Long-chain ketone nitrile compound as well as preparation method and application thereof

Abstract

The invention discloses a long-chain ketone nitrile compound as well as a preparation method and application thereof. Specifically, the invention relates to a compound as shown in a formula I, a composition containing the compound as shown in the formula I and application of the compound and the composition. The compound provided by the invention has excellent bactericidal, acaricidal and insecticidal activity. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of pesticide science, and specifically relates to a long-chain ketone nitrile compound and a preparation method and application thereof. Background Art

[0002] Crop pathogens, mites and insects often cause significant losses to cash crops such as grain, vegetables, fruits, cotton and ornamental plants. Using chemical fungicides, miticides and insecticides to 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, mites and pests have developed serious resistance to existing agricultural protective agents, and the ecological and environmental safety issues of pesticides are becoming increasingly prominent. As a major pesticide producer, my country has a huge amount of chemical fungicides, miticides and insecticides, a broad market prospect and a strong demand for new products.

[0003] Therefore, there is an urgent need in the art to develop a new class of compounds with excellent fungicidal, acaricidal or insecticidal activities. Summary of the invention

[0004] The purpose of the present invention is to provide a long-chain ketonitrile compound with excellent bactericidal, acaricidal and insecticidal activities, the compound has a novel chemical structure, excellent control effect, is safe for the environment and ecology, and has less toxic and side effects.

[0005] In the first aspect of the present invention, there is provided a compound of formula (I), or a geometric isomer thereof, or a stereoisomer thereof, or a pesticide-acceptable salt or prodrug thereof:

[0006]

[0007] in,

[0008] A is selected from the following group: substituted or unsubstituted 6-14 membered aryl, substituted or unsubstituted 5-14 membered heteroaryl containing 1-3 selected from N, O or S, substituted or unsubstituted 3-8 membered heterocycloalkyl containing 1-3 selected from N, O or S, substituted or unsubstituted 3-8 membered heterocycloalkenyl containing 1-3 selected from N, O or S;

[0009] The substituent is selected from the group consisting of halogen, C 1-6 Alkyl, halogenated C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-7 Cycloalkyl, C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkoxy, C 3-6 Cycloalkylthio, oxo, -CN, -NO2, -SO2R 3、-COR 3 、-COOR 3 、-CONR 3 R 4 and -SO2NR 3 R 4 ;

[0010] R 3 , R 4 Selected from the group consisting of hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl;

[0011] B is S or O;

[0012] n is 1, 2 or 3;

[0013] D is selected from the following groups: substituted or unsubstituted 6-14 membered aryl, substituted or unsubstituted 3-8 membered cycloalkyl, substituted or unsubstituted 5-14 membered heteroaryl containing 1-3 selected from N, O or S, substituted or unsubstituted condensed ring, 9-12 membered condensed heteroaryl containing 1-3 selected from N, O or S, substituted or unsubstituted 3-8 membered heterocycloalkyl containing 1-3 selected from N, O or S.

[0014] Wherein, the substituent is selected from the following group: halogen, substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 1-6 Alkoxy, substituted or unsubstituted mercapto, substituted or unsubstituted silicon, C 6-10 Aryl-alkoxy, C 6-10 Heteroaryl-alkoxy, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted C 2-6 Alkenyl, substituted or unsubstituted C 2-6 Alkynyl, substituted or unsubstituted azavinyl, substituted or unsubstituted C 5-7 Cycloalkenyl, substituted or unsubstituted phenyl, -N=N-substituted or unsubstituted phenyl, substituted or unsubstituted heteroaryl containing 1-3 groups selected from N, O or S, substituted or unsubstituted naphthyl, substituted or unsubstituted 5-membered or 6-membered heterocycloalkyl containing 1-3 groups selected from N, O or S, substituted or unsubstituted amide, -CN, -NH2; or

[0015] The adjacent substituents are connected to form a substituted or unsubstituted C3-8 cycloalkyl, a substituted or unsubstituted C3-8 heterocycloalkyl containing 1-3 atoms selected from N, O or S, or a substituted or unsubstituted phenyl;

[0016] The substituent is selected from the group consisting of halogen, C 1-6 Alkyl, halogenated C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C1-6 Alkoxy, -CN, substituted or unsubstituted phenyl, substituted or unsubstituted mercapto; or

[0017] A substituted or unsubstituted C3-8 cycloalkyl group formed by adjacent substituents, or a substituted or unsubstituted C3-8 heterocycloalkyl group containing 1 to 3 atoms selected from N, O or S;

[0018] The substituent is selected from the group consisting of halogen, C 1-6 Alkyl, halogenated C 1-6 alkyl

[0019] 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 substituent is selected from the following group: halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-7 Cycloalkyl, C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkylthio, -CN, -NO2, -SO2R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 , and -SO2NR 3 R 4 .

[0020] In another preferred embodiment, A is selected from the following group:

[0021]

[0022] in,

[0023] g is independently 0, 1, 2, 3, 4 or 5;

[0024] R' is independently selected from the following group: halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-7 Cycloalkyl, C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkoxy, C 1-6Alkylthio, C 3-6 Cycloalkylthio, CN, NO2, SO2R 3 , COR 3 、COOR 3 ,CONR 3 R 4 , and SO2NR 3 R 4 ; R 3 and R 4 Each independently selected from the group consisting of hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl.

[0025] In another preferred embodiment, A is selected from the following group:

[0026]

[0027]

[0028] In another preferred embodiment, the definitions of B, n, and D are shown in Table a below:

[0029] Table a

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060] In another preferred embodiment, n is 1 or 2, preferably 1.

[0061] In another preferred embodiment, the compound has the structural formula (Ia):

[0062]

[0063] Wherein, A, B and D are as defined above.

[0064] In another preferred embodiment, the compound has the structural formula (Ib):

[0065]

[0066] Wherein, B and D are as defined above.

[0067] In another preferred embodiment, B is O.

