0066] 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.

[0067] As used herein, the term "comprising" or "including (comprising)" may be open, semi-closed and closed. In other words, the term also includes "consisting essentially of" or "consisting of".

[0068] As used herein, the term "room temperature" or "normal temperature" refers to a temperature of 4-40°C, preferably, 25±5°C.

[0069] The prefix "C u-v " indicates that the following groups have u to v carbon atoms, such as "C 1-6 " can be C1, C2, C3, C4, C5 or C6. For example, "C 1-6 "Alkyl" means that the alkyl group has 1 to 6 carbon atoms.

[0070] The term "plurality" refers to 2 or more, such as 2, 3, 4, 5 or 6.

[0071] The term "halogen" or "halo" refers to fluorine, chlorine, bromine, iodine.

[0072] The term "alkyl" refers to a straight or branched chain unsubstituted alkyl having 1 to 6 carbon atoms (i.e., C 1-6 Alkyl), preferably a hydrocarbon group of 1 to 4 carbon atoms (i.e., C 1-4 Alkyl), more preferably hydrocarbon group of 1 to 3 carbon atoms (i.e., C 1-3 Examples of "alkyl" include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl and 3-methylpentyl, and the like.

[0073] The term "alkenyl" refers to an alkenyl group having 2 to 6 carbon atoms (i.e., C 2-6 alkenyl), preferably 2-4 carbon atoms (i.e., C 2-4 alkenyl) or 2-3 carbon atoms (i.e., C 2-3 The alkylene group is a straight or branched hydrocarbon group having 1 to 2 carbon-carbon double bonds. Examples of alkylene groups include, but are not limited to, vinyl, propenyl, butadienyl (including 1,2-butadienyl and 1,3-butadienyl).

[0074] The term "alkynyl" refers to a group having 2 to 6 carbon atoms (i.e., C 2-6 Alkynyl), preferably 2-4 carbon atoms (i.e., C 2-4 Alkynyl) or 2-3 carbon atoms (i.e., C 2-3 alkynyl), and a straight or branched hydrocarbon group having 1 to 2 carbon-carbon triple bonds.

[0075] The term "alkylene" refers to a saturated divalent hydrocarbon radical (i.e., C 1-6Alkylene), preferably a hydrocarbon group of 1 to 4 carbon atoms (i.e., C 1-4 Alkylene), more preferably 1-3 carbon atoms (i.e., C 1-3 Examples of "alkylene" include, but are not limited to, methylene, ethylene, isopropylene, and the like. Alkenylene and alkynylene are divalent groups derived from alkenyl and alkynyl as defined above, respectively, by losing two hydrogen atoms.

[0076] The term "cycloalkyl" refers to a non-aromatic, saturated or partially unsaturated cyclic hydrocarbon group, which may be arbitrarily substituted with one or more substituents described herein. The cycloalkyl group may be a paracyclic, spirocyclic or bridged ring. As used herein, a cycloalkyl group has 3 to 7 ring carbon atoms (i.e., C 3-7 Cycloalkyl) or 3 to 6 ring carbon atoms (i.e. C 3-6 Cycloalkyl). Examples of monocyclic cycloalkyls include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 1-cyclopent-1-enyl, 1-cyclopent-2-enyl, 1-cyclopent-3-enyl, cyclohexyl, 1-cyclohex-1-enyl, cycloheptyl, cyclooctyl. Exemplary bridged bicyclic cycloalkyls include, but are not limited to, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, bicyclo[3.2.2]nonane.

[0077] The terms "aromatic ring" and "aryl" refer to aromatic carbocyclic groups having a single ring (e.g., monocyclic) or multiple rings (e.g., bicyclic or tricyclic), including fused systems. As used herein, aryl has 6 to 10 ring carbon atoms (i.e., C 6-10 Aryl includes bicyclic groups including an aromatic ring fused to a saturated or partially unsaturated carbocyclic or heterocyclic ring (e.g., benzo[C] 3-6 Cycloalkyl or benzo 4-6 membered heterocyclyl). Typical aryl groups include but are not limited to the following groups: benzene, naphthalene, anthracene, 1,2-dihydronaphthalene, 1,2,3,4-tetrahydronaphthyl, 2,3-dihydrobenzofuranyl, etc. The "aryl" category includes structures of aryl rings fused to cycloalkyl and heterocycloalkyl.

[0078] The terms "heterocycle", "heterocyclyl" and "heterocycloalkyl" refer to an optionally substituted, fully saturated or partially saturated (containing 1 or 2 double bonds) non-aromatic ring group, for example, it can be a 3-7 membered monocyclic ring, a 7-11 membered bicyclic ring or a 10-15 membered tricyclic ring system, which has at least one heteroatom in at least one carbon atom-containing ring. Each ring of the heterocyclic group containing a heteroatom can have 1, 2, 3 and 4 heteroatoms selected from O, N, S, SO and SO2. As used herein, the heterocyclic group has 3 to 10 ring atoms (i.e., 3-10 membered heterocyclic group), 3 to 8 ring atoms (i.e., 3-8 membered heterocyclic group), 3-8 membered heterocyclic group or 3 to 6 ring atoms (i.e., 3-6 membered heterocyclic group) or 5 to 6 ring atoms (i.e., 5-6 membered heterocyclic group). The “heterocyclyl” may be arbitrarily substituted with one or more substituents described herein. Examples of the “heterocyclyl” include, but are not limited to, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, morpholino, thiomorpholino, piperazinyl, homopiperazinyl, glycidyl, imidazolidinyl, 3-azabicyclo[3.1.0]hexanyl, 3-azabicyclo[4.1.0]heptanyl, azabicyclo[2.2.2]hexanyl, N-pyridylurea, pyrimidinone and 1,1-dioxo-thiomorpholinyl.

