CN117658935A - Ketone nitrile compound and preparation method and application thereof - Google Patents

Ketone nitrile compound and preparation method and application thereof Download PDF

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CN117658935A
CN117658935A CN202211007536.7A CN202211007536A CN117658935A CN 117658935 A CN117658935 A CN 117658935A CN 202211007536 A CN202211007536 A CN 202211007536A CN 117658935 A CN117658935 A CN 117658935A
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substituted
group
alkyl
compound
unsubstituted
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程家高
周聪
彼得·迈恩菲什
李忠
邵旭升
徐晓勇
钱旭红
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East China University of Science and Technology
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East China University of Science and Technology
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Abstract

The invention discloses a ketonitrile compound and a preparation method and application thereof. In particular, the invention relates to a compound shown as a formula I or a formula I', a composition containing the compound and application thereof. The compounds of the present invention have excellent bactericidal, acaricidal and insecticidal activity.

Description

Ketone nitrile compound and preparation method and application thereof
Technical Field
The invention belongs to the field of agrology, and particularly relates to a ketonitrile compound, and a preparation method and application thereof.
Background
The crop pathogenic bacteria, mites and insects often cause great losses to economic crops such as grains, vegetables, fruits, cotton, ornamental plants and the like, and the chemical bactericides, acaricides and insecticides are used for controlling the economic crops to increase the yield and harvest, so that the grain production safety is ensured, and the living standard of people is vital. However, due to the unreasonable use of the existing pesticide varieties, pathogenic bacteria, mites and pests have serious resistance to the existing agricultural protective agents, and the ecological environment safety problem of the pesticide is increasingly prominent. The chemical bactericide, acaricide and insecticide are used in large countries as pesticides, and have wide market prospect and vigorous requirements on new products. In view of the foregoing, there is a strong need in the art to develop a new class of compounds having excellent bactericidal, acaricidal or insecticidal activity.
Disclosure of Invention
The invention aims to provide a ketonitrile compound with excellent bactericidal, acaricidal and insecticidal activities, which has novel chemical structure, excellent control effect, environmental ecology safety and small toxic and side effects.
In a first aspect of the invention there is provided a compound of formula I or formula I', or a geometric isomer, stereoisomer, or an agropharmaceutically acceptable salt or prodrug thereof,
in the method, in the process of the invention,
a is selected from R 1 Or R is 2 ；
R 1 Is unsubstituted or substituted C 6-14 An aryl group; r is R 1 Wherein said substitution means that hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: 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 radicals C 3-6 Cycloalkylthio, -CN, -NO 2 、-SO 2 R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and-SO 2 NR 3 R 4 ；
R 2 Is unsubstituted or substituted 5-14 membered heteroaryl; r is R 2 Wherein said substitution means that hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: 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 radicals C 3-6 Cycloalkylthio, -CN, -NO 2 、-SO 2 R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and-SO 2 NR 3 R 4 ；
R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Each independently selected from the group consisting of substituted or unsubstituted: hydrogen, halogen, cyano, NO 2 、COR m 、COOR m 、OCOR m 、CONR n R m 、SO 2 NR n R m 、C 1-6 Alkyl, C 1-6 Heteroalkyl, C 1-6 Alkoxy, C 1-6 alkyl-S-, C 3-6 Cycloalkyl, 3-6 membered heterocyclyl, C 6-14 Aryl, 5-14 membered heteroaryl; wherein said substitution means by one or more R a Substitution;
alternatively, R 3 And R is 4 Together with the N atom to which they are attached form a substituted or unsubstituted 3-6 membered heterocyclic group; wherein said substitution means by one or more R a Substitution;
alternatively, R 5 And R is 6 Together with the C atom to which they are attached form a substituted or unsubstituted C 4-8 Cycloalkyl or substituted or unsubstituted 4-8 membered heterocyclyl; wherein said substitution means by one or more R a Substitution;
alternatively, R 6 And R is 7 Together with the C atom to which they are attached form a substituted or unsubstituted C 4-8 Cycloalkyl or substituted or unsubstituted 4-8 membered heterocyclyl; wherein said substitution means by one or more R a Substitution;
alternatively, R 7 And R is 8 Together with the C atom to which they are attached form a substituted or unsubstituted C 4-8 Cycloalkyl or substituted or unsubstituted 4-8 membered heterocyclyl; wherein said substitution means by one or more R a Substitution;
alternatively, R 8 And R is 9 Together with the C atom to which they are attached form a substituted or unsubstituted C 4-8 Cycloalkyl or substituted or unsubstituted 4-8 membered heterocyclyl; wherein said substitution means by one or more R a Substitution;
R n and R is m Each independently selected from the group consisting of: hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclyl, C 6-14 Aryl, 5-14 membered heteroaryl;
R a each independently selected from the group consisting of: hydrogen, halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6 Alkenyl, halo C 2-6 Alkynyl, C 1-6 Alkylthio, C 3-6 Cycloalkoxy radicals C 3-6 Cycloalkylthio, -CN, -NO 2 Oxo, C 3-7 Cycloalkyl, 3-6 membered heterocyclyl, -n=n-phenyl, SO 2 R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and-SO 2 NR 3 R 4 Wherein the phenyl group in-n=n-phenyl may be substituted with one or more groups selected from the group consisting of: halogen, -CN, -NO 2 、C 1-6 Alkyl, C 1-6 Alkoxy, halo C 1-6 Alkyl, halogenated C 1-6 An alkoxy group.
In another preferred embodiment, formula I and formula I' are tautomers
In another preferred embodiment, a is selected from the group consisting of substituted or unsubstituted: phenyl, naphthyl, thiazolyl, thiadiazolyl, isothiazolyl, tetrazolyl, pyridinyl, thiomorpholin-S-oxide, thiomorpholin-S, S-oxide, pyrimidinyl, indole, quinoline, isoquinoline, pyridazinyl, pyrazinyl, triazinyl, thienyl, oxazolyl, oxadiazolyl, isoxazolyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl; wherein, the substitution means that hydrogen on the group is substituted by 1-5 groups selected from the following groups: halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-7 Cycloalkyl, C 1-6 Alkoxy, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkoxy radicals C 3-6 Cycloalkylthio, CN, NO 2 、SO 2 R 3 、COR 3 、COOR 3 、CONR 3 R 4 And SO 2 NR 3 R 4 ；R 3 And R is 4 Each independently selected from the group consisting of: hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclyl.
In another preferred embodiment, a is selected from:
in the method, in the process of the invention,
g is independently 0, 1, 2, 3, 4 or 5;
each R' is independently selected from the group consisting of: hydrogen, halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-7 Cycloalkyl, C 1-6 Alkoxy, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkoxy radicals C 1-6 Alkylthio, C 3-6 Cycloalkylthio, CN, NO 2 、SO 2 R 3 、COR 3 、COOR 3 、CONR 3 R 4 And SO 2 NR 3 R 4 ；
R 3 And R is 4 Each independently selected from the group consisting of: hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclyl.
In another preferred embodiment, each R' is independently selected from the group consisting of: hydrogen, F, cl, br, I, CF, methyl.
In another preferred embodiment, a is selected from:
in another preferred embodiment, R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Each independently selected from the group consisting of substituted or unsubstituted: hydrogen, halogen, cyano, C 1-6 Alkyl, C 1-6 Alkoxy, halo C 1-6 Alkyl, NO 2 、COOC 1-6 Alkyl, CONHC 1-6 Alkyl, COC 1-6 Alkyl, SO 2 NHC 1-6 Alkyl, si (C) 1-6 Alkyl group 3 、C 1-6 alkyl-S-, SF 5 、C 3-6 Cycloalkyl, phenyl, pyridyl, isoquinoline, pyridazinyl, pyrazinyl, triazinyl, thienyl, oxazolyl, oxadiazolyl, isoxazolyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, Wherein said substitution means by one or more R a Substitution; r is R a Is defined as above;
preferably, R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Each independently selected from: hydrogen, F, cl, br, I, cyano, COOCH 3 、COOCH 2 CH 3 、CONHCH 3 、COCH 3 、SO 2 NHCH 3 、SO 2 NHCH 2 CH 3 、NO 2 、CH 3 、OCH 3 、CF 3 Phenyl, 4-Cl-C 6 H 4 、OCF 3 、OCHF 2 、SCH 3 、C(CH 3 ) 3 、SF 5 、CH 2 CF 3 、OCH(CH 3 ) 2 、/> CH(CH 3 ) 2 、/>
Alternatively, R 5 And R is 6 Together with the C atom to which it is attached to form
Alternatively, R 6 And R is 7 Together with the C atom to which it is attached to form Wherein the dotted line is the attachment site to the benzene ring.