[0068] In another preferred embodiment, D is selected from the following group:

[0069]

[0070]

[0071] The second aspect of the present invention provides a method for preparing a compound of formula I, or a geometric isomer thereof, a stereoisomer thereof, or a pesticide-acceptable salt or a prodrug thereof, the method comprising the steps of:

[0072] In an inert solvent, in the presence of a base, compound II-1 reacts with compound II-2 to prepare a compound of formula I.

[0073]

[0074] Wherein, L is selected from the following group: methoxy, ethoxy, Cl;

[0075] The definitions of A, B, n and D are as described in the first aspect of the present invention.

[0076] The third aspect of the present invention provides a use of a compound as shown in formula (I), or its geometric isomers, or its stereoisomers, or its pesticide acceptable salt or prodrug,

[0077] (i) It can be used to control 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 with Rhizoctonia, Sporodiscus, Pseudoceromyces, Puccinia, Puccinia, Pythium and the like;

[0078] (ii) can be used to kill and / or control at least one pest of the order Acarina, Synoptera, Orthoptera, Fusarium, Isoptera, Pseudotoptera, Thysanoptera, Heteroptera, Homoptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Siphonaptera and plant parasitic nematodes and / or its nymphs and / or its eggs;

[0079] (iii) for bactericidal and / or acaricidal and / or insecticidal use; and / or

[0080] (iv) for preparing a composition or formulation for killing fungi and / or mites and / or insects.

[0081] A fourth aspect of the present invention provides a composition comprising:

[0082] (i) the compound as described in the first aspect of the present invention, or its geometric isomer, or its stereoisomer, or its pesticide-acceptable salt or prodrug; and

[0083] (ii) a pesticidally acceptable carrier and / or surfactant.

[0084] The fifth aspect of the present invention provides a method for killing bacteria and / or mites and insects, comprising the steps of: contacting bacteria and / or mites and insects with an effective amount of the compound as described in the first aspect of the present invention, or its geometric isomers, or its stereoisomers, or its pesticide-acceptable salts or prodrugs, or the composition as described in the fourth aspect of the present invention.

[0085] 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

[0086] After extensive and in-depth research, the inventor unexpectedly discovered a class of long-chain ketone nitrile compounds with novel structures (as shown in Formula I). ​​On the basis of extending the carbon chain, the compounds were screened in large quantities for A and D structures, and further innovations were made in the structure. The results of biological test experiments showed that the compounds had excellent bactericidal and / or acaricidal and / or insecticidal activities. On this basis, the inventors completed the present invention.

[0087] the term

[0088] As used herein, the term "halogen" refers to fluorine, chlorine, bromine or iodine.

[0089] Unless otherwise defined, the term "alkyl" by itself or as part of another substituent refers to a straight or branched chain hydrocarbon radical having the specified number of carbon atoms (i.e., C1-6 means 1-6 carbons). Examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, and the like.

[0090] Unless otherwise defined, the term "alkenyl" refers to an unsaturated alkyl group having one or more double bonds. Similarly, the term "alkynyl" refers to an unsaturated alkyl group having one or more triple bonds. Examples of such unsaturated alkyl groups include vinyl, 2-propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and higher homologs and isomers.

[0091] Unless otherwise defined, the term "cycloalkyl" refers to a saturated or unsaturated cyclic hydrocarbon group having a specified number of ring atoms (e.g., C3-8 cycloalkyl). Examples of such cycloalkyl groups include (but are not limited to) cyclopentyl, cyclohexyl, and the like.

[0092] Unless otherwise defined, the term "aryl" means a polyunsaturated (usually aromatic) hydrocarbon radical which may be a single ring or multiple rings (up to three) which are fused together or linked covalently. Examples of aryl groups include: phenyl.

[0093] Unless otherwise defined, the term "heterocycloalkyl" or "heterocyclyl" refers to a cycloalkyl containing 1-3 heteroatoms selected from N, O or S, wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom is optionally quaternized. Heterocycloalkyl can be a monocyclic, bicyclic or polycyclic system. Non-limiting examples of heterocycloalkyl include pyrrolidine, imidazolidine, pyrazolidine, butyrolactam, valerolactam, imidazolidinone, hydantoin, dioxolane, phthalimide, piperidine, 1,4-dioxane, morpholine, thiomorpholine, thiomorpholine-S-oxide, thiomorpholine-S, S-oxide, piperazine, pyran, pyridone, 3-pyrroline, thiopyran, pyrone, tetrahydrofuran, tetrahydrothiophene, quinuclidine, etc. Heterocycloalkyl can be connected to the rest of the molecule via a ring carbon or a heteroatom. For terms such as cycloalkylalkyl and heterocycloalkylalkyl, it is intended that the cycloalkyl or heterocyclyl group is attached to the rest of the molecule through an alkyl or alkylene linker.

[0094] Unless otherwise defined, the term "heteroaryl" refers to an aryl group (or ring) containing 1-3 heteroatoms selected from N, O or S, wherein the nitrogen and sulfur atoms are optionally oxidized and the nitrogen atom is optionally quaternized. The heteroaryl group can be attached to the rest of the molecule through a heteroatom. Non-limiting examples of heteroaryl groups include pyridinyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, quinolyl, quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, benzotriazinyl, purinyl, benzimidazolyl, benzopyrazolyl, benzotriazolyl, benzisoxazolyl, isobenzofuryl, isoindolyl, indolizinyl, benzotriazinyl, thienopyridinyl, thienopyrimidinyl, pyrazolopyrimidinyl, imidazopyridine, benzothiazolyl, benzofuranyl, benzothiophenyl, indolyl, quinolyl, isoquinolyl, isothiazolyl, pyrazolyl, indazolyl, pteridinyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, pyrrolyl, thiazolyl, furanyl, thienyl, and the like.

[0095] As used herein, the term "heteroatom" includes oxygen (O), nitrogen (N), sulfur (S) and silicon (Si).

[0096] For compounds provided herein, a bond from a substituent (typically an R group) to the center of an aromatic ring (e.g., benzene, pyridine, etc.) will be understood to mean a bond providing a connection at any available vertex of the aromatic ring. In some embodiments, this description also includes connections fused to the aromatic ring. For example, a bond drawn to the center of an indole benzene moiety will represent a bond connected to any available vertex of a six-membered or five-membered ring moiety of indole.