[0079] The term "heteroaryl" or "heteroaromatic ring" refers to a heteroaromatic system containing one or more (e.g., 1, 2, 3, and 4) heteroatoms selected from O, N, S, SO, and SO2, including monocyclic, bicyclic, or polycyclic fused systems. The heteroaryl group may be arbitrarily substituted with one or more substituents described herein. As used herein, the heteroaryl group may have 5 to 10 ring atoms (i.e., 5-10 membered heteroaryl), 5 to 8 ring atoms (i.e., 3-8 membered heteroaryl), or 5 to 6 ring atoms (i.e., 5-6 membered heteroaryl). The heteroaryl group may have 1 to 3 ring heteroatoms, 1 to 2 ring heteroatoms, or 1 ring heteroatom, wherein the ring heteroatoms are independently selected from O, N, S, SO, and SO2. Examples of "heteroaryl" include, but are not limited to, pyrrolyl, pyridinyl, pyrazolyl, imidazolyl, pyrazinyl, imidazopyridinyl, benzofuranyl, pyrimidinyl, triazolyl, tetrazolyl, furanyl, thienyl, thiazolyl, quinolyl, isoquinolyl, indolyl, and the like.

[0080] The term "substituted" means that one or more hydrogen atoms in a specific group are replaced by any substituent mentioned in the present specification. If not otherwise specified, the substitution means that one or more (such as 2, 3, 4 or 5) hydrogen atoms on the group are independently replaced by a group selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6Alkenyl, halogenated C 2-6 Alkynyl, C 1-6 Alkyl-S-, halo-C 1-6 Alkyl-S-, -Si(C 1-6 alkyl)3, -C(CH3)=NO-CH3, C 3-6 Cycloalkyloxy, C 3-6 Cycloalkylthio, -CN, -NO2, oxo, C 3-7 Cycloalkyl, C 3-6 Cycloalkyl-C 3-6 Cycloalkyl, 3-6 membered heterocyclic group, C 6-10 Aryl, 5-6 membered heteroaryl, benzyl, SO2R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and -SO2NR 3 R 4 ; R 3 and R 4 are each independently selected from hydrogen, C 1-6 Alkyl, C 1-6 Haloalkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclic group.

[0081] Active ingredients

[0082] The present invention provides a compound of formula (I), its geometric isomers, optical isomers, or pesticide-acceptable salts thereof:

[0083]

[0084] wherein n, A and B are as defined above.

[0085] In another preferred embodiment, A is selected from A1-A88.

[0086] In another preferred embodiment, B is selected from the B groups in Table a.

[0087] In another preferred embodiment, the compound is any one of the compounds in the examples.

[0088] The present invention is intended to include salts of compounds. A "pesticide-acceptable salt" may have more than one charged atom, and multiple charged atoms may have multiple counterions. In an exemplary embodiment, a salt form of the compound is produced that can convert an otherwise oily or viscous compound into a more easily handled solid material. In another exemplary embodiment, converting the free base of the compound of the present invention into the corresponding salt can increase the solubility of the compound in an aqueous medium, while being able to affect biological properties such as bioavailability, pharmacokinetics, and pharmacodynamics. Therefore, any salt form, such as a pharmaceutically acceptable salt of the compound of the present invention, including a salt of an inorganic acid or a salt of an organic acid is within the scope of the present invention. At the same time, various crystalline forms such as the pharmaceutically acceptable salts of the compound of the present invention are also within the scope of the present invention. Any prodrug of the compound of the present invention is also within the scope of the present invention. For example, R and R t It may be any group that is cleavable in vivo to produce an amine, such as a primary or secondary amine.

[0089] As used herein, the term "agrichemically acceptable salt" refers to salts that are suitable for contact with the tissues of humans and lower animals without excessive toxicity, irritation, allergic reactions, etc. and commensurate with a reasonable benefit / risk ratio within the scope of reasonable medical judgment. Pharmaceutically acceptable salts are well known in the art. Pharmaceutically acceptable salts of the compounds of the present invention include those derived from suitable inorganic and organic acids and bases. Examples of pesticide-acceptable non-toxic acid addition salts are salts formed by amino groups with inorganic acids (such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid and perchloric acid) or with organic acids (such as acetic acid, oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid or malonic acid) or by using other methods used in the art (such as ion exchange). Other pharmaceutically acceptable salts include, but are not limited to, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bisulfate, borate, butyrate, camphorate, camphorsulfonate, citrate, cyclopentanepropionate, digluconate, dodecylsulfate, ethanesulfonate, formate, fumarate, glucoheptonate, glycerophosphate, gluconate, hemisulfate, heptanoate, hexanoate, hydroiodide, 2-hydroxy-ethanesulfonate, lactobionate, lactate, laurate, lauryl sulfate, malate, maleate, malonate, methanesulfonate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, pivalate, propionate, stearate, succinate, sulfate, tartrate, thiocyanate, p-toluenesulfonate, undecanoate, valerate, and the like.