In a further preferred embodiment of the present invention,selected from->
Wherein R 'is' 5 、R’ 6 、R’ 7 、R’ 8 、R’ 9 Each independently selected from the group consisting of substituted or unsubstituted: hydrogen, halogen, cyano, NO 2 、COR m 、COOR m 、OCOR m 、CONR n R m 、SO 2 NR n R m 、C 1-6 Alkyl, C 1-6 Heteroalkyl, C 1-6 Alkoxy, C 1-6 alkyl-S-, C 3-6 Cycloalkyl, 3-6 membered heterocyclyl, C 6-14 Aryl, 5-14 membered heteroaryl; wherein said substitution means by one or more R a Substitution;
the B ring, C ring, D ring and E ring are each independently selected from substituted or unsubstituted C 4-8 Cycloalkyl or substituted or unsubstituted 4-8 membered heterocyclyl; wherein said substitution means by one or more R a Substitution;
preferably, the method comprises the steps of,selected from: />
R 5 、R 6 、R 7 、R 8 、R 9 、R n 、R m And R is a Is defined as above.
In another preferred embodiment, R 5 、R 6 、R 7 、R 8 、R 9 Each independently having the definition as shown in table a.
In another preferred embodiment, the compound is selected from the group consisting of:
/>
in the formulae, R 5 、R 6 、R 7 、R 8 、R 9 Having a definition table a as shown in table a
/>
/>
/>
In another preferred embodiment, the compound is the compound shown in the examples.
In a second aspect of the present invention, there is provided a process for the preparation of a compound as described in the first aspect, or a geometric isomer, stereoisomer, or an agropharmaceutically acceptable salt or prodrug thereof, comprising the steps of:
/>
wherein L is methoxy, ethoxy or Cl, A, R 5 、R 6 、R 7 、R 8 、R 9 Is defined as above;
(s 1) reacting the compound II-1 with the compound II-2 in an inert solvent in the presence of a base to obtain the compound of formula I.
In another preferred embodiment, step (s 1) is: the compound of formula II-1 and the compound of formula II-2 are reacted in the presence of 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 t-butoxide, potassium t-butoxide, lithium diisopropylamide, diisopropylethylamine, pyridine, or a combination thereof) in a solvent (preferably, the solvent is selected from benzene, toluene, ethyl acetate, acetonitrile, dichloromethane, dichloroethane, tetrahydrofuran, diethyl ether, methyl t-butyl ether, 1, 4-dioxane, PEG400, n-heptane, n-hexane, cyclohexane, petroleum ether, dimethylformamide, dimethylsulfoxide, or a combination thereof) at 0-25℃or 0℃to reflux temperature to obtain the compound of formula I.
In a third aspect the present invention provides the use of a compound according to the first aspect, or a geometric isomer, a stereoisomer, or an agropharmaceutically acceptable salt or prodrug thereof,
(i) Can be used for preventing and treating at least one plant disease of anthracnose, leaf spot disease, rust disease, powdery mildew, banded sclerotial blight, leaf blight, gray mold, southern blight, damping off, scab, holothurian and target spot disease caused by infection of rhizoctonia, spore dish fungus, pseudoperonospora, monad rust fungus, phaeobasidium, pythium and the like;
(ii) Can be used for killing and/or preventing and controlling at least one pest and/or nymph and/or ovum of Acarina, symphytales, lepidoptera, coleoptera, hymenoptera, diptera, flea and plant parasitic nematodes;
(iii) For killing bacteria and/or mites and/or insects; and/or
(v) For preparing a composition or formulation for killing bacteria and/or mites and/or insects.
In another preferred embodiment, the compounds of formula I are used for killing and/or controlling crop pathogens in agriculture, pastures, lawns and/or indoors.
In another preferred embodiment, the compounds of the formula I are used for killing and/or controlling mites and/or insects in agriculture, pastures, lawns and/or indoors.
In another preferred example, examples of the plant disease include soybean, corn, wheat, melon, rice, strawberry, peanut, cotton; examples of the plant diseases include soybean rust, corn rust, wheat powdery mildew, melon powdery mildew, rice sheath blight, wheat sheath blight, strawberry gray mold, peanut southern blight, cotton damping off, wheat scab, wheat take-all and cucumber target spot, wherein the melon powdery mildew includes cucumber powdery mildew and the like; the pathogenic bacteria include phakopsora pachyrhizus (Phakopsora pachyrhizi syd.), puccinia maydis (Puccinia sorghi Schw), erysiphe necator (Blumeria graminis), erysiphe necator (Erysiphe cucurbitacearum), erysiphe necator (Sphaerotheca cucurbitae), cermets pelorum (Thanatephorus cucumeris), rhizoctonia cerealis (rhizoctonia), and rhizoctonia solani (rhizoctonia solani), botrytis cinerea (Botrytis cinerea pers.), grass Gu Lianpao (Fusarium graminearum schw.), fusarium avenae (Fusarium avenaceum), fusarium moniliforme (Fusarium moniliforme field), unicona rust (Uromyces), phytophthora (Phytophthora), pythium). Preferably, the plant disease is caused by rust of broad bean, phytophthora capsici, humic acid, etc.
In another preferred embodiment, the mites are pest mites.
In another preferred embodiment, the mites are selected from the group consisting of: tetranychus urticae (Tetranychus urticae Koch), tetranychus hawkthorn (Tetranychus viennensis Zacher), tetranychus truncatum (Tetranychus truncatus Ehara), tetranychus cinnabarinus (Tetranychus cinnabarinus Boisduval), tetranychus urticae (Panonychus ulmi Koch), tetranychus citri (Panonychus citri McGregor), tetranychus fuliginosus (Bryobia rubrioculus Scheuten), myriopsis glabra (Petrobia latens Muller), acidia spinosa (Oligonychus ununguis Jacobi), brevibacterium flavum (Brevipalpus obovatus Donnadieu), brevibacterium (B.lewisi McGregor), tetranychus telarius (Tenuipalpus taonicas Ma et Yuan), diospyros kaki (Tenuipalpus zhizhilashviliae Reck), eriobus vitis vinifera (C.vitis Pagenstecher), cyprinus spinosa (A.stelewis Keifer), lycium (A.macroodonis Keifer), pyrus She Zhongying (Eriophyes pyri Pagenst), pyrus She Xiuman (Epitrimerus pirifolia Keifer), tarsonius lateral, myzus sinensis (Polyphagotarsonemus latus Banks), myzus persicae (Penthaleus maJor Duges), and Alnus lazus (Rhizoglyphus callae Oudemans).