[0097] In the present invention, the term "halo" means substituted with halogen.

[0098] As used herein, the term "substituted" refers to one or more hydrogen atoms on a specific group being replaced by a specific substituent. The specific substituent is a substituent described above or a substituent appearing in the embodiments. Unless otherwise specified, a substituted group may have a substituent selected from a specific group at any substitutable site of the group, and the substituent may be the same or different at each position. It will be understood by those skilled in the art that the combinations of substituents contemplated by the present invention are those that are stable or chemically feasible.

[0099] As used herein, the terms "comprising", "including" or "comprising" indicate that various components can be used together in the mixture or composition of the present invention. Therefore, the terms "consisting essentially of" and "consisting of" are included in the term "comprising".

[0100] Unless otherwise specified, the compound shown in Formula I of the present invention includes geometric isomers (represented by Z and E, respectively, in different configurations) that can be formed due to the connection of different substituents to carbon-carbon double bonds or carbon-nitrogen double bonds, and the present invention includes Z-type isomers and E-type isomers and mixtures of any ratio thereof. The compound shown in Formula I of the present invention includes stereoisomers (represented by R and S, respectively, in different configurations) that can be formed due to the connection of different substituents to carbon-nitrogen atoms, and the present invention includes R-type isomers and S-type isomers and mixtures of any ratio thereof. The compound shown in Formula I of the present invention includes not only geometric isomers (Z / E formula) and stereoisomers (R / S formula), but also mixtures of any ratios of geometric isomers and stereoisomers.

[0101] As used herein, "effective amount" refers to an amount of the compound sufficient to produce fungicidal, acaricidal and insecticidal effects without causing serious negative effects.

[0102] As used herein, for example, "1 to 3" means 1, 2, or 3, "1 to 5" means 1, 2, 3, 4, or 5, and "1-10" means 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0103] It should be understood that when a group is present in multiple different positions of a compound at the same time, its definition at each position is independent of each other and may be the same or different. That is, the term "selected from the following group:" has the same meaning as the term "each independently selected from the following group:".

[0104] Ketone nitrile compounds

[0105] As used herein, the term "compounds of the present invention" refers to a class of long-chain ketone nitrile compounds as shown in Formula I, and the term also includes geometric isomers, or stereoisomers thereof, or salts thereof, and various isomer mixtures.

[0106] Specifically, the present invention provides a long-chain ketone nitrile compound as shown in Formula I,

[0107]

[0108] Among them, the definitions of A, B, n, and D are as described above.

[0109] Preferably, 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 refers to the replacement of hydrogen on the group by 1-5 groups selected from the following group: halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-7 Cycloalkyl, C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkylthio, CN, NO2, SO2R 3 , COR 3 、COOR 3 ,CONR 3 R 4 , and SO2NR 3 R 4 ;

[0110] R 3 , R 4 Selected from the group consisting of hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl.

[0111] Preferably, A is selected from the structural formula (A1-A74) as described above.

[0112] Preferably, the definitions of B, n, and D are as shown in Table a.

[0113] As used herein, the term "pesticide acceptable salt" means that the anion of the salt is known and acceptable when forming a pesticide pharmaceutically acceptable salt. Preferably, the salt is water-soluble. Suitable acid addition salts formed by the compound of formula (I) include salts formed by inorganic acids, such as hydrochlorides, phosphates, sulfates, nitrates; and salts formed by organic acids, such as acetates, benzoates, etc.

[0114] Preparation method of the compound of the present invention

[0115] The preparation method of the compound of formula I of the present invention is described in more detail below, but these specific methods do not constitute any limitation to the present invention. The compounds of the present invention can also be conveniently prepared by optionally combining various synthetic methods described in this specification or known in the art, and such combination can be easily carried out by a technician in the field to which the present invention belongs.

[0116] Typically, the preparation process of the compound of the present invention is as follows, wherein the raw materials and reagents used can be purchased through commercial channels unless otherwise specified.

[0117] The present invention provides a general method for preparing the compound (Formula I) according to the first aspect of the present invention.

[0118] Specifically, the method comprises the steps of: reacting compound II-1 with compound II-2 in an inert solvent in the presence of a base to obtain a compound of formula I;

[0119]

[0120] Wherein, L is selected from the following group: methoxy, ethoxy, Cl;

[0121] The definitions of A, B, n and D are as described in the first aspect of the present invention.

[0122] Preferably, the method comprises the steps of: reacting a compound of formula II-1 with a compound of formula II-2 in an inert solvent in the presence of a base at 0-25°C or 0°C to reflux temperature to obtain a compound of formula I.

[0123] Preferably, the inert solvent is selected from the group consisting of 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.

[0124] Preferably, the base is selected from the group consisting of 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)

[0125] Combinations containing the compounds of the present invention and uses of the compounds of the present invention and their compositions

[0126] The present invention provides a compound as shown in formula I or an agricultural composition comprising the long-chain ketone nitrile compound as shown in formula I and uses thereof.

[0127] The long-chain ketonitrile compounds represented by formula I of the present invention are also 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, Pseudocercozeb, 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 pachyrhizisyd., Puccinia sorghi Schw, Blumeria graminis, Erysiphe cucurbitacearum, Sphaerotheca cucurbitae, Thanatephorus cucurbitus, etc. cucumeris), Rhizoctonia cerealis, and Rhizoctonia solani, Botrytis cinerea Pers., Fusarium graminearum schw., Fusarium avenaceum, Fusarium moniliformesheld., Uromyces, Phytophthora, Pythium.