[0090] The compounds of the present invention may exist in an amorphous or crystalline form, such as a solvate, a hydrate, or the like.

[0091] The compounds of the present invention may contain asymmetric centers or chiral centers, and therefore different stereoisomeric forms exist. The compounds may be chiral, racemic or may exist as compositions comprising one or more stereoisomers. The present invention includes enantiomers, diastereomers, racemic mixtures, mixtures enriched in enantiomers and mixtures enriched in diastereomers. If a specific enantiomer of the compounds of the present invention is desired, it may be prepared by asymmetric synthesis, or by derivatization with a chiral auxiliary, wherein the obtained diastereomeric mixture is separated and the auxiliary group is split to provide a pure desired enantiomer. Alternatively, when the molecule contains a basic functional group such as an amino group, or an acidic functional group such as a carboxyl group, a diastereomeric salt may be formed with an appropriate optically active acid or base, and the diastereomers thus formed may be split by fractional crystallization or chromatography as known in the art, and the pure enantiomers may be subsequently recovered. In addition, the separation of enantiomers and diastereomers may be achieved by chromatography using a chiral stationary phase.

[0092] In this article, when the stereochemistry of any particular chiral atom is not determined, all stereoisomers are considered. In addition, the present invention relates to all geometric and positional isomers. The compounds of this invention can exist in different tautomeric forms, and all these forms are included within the scope of the present invention. All stereoisomers of the compounds of this invention are expected to include mixtures or pure or substantially pure forms.

[0093] In this article, unless otherwise stated, structures depicted herein are also intended to include compounds that differ only in the presence of one or more isotopically enriched atoms. In addition to therapeutic uses, such compounds can be used, for example, as analytical tools or probes in biological assays. Any formula or structure given herein is also intended to represent unlabeled forms of the compound as well as isotopically labeled forms. Isotopically labeled compounds have structures described by the formulas given herein, except that one or more atoms are replaced by atoms with selected atomic masses or mass numbers. Examples of isotopes that can be incorporated into the compounds of the present disclosure include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, fluorine and chlorine, such as, but not limited to, 2 H (deuterium, D), 3 H (tritium), 11 C. 13 C. 14 C. 15 N. 18 F. 31 P. 32 P. 35 S. 36 Cl and 125 I. Various isotopically labeled compounds of the present disclosure, for example, incorporating radioactive isotopes such as 3 H and 14C, can be used in metabolic studies, reaction kinetics studies, detection or imaging techniques, such as positron emission tomography (PET) or single photon emission computed tomography (SPECT), including drug or substrate tissue distribution analysis or radiotherapy of patients.

[0094] Composition and application thereof

[0095] The term "active substance of the present invention" or "active compound of the present invention" refers to the compound of the present invention, its geometric isomers, optical isomers, or pesticide-acceptable salts, which have significant fungicidal activity, a broad fungicidal spectrum, and strong stability.

[0096] The present invention also provides a compound as shown in formula I, an optical isomer thereof, or a pesticide acceptable salt thereof, or a pesticide composition comprising the same, and the use thereof as an agricultural fungicide for controlling plant pathogens.

[0097] The compound represented by formula I of the present invention is suitable for preventing and controlling at least one plant disease selected from the group consisting of anthracnose, leaf spot, rust, powdery mildew, sheath blight, leaf blight, gray mold, white rot, damping-off, head blight, take-all and target spot caused by infection by Rhizoctonia, Sporocolon, Pseudocercospora, Puccinia, Puccinia, Pythium and the like. Examples of plants with plant fungal diseases include soybean, corn, wheat, melon, rice, strawberry, peanut, and cotton; examples of plant fungal diseases include soybean rust, corn rust, wheat powdery mildew, melon powdery mildew, rice sheath blight, wheat sheath blight, strawberry gray mold, peanut white rot, cotton damping-off, wheat head blight, wheat take-all, and cucumber target spot, wherein the melon powdery mildew includes cucumber powdery mildew, etc.; the pathogens include Phakopsora pachyrhizi syd., Puccinia sorghi Schw, Blumeria graminis, Erysiphecucurbitacearum, Sphaerotheca cucurbitae, Thanatephorus cucurbitus, etc. cucumeris), Rhizoctonia cerealis, and Rhizoctonia solani, Botrytis cinerea Pers., Fusarium graminearum schw., Fusarium avenaceum, Fusarium moniliformesheld., Uromyces, Phytophthora, Pythium.