In another preferred embodiment, the pest is selected from the group consisting of: white pine (Scutigerella immaculat), domestic cricket (Acheta domesticus), gryllotalpa (Gryllotalpa sp.), african planthopper (Locusta inigratoria), black locust (Melanopsis sp.), desert locust (Schistocer cagregaria), oriental cockroach (Blatta orientalis), american cockroach (Periplanet aainericana), florida cockroach (Leucophae amaderae), german cockroach (Blattella gerrnanica), alternaria (Reticillium sp.), human body lice (Pediculus humanuscorporis), haematopodium (Haemapin sp.), trichinella (Linnathus sp.), trichodectes sp.), beairus (Dainalia sp.), trichodectes (Hercinothrips fernoralis), throthrips tabaci (Thrombina tabaci), thrombina (Periplanet aainericana), french maritima (Frankliniella occidentalis), flat stink bug (Euja sp.), alterna (Eury) cotton plant bug sp.), altern (Aphis (5284), aphis (P), applica (35), aphis (P.sub.sp.), trichthyophthalminia (35), aphis (P.sp.), trichthy (Aphis (35), aphis (P.sub.sp.), trichodendrus (35), aphis (P.sp.), trichprinus (Hercinothrips fernoralis), aphis (P.sp), triptera (35), aphis (yellow plug) and Aphis (35) The plant species include, but are not limited to, trigonella gracilis (Macrosiphurn avenae), myzus spp. The genus Oncomelania (Myzus spp.), aleurites negundo (Phorodon humuli), aleurites gracilis (Rhopalos iphuin padi), einasca sp. The genus Einascas (Einascaca spp.), oryza sativa (Nephotettix cincticeps), trigonella foetida (Lecanium corn i), levalis elegans (Saissetia oleae), latifolia (Laodelphax striatellus), brown planthoppers (Nilaparvata lugens), lecanis ruber (Aonidiella aurantii), hedera verrucosa (Aspidiotus hederae), lecanis species (pseudococus spp.) the species (Psyla sp. The species), leucopia erythrosepa (Pectinophora gossypiella), pinus meris (Bupalus piniarius), leptoradix Ophiopogonis (Cheirnatobia brurnata), leptopetalum (Lithocolletis blancardella), malus pumila (Hyponomeuta padella) plutella xylostella (Plutella xylostella), armyworm yellow-brown (Malacosoina neustria), huang Due (Euproctis chrysorrhoea), moth (lyinantia spp.), cotton-seed moth (Bucculatrix thurberiella), citrus-seed moth (Phyllocrnistis citrella), cutworm (Agrotis spp.), incised root worm (Euxoa spp.), spodoptera (Feltia spp.), egyptian diamond-back (Emerias insulona), spodoptera (Heliotis spp.), cabbage looper (Mainestra brassicae), eye-drop moth (Panolis flammea), prodenia litura (Spodoptera litura), spodoptera frugiperda (Spodoptera frugiperda), ash-fin moth (Spodoptera spp.), flour moth (Trichoplusia ni), apple diamond back (Carpocap saporiionella), cotton-seed moth (Heliotus spp), pink butterfly (Pieris spp.), graminea (Chilo spp.), corn borer (Pyrausta nubilalis), mediterranean Pink borer (Ephestia kuehniella), chilo borer (Galleria mellonella), pionella (Tineola bisselliella), paphia nodosa (Tinea pellionella), phaequoria fusca (Hofrnannophilap seudospretella), paphia lineolata (Cacoecia podana), phaequoria immaturus (Choristoneuna fuiniferana), vitis vinifera (Clysia ambiguella), pachyrhizus macroreticularis (Homona rnagnan irna), torula glabra (Torilidana), oryza species (Cnaphalocerus spp), orthosiphon oryzae (Oulema oryza), trichinella (Anobium punctatuin), pogostemon, orthosiphon (Rhizopertha dominica), orthosiphon (Bruchidius obtectus), phaeda (Acanthoscelides obtectus), trichinella parviformis (Clysia ambiguella) North America longhornworm ((Hylotrupes baJulus), yang Shuying leaf beetles (Agelastica alni), potato beetles (Leptinotarsa deceml ineata), horseradish beetles (Phaedon cochleariae), leaf beetles (Diabrotica spp.), botrytis cinerea (Psylliodes chrysocephal), laurechis mexicana (Epilachna vanivestis), pachyrhizus (Oryzaephilus suninamensis), phaliota (Anthonomus spp.), oryza (Sitophilus spp.), heterocarpa (Otiorrhynchus sulcatus), banana coryza (Cosinopolites sordidus), chinese cabbage tortoise (Ceuthorrhynchus assimilis), alfalfa leaf (Hypera postica), pithecellobium (Dermes spp.), pithecellobium (Trogomerrus spp), pithecellobium ((Anthrenus spp.)), pithecellobium The method comprises the steps of (1) using a first metal compound selected from the group consisting of the bark beetle (atagene spp.), the bark beetle (Lyctus spp.), the rape beetle (Meligethes aeneus), the spider beetle (Ptinus spp.), huang Zhujia (Niptus bololeucus), the spider beetle (Gibbium psylloides), the pseudo-oryza (Tribollin spp.), the yellow meal worm (Tenebnio rnolitor), the click beetle ((Agriots spp.), the wide chest beetle (Conoderus spp.), the five-month gill metal compound (Melolontha inelolontha), the potato gill metal compound (Ainphimallon solstitialis), the brown beetle (Costelytra zealandica), the rice root image (Li ssorhoptrus oryzophilus), the pine beetle (Dipnion spp.), the fruit beetle (Hoplopa spp.), the Mao Yi (Lasius spp.), the small meal beetle (Monornonium pharaonis), the bee beetle (Vespa spp)), the Aedes (Azebra spp), the beatifer (Bebrux), the beatifera (P), the beatifer (P), the beetle (37), the flower beetle (P), the flower beetle (37) and the flower beetle (P., grass species flies (phobilia spp.), chenopodium (Pegomyia hyoscyarni), medlars (Ceratitis capitata), medlars (Dacus oleracea), medlars (Tipula paludosa), black flies (hylemia spp.), liriomyza spp.), porus (Xenopsylla cheopis), ceripola (ceripola spp.), pratopsis (pratophilus spp.), pratophilus spp), like perfora nematodes (Radopholus similis), phoma parvulus (Ditylenchus dipsaci), hemiapheresis (Tylenchulus sernipenetrans), heterodera (hetodera spp), heterodera (Globodera spp), meloidogyne (Meloidogyne spp), bursaphelenchus (longicosis spp), bursaphelenchus (apricots spp), bursaphelenchus nematode (apricots spp.), bursaphelenchus spp.
In a fourth aspect of the invention, there is provided a composition comprising (i) as active ingredient a compound according to the first aspect, or a geometric isomer, stereoisomer, or an agropharmaceutically acceptable salt or prodrug thereof; and (ii) a carrier and/or surfactant.
In another preferred embodiment, the composition contains 0.001-99.999wt% of the compound.
In another preferred embodiment, the composition is a pesticide composition; preferably, it is a fungicidal composition, a acaricidal composition and an insecticidal composition.
In a fifth aspect of the present invention there is provided a method of killing bacteria and/or mites, comprising the steps of: contacting a fungus and/or mite, a pest with an effective amount of a compound as described in the first aspect, or a geometric isomer, stereoisomer, or an agropharmaceutically acceptable salt or prodrug thereof, or a composition as described in the fourth aspect.
It is understood that within the scope of the present invention, the above-described technical features of the present invention and technical features specifically described below (e.g., in the examples) may be combined with each other to constitute new or preferred technical solutions. And are limited to a space, and are not described in detail herein.
Detailed Description
The inventor has studied extensively and intensively, and has found that ketone nitrile compounds (shown as formula I) with novel structures have excellent bactericidal and/or acaricidal and/or insecticidal activity. Based on this, the inventors completed the present invention.
Terminology
As used herein, the term "halogen" refers to fluorine, chlorine, bromine or iodine.
Unless otherwise defined, the term "alkyl" by itself or as part of another substituent means a straight or branched hydrocarbon radical having the indicated number of carbon atoms (i.e., C 1-6 Representing 1-6 carbons). Examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl and the like.
The term "heteroalkyl" by itself or as part of another substituent, unless otherwise defined, refers to a group as described above in which the C atom of an alkyl group of the indicated number of carbon atoms is replaced with a heteroatom such as O, S, si, P. Examples of heteroalkyl groups include Si (CH) 3 ) 3 、CH 2 OCH 3 Etc.
Unless otherwise stated, 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. Alkenyl groups are preferably C 2-6 Alkenyl, alkynyl, preferably C 2-6 Alkynyl groups. 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.
Unless otherwise defined, the term "cycloalkyl" refers to a compound having the indicated number of ring atoms (e.g., C 3-6 Cycloalkyl) is a saturated or unsaturated cyclic hydrocarbon group. Examples of such cycloalkyl groups include, but are not limited to, cyclopenteneA group, a cyclohexyl group, and the like.
Unless otherwise stated, the term "aryl" refers to a polyunsaturated (usually aromatic) hydrocarbon group, which may be a single ring or multiple rings (up to three rings) fused together or covalently linked. Examples of aryl groups include: phenyl and naphthyl.
Unless otherwise defined, the term "heterocycloalkyl" or "heterocyclyl" refers to cycloalkyl groups containing one to five heteroatoms selected from N, O and S, wherein the nitrogen and sulfur atoms are optionally oxidized and the nitrogen atom is optionally quaternized. Heterocycloalkyl groups may be monocyclic, bicyclic or polycyclic ring systems. The heterocyclic group is preferably a 3-to 12-membered, more preferably a 4-to 10-membered, more preferably a 5-to 6-membered heterocyclic group. Non-limiting examples of heterocycloalkyl groups include pyrrolidine, imidazolidine, pyrazolidine, butyrolactam, valerolactam, imidazolidone, hydantoin, dioxolane, phthalimide, piperidine, 1, 4-dioxane, morpholine, thiomorpholine-S-oxide, thiomorpholine-S, S-oxide, piperazine, pyran, pyridone, 3-pyrroline, thiopyran, pyrone, tetrahydrofuran, tetrahydrothiophene, quinuclidine, and the like. Heterocycloalkyl groups can be attached to the remainder of the molecule via a ring carbon or heteroatom. Terms such as cycloalkylalkyl and heterocyclylalkyl refer to a cyclic alkyl or heterocyclic group attached to the remainder of the molecule through an alkyl or alkylene linker.