[0128] The long-chain ketonitrile compounds represented by formula I of the present invention show excellent mite control activity against various pests in agriculture or other fields, especially against Arachnida (Arachnida) Acarina (Acarina) pest mites, such as Tetranychus urticae Koch, Tetranychus viennensis Zacher, Tetranychus truncatus Ehara, Tetranychus cinnabarinus Boisduval, Panonychus ulmi Koch, Panonychus citri McGregor, Bryobia rubrioculus Scheuten, Petrobia latens Muller, Oligonychus ununguis Jacobi, Brevipalpus obovatus Donnadieu, B. lewis McGregor), Tenuipalpus taonicas Ma et Yuan, Tenuipalpus zhizhilashviliae Reck, C. vitis Pagenstecher, A. steinwedeni Keifer, A. macrodonis Keifer, Eriophyes pyri Pagenst, Epitrimerus pirifolia Keifer, Polyphagotarsonemus latus Banks, Penthaleus maJor Duges, Rhizoglyphus callae Oudemans, etc. "Mite control" means that it has acaricidal activity at each stage of the mite life cycle (egg, larva, adult). Therefore, the technical solution of the present invention also includes the use of the long-chain ketonitrile compound shown in Formula I as a miticide in agriculture or other fields.

[0129] The long-chain ketonitrile compounds represented by formula I of the present invention are also suitable for controlling at least one pest of the order Synptera, Orthoptera, Fusarium, Isoptera, Acropora, Thysanoptera, Heteroptera, Homoptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Siphonaptera and plant parasitic nematodes in agriculture or other fields.

[0130] The order of the Synphyla, for example, Scutigerella immaculat and the like.

[0131] The Orthoptera, for example, Acheta domesticus, Gryllotalpa spp., Locusta inigratoria, Melanoplus spp., Schistocer cagregaria, etc.;

[0132] The order of Blattaria includes, for example, Blatta orientalis, Periplanet aainericana, Leucophae amaderae, Blatta orientalis, and the like.

[0133] The order of the Isoptera, for example, Reticuliterines spp. and the like.

[0134] The order of the Phthiraptera includes, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Dainalinia spp. and the like.

[0135] The order of Thysanoptera includes, for example, Hercinothrips fernoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis and the like.

[0136] The Heteroptera, for example, Eurygaster spp., Dysdercus interrnedius, Piesrna quadrata, Cimexiectularius, Rhodnius prolixus, Triatoma spp., and the like.

[0137] The Homoptera, for example, Aleurodes brassicae, Beinisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis poini, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pernphigus spp., Macrosiphurn avenae, Myzus spp., Phorodon humuli, Rhopalos iphuin padi, Einpoasca spp. spp.), rice black-tailed leafhopper (Nephotettixcincticeps), scale insect (Lecanium corni), olive wax scale (Saissetia oleae), gray planthopper (Laodelphax striatellus), brown planthopper (Nilaparvata lugens), red round scale (Aonidiella aurantii), ivy round shield scale (Aspidiotus hederae), mealybug species (Pseudococcus spp.), psylla species (Psylla spp.), etc.

[0138] The Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheirnatobia brurnata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosoina neustria, Euproctis chrysorrhoea, Lyinantriaspp., Bucculatrix thurberiella, Phyllocrnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp.), Cabbage armyworm (Mainestra brassicae), Small-eyed night moth (Panolis flarnmea), Spodoptera litura, Spodoptera frugiperda, Gray-winged night moth (Spodoptera spp.), Trichoplusia ni, Apple moth (Carpocap saporiionella), Pieris spp., Grass moth (Chilo spp.), Corn borer (Pyrausta nubilalis), Mediterranean powdery moth (Ephestia kuehniella), Greater wax moth (Galleria mellonella), Curtain moth (Tineola bisselliella), Bag moth (Tinea pellionella), Brown weaver moth (Hofrnannophilap seudospretella), Flax moth (Cacoecia podana), Extreme color moth (Choristoneuna fuiniferana), Clysia ambiguella, Homonarnagnan irna, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae, etc.

[0139] The order of the Coleoptera, for example, Anobium punctatuin, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes baJulus, Agelasta alni, Leptinotarsa ​​decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephal, Epilachna vanivestis, Oryzaephilus suninamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus), Cosinopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderna spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus bololeucus, Gibbium psylloides, Triboliurn spp., Tenebnio rnolitor, Agriotes spp., Conoderus spp.), Western May Beetle (Melolonthainelolontha), Potato Beetle (Ainphimallon solstitialis), Brown New Zealand Beetle (Costelytra zealandica), Rice Root Beetle (Lis sorhoptrus oryzophilus), etc.

[0140] The order of Hymenoptera, for example, Dipnion spp., Hoplocampa spp., Lasius spp., Monornonium pharaonis, Vespa spp., etc.;

[0141] From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora vicina, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stornoxy spp., Oestrus spp., Hypoderrna spp., Tabanus spp., Bibio hortulanus, Oscinella frit), Phorbia spp., Pegomyia hyoscyarni, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriotnyza spp., etc.

[0142] The order of the Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spp. and the like.

[0143] The plant parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus sernipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinerna spp., Trichodorus spp., Bursaphelenchus spp., etc. Therefore, the technical scheme of the present invention also includes the use of the long-chain ketonitrile compounds shown in Formula I as pesticides in agriculture or other fields.

[0144] Therefore, the technical solution of the present invention also includes the use of the long-chain ketone nitrile compound shown in Formula I as a fungicide in agriculture or other fields.

[0145] The long-chain ketonitrile compounds of formula I of the present invention can be prepared into fungicide and / or acaricide and / or insecticide 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.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] The long-chain ketonitrile compounds 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 methoxyacrylates, amides, triazoles, etc.

[0154] In addition, the long-chain ketone nitrile 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 effect of active compounds. Since the active compounds themselves are active, it is not necessary to add synergists.

[0155] 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.

[0156] The main advantages of the present invention are:

[0157] (a) The compounds of the present invention have excellent fungicidal activity;

[0158] (b) The compounds of the present invention also have excellent acaricidal and insecticidal activities;

[0159] (c) The synthesis steps of the compound of the present invention are short and the overall yield is good;

[0160] (d) The compounds of the present invention have significant structural innovation compared with existing compounds of the same type;

[0161] (f) The compounds of the present invention have excellent bactericidal, acaricidal and insecticidal activities and have little impact on the environment.

[0162] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods for the unrecorded specific conditions in the following examples are usually based on conventional conditions or the conditions recommended by the manufacturer. Unless otherwise stated, percentages and parts are weight percentages and weight parts.