[0098] Therefore, the technical solution of the present invention also includes the use of the thioester compound shown in Formula I as a fungicide in agriculture or other fields.

[0099] The thioester compounds represented by formula I of the present invention can be prepared into fungicide compositions by conventional methods. These active compounds can be made into conventional preparations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active substances, microcapsules in polymers, coating compounds for seeds, and preparations used with combustion devices, such as fumigation cartridges, fumigation pots and fumigation trays, and ULV cold mist and hot mist preparations.

[0100] These preparations can be produced in a known manner, for example by mixing the active compound with an extender, i.e. a liquid, liquefied gas or solid diluent or carrier and optionally a surfactant, i.e. an emulsifier and / or dispersant and / or foam former. For example, when water is used as the extender, an organic solvent can also be used as an auxiliary agent.

[0101] When a liquid solvent is used as a diluent or carrier, it is basically suitable, such as: aromatic hydrocarbons, for example xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons, for example chlorobenzene, vinyl chloride or methylene chloride; aliphatic hydrocarbons, for example cyclohexane or paraffins, for example mineral oil fractions; alcohols, for example ethanol or ethylene glycol and their ethers and lipids; ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or unusual polar solvents, for example dimethylformamide and dimethyl sulfoxide, and water.

[0102] A diluent or carrier for liquefied gas refers to a liquid that will become a gas at normal temperature and pressure, such as an aerosol propellant, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

[0103] Solid carriers can be ground natural minerals, such as kaolin, clay, talc, quartz, atavistic clay, montmorillonite, or diatomaceous earth; and ground synthetic minerals, such as highly dispersed silicic acid, alumina and silicates. Solid carriers for particles are ground and classified natural zircons, such as calcite, marble, pumice, sepiolite and dolomite, and inorganic and organic coarse powders and particles of organic materials such as sawdust, coconut shells, corn cobs and tobacco stems.

[0104] Nonionic and anionic emulsifiers can be used as emulsifiers and / or foam formers. For example, polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and albumin hydrolysates. Dispersants include lignin sulfite waste liquor and methylcellulose.

[0105] Binders such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, may be used in the formulation.

[0106] Colorants such as inorganic dyes, such as iron oxide, cobalt oxide and Prussian blue; organic dyes, such as azo dyes or metal phthalocyanine dyes; and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, aluminum and zinc, etc. may be used.

[0107] The thioester compound represented by formula I of the present invention can be prepared into a mixture with other active compounds and exist in their commercial preparations or in the use dosage forms prepared from these preparations. These other active compounds are insecticides, bactericides, fungicides, herbicides, growth control agents, etc. Insecticides include, for example, phosphates, carbamates, chlorinated hydrocarbons, and substances produced by microorganisms, such as avermectin, etc., and fungicides include strobilurins, amides, triazoles, etc.

[0108] In addition, the thioester compounds represented by formula I of the present invention can also be prepared into a mixture with synergists and exist in their commercial preparations or in dosage forms prepared from these preparations. These synergists are compounds that enhance the effects of active compounds. Since the active compounds themselves are active, it is not necessary to add synergists.

[0109] These formulations usually contain 0.001-99.99% by weight, preferably 0.01-99.9% by weight, more preferably 0.05-90% by weight of the active compound of the invention, based on the total weight of the insecticide composition. The concentration of the active compound in the commercial formulation or use form may vary over a wide range. The concentration of the active compound in the use form may be from 0.0000001-100% (g / v), preferably between 0.0001 and 1% (g / v). It should be understood that various changes and modifications may be made within the scope defined by the claims of the present invention.

[0110] Preparation method of the compound of the present invention

[0111] The target compound of the present invention can be obtained by reacting the compounds represented by formula II-1, formula II-2 and formula II-3 or II-4. The conditions of the method, such as raw materials, solvents, temperature, acid, ratio, reaction time can be selected as needed. For example, reference can be made to (but not limited to) the following embodiments.

[0112] Preferably, the method comprises the steps of:

[0113]

[0114] Wherein, A, B, and n are as defined in claim 1;

[0115] (s1) reacting compound II-1 with an acylating agent in an inert solvent to obtain compound II-2; and

[0116] (s2) II-2 is reacted with II-3 or II-4 in an inert solvent in the presence of a base to obtain a compound of formula I.

[0117] Preferably, step (s1) is: in an inert solvent (preferably, the solvent is selected from: benzene, toluene, ethyl acetate, acetonitrile, dichloromethane, dichloroethane, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1,4-dioxane, PEG400, n-heptane, n-hexane, cyclohexane, petroleum ether, dimethylformamide, dimethyl sulfoxide, or a combination thereof), compound II-1 reacts with an acylating agent (thionyl chloride, oxalyl chloride, triphosgene, sulfonyl chloride, or a combination thereof) to obtain compound II-2;

[0118] Preferably, step (s2) is: in a solvent (preferably, the solvent is selected from: benzene, toluene, ethyl acetate, acetonitrile, dichloromethane, dichloroethane, tetrahydrofuran, ether, methyl tert-butyl ether, 1,4-dioxane, PEG400, n-heptane, n-hexane, cyclohexane, petroleum ether, dimethylformamide, dimethyl sulfoxide, or a combination thereof), in a base (preferably, the base is selected from: sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride, sodium methoxide, sodium ethoxide, triethylamine, dimethylaminopyridine, sodium tert-butoxide, potassium tert-butoxide, lithium diisopropylamide, diisopropylethylamine, pyridine, or a combination thereof), II-2 reacts with II-3 or II-4 (such as at 0-25°C or at 0°C to reflux temperature) to obtain a compound of formula I.