Unless otherwise defined, the term "heteroaryl" refers to an aryl group (or ring) containing 1 to 5 heteroatoms selected from N, O, and S, wherein the nitrogen and sulfur atoms are optionally oxidized and the nitrogen atom is optionally quaternized. Heteroaryl groups may be attached to the remainder of the molecule through heteroatoms. Heteroaryl is preferably a 5-14 membered heteroaryl, more preferably a 5-6 membered heteroaryl. Non-limiting examples of heteroaryl groups include pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, benzotriazinyl (benzotriazinyl), purinyl, benzimidazolyl, benzopyrazolyl, benzotriazolyl, benzisoxazolyl, isobenzofuranyl (isobenzofuryl), isoindolyl, indolizinyl, benzotriazinyl, thienopyridinyl, thienopyrimidinyl, pyrazolopyrimidinyl, imidazopyridine, benzothiazolyl, benzofuranyl, benzothienyl, indolyl, quinolinyl, isoquinolinyl, isothiazolyl, pyrazolyl, indazolyl, pteridinyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, pyrrolyl, thiazolyl, furanyl, thienyl, and the like.
As used herein, the term "heteroatom" is intended to include oxygen (O), nitrogen (N), sulfur (S) and silicon (Si).
For the 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 refer to a bond that provides a connection at any available vertex of the aromatic ring. In some embodiments, the description also includes linkages on rings fused to aromatic rings. For example, a bond drawn to the center of the indole benzene moiety will represent a bond to any available vertex of the six-or five-membered ring portion of the indole.
As used herein, the terms "comprising," "including," or "comprising" mean that the various ingredients can be used together in a mixture or composition of the invention. Thus, the terms "consisting essentially of and" consisting of are encompassed by the term "containing.
Unless otherwise indicated, the compounds of formula I of the present invention include geometric isomers (Z and E are each shown in different configurations) which may be formed by the attachment of a carbon-carbon double bond or a carbon-nitrogen double bond to different substituents, and the present invention includes Z-type isomers and E-type isomers and mixtures thereof in any ratio. The compounds of formula I of the present invention include stereoisomers (R and S are shown in different configurations) which may be formed by the attachment of different substituents to the carbon and nitrogen atom, and the present invention includes R-type isomers and S-type isomers and mixtures thereof in any ratio. The compounds of formula I of the present invention include not only geometric isomers (Z/E formulae) and stereoisomers (R/S formulae), but also mixtures of geometric isomers and stereoisomers in any ratio.
As used herein, "effective amount" refers to: the amount of the compound is sufficient to produce a bactericidal, acaricidal and insecticidal effect without serious adverse effects.
As used herein, for example, "1 to 5" means 1, 2, 3, 4, or 5, "1-10" means 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
Ketone nitrile compounds
As used herein, the term compound of the present invention refers to a class of ketonitriles as shown in formula I, which term also includes geometric isomers, or stereoisomers thereof, or salts, various isomer mixtures thereof.
In particular, the invention provides a ketonitrile compound shown as a formula I or a formula I',
in A, R 5 、R 6 、R 7 、R 8 、R 9 The definition of (c) is as described above,
preferably, a is selected from the group consisting of substituted or unsubstituted: phenyl, naphthyl, thiazolyl, thiadiazolyl, isothiazolyl, tetrazolyl, pyridinyl, thiomorpholin-S-oxide, thiomorpholin-S, S-oxide, pyrimidinyl, indole, quinoline, isoquinoline, pyridazinyl, pyrazinyl, triazinyl, thienyl, oxazolyl, oxadiazolyl, isoxazolyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl; wherein, the substitution means that hydrogen on the group is substituted by 1-5 groups selected from the following groups: halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-7 Cycloalkyl, C 1-6 Alkoxy, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkoxy radicals C 3-6 Cycloalkylthio, CN, NO 2 、SO 2 R 3 、COR 3 、COOR 3 、CONR 3 R 4 And SO 2 NR 3 R 4 ；R 3 And R is 4 Each independently selected from the group consisting of: hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclyl;
preferably, A is selected from the structures represented by the following structural formulae A1-A70
Preferably, R 5 、R 6 、R 7 、R 8 、R 9 Is defined as in Table a
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Preferably, A in the compounds of formula I or formula I' of the invention is A1-A70, R as described above 5 、R 6 、R 7 、R 8 、R 9 Having the definition as shown in table a.
The compound number of the embodiment of the invention consists of two parts, am-n, wherein Am is the structure shown in A1-A70, n is the number in table a, such as A2-92,
namely: in formula I or formula I', A2 is92 is R corresponding to the number 90 in Table a 5 、R 6 、R 7 、R 8 、R 9 Radicals, i.e. R 5 、R 6 、R 7 、R 8 、R 9 H and->H、H、H。
Process for the preparation of the compounds of the invention
The process for the preparation of the compounds of formula I according to the invention is described in more detail below, but these particular processes do not constitute any limitation on the invention. The compounds of the present invention may also be conveniently prepared by optionally combining the various synthetic methods described in this specification or known in the art, such combinations being readily apparent to those skilled in the art to which the present invention pertains.
The present invention also provides a general method for preparing the compounds of the first aspect, i.e. the compounds of formula I.
Preferably, the method comprises the steps of:
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wherein L is methoxy, ethoxy or Cl, A, R 5 、R 6 、R 7 、R 8 、R 9 As described above;
(s 1) reacting the compound II-1 with the compound II-2 in an inert solvent in the presence of a base to obtain the compound of formula I.
Preferably, step (s 1) is: the compound of formula II-1 and the compound of formula II-2 are reacted in the presence of 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 t-butoxide, potassium t-butoxide, lithium diisopropylamide, diisopropylethylamine, pyridine, or a combination thereof) in a solvent (preferably, the solvent is selected from benzene, toluene, ethyl acetate, acetonitrile, dichloromethane, dichloroethane, tetrahydrofuran, diethyl ether, methyl t-butyl ether, 1, 4-dioxane, PEG400, n-heptane, n-hexane, cyclohexane, petroleum ether, dimethylformamide, dimethylsulfoxide, or a combination thereof) at 0-25℃or 0℃to reflux temperature to obtain the compound of formula I.
Combinations comprising the compounds of the invention and the use of the compounds and compositions of the invention
The invention also provides a compound shown in the formula I or an agricultural composition containing the ketonitrile compound shown in the formula I and application thereof.
The ketonitrile compound shown in the formula I is also suitable for preventing and treating at least one plant disease of anthracnose, leaf spot disease, rust disease, powdery mildew, sheath blight, leaf blight, gray mold, southern blight, damping off, scab, take-off, take-all and target spot disease caused by the infection of rhizoctonia, sporotrichum, pseudoperonospora, monad rust, phaeomyces, procymia, and the like. Examples of plants of the plant mycoses include soybean, corn, wheat, melon, rice, strawberry, peanut, cotton; examples of the plant fungal diseases include soybean rust, corn rust, wheat powdery mildew, melon powdery mildew, rice sheath blight, wheat sheath blight, strawberry gray mold, peanut southern blight, cotton seedling blight, wheat scab, wheat take-all and cucumber target spot, wherein the melon powdery mildew includes cucumber powdery mildew and the like; the pathogenic bacteria include phakopsora pachyrhizus (Phakopsora pachyrhizi syd.), puccinia maydis (Puccinia sorghi Schw), erysiphe necator (Blumeria graminis), erysiphe necator (Erysiphe cucurbitacearum), erysiphe necator (Sphaerotheca cucurbitae), cermets pelorum (Thanatephorus cucumeris), rhizoctonia cerealis (rhizoctonia), and rhizoctonia solani (rhizoctonia solani), botrytis cinerea (Botrytis cinerea pers.), grass Gu Lianpao (Fusarium graminearum schw.), fusarium avenae (Fusarium avenaceum), fusarium moniliforme (Fusarium moniliforme field), unicona rust (Uromyces), phytophthora (Phytophthora), pythium).