[0163] Example 1 Preparation of Compound A1-1

[0164]

[0165] Weigh o-fluorophenylpropionitrile (300 mg, 2 mmol) in a 50 ml round-bottomed bottle, add 6 ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10 min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612 mg, 3 mmol), remove the ice bath, and stir at room temperature for 4 h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10 mL × 3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE: EA = 1: 1) to obtain the product with a yield of 90.21%.

[0166] 1H NMR(400MHz,Chloroform-d)δ7.80(s,1H),7.35–7.18(m,4H),7.04(td,J=7.7,1.2Hz,1H),4.62(t, J=7.0Hz,1H),3.84(s,3H),3.39(ddd,J=12.4,6.9,0.7Hz,1H),3.30(ddd,J=12.3,7.0,0.7Hz,1H).

[0167] Example 2 Preparation of Compound A1-2

[0168]

[0169] Weigh m-fluorophenylpropionitrile (300 mg, 2 mmol) in a 50 ml round bottom bottle, add 6 ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10 min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612 mg, 3 mmol), remove the ice bath, and stir at room temperature for 4 h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10 mL × 3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE: EA = 1: 1) to obtain the product with a yield of 90.21%.

[0170] 1 H NMR(400MHz,Chloroform-d)δ7.81(s,1H),7.43–7.19(m,2H),7.09–7.04(m,2H),6 .98(tt,J=7.5,1.5Hz,1H),4.64(t,J=7.0Hz,1H),3.84(s,3H),3.34–3.15(m,2H).

[0171] Example 3 Preparation of Compound A1-5

[0172]

[0173] Weigh m-chlorophenylpropionitrile (330 mg, 2 mmol) in a 50 ml round-bottom flask, add 6 ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10 min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612 mg, 3 mmol), remove the ice bath, and stir at room temperature for 4 h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10 mL × 3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE: EA = 1: 1) to obtain the product with a yield of 90.21%.

[0174] 1 H NMR (400MHz, Chloroform-d) δ7.84(s,1H),7.44–7.17(m,4H),7.11–7.07(m,1H),4.61(t,J=7.0Hz,1H),3.84(s,3H),3.41–3.14(m,2H).

[0175] Example 4 Preparation of Compound A1-20

[0176]

[0177] Weigh 400 mg of m-trifluoromethylbenzene propionitrile (2 mmol) in a 50 ml round bottom bottle, add 6 ml of THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10 min, add ethyl 1-methyl-3-difluoromethylpyrazole-5-carboxylate (612 mg, 3 mmol), remove the ice bath, and stir at room temperature for 4 h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10 mL × 3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE: EA = 1: 1) to obtain the product with a yield of 90.21%.

[0178] 1 H NMR(400MHz,Chloroform-d)δ7.86(s,1H),7.52–7.44(m,3H),7.27(t,J=57.3Hz ,1H),7.12–7.09(m,1H),4.28(t,J=7.0Hz,1H),3.84(s,3H),3.33–3.09(m,2H).

[0179] Example 5 Preparation of Compound A1-21

[0180]

[0181] Weigh p-trifluoromethylbenzene propionitrile (400 mg, 2 mmol) in a 50 ml round bottom bottle, add 6 ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10 min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612 mg, 3 mmol), remove the ice bath, and stir at room temperature for 4 h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10 mL × 3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE: EA = 1: 1) to obtain the product with a yield of 85.63%.

[0182] 1H NMR (500MHz, Chloroform-d) δ7.65–7.62(m,2H),7.44–7.20(m,3H),4.27(t,J=7.0Hz,1H),3.92(s,3H),3.31–3.20(m,2H).

[0183] Example 6 Preparation of Compound A1-23

[0184]

[0185] Weigh 3-trifluoromethoxybenzene propionitrile (430 mg, 2 mmol) in a 50 ml round bottom bottle, add 6 ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10 min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612 mg, 3 mmol), remove the ice bath, and stir at room temperature for 4 h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10 mL × 3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE: EA = 1: 1) to obtain the product with a yield of 86.91%.

[0186] 1 H NMR (400MHz, Chloroform-d) δ7.86 (s, 1H), 7.40–7.15 (m, 2H), 7.09–6.97 (m, 3H), 4.28 (t, J = 7.0Hz, 1H), 3.85 (s, 3H), 3.41–3.07 (m, 2H).

[0187] Example 7 Preparation of Compound A1-24

[0188]

[0189] Weigh p-trifluoromethoxybenzene propionitrile (430 mg, 2 mmol) in a 50 ml round bottom bottle, add 6 ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10 min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612 mg, 3 mmol), remove the ice bath, and stir at room temperature for 4 h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10 mL × 3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE: EA = 1: 1) to obtain the product with a yield of 86.91%.

[0190] 1H NMR (400MHz, Chloroform-d) δ7.37(t,J=57.3Hz,1H),7.09(s,4H),4.26(t,J=7.0Hz,1H),3.92(s,3H),3.30–3.19(m,2H).

[0191] Example 8 Preparation of Compound A1-25

[0192]

[0193] Weigh o-thiotrifluoromethylbenzenepropionitrile (462 mg, 2 mmol) in a 50 ml round bottom bottle, add 6 ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10 min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612 mg, 3 mmol), remove the ice bath, and stir at room temperature for 4 h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10 mL × 3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE: EA = 1: 1) to obtain the product with a yield of 86.91%.

[0194] 1 H NMR(400MHz,Chloroform-d)δ7.86(s,1H),7.55(dd,J=7.4,1.4Hz,1H),7.42–7.35(m,1H),7.28–7.13(m,3H) ,4.29(t,J=7.0Hz,1H),3.85(s,3H),3.40(ddd,J=12.5,7.0,0.9Hz,1H),3.33(ddd,J=12.4,7.0,1.0Hz,1H).

[0195] Example 9 Preparation of Compound A1-55

[0196]

[0197] Weigh 3-chloro-5-trifluoromethoxybenzene propionitrile (500mg, 2mmol) in a 50ml round-bottom flask, add 6ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612mg, 3mmol), remove the ice bath, and stir at room temperature for 4h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10mL×3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE:EA=1:1) to obtain the product with a yield of 86.91%.