[0119] The main advantages of the present invention include:

[0120] (a) The compounds of the present invention have excellent fungicidal activity;

[0121] (b) The synthesis steps of the compound of the present invention are short and the overall yield is good;

[0122] (c) The compounds of the present invention have significant structural innovation compared with existing compounds of the same type;

[0123] (d) The compounds of the present invention have little impact on the environment.

[0124] The present invention will be further described below in conjunction with specific implementation. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples without specifying specific conditions are usually based on conventional conditions or the conditions recommended by the manufacturer. Unless otherwise stated, percentages and parts are calculated by weight.

[0125] Example 1 Preparation of Compound A1-14

[0126]

[0127] Weigh 10mmol of 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid into a 50mL two-necked reaction bottle, add 15mL of anhydrous dichloromethane, then add 2-3 drops of N,N-dimethylformamide, slowly add 30mmol of oxalyl chloride under nitrogen protection, stir at room temperature for 1h to obtain a clear liquid. Remove the solvent and excess oxalyl chloride by rotary evaporation to obtain a clear liquid, i.e., the crude product of 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid chloride, which is directly used in the next step without treatment.

[0128] Weigh 3mmol 4-(trifluoromethyl)thiophenol in a 50mL two-necked reaction bottle, add 10mL anhydrous tetrahydrofuran, then add 9mmol triethylamine, stir in an ice bath under nitrogen protection for 20 minutes, and slowly add arylformyl chloride (9mmol) dropwise. After the addition is complete, remove the ice bath and stir at room temperature overnight. After the reaction is completed, rotary evaporation for desolventization. Add a small amount of ethyl acetate to dissolve, and filter to remove insoluble matter. The filtrate is rotary evaporated for desolventization, and purified by silica gel column chromatography for 73%. 1 HNMR (400MHz, CDCl3) δ8.48(s,1H),7.28(d,J=2.0Hz,2H),7.09(t,J=56.4Hz,1H),6.77(d,J=2.0Hz,2H),2.57(s,3H)ppm

[0129] Example 2 Preparation of Compound A1-389

[0130]

[0131] Weigh 10mmol of 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid into a 50mL two-necked reaction bottle, add 15mL of anhydrous dichloromethane, then add 2-3 drops of N,N-dimethylformamide, slowly add 30mmol of oxalyl chloride under nitrogen protection, stir at room temperature for 1h to obtain a clear liquid. Remove the solvent and excess oxalyl chloride by rotary evaporation to obtain a clear liquid, i.e., the crude product of 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid chloride, which is directly used in the next step without treatment.

[0132] Weigh 3mmol 2-mercapto-5-(trifluoromethyl)pyridine in a 50mL two-necked reaction bottle, add 10mL anhydrous tetrahydrofuran, then add 9mmol triethylamine, stir in an ice bath under nitrogen protection for 20 minutes, and slowly add arylformyl chloride (9mmol) dropwise. After the addition is complete, remove the ice bath and stir at room temperature overnight. After the reaction is completed, rotary evaporation for desolventization. Add a small amount of ethyl acetate to dissolve, and filter to remove insoluble matter. The filtrate is rotary evaporated for desolventization, and purified by silica gel column chromatography for 79%. 1HNMR (400MHz, CDCl3) δ8.88(s,1H),8.09(s,1H),8.00(dd,J=8.2,2.4Hz,1H),7.94(d,J=8.2Hz,1H),6.99(t,J=56.4Hz,1H),4.03(s,3H)ppm

[0133] Example 3 Preparation of Compound A54-389

[0134]

[0135] Weigh 10mmol of 2-methyl-3-furan-3-carboxylic acid into a 50mL two-necked reaction bottle, add 15mL of anhydrous dichloromethane, then add 2-3 drops of N,N-dimethylformamide, slowly add 30mmol of oxalyl chloride under nitrogen protection, stir at room temperature for 1h to obtain a clear liquid. Remove the solvent and excess oxalyl chloride by rotary evaporation to obtain a clear liquid, i.e., the crude product of 1-methyl-3-difluoromethylpyrazole-5-carbonyl chloride, which is directly used in the next step without treatment.