The ketonitrile compound represented by formula I of the present invention shows excellent mite control activity against various pests in agriculture or other fields, particularly against spider mites (agarina) of arachnidae (agarina), such as tetranychus urticae (Tetranychus urticae Koch), tetranychus hawkthorn (Tetranychus viennensis Zacher), tetranychus truncus (Tetranychus truncatus Ehara), tetranychus cinnabarinus (Tetranychus cinnabarinus Boisduval), panonychus ulmi (Panonychus ulmi Koch), panonychus citri (Panonychus citri McGregor), moss mite (Bryobia rubrioculus Scheuten), cornus (Petrobia latens Muller), needle She Xiaozhao mite (Oligonychus ununguis Jacobi), white spirit mite (Brevipalpus obovatus Donnadieu), brachysporus jejuniper (b.lewisi McGregor), peach fine silk mite (Tenuipalpus taonicas Ma et Yuan), persimmon fine silk mite (Tenuipalpus zhizhilashviliae Reck), vania vitis (c.tagene chemical), point She Yingman (a. Stenidensis, matrimony vine mite (a. Macromonokeifer), pear She Zhongying mite (Eriophyes pyri Pagenst), she Xiuman (Epitrimerus pirifolia Keifer), white spirit mite (Rhizoglyphus callae Oudemans), taro mite (Penthaleus maJor Duges), etc. "mite control" means that it has acaricidal activity at each stage of the mite life cycle (eggs, larvae, adults). Therefore, the technical scheme of the invention also comprises the application of the ketonitrile compound shown in the formula I as an acaricide in agriculture or other fields.
The ketonitrile compounds shown in the formula I are also suitable for preventing and controlling at least one pest of the comprehensive orders, orthoptera, blatta, isoptera, lupulus, thysanoptera, heteroptera, homoptera, lepidoptera, coleoptera, hymenoptera, diptera, flea and plant parasitic nematodes in agriculture or other fields.
The order of the Syrnphyla, for example, white pine moth (Scutigerella immaculat), etc.
The order Orthoptera (orthotera), for example, family cricket (Acheta domesticus), mole cricket genus (Grylotalpa spp.), african migratory locust (Locusta inigratoria), black locust (Melanoplus spp.), desert locust (Schistocer cagregaria), and the like;
the Blattaria (Blattaria) is, for example, oriental cockroach (Blatta orientalis), american cockroach (Periplanet aainericana), florida cockroach (Leucophae amaderae), german cockroach (Blattella gerrnanica), or the like.
The Isoptera (Isoptera), e.g., the genus rotitermes (rotitermes spp.), and the like.
Such as pediculus humanus (phthoptera), for example, pediculus humanus (Pediculus humanuscorporis), pediculus sanguinea (haematoplus spp.), pediculus pubescens (Linognathus spp.), pediculus (trichodes spp.), pediculus equi (Dainalinia spp.), and the like.
The Thysanoptera (Thysanoptera), for example, thrips palmi (Hercinothrips fernoralis), thrips tabaci (threps tabaci), thrips palmi (threps palmi), thrips franklinii (Frankliniella occidentalis), and the like.
The Heteroptera (Heteroptera), for example, the genus flat bugs (Eurygaster spp.), intermediate cotton bugs (Dysdercus interrnedius), lygus dorsum (Piesrna quateata), temperate bugs (cimexifectulius), echinocgus (Rhodnius prolixus), echinocgus (Triatoma spp.), and the like.
The homoptera (hootoptera) are, for example, white fly (Aleurodes brassicae), bemisia tabaci (benisia tabaci), white fly (Trialeurodes vaporariorum), cotton aphid (Aphis gossypii), cabbage aphid (Brevicoryne brassicae), tea leaf mustard cryptotazia (Cryptomyzus ribis), black bean aphid (Aphis fabae), apple yellow aphid (Aphis porini), apple cotton aphid (Eriosoma lanigerum), green plum big tail aphid (Hyalopterus arundinis), grape root nodule aphid (Phylloxera vastatrix), leptinotus (Pernphigus spp.), wheat long tube aphid (Macrosiphurn avenae), myzus spp.), verruca negundo (phobia humuli), cereal grain boundary pipe aphid (Rhopalos iphuin padi), leafhopper (einpoca spp), black tail cicada (Nephotettix cincticeps), scale insect (lecanii), elema elemene (sasetia), brown mealy (Laodelphax striatellus), brown planthopper (25), green plant fulgorilla (Aonidiella aurantii), and the like.
The Lepidoptera (Lepidoptera), e.g., the species of the genus Hedyotis (Pectinophora gossypiella), pinctada matsutake (Bupalus piniarius), dongchi moth (Cheirnatobia brurnata), malus pumila (Lithocolletis blancardella), malus pumila (Hyponomeuta padella), plutella xylostella (Plutella xylostella), phaeda flavescens ((Malacosoina neustria), huang Due (Euproctis chrysorrhoea), phaeda (Lyinantia spp.), phaeda gossypii (Bucculatrix thurberiella), phaeda citrifolia (Phyllocrnistis citrella) Gekko sp, euxoa spp, spodoptera, feltia spp, egyptian diamond-on (Emerias insulosa), spodoptera, brassica oleracea (Heliothis spp), brassica oleracea (Mainestra brassicae), spodoptera frugiperda (Panulis flammea), spodoptera litura (Spodoptera litura) Spodoptera frugiperda (Spodoptera frugiperda), night-wing (Spodoptera spp.), night-wing moth (Trichoplusia ni), apple plutella xylostella (Carpocap saporiionella), cabbage butterfly (Pieris spp), grass borer (Chilo spp), corn borer (Pyrausta nubilalis), mediterrapin borer (Ephestia kuehniella), wax moth (Galleria mellonella), curtain moth (Tineola bisselliella), bag moth (Tinea pellionella), brown moth (Hofrnannophilap seudospretella), flax yellow moth (Cacoecia podana), polar cabbage moth (Choristoneuna fuiniferana), grape fruit moth (Clysia ambiguella), tea moth (Homona rnagnan irna), torilla japonica (Torvulina) and the like, cnaphalocerus spp, rice negative mud worms (Oulema oryzae), and the like.
The Coleoptera (Coleoptera), for example, beetle (Anobium punctatuin), bark beetle (Rhizopertha dominica), weevil (Bruchidius obtectus), bean image (Acanthoscelides obtectus), longicorn ((Hylotrupes baJulus), yang Shuying leaf beetle (Agelastica alni), potato beetle (Lept inotarsa deceml ineata), horseradish beetle (Phaedon cochleariae), leaf beetle (Diabrotica spp.), rape golden-head flea beetle (Psylliodes chrysocephal), beaybug (Epilachna vanivestis), saw-grain beetle (Oryzaephilus suninamensis), flower image (Anthonomus spp.), valley image (Sitophilus spp.), black grape image (Otiorrhynchus sulcatus), banana corm beetle (Cosinopolites sordidus), cabbage tortoise (Ceuthorrhynchus assimilis), alfalfa leaf image (Hypera pomica) the genus pinus (Dermestes spp.), pinus (Trogomera spp.), pinus (Anthrenus spp.), pinus (atagenus spp.), pinus (Lyctus spp.), pinus (Meligethes aeneus), pinus (Ptinus spp.), huang Zhujia (Niptus bololeucus), pinus (Gibbium psylloides), tribollin spp.), yellow meal worm (Tenebnio rnolitor), click beetle (Agriotes spp.), wide chest click beetle (Conoderus spp.), west wuyue gill angle beetle (Melolontha inelolontha), potato gill angle beetle (Ainphimallon solstitialis), new Zealand Rigida gill angle beetle (Costelytra zealandica), talarch angle beetle (Costelytra zealandica), root image of Oryza sativa (Li s sorhoptrus oryzophilus), etc.
The Hymenoptera (Hymenoptera), for example, the genus pinus (Dipnion spp.), the genus hornet (hollocamapa spp.), the genus Mao Yi (Lasius spp.), the genus halimasch (Monornonium pharaonis), the genus wasp (Vespa spp.), and the like;
the Diptera (Diptera), for example, aedes spp, anopheles spp, culex spp, drosophila melanogaster Drosophila melanogaster, musca spp, toilet fly spp, red head Calliphora vicina, lucilia spp, chrysomya spp, huang Ying, cuterebra spp, gastroma hypersomus spp, hypcopa spp, stings, strongnoxy, spp, and the like the genus myza (Oestrus spp.), piriomyza (Hypodarnna spp.), tabanus spp, garden Mao Wen (Bibio Horvulus), swedish wheat straw fly (Oscinella flit), tsetse fly (Pegomyia hyoscyarni), mediterranean wax fly (Ceratitis capitata), canarium album (Dacus oleracea), aerobusta (Tipula paludosa), black fly (Hylemia spp.), sporotza spp, and the like.