[0198] 1H NMR (400MHz, Chloroform-d) δ7.86 (s, 1H), 7.29 (s, 0H), 7.01 (p, J = 1.1Hz, 1H), 6.93(dt,J=7.9,1.4Hz,2H),4.32–4.26(m,1H),3.84(s,3H),3.30–3.18(m,2H).

[0199] Example 10 Preparation of Compound A1-59

[0200]

[0201] Weigh 3-(3-(2-chloro-4-(trifluoromethyl)phenoxy)phenyl)propionitrile (650mg, 2mmol) in a 50ml round-bottom flask, add 6ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612mg, 3mmol), remove the ice bath, and stir at room temperature for 4h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10mL×3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE:EA=1:1) to obtain the product with a yield of 86.91%.

[0202] 1 H NMR(400MHz,Chloroform-d)δ7.90(s,1H),7.82(d,J=1.5Hz,1H),7.65(dd,J=7.5,1.5Hz,1H),7.32(t,J=7.5Hz,1H),7.29– 7.21(m,2H),7.06(d,J=7.5Hz,1H),7.02(q,J=1.4Hz,1H),6.92(dt,J=7.3,1.5Hz,1H),5.52(t,J=1.0Hz,1H),3.84(s,3H).

[0203] Example 11 Preparation of Compound A1-62

[0204]

[0205] Weigh 3-(3-((3-chloro-5-(trifluoromethyl)pyridin-2-yl)oxy)phenyl)propionitrile (653mg, 2mmol) in a 50ml round-bottom flask, add 6ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612mg, 3mmol), remove the ice bath, and stir at room temperature for 4h. After the reaction is completed, water is added to quench the reaction, a small amount of dilute hydrochloric acid is added to adjust to acidity, and ethyl acetate is extracted (10mL×3). The organic phases are combined and washed with saturated sodium chloride solution and dried over anhydrous sodium sulfate. The product is obtained by column chromatography (PE:EA=1:1) with a yield of 86.91%.

[0206] 1 H NMR(400MHz,Chloroform-d)δ8.59(d,J=1.4Hz,1H),7.94(d,J=1.6Hz,1H),7.90(s,1H ),7.33–7.20(m,3H),6.98(dt,J=8.6,1.4Hz,2H),5.49(t,J=1.0Hz,1H),3.85(s,3H).

[0207] Example 12 Preparation of Compound A1-92

[0208]

[0209] Weigh 3-(3',4',5'-trifluoro-[1,1'-biphenyl]-3-yl)propionitrile (525mg, 2mmol) in a 50ml round-bottom bottle, add 6ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612mg, 3mmol), remove the ice bath, and stir at room temperature for 4h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10mL×3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE:EA=1:1) to obtain the product with a yield of 86.91%.

[0210] 1 H NMR(400MHz,Chloroform-d)δ7.86(s,1H),7.58–7.50(m,2H),7.41–7.35(m,3H),7.21 –7.15(m,1H),4.28(t,J=7.0Hz,1H),3.85(s,3H),3.23(qdt,J=12.4,7.0,1.0Hz,2H).

[0211] Example 13 Preparation of Compound A1-93

[0212]

[0213] Weigh 3-(3',4',5'-trichloro-[1,1'-biphenyl]-3-yl)propionitrile (620mg, 2mmol) in a 50ml round-bottom bottle, add 6ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612mg, 3mmol), remove the ice bath, and stir at room temperature for 4h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10mL×3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE:EA=1:1) to obtain the product with a yield of 86.91%.

[0214] 1 H NMR(400MHz,Chloroform-d)δ7.88(s,1H),7.59–7.52(m,2H),7.50(s,1H),7.40–7.33(m,1H),7.21–7.14(m,1 H), 4.64 (t, J = 7.0Hz, 1H), 3.86 (s, 3H), 3.25 (ddt, J = 12.4, 7.1, 1.0Hz, 1H), 3.18 (ddt, J = 12.4, 7.0, 1.0Hz, 1H).

[0215] Example 14 Preparation of Compound A1-166

[0216]

[0217] Weigh 3-(4-(3,4,5-trifluorophenyl)furan-2-yl)propionitrile (502mg, 2mmol) in a 50ml round-bottom flask, add 6ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612mg, 3mmol), remove the ice bath, and stir at room temperature for 4h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10mL×3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE:EA=1:1) to obtain the product with a yield of 86.91%.

[0218] 1H NMR(400MHz,Chloroform-d)δ7.90(s,1H),7.41–7.31(m,3H),6.07(d,J=1.4Hz,1H),3.95 (t,J=7.0Hz,1H),3.85(s,3H),3.45(dd,J=12.4,7.1Hz,1H),3.34(dd,J=12.4,7.1Hz,1H).

[0219] Example 15 Preparation of Compound A1-181

[0220]

[0221] Weigh 3-(4-(3,5-dichlorophenyl)thiophen-2-yl)propionitrile (564mg, 2mmol) in a 50ml round-bottom flask, add 6ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612mg, 3mmol), remove the ice bath, and stir at room temperature for 4h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10mL×3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE:EA=1:1) to obtain the product with a yield of 86.91%.

[0222] 1 H NMR(400MHz,Chloroform-d)δ7.86(s,1H),7.79(d,J=1.5Hz,1H),7.46–7.40(m,2H),7.28(t,J=1.5Hz,1H),7.12 (d,J=1.5Hz,1H),4.31(t,J=7.0Hz,1H),3.86(s,3H),3.46(dd,J=12.5,7.0Hz,1H),3.40(dd,J=12.5,7.0Hz,1H).

[0223] Example 16 Preparation of Compound A1-201

[0224]

[0225] Weigh 3-(7-(3,4,5-trifluorophenyl)benzofuran-2-yl)propionitrile (602mg, 2mmol) in a 50ml round-bottom flask, add 6ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (612mg, 3mmol), remove the ice bath, and stir at room temperature for 4h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10mL×3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE:EA=1:1) to obtain the product with a yield of 86.91%.