[0136] Weigh 3mmol 2-mercapto-5-(trifluoromethyl)pyridine in a 50mL two-necked reaction bottle, add 10mL anhydrous tetrahydrofuran, then add 9mmol triethylamine, stir in an ice bath under nitrogen protection for 20 minutes, and slowly add arylformyl chloride (9mmol) dropwise. After the addition is complete, remove the ice bath and stir at room temperature overnight. After the reaction is completed, rotary evaporation for desolventization. Add a small amount of ethyl acetate to dissolve, and filter to remove insoluble matter. The filtrate is rotary evaporated for desolventization, and purified by silica gel column chromatography for 66%. 1 HNMR (400MHz, CDCl3) δ8.87(s,1H),7.97(dd,J=8.2,2.4Hz,1H),7.90(d,J=8.2Hz,1H),7.27(d,J=2.2Hz,1H),6.75(d,J=2.2Hz,1H),2.58(s,3H)ppm

[0137] Example 4 Preparation of Compound A54-153

[0138]

[0139] Weigh 10mmol of 2-methyl-3-furan-3-carboxylic acid into a 50mL two-necked reaction bottle, add 15mL of anhydrous dichloromethane, then add 2-3 drops of N,N-dimethylformamide, slowly add 30mmol of oxalyl chloride under nitrogen protection, stir at room temperature for 1h to obtain a clear liquid. Remove the solvent and excess oxalyl chloride by rotary evaporation to obtain a clear liquid, i.e., the crude product of 2-methyl-3-furan-3-carboxylic acid chloride, which is directly used in the next step without treatment.

[0140] Weigh 3mmol 2-mercapto-5-(trifluoromethyl)pyridine in a 50mL two-necked reaction bottle, add 10mL anhydrous tetrahydrofuran, then add 9mmol triethylamine, stir in an ice bath under nitrogen protection for 20 minutes, and slowly add arylformyl chloride (9mmol) dropwise. After the addition is complete, remove the ice bath and stir at room temperature overnight. After the reaction is completed, rotary evaporation for desolventization. Add a small amount of ethyl acetate to dissolve, and filter to remove insoluble matter. The filtrate is rotary evaporated for desolventization, and purified by silica gel column chromatography for 78%. 1 HNMR(400MHz,Chloroform-d)δ7.60–7.54(m,2H),7.52–7.46(m,2H),7.41–7.35(m ,3H),7.28–7.22(m,2H),6.88(d,J=7.5Hz,1H),2.55(s,2H),2.42(d,J=1.0Hz,3H).

[0141] Example 5 Preparation of Compound A16-382

[0142]

[0143] Weigh 10mmol of 1-methyl-3-trifluoromethyl-5-pyrazolecarboxylic acid into a 50mL two-necked reaction bottle, add 15mL of anhydrous dichloromethane, then add 2-3 drops of N,N-dimethylformamide, slowly add 30mmol of oxalyl chloride under nitrogen protection, stir at room temperature for 1h to obtain a clear liquid. Remove the solvent and excess oxalyl chloride by rotary evaporation to obtain a clear liquid, i.e., the crude product of 2-methyl-3-furan-3-carbonyl chloride, which is directly used in the next step without treatment.

[0144] Weigh 3mmol 3,5-dimethylbenzyl mercaptan in a 50mL two-necked reaction bottle, add 10mL anhydrous tetrahydrofuran, then add 9mmol triethylamine, stir in an ice bath under nitrogen protection for 20 minutes, and slowly add arylformyl chloride (9mmol) dropwise. After the addition is complete, remove the ice bath and stir at room temperature overnight. After the reaction is completed, rotary evaporation is performed to remove the solvent. Add a small amount of ethyl acetate to dissolve and filter to remove insoluble matter. The filtrate is rotary evaporated to remove the solvent and purified by silica gel column chromatography for 58%. 1 H NMR (500MHz, Chloroform-d) δ8.02(s,1H),7.20(t,J=1.5Hz,1H),7.12(q,J=1.1Hz,2H),4.42(t,J=1.0Hz,2H),3.86(s,3H).

[0145] Other thioester compounds of the present invention as shown in Formula I can also be prepared using appropriate starting materials and referring to the methods of the above examples.

[0146] Other example compounds were prepared with different starting materials by referring to the above preparation method. The example compounds of the present invention are shown in Table b (the specific compound structures of the present invention are numbered according to the compound AX1-X2, which refers to the structure corresponding to the number of X1 in A1-A88 in the general formula I, and n and B correspond to the structure corresponding to the number of X2 in Table a, such as compound A1-3, when A is A1, n is 0 and B is The corresponding compound);

[0147] Table b Some examples of compounds and structural characterization

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219] Biological Activity Assay Examples

[0220] Evaluation of fungicidal activity against Botrytis cinerea, Sclerotinia sclerotiorum, Rhizoctonia solani, Gibberella spp., Puccinia pulex, Phytophthora spp., Pythium spp., and Downy mildew The tested compounds were dissolved in DMSO to prepare a 10,000 mg / L stock solution, which was then mixed with PDA. The culture medium containing the compound at a concentration of 100 mg / L was poured into sterile petri dishes for preliminary screening. After culturing at 25°C for 48–120 h, the colony diameter of each strain was measured. The inhibition percentage was calculated as (CA) / (CB)×100%, where A represents the colony diameter in the petri dish containing the test compound, B represents the mycelial disk diameter, and C represents the average colony diameter in the control petri dish. The commercial fungicide fluopicolide was used as a positive control. Each treatment was repeated three times. The results of the fungicidal activity determination of some compounds are shown in Table c.