The order of Siphonaptera (Siphonaptera), for example, porphyra tenera (Xenopsylla cheopis), porphyra (Ceratophyllus spp.), and the like.
The plant parasitic nematodes include, for example, pratylenchus spp, rhabdosia (Radopholus similis), rhabdosia (Ditylenchus dipsaci), hemipuncture nematode Tylenchulus sernipenetrans, heterodera spp, globodera spp, meloidogyne spp, aphelenchus spp, long-needle nematode spp, aphelenchus spp, trichina spp, bursaphelenchus spp, and the like, and thus, the technical scheme of the present invention also includes the use of the ketonitrile compounds represented by formula I as pesticides in agriculture or other fields.
Therefore, the technical scheme of the invention also comprises the application of the ketonitrile compound shown in the formula I as a bactericide in agriculture or other fields.
The ketonitrile compounds of the formula I according to the invention can be prepared in a customary manner as fungicidal and/or acaricidal and/or insecticidal compositions. These active compounds can be formulated as conventional formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with the active substance, microcapsules in polymers, coated compounds for seeds, and formulations for use with combustion devices, such as fumigating cartridges, fumigating cans and fumigating trays, and ULV Cold and hot mist (Cold mist) formulations.
These formulations can be produced by known methods, for example by mixing the active compound with extenders, which are liquid or liquefied gas or solid diluents or carriers, and optionally surfactants, i.e. emulsifiers and/or dispersants and/or foam formers. For example, when water is used as the extender, organic solvents may also be used as adjuvants.
When a liquid solvent is used as a diluent or carrier, it is basically suitable, for example: aromatic hydrocarbons such as xylene, toluene or alkyl naphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons, such as cyclohexane or paraffin waxes, such as mineral oil fractions; alcohols, such as ethanol or ethylene glycol, and their ethers and lipids; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or less commonly polar solvents such as dimethylformamide and dimethylsulfoxide, and water.
The diluent or carrier for the liquefied gas refers to a liquid that will become a gas at normal temperature and pressure, such as an aerosol propellant, e.g., halogenated hydrocarbons, as well as butane, propane, nitrogen, and carbon dioxide.
The solid carrier may be ground natural minerals such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomaceous earth; and ground synthetic minerals such as highly dispersed silicic acid, alumina, and silicate. Solid carriers for the particles are crushed and graded natural zircon, such as calcite, marble, pumice, sepiolite and dolomite, as well as particles synthesized from inorganic and organic grits, and particles of organic materials such as sawdust, coconut shells, corn cobs and tobacco stalks, and the like.
Nonionic and anionic emulsifying trains can be used as emulsifiers and/or foam formers. Such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, and albumin hydrolysates. The dispersing agent comprises lignin sulfite waste liquid and methyl cellulose.
Binders such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions, for example gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulation.
Colorants such as inorganic dyes, e.g., iron oxide, cobalt oxide, and Prussian blue; organic dyes such as azo dyes or metal phthalocyanine dyes; and with trace nutrients such as salts of iron, manganese, boron, copper, cobalt, aluminum, and zinc, and the like.
The ketonitriles of formula I of the invention can be present in their commercial formulations as a mixture with other active compounds, or in the dosage forms prepared from these formulations, which are pesticides, bactericides, fungicides, herbicides, growth control agents and the like. Pesticides include, for example, phosphates, carbamates, chlorinated hydrocarbons, and substances produced by microorganisms, such as avermectin, and the like, and fungicides include methoxy acrylates, amides, triazoles, and the like.
In addition, the ketonitrile compounds of the formula I according to the invention can also be present in their commercial preparations or in the dosage forms prepared from these preparations in a mixture with synergists, which are compounds which increase the action of the active compounds, since the active compounds themselves are active, it being possible for the synergists not to be necessary.
These formulations generally contain from 0.001 to 99.99% by weight, preferably from 0.01 to 99.9% by weight, more preferably from 0.05 to 90% by weight of the active compound of the invention, based on the total weight of the pesticide composition. The concentration of the active compound in the commercial preparation or use dosage form may vary widely. The concentration of the active compound in the dosage form employed may vary from 0.0000001 to 100% (g/v), preferably between 0.0001 and 1% (g/v), and various changes and modifications may be made within the scope of the present invention as defined in the claims.
The main advantages of the invention include:
(a) The compound has excellent bactericidal activity;
(b) The compound also has excellent acaricidal and insecticidal activity;
(c) The compound has short synthesis steps and good total yield;
(d) Compared with the existing compounds of the same type, the compound of the invention has obvious structural innovation;
(f) The compound has excellent bactericidal, acaricidal and insecticidal activities and has small influence on the environment.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.
EXAMPLE 1 preparation of Compounds A1-39
NaH (500 mg,12.5 mmol) was weighed into a 50ml two-necked flask, 30ml THF was added, and stirred and dispersed uniformly under ice bath; to a suspension of NaH in THF was weighed out trimethylsilylbenzyl cyanide (1.89 g,10 mmol) and added dropwise. After stirring for 20min, ethyl 1-methyl-3-difluoromethylpyrazole-5-carboxylate (2.04 g,10 mmol) was added dropwise and the mixture was refluxed. After the reaction is finished, a small amount of water is added under ice bath to quench the reaction, and dilute hydrochloric acid is added to adjust the reaction to acidity. Ethyl acetate extraction (20 ml×3), and the combined organic phases were washed with saturated sodium chloride solution and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and n-heptane was added to the residue to precipitate a white solid in 74.2% yield.
1 H NMR(400MHz,Chloroform-d)δ7.98(s,1H),7.59(d,J＝8.1Hz,2H),7.42(d,J＝8.0Hz,2H),7.02(t,J＝53.7Hz,1H),5.14(s,1H),3.97(s,3H),0.29(s,9H).
EXAMPLE 2 preparation of Compounds A1-39
Into the two-necked flask were charged ethyl 1-methyl-3-difluoromethylpyrazole-5-carboxylate (2.04 g,10 mmol), p-trimethylsilyl benzyl cyanide (1.89 g,10 mmol), 30ml of n-hexane, 5ml of ethylene glycol monomethyl ether, followed by a water separator and a condensate return line. After the nitrogen substitution of the reaction system, the mixture was refluxed at 110℃for 2 hours, and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml,12.0 mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was adjusted to acidity by adding dilute hydrochloric acid, extracted with ethyl acetate (20 ml×3), and the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the white solid was isolated and purified by silica gel column chromatography in 80.5% yield. 1 H NMR(400MHz,Chloroform-d)δ7.98(s,1H),7.59(d,J＝8.1Hz,2H),7.42(d,J＝8.0Hz,2H),7.02(t,J＝53.7Hz,1H),5.14(s,1H),3.97(s,3H),0.29(s,9H).
EXAMPLE 3 preparation of Compound A1-1
Two-mouth bottle withEthyl 1-methyl-3-difluoromethylpyrazole-5-carboxylate (2.04 g,10 mmol), 2-fluoro-benzyl cyanide (1.35 g,10 mmol), n-heptane 30ml, ethylene glycol monomethyl ether 5ml were added followed by a water separator and a condensate return line. After the nitrogen substitution of the reaction system, the mixture was refluxed at 110℃for 2 hours, and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml,12.0 mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was adjusted to acidity by adding dilute hydrochloric acid, extracted with ethyl acetate (20 ml×3), and the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the yellow gum was isolated and purified by silica gel column chromatography in 64.2% yield. 1 H NMR(400MHz,Chloroform-d)δ8.05(s,1H),7.41(dd,J＝3.8,1.5Hz,2H),7.36–7.32(m,2H),6.95(d,J＝53.7Hz,1H),5.43(s,1H),3.93(s,3H).