[0226] 1 H NMR(400MHz,Chloroform-d)δ7.86(s,1H),7.72(d,J=1.5Hz,2H),7.55(d,J=1.4Hz,1H),7.52(d,J=1.4Hz,1H),7 .48–7.43(m,1H),4.00(t,J=7.0Hz,1H),3.86(s,3H),3.49(dd,J=12.5,7.0Hz,1H),3.36(dd,J=12.4,7.1Hz,1H).

[0227] Example 17 Preparation of Compound A71-24

[0228]

[0229] Weigh p-trifluoromethoxybenzene propionitrile (430 mg, 2 mmol) in a 50 ml round-bottom flask, add 6 ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10 min, add ethyl o-toluate (612 mg, 3 mmol), remove the ice bath, and stir at room temperature for 4 h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10 mL × 3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE: EA = 1: 1) to obtain the product with a yield of 86.91%.

[0230] 1 H NMR(400MHz,Chloroform-d)δ7.75(dd,J=7.5,1.5Hz,1H),7.39(td,J=7.4,1.6Hz,1H),7.32(td,J=7.5,1.6H z,1H),7.26–7.23(m,1H),7.12–7.06(m,4H),4.54(t,J=7.0Hz,1H),3.27–3.10(m,2H),2.42(d,J=0.7Hz,3H).

[0231] Example 18 Preparation of Compound A4-1

[0232]

[0233] Weigh o-fluorophenylpropionitrile (300 mg, 2 mmol) in a 50 ml round bottom bottle, add 6 ml THF, add potassium tert-amyl alcohol under ice bath conditions, stir for 10 min, add 1-methyl-3-difluoromethylpyrazole-5-carboxylic acid ethyl ester (670 mg, 3 mmol), remove the ice bath, and stir at room temperature for 4 h. After the reaction is completed, add water to quench the reaction, add a small amount of dilute hydrochloric acid to adjust to acidity, extract with ethyl acetate (10 mL × 3), combine the organic phases, wash with saturated sodium chloride solution, and dry over anhydrous sodium sulfate. Column chromatography (PE: EA = 1: 1) to obtain the product with a yield of 89.36%.

[0234] 1 H NMR(400MHz,Chloroform-d)δ7.36–7.19(m,4H),7.04(td,J=7.8,1.4Hz,1H),4.29(t,J=7.0 Hz,1H),3.93(s,2H),3.36(ddd,J=12.4,7.0,0.9Hz,1H),3.29(ddd,J=12.4,7.0,0.8Hz,1H).

[0235] Referring to the above preparation method, other example compounds were also prepared with different starting materials. The example compounds of the present invention are shown in Table b; other long-chain ketone nitrile compounds of the present invention as shown in Formula I can also be prepared using appropriate starting materials and referring to the method of the above example:

[0236] Table b Structural characterization of some examples of compounds

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280] Biological activity test examples

[0281] Test Example 1 Evaluation of fungicidal activity against Botrytis cinerea, Sclerotium sclerotium, Rhizoctonia solani, Gibberella, Rust fungus, Phytophthora, Pythium, and Downy mildew

[0282] The tested compounds were dissolved in DMSO to prepare a 1000 mg / L stock solution, which was then mixed with PDA. The culture medium containing the compound at a concentration of 100 μg / mL was poured into sterile culture dishes for preliminary screening. After culturing at 25°C for 48–120 hours, 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 culture dish containing the test compound, B represents the mycelial disk diameter, and C represents the average colony diameter in the control culture dish. The commercial fungicide fluopicolide was used as a positive control. Each treatment was repeated three times. The results of the bactericidal activity determination of some compounds are shown in Table c.

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300] It can be seen from the above experimental results that the compounds of the present invention and the commercial reference substances have basically equivalent fungicidal activity in the evaluation of fungicidal activity against Botrytis cinerea, Sclerotinia sclerotiorum, Rhizoctonia solani, Gibberellic acid, Rust, Phytophthora, Pythium, and Downy Mildew, such as compounds A1-9, A1-22, A1-39, A1-41, A1-54, A1-55, A1-60, A1-63, A1-69, A1-70, A1-85, A1-97, A17-99, A1-103, A1-106, A1-117, A1-123, A1-168, A1-169, A1-362, A1-378, etc.

[0301] Test Example 2 Evaluation of the acaricidal activity against Tetranychus urticae and Tetranychus cinnabarinus

[0302] After the test compound is dissolved in dimethyl sulfoxide, it is diluted with a triton aqueous solution to a test concentration of 500 mg / L, and the liquid is evenly sprayed on the front and back of the bean leaf cut pieces. After the liquid is dried, the bean leaf cut pieces are inoculated with mixed individuals of two-spotted spider mites or cinnabar spider mites, and the base number is recorded. Observe in a standard observation room (23-25°C, RH40-60%), conduct an investigation after 192 hours, and record the number of live insects on the bean leaves. Avermectin is used as a positive control, and the triton aqueous solution is used as a blank control. The results of the activity test of some compounds against two-spotted spider mites are shown in Table 3. The results of the acaricidal activity test of some compounds are shown in Table d.

[0303] Test Example 3 Evaluation of insecticidal activity against Plutella xylostella and Mythimna separata

[0304] Take a culture dish, cover the bottom of the dish with a layer of filter paper, and add an appropriate amount of tap water to keep it moist. After removing the wax layer on the surface of the cabbage leaves, make a cabbage leaf disc with a diameter of about 6 cm, and place the leaves with the back facing up in the culture dish. After the test compound is dissolved in dimethyl sulfoxide (DMSO), it is diluted with a triazone aqueous solution to a test concentration of 500 μg / mL, and the solution is evenly sprayed on the front and back of the leaves. After the leaves are naturally dried in the shade, inoculate the larvae of the diamondback moth or the armyworm, set up 3 replicates, set avermectin as the positive control, and the triazone aqueous solution as the blank control. Move the culture dish to a standard observation room (23-25℃, RH40-60%). Conduct a test survey 72 hours after treatment, record the number of dead and live insects of the test insects, and calculate the mortality rate. The results of the insecticidal activity determination of some compounds are shown in Table d.