[0221] Table c Bactericidal activity test results of some compounds at 100 mg / mL

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248] It can be seen from the above experimental results that the compounds of the present invention have excellent fungicidal activity, and have basically equivalent fungicidal activity to the commercial reference substance in the evaluation of fungicidal activity against Botrytis cinerea, Sclerotinia sclerotiorum, Rhizoctonia solani, Gibberellic acid, Rust, Phytophthora, Pythium, and Downy Mildew, especially compounds A1-9, A1-14, A1-140, A2-35, A3-236, A5-35, A8-55, A13-45, A30-5, A38-239, A46-205, A50-73, A75-5, A79-158, A83-108, A86-5, A86-15, A88-15, A88-27, etc.

[0249] Table d: Antibacterial activity of compounds against Rhizoctonia solani EC 50

[0250] Compound No. <![CDATA[EC 50 ]]> Compound No. <![CDATA[EC 50 ]]> A30-5 0.445 A3-236 1.025 A75-5 0.400 A62-5 0.911 A77-5 0.725 A76-5 0.668 A13-45 0.986 A86-15 0.299 A75-5 1.220 A86-27 0.164 A86-5 0.667 A88-5 0.256 A73-5 0.706 A88-15 0.412 A71-5 0.596 A88-27 0.125 A46-205 0.874 Furoxamide 1.480

[0251] As can be seen from Table d above, multiple compounds of the present invention have bactericidal effects on Rhizoctonia solani EC 50 It is better than the commercial compound furamide, which shows the superiority of the compound of the present invention.

[0252] All documents mentioned in the present invention are cited as references in this application, just as each document is cited as reference individually. In addition, it should be understood that after reading the above teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. A compound of formula I, its geometric isomers, stereoisomers, or pesticide-acceptable salts thereof, In the formula, A is selected from substituted or unsubstituted C 6-10 aryl, unsubstituted or substituted 5-10 membered heteroaryl, substituted or unsubstituted saturated or partially saturated 5-10 membered heterocyclic group; wherein the substitution means that one or more (such as 2, 3, 4 or 5) hydrogen atoms on the group are independently replaced by a group selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6 Alkenyl, halogenated C 2-6 Alkynyl, C 1-6 Alkyl-S-, C 3-6 Cycloalkyloxy, C 3-6 Cycloalkylthio, -CN, -NO2, oxo, C 3-7 Cycloalkyl, 3-6 membered heterocyclic group, C 6-10 Aryl, 5-6 membered heteroaryl, -N=N-phenyl, benzyl, SO2R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and -SO2NR 3 R 4 ;in, The phenyl group in -N=N-phenyl may be substituted by one or more groups selected from the group consisting of halogen, -CN, -NO2, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy; B is substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted 5-10 membered heteroaryl (such as -benzo 5-6 membered heteroaryl or benzo 5-6 membered heteroaryl-), substituted or unsubstituted (phenyl or 5-10 membered heteroaryl)-L-(phenyl or 5-6 membered heteroaryl), substituted or unsubstituted -C 5-6 Heteroarylphenyl-phenyl, substituted or unsubstituted-phenyl 5-6 heteroaryl-phenyl, substituted or unsubstituted phenyl-phenyl-N=N-phenyl or substituted or unsubstituted benzo(C 3-6 wherein the substitution refers to one or more (such as 2, 3, 4 or 5) hydrogen atoms on the group being independently replaced by a group selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6 Alkenyl, halogenated C 2-6 Alkynyl, C 1-6 Alkyl-S-, halo-C 1-6 Alkyl-S-, -Si(C 1-6 Alkyl)3, -C(CH3)=NOC 1-3 Alkyl, C 3-6 Cycloalkyloxy, C 3-6 Cycloalkylthio, -CN, -NO2, oxo, C 3-7 Cycloalkyl, C 3-6 Cycloalkyl-C 3-6 Cycloalkyl, 3-6 membered heterocyclic group, C 6-10 Aryl, 5-6 membered heteroaryl, -N=N-phenyl, benzyl, SO2R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and -SO2NR 3 R 4 wherein the phenyl group in -N=N-phenyl may be substituted by one or more groups selected from the group consisting of halogen, -CN, -NO2, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy; n is 0, 1, 2 or 3; L is none, O, -C1-C3 alkyl-, ethynyl, halogen-substituted or unsubstituted vinyl, NH, CONH or -C(CH3)=NO-CH2-; R 3 and R 4 are each independently selected from hydrogen, C 1-6 Alkyl, C 1-6 Haloalkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclic group.

2. The compound according to claim 1, its geometric isomers, stereoisomers, or pesticide-acceptable salts thereof, characterized in that: A is selected from substituted or unsubstituted phenyl or substituted or unsubstituted 5-6 membered heteroaryl having 1, 2, 3 or 4 heteroatoms selected from O, N, S, SO and SO2, preferably, the substitution means that 1 or more (such as 2, 3, 4 or 5) hydrogens on the group are independently replaced by groups selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl and halogenated C 1-6 Alkoxy.