EXAMPLE 4 preparation of Compounds A1-30
K is added into a single-mouth bottle 2 CO 3 (1.66 g,12 mmol) and tetrahydrofuran (20 mL), and a mixture of ethyl 1-methyl-3-difluoromethylthiazole-5-carboxylate (1.82 g,10 mmol) and p-methoxyphenylacetonitrile (1.47 g,10 mmol) was added dropwise under ice-bath cooling. After the dripping is finished, removing the ice bath, pouring the reaction liquid into water, extracting by ethyl acetate, taking the water phase, adding dilute hydrochloric acid to adjust to acidity, extracting by ethyl acetate (20 mL multiplied by 3), merging the organic phases, washing by saturated sodium chloride solution, and drying by anhydrous sodium sulfate. The solvent was removed under reduced pressure to give a crude product, which was purified by silica gel column chromatography to give a white solid in 41.2% yield. 1 H NMR(400MHz,Chloroform-d)δ7.91(s,1H),7.29(d,J＝8.2Hz,2H),7.22(d,J＝8.0Hz,2H),7.00(t,J＝53.7Hz,1H),5.13(s,1H),3.92(s,3H),3.75(s,3H).
EXAMPLE 5 preparation of Compound A12-1
In two-mouth bottleEthyl 1-methyl-3-difluoromethylpyrazole-5-carboxylate (2.22 g,10 mmol), 2-fluoro-benzyl cyanide (1.35 g,10 mmol), 30ml of n-hexane, 5ml of ethylene glycol monomethyl ether were added, followed by a water separator and a condensate return line. After the nitrogen substitution of the reaction system, the mixture was refluxed at 110℃for 2 hours, and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml,12.0 mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was adjusted to acidity by adding dilute hydrochloric acid, extracted with ethyl acetate (20 ml×3), and the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. The solvent is removed under reduced pressure to obtain crude product, and white solid is obtained through silica gel column chromatography separation and purification, and the yield is 62.6%. 1 H NMR(400MHz,Chloroform-d)δ7.41(q,J＝3.9Hz,2H),7.36–7.32(m,2H),6.96(t,J＝54.2Hz,1H),5.43(s,1H),3.95(s,3H)
EXAMPLE 6 preparation of Compounds A13-30
To the flask was added ethyl 2-methyl-4-trifluoromethyl-oxazole-5-carboxylate (2.23 g,10 mmol), 4-methoxy-benzyl cyanide (1.47 g,10 mmol), 30ml of n-hexane, 5ml of ethylene glycol monomethyl ether, followed by a water separator and a condensate return line. After the nitrogen substitution of the reaction system, the mixture was refluxed at 110℃for 2 hours, and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml,12.0 mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was adjusted to acidity by adding dilute hydrochloric acid, extracted with ethyl acetate (20 ml×3), and the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. The solvent is removed under reduced pressure to obtain crude product, white solid is obtained through silica gel column chromatography separation and purification, and the yield is 74.0%. 1 H NMR(400MHz,Chloroform-d)δ7.29(d,J＝8.2Hz,2H),7.22(d,J＝8.0Hz,2H),5.08(s,1H),3.92(s,3H),2.68(s,3H).
EXAMPLE 7 preparation of Compounds A57-27
To the flask was added ethyl 5-methyl-triazine-4-carboxylate (1.67 g,10 mmol), 4-methyl-benzyl cyanide (1.31 g,10 mmol), 30ml of n-hexane, 5ml of ethylene glycol monomethyl ether, followed by a water separator and a condensate return line. After the nitrogen substitution of the reaction system, the mixture was refluxed at 110℃for 2 hours, and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml,12.0 mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was adjusted to acidity by adding dilute hydrochloric acid, extracted with ethyl acetate (20 ml×3), and the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. The solvent is removed under reduced pressure to obtain crude product, and white solid is obtained through silica gel column chromatography separation and purification, and the yield is 70.9.2%. 1 H NMR(400MHz,Chloroform-d)δ7.72(d,J＝7.2Hz,1H),7.44(t,J＝4.0Hz,2H),7.38(d,J＝4.0Hz,2H),5.14(s,1H),3.24(s,3H),2.35(s,3H).
Other ketonitriles of the invention of formula I can also be prepared by the methods described in the examples above using the appropriate starting materials.
Other example compounds were also prepared from different starting materials with reference to the above preparation method, the example compounds of the invention are shown in table b;
table b partial example compound structural characterization
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Examples of biological Activity assays
Evaluation of Bactericidal Activity against Streptomyces, sclerotinia, rhizoctonia solani, gibberella, monilinia, phytophthora, pythium and downy mildew
The compounds tested were dissolved in DMSO to prepare a 1000mg/L stock solution, which was then mixed with PDA. The culture medium containing 100mg/L of the compound was poured into a sterile petri dish for preliminary screening. After culturing at 25℃for 48-120 hours, the colony diameter of each strain was measured. Percent inhibition was calculated as (C-A)/(C-B). Times.100%, where A represents the colony diameter in the culture dish containing the test compound, B represents the hyphal disc diameter, and C represents the average colony diameter in the control dish. The commercial bactericide fluxapyroxad hydroxylamine was used as a positive control. Each treatment was repeated three times. The results of the bactericidal activity of some of the compounds are shown in table c.
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Evaluation of mite killing Activity against Tetranychus urticae (Tetranychus urticae) and Tetranychus cinnabarinus (Tetranychus cinnabarinus)
After the compound to be tested is dissolved by dimethyl sulfoxide, the compound to be tested is diluted to the test concentration of 500mg/L by a triton aqueous solution, and the liquid medicine is uniformly sprayed on the front side and the back side of the bean leaf cut pieces. After the liquid medicine is dried, the bean leaf cutting piece is connected with a mixed individual of tetranychus urticae or tetranychus cinnabarinus, and the cardinal number is recorded. The number of living insects on the leaves of beans was recorded by observation in a standard observation room (23-25 ℃ C., RH 40-60%) and investigation after 192 hours. Avermectin is used as positive control, and the triton water solution is used as blank control. The results of the activity of some compounds against Tetranychus urticae are shown in Table 3. The results of the mite-killing activity of some of the compounds are shown in Table d.
Evaluation of insecticidal Activity against Plutella xylostella (Plutella xylostella) and Clay (Mythimna separata)
And taking a culture dish, covering a layer of filter paper on the bottom of the dish, and dripping a proper amount of tap water to preserve moisture. After removing the surface wax layer from the cabbage leaves, cabbage leaf discs of approximately 6cm diameter are produced and placed back up in a petri dish. After the compound to be tested is dissolved by dimethyl sulfoxide (DMSO), the compound to be tested is diluted to a test concentration of 500mg/L by a triton aqueous solution, and the liquid medicine is uniformly sprayed on the front side and the back side of the leaf. After the leaves are naturally dried in the shade, the larvae of plutella xylostella or armyworm are inoculated, 3 times of repetition are carried out, avermectin is set as positive control, and the triton aqueous solution is set as blank control. The dishes were moved into standard viewing chambers (23-25 ℃, 40-60% RH). Test investigation was performed 72 hours after the treatment, the numbers of dead and live insects were recorded, and the mortality was calculated. The results of the insecticidal activity of some of the compounds are shown in Table d.
Table d results of determination of insecticidal Activity at 500mg/mL of partial Compound
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From the above experimental results, it can be seen that: the compound not only shows better bactericidal activity, but also has good or better activity on tetranychus urticae, tetranychus cinnabarinus, plutella xylostella and armyworm. For example, the compounds A1-41, A1-62, A4-41, A5-62, A7-62, A20-41, A12-42, A14-41, A15-41, A19-42, A21-62, A24-62, A36-65, A50-62, etc.
All documents mentioned in this application are incorporated by reference as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the claims appended hereto.