[0305] Table d Insecticidal activity test results of some compounds at 500 μg / mL

[0306]

[0307]

[0308]

[0309]

[0310] From the above experimental results, it can be seen that the compounds of the present invention not only show good fungicidal activity, but also have good or good activity against two-spotted spider mites, cinnabarinus spider mites, diamondback moths and armyworms, such as compounds A1-41, A1-62, A1-85, A1-86, A1-90, A1-91, A1-101, A1-102, A1-103, etc.

[0311] 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 represented by formula (I), or its geometric isomers, or its stereoisomers, or its pesticide-acceptable salts or prodrugs: in, A is selected from the following group: substituted or unsubstituted 6-14 membered aryl, substituted or unsubstituted 5-14 membered heteroaryl containing 1-3 selected from N, O or S, substituted or unsubstituted 3-8 membered heterocycloalkyl containing 1-3 selected from N, O or S, substituted or unsubstituted 3-8 membered heterocycloalkenyl containing 1-3 selected from N, O or S; The substituent is selected from the group consisting of halogen, C 1-6 Alkyl, halogenated C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-7 Cycloalkyl, C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkoxy, C 3-6 Cycloalkylthio, oxo, -CN, -NO2, -SO2R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and -SO2NR 3 R 4 ; R 3 , R 4 Selected from the group consisting of hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl; B is S or O; n is 1, 2 or 3; D is selected from the following group: substituted or unsubstituted 6-14 membered aryl, substituted or unsubstituted 3-8 membered cycloalkyl, substituted or unsubstituted 5-14 membered heteroaryl containing 1-3 selected from N, O or S, substituted or unsubstituted fused ring, 9-12 membered fused heteroaryl containing 1-3 selected from N, O or S, substituted or unsubstituted 3-8 membered heterocycloalkyl containing 1-3 selected from N, O or S; Wherein, the substituent is selected from the following group: halogen, substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 1-6 Alkoxy, substituted or unsubstituted mercapto, substituted or unsubstituted silicon, C 6-10 Aryl-alkoxy, C 6-10 Heteroaryl-alkoxy, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted C 2-6 Alkenyl, substituted or unsubstituted C 2-6 Alkynyl, substituted or unsubstituted azavinyl, substituted or unsubstituted C 5-7 Cycloalkenyl, substituted or unsubstituted phenyl, -N=N-substituted or unsubstituted phenyl, substituted or unsubstituted heteroaryl containing 1-3 groups selected from N, O or S, substituted or unsubstituted naphthyl, substituted or unsubstituted 5-membered or 6-membered heterocycloalkyl containing 1-3 groups selected from N, O or S, substituted or unsubstituted amide, -CN, -NH2; or The adjacent substituents are connected to form a substituted or unsubstituted C3-8 cycloalkyl, a substituted or unsubstituted C3-8 heterocycloalkyl containing 1-3 atoms selected from N, O or S, or a substituted or unsubstituted phenyl; The substituent is selected from the group consisting of halogen, C 1-6 Alkyl, halogenated C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 Alkoxy, -CN, substituted or unsubstituted phenyl, substituted or unsubstituted mercapto; or A substituted or unsubstituted C3-8 cycloalkyl group formed by adjacent substituents, or a substituted or unsubstituted C3-8 heterocycloalkyl group containing 1 to 3 atoms selected from N, O or S; The substituent is selected from the group consisting of halogen, C 1-6 Alkyl, halogenated C 1-6 alkyl.

2. The compound according to claim 1, or its geometric isomer, or its stereoisomer, or its pesticide-acceptable salt or prodrug, characterized in that: A is selected from the following group:

3. The compound according to claim 1, or its geometric isomer, or its stereoisomer, or its pesticide acceptable salt or prodrug, characterized in that: The definitions of B, n, and D are shown in the following table:

4. The compound according to claim 1, or its geometric isomer, or its stereoisomer, or its pesticide acceptable salt or prodrug, characterized in that: The compound has the structural formula (Ia): Wherein, the definitions of A, B and D are as described in claim 1.

5. The compound according to claim 1, or its geometric isomer, or its stereoisomer, or its pesticide acceptable salt or prodrug, characterized in that: The compound has the structural formula (Ib): Wherein, the definitions of B and D are as described in claim 1.

6. The compound according to claim 1, or its geometric isomer, or its stereoisomer, or its pesticide acceptable salt or prodrug, characterized in that: D is selected from the following group:

7. A method for preparing a compound represented by formula (I), or a geometric isomer thereof, or a stereoisomer thereof, or a pesticide-acceptable salt or prodrug thereof, characterized in that: The method comprises the steps of: In an inert solvent, in the presence of a base, compound II-1 reacts with compound II-2 to prepare a compound of formula I; Wherein, L is selected from the following group: methoxy, ethoxy, Cl; A, B, n, D are as defined in claim 1.

8. A use of the compound according to claim 1, or its geometric isomer, or its stereoisomer, or its pesticide acceptable salt or prodrug, characterized in that: (i) It can be used to control 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 with Rhizoctonia, Sporodiscus, Pseudoceromyces, Puccinia, Puccinia, Pythium and the like; (ii) can be used to kill and / or control at least one pest of the order Acarina, Synoptera, Orthoptera, Fusarium, Isoptera, Pseudotoptera, Thysanoptera, Heteroptera, Homoptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Siphonaptera and plant parasitic nematodes and / or its nymphs and / or its eggs; (iii) for bactericidal and / or acaricidal and / or insecticidal use; and / or (iv) for preparing a composition or formulation for killing fungi and / or mites and / or insects.

9. A composition, characterized in that include: (i) the compound according to claim 1, or its geometric isomer, or its stereoisomer, or its pesticide-acceptable salt or prodrug; and (ii) a pesticidally acceptable carrier and / or surfactant.

10. A method for killing bacteria and / or mites and insects, characterized in that: The method comprises the steps of: contacting bacteria and / or mites and insects with an effective amount of the compound according to claim 1, or its geometric isomers, or its stereoisomers, or its pesticide-acceptable salts or prodrugs, or the composition according to claim 9.

Images