3. The compound according to claim 1, its geometric isomers, stereoisomers, or pesticide-acceptable salts thereof, characterized in that: A is selected from the following group: In various Each g is independently 0, 1, 2, 3, 4 or 5; Each R' is independently selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6 Alkenyl, halogenated C 2-6 Alkynyl, C 1-6 Alkyl-S-, C 3-6 Cycloalkyloxy, C 3-6 Cycloalkylthio, -CN, -NO2, oxo, C 3-7 Cycloalkyl, 3-6 membered heterocyclic group, C 6-10 Aryl, 5-6 membered heteroaryl, -N=N-phenyl, benzyl, SO2R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and -SO2NR 3 R 4 ; R 3 and R 4 are each independently selected from hydrogen, C 1-6 Alkyl, C 1-6 Haloalkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclic group.

4. The compound according to claim 1, its geometric isomers, stereoisomers, or pesticide-acceptable salts thereof, characterized in that: A is selected from the following structures A1-A88:

5. The compound according to claim 1, its geometric isomers, stereoisomers, or pesticide-acceptable salts thereof, characterized in that: B is substituted or unsubstituted phenyl or naphthyl, substituted or unsubstituted phenyl-phenyl, substituted or unsubstituted phenyl-O-phenyl, substituted or unsubstituted-phenyl-O-5-6 membered heteroaryl, substituted or unsubstituted-phenyl-5-6 membered heteroaryl, substituted or unsubstituted-5-6 membered heteroaryl-phenyl, substituted or unsubstituted-5-6 membered heteroaryl-5-6 membered heteroaryl, substituted or unsubstituted-5-6 membered heteroarylphenyl-phenyl, substituted or unsubstituted-phenyl-CF=CH-phenyl, substituted or unsubstituted-phenyl-ethynyl-phenyl, substituted or unsubstituted-phenyl-C( CH3)=NO-CH2-phenyl, substituted or unsubstituted-phenyl-NH-phenyl, substituted or unsubstituted-phenyl-CONH-phenyl, substituted or unsubstituted-phenyl-phenyl-N=N-phenyl, substituted or unsubstituted-phenyl-C5-C6 cycloalkyl, substituted or unsubstituted-phenyl-5-6-membered heterocyclyl, substituted or unsubstituted-phenyl-5-6-membered heteroaryl, substituted or unsubstituted-phenyl-cyclopropyl-cyclopropyl, wherein the substitution refers to that one or more (such as 2, 3, 4 or 5) hydrogens on the group are independently replaced by a group selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6 Alkenyl, halogenated C 2-6 Alkynyl, C 1-6 Alkyl-S-, halo-C 1-6 Alkyl-S-, -Si(C 1-6 alkyl)3, -C(CH3)=NO-CH3, C 3-6 Cycloalkyloxy, C 3-6 Cycloalkylthio, -CN, -NO2, oxo, C 3-7 Cycloalkyl, C 3-6 Cycloalkyl-C 3-6 Cycloalkyl, 3-6 membered heterocyclic group, C 6-10 Aryl, 5-6 membered heteroaryl, benzyl, SO2R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and -SO2NR 3 R 4 ; R 3 and R 4 are each independently selected from hydrogen, C 1-6 Alkyl, C 1-6 Haloalkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclic group; Preferably, the substitution refers to that one or more (such as 2, 3, 4 or 5) hydrogen atoms on the group are independently replaced by a group selected from the group consisting of halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 1-6 Alkyl-S-, halo-C 1-6 Alkyl-S-, -Si(C 1-6 alkyl)3, -C(CH3)=NO-CH3, -CN.

6. The compound according to claim 1, its geometric isomers, stereoisomers, or pesticide-acceptable salts thereof, characterized in that: B and n are defined as shown in Table a: Table a 7. A pesticide composition comprising (i) as an active ingredient a compound according to any one of claims 1 to 6, its geometric isomers, stereoisomers, or a pesticide-acceptable salt thereof; and (ii) a pesticide-acceptable carrier.

8. Use of the compound according to any one of claims 1 to 6, its geometric isomers, stereoisomers, or its pesticide acceptable salts, or the pesticide composition according to any one of claim 7 in the preparation of pesticides for killing and / or controlling plant pathogens or plant diseases caused by them.

9. A method for killing and / or controlling plant pathogens, comprising the steps of contacting the compound according to any one of claims 1 to 6, its geometric isomers, stereoisomers, or its pesticide-acceptable salts, or the pesticide composition according to claim 7 with plant pathogens, thereby killing and / or controlling the plant pathogens.

10. A method for preparing the compound of claim 1, its geometric isomers, stereoisomers, or pesticide-acceptable salts thereof, the method comprising the steps of: in, A, B, n are as described above; (s1) reacting compound II-1 with an acylating agent in an inert solvent to obtain compound II-2; and (s2) II-2 is reacted with II-3 or II-4 in an inert solvent in the presence of a base to obtain a compound of formula I.

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