Claims (11)

1. A compound of formula I or formula I', or a geometric isomer, stereoisomer, or an agropharmaceutically acceptable salt or prodrug thereof,
in the method, in the process of the invention,
a is selected from R 1 Or R is 2 ；
R 1 Is unsubstituted or substituted C 6-14 An aryl group; r is R 1 Wherein said substitution means that hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: 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 radicals C 3-6 Cycloalkylthio, -CN, -NO 2 、-SO 2 R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and-SO 2 NR 3 R 4 ；
R 2 Is unsubstituted or substituted 5-14 membered heteroaryl; r is R 2 Wherein said substitution means that hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: 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 radicals C 3-6 Cycloalkylthio, -CN, -NO 2 、-SO 2 R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and-SO 2 NR 3 R 4 ；
R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Each independently selected from the group consisting of substituted or unsubstituted: hydrogen, halogen, cyano, NO 2 、COR m 、COOR m 、OCOR m 、CONR n R m 、SO 2 NR n R m 、C 1-6 Alkyl, C 1-6 Heteroalkyl, C 1-6 Alkoxy, C 1-6 alkyl-S-, C 3-6 Cycloalkyl, 3-6 membered heterocyclyl, C 6-14 Aryl, 5-14 membered heteroaryl; wherein said substitution means by one or more R a Substitution;
alternatively, R 3 And R is 4 Together with the N atom to which they are attached form a substituted or unsubstituted 3-6 membered heterocyclic group; wherein said substitution means by one or more R a Substitution;
alternatively, R 5 And R is 6 Together with the C atom to which they are attached form a substituted or unsubstituted C 4-8 Cycloalkyl or substituted or unsubstituted 4-8 membered heterocyclyl; wherein said substitution means by one or more R a Substitution;
alternatively, R 6 And R is 7 Together with the C atom to which they are attached form a substituted or unsubstituted C 4-8 Cycloalkyl or substituted or unsubstituted 4-8 membered heterocyclyl; wherein said substitution means by one or more R a Substitution;
alternatively, R 7 And R is 8 Together with the C atom to which they are attached form a substituted or unsubstituted C 4-8 Cycloalkyl or substituted or unsubstituted 4-8 membered heterocyclyl; wherein said substitution means by one or more R a Substitution;
alternatively, R 8 And R is 9 Together with the C atom to which they are attached form a substituted or unsubstituted C 4-8 Cycloalkyl or substituted or unsubstituted 4-8 membered heterocyclyl; wherein said substitution means by one or more R a Substitution;
R n and R is m Each independently selected from the group consisting of: hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclyl, C 6-14 Aryl, 5-14 membered heteroaryl;
R a each independently selected from the group consisting of: hydrogen, halogen, C 1-6 Alkyl, C 1-6 Alkoxy, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl, halo C 2-6 Alkenyl, halo C 2-6 Alkynyl, C 1-6 Alkylthio, C 3-6 Cycloalkoxy radicals C 3-6 Cycloalkylthio, -CN, -NO 2 Oxo, C 3-7 Cycloalkyl, 3-6 membered heterocyclyl, -n=n-phenyl, SO 2 R 3 、-COR 3 、-COOR 3 、-CONR 3 R 4 and-SO 2 NR 3 R 4 Wherein the phenyl group in-n=n-phenyl may be substituted with one or more groups selected from the group consisting of: halogen, -CN, -NO 2 、C 1-6 Alkyl, C 1-6 Alkoxy, halo C 1-6 Alkyl, halogenated C 1-6 An alkoxy group.
2. A compound of claim 1, or a geometric isomer, stereoisomer, or an agropharmaceutically acceptable salt or prodrug thereof, wherein a is selected from the group consisting of substituted or unsubstituted: phenyl, naphthyl, thiazolyl, thiadiazolyl, isothiazolyl, tetrazolyl, pyridinyl, thiomorpholin-S-oxide, thiomorpholin-S, S-oxide, pyrimidinyl, indole, quinoline, isoquinoline, pyridazinyl, pyrazinyl, triazinyl, thienyl, oxazolyl, oxadiazolyl, isoxazolyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl; wherein, the substitution means that hydrogen on the group is substituted by 1-5 groups selected from the following groups: halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-7 Cycloalkyl, C 1-6 Alkoxy, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkoxy radicals C 3-6 Cycloalkylthio, CN, NO 2 、SO 2 R 3 、COR 3 、COOR 3 、CONR 3 R 4 And SO 2 NR 3 R 4 ；R 3 And R is 4 Each independently selected from the group consisting of: hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclyl.
3. A compound I according to claim 1 or 2, or a geometric isomer, a stereoisomer, or an agropharmaceutically acceptable salt or prodrug thereof, wherein a is selected from:
In the method, in the process of the invention,
g is independently 0, 1, 2, 3, 4 or 5;
each R' is independently selected from the group consisting of: hydrogen, halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-7 Cycloalkyl, C 1-6 Alkoxy, halo C 1-6 Alkyl, halogenated C 1-6 Alkoxy, C 1-6 Alkylthio, C 3-6 Cycloalkoxy radicals C 1-6 Alkylthio, C 3-6 Cycloalkylthio, CN, NO 2 、SO 2 R 3 、COR 3 、COOR 3 、CONR 3 R 4 And SO 2 NR 3 R 4 ；
R 3 And R is 4 Each independently selected from the group consisting of: hydrogen, C 1-6 Alkyl, C 3-6 Cycloalkyl, 3-6 membered heterocyclyl.
4. A compound I according to any one of claims 1 to 3, or a geometric isomer, a stereoisomer, or an agropharmaceutically acceptable salt or prodrug thereof, wherein a is selected from:
5. the compound I of any one of claim 1 to 4, or a geometric isomer, a stereoisomer thereof, or an agropharmaceutically acceptable salt or prodrug thereof,selected from->
Wherein R 'is' 5 、R’ 6 、R’ 7 、R’ 8 、R’ 9 Each independently selected from the group consisting of substituted or unsubstituted: hydrogen, halogen, cyano, NO 2 、COR m 、COOR m 、OCOR m 、CONR n R m 、SO 2 NR n R m 、C 1-6 Alkyl, C 1-6 Heteroalkyl, C 1-6 Alkoxy, C 1-6 alkyl-S-, C 3-6 Cycloalkyl, 3-6 membered heterocyclyl, C 6-14 Aryl, 5-14 membered heteroaryl; wherein said substitution means by one or more R a Substitution;
the B ring, C ring, D ring and E ring are each independently selected from substituted or unsubstituted C 4-8 Cycloalkyl or substituted or unsubstituted 4-8 membered heterocyclyl; wherein said substitution means by one or more R a Substitution;
preferably, the method comprises the steps of,selected from: />
R 5 、R 6 、R 7 、R 8 、R 9 、R n 、R m And R is a Is defined as in claim 1.
6. A compound I as defined in any one of claims 1 to 5, or a few thereofWhich isomer, stereoisomer, or a pharmaceutically acceptable salt or prodrug thereof, is characterized by R 5 、R 6 、R 7 、R 8 、R 9 Having the definition as shown in table a.
7. The compound I, or a geometric isomer, a stereoisomer, or an agropharmaceutically acceptable salt or prodrug thereof, of any one of claims 1 to 6, wherein the compound is selected from the group consisting of:
in the formulae, R 5 、R 6 、R 7 、R 8 、R 9 Having the definitions as shown in Table a
Table a
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8. A process for the preparation of a compound according to claim 1, or a geometric isomer, a stereoisomer, or an agropharmaceutically acceptable salt or prodrug thereof, comprising the steps of:
wherein L is methoxy, ethoxy or Cl, A, R 5 、R 6 、R 7 、R 8 、R 9 Is defined as in claim 1;
(s 1) reacting the compound II-1 with the compound II-2 in an inert solvent in the presence of a base to obtain the compound of formula I.
9. The use of a compound according to any one of claim 1 to 7, or a geometric isomer, a stereoisomer thereof, or an agropharmaceutically acceptable salt or prodrug thereof,
(i) Can be used for preventing and treating at least one plant disease of anthracnose, leaf spot disease, rust disease, powdery mildew, banded sclerotial blight, leaf blight, gray mold, southern blight, damping off, scab, holothurian and target spot disease caused by infection of rhizoctonia, spore dish fungus, pseudoperonospora, monad rust fungus, phaeobasidium, pythium and the like;
(ii) Can be used for killing and/or preventing and controlling at least one pest and/or nymph and/or ovum of Acarina, symphytales, lepidoptera, coleoptera, hymenoptera, diptera, flea and plant parasitic nematodes;
(iii) For killing bacteria and/or mites and/or insects; and/or
(v) For preparing a composition or formulation for killing bacteria and/or mites and/or insects.
10. A composition comprising (i) as active ingredient a compound according to any one of claims 1 to 7, or a geometric isomer, stereoisomer, or a pharmaceutically acceptable salt or prodrug thereof; and (ii) a carrier and/or surfactant.
11. A method of killing bacteria and/or mites and insects comprising the steps of: contacting a fungus and/or mite, a pest with an effective amount of a compound according to any one of claims 1-7, or a geometric isomer, stereoisomer, or an agropharmaceutically acceptable salt or prodrug thereof, or a composition according to claim 10.
CN202211007536.7A 2022-08-22 2022-08-22 Ketone nitrile compound and preparation method and application thereof Pending CN117658935A (en)

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