CN115304510B - Aryl substituted meta-diamide compound or salt and composition thereof acceptable as pesticides and application thereof - Google Patents

Aryl substituted meta-diamide compound or salt and composition thereof acceptable as pesticides and application thereof Download PDF

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CN115304510B
CN115304510B CN202211108965.3A CN202211108965A CN115304510B CN 115304510 B CN115304510 B CN 115304510B CN 202211108965 A CN202211108965 A CN 202211108965A CN 115304510 B CN115304510 B CN 115304510B
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nematodes
compound
salt
acceptable
reaction
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CN115304510A (en
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葛家成
胡堂路
邱佳鹏
李丽
邢阳阳
孙鹏
张亚弢
张永芳
王伟香
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Hailir Pesticides and Chemicals Group Co Ltd
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Hailir Pesticides and Chemicals Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P5/00—Nematocides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

Abstract

The invention belongs to the field of pesticides, and in particular relates to an aryl substituted meta-diamide compound or an acceptable salt, a composition and application thereof as pesticides, wherein the compound has a structure shown in a formula (I):

Description

Aryl substituted meta-diamide compound or salt and composition thereof acceptable as pesticides and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a metadiamide compound or a salt and a composition thereof which are acceptable as pesticides, and application of the compound or the salt and the composition thereof which are acceptable as pesticides.
Background
Bisamide pesticides and metadiamide pesticides are hot spots in the pesticide research field of various large agricultural chemical enterprises in recent years, and under the condition that the problem of resistance of the bisamide pesticides is increasingly serious, the insecticidal activity of the metadiamide compounds arouses the attention of pesticide researchers, for example, CN102119143B reports a series of metadiamide compounds and insecticidal activities thereof, discloses compounds CK1 (compound numbers: 7-1431), CK2 (compound numbers: 7-1442), CK3 (compound numbers: 7-1459) and CK4 (compound numbers: 7-1574), and discloses insecticidal activities of the compounds, wherein CK4 (ISO common names of brofilolide and Chinese common names of bromofluorobenzene bisamide) and CK5 (Chinese names of cyclopropane flubendiamide) have been commercialized; in addition, other metadiamide compounds are also disclosed in the prior art, and the specific structure is as follows:
although the current commercial metadiamide compounds can overcome the problem of the resistance of the diamide compounds to a certain extent, along with the continuous improvement of the use requirements of pesticides in reality, the development of more efficient pesticides still has to be solved.
Technical problem
In order to solve the problems in the prior art, the invention provides an aryl substituted meta-diamide compound or a salt, a composition and application thereof which are acceptable as pesticides, has excellent lasting effect and quick-acting performance on killing pests, and is not easy to generate interactive resistance with the existing diamide compound.
Technical solution
The technical scheme adopted by the invention for achieving the purpose is as follows: an aryl substituted metadiamide compound or a salt thereof which is acceptable as pesticide, and the structural formula is shown as formula (I):
in the formula (I), R 1 、R 2 、R 3 Are independently selected from H, halogen, CN, C 1 -C 6 Alkyl, halogenated C 1 -C 6 Alkyl or C 3 -C 6 Cycloalkyl;
R 4 is C 1 -C 6 An alkylene group;
R 5 selected from H, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, halo C 1 -C 6 Alkyl, CN substituted C 1 -C 6 Alkyl or C 3 -C 6 Cycloalkyl-substituted C 1 -C 6 An alkyl group;
G 1 、G 2 each independently selected from O or S;
X 1 、X 2 independently selected from H, F, CN or NO 2 ，X 1 、X 2 Not simultaneously H;
q is selected from aryl or heteroaryl substituted with a substituent or unsubstituted.
Further, in formula (I), R 1 、R 2 Are independently selected from H, halogen, CN, C 1 -C 4 Alkyl, halogenated C 1 -C 4 Alkyl or C 3 -C 6 Cycloalkyl, R 3 Is halogenated C 3 -C 6 An alkyl group;
further, R 1 、R 2 Are each independently selected from H, F, cl, br, CN, me, et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CF 3 、CHF 2 、CH 2 F、CCl 3 、CHCl 2 、CH 2 Cl, cyclopropaneA radical, cyclobutyl, cyclopentyl or cyclohexyl, R 3 Is halogenated C 3 -C 4 An alkyl group;
still further, R 1 、R 2 Are independently selected from Br, I, CF 3 ，R 1 、R 2 Identical or different, R 3 Is heptafluoroisopropyl or nonafluoro-2-butyl.
Further, in formula (I), R 4 Selected from-CH 2 -or-CH 2 CH 2 -；
R 5 Selected from H, me, et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, cyclopropane substituted methyl or cyclopropane substituted ethyl;
further, R 5 Selected from Me, et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu or t-Bu.
Further, in formula (I), X 1 、X 2 Are respectively and independently selected from H, F or CN, X 1 、X 2 And not H at the same time.
Further, in formula (I), G 1 、G 2 All are O; or, G 1 S, G of a shape of S, G 2 Is O.
Further, in formula (I), Q is selected from phenyl, pyridyl, thienyl, furyl or pyrazolyl substituted with 1-3 substituents or unsubstituted;
further, the substituents are selected from F, cl, br, CN, me, et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CF 3 、 CHF 2 、CH 2 F、CCl 3 、CHCl 2 、CH 2 Cl, cyclopropane, cyclobutane, cyclopentane or cyclohexane.
Further, formula (I) is:
the salt which is acceptable as pesticide can be a salt prepared by reacting the aryl substituted meta diamide compound of the invention with a chemically acceptable acid, wherein the chemically acceptable acid can be an inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid, etc.) or an organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid, etc.); the pesticide acceptable salt can also be a salt prepared by reacting the aryl substituted meta diamide compound of the invention with a chemically acceptable base, wherein the chemically acceptable base can be an inorganic base (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or an organic base (such as trimethylamine, triethylamine and the like).
Further, the salt which is acceptable as a pesticide may be potassium salt, sodium salt, ammonium salt, calcium salt, pyridinium salt, choline salt, hydrochloride, phosphate, acetate, benzenesulfonate or oxalate.
The invention also discloses an insecticidal composition, which comprises an insecticidal effective amount of at least one of aryl substituted metadiamides or salts thereof as pesticides; further, a formulation carrier or formulation aid is included.
The present invention also discloses a method for controlling plant pests comprising applying a pesticidally effective amount of at least one of the aryl substituted meta diamides as described above or as pesticidally acceptable salts thereof or of a pesticidal composition as described above to the crop or the pest and/or its habitat.
The invention also discloses the use of the aryl substituted meta diamides as described above or at least one of their pesticidally acceptable salts or the pesticidal compositions as described above for controlling plant pests in agriculture and other fields.
In the definition of the structural formula of the above compounds, the terms used have the following meanings:
halogen or halogen: refers to fluorine, chlorine, bromine and iodine.
C 1 -C 6 Alkyl: straight or branched alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl or n-butyl, isobutyl, sec-butyl, tert-butyl and the like.
Halogenated C 1 -C 6 Alkyl: having 1 to 6 carbon atomsStraight or branched alkyl groups, hydrogen atoms on these alkyl groups may be partially or wholly substituted with halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like.
The compounds of formula I of the present invention may be prepared by the following process, wherein the groups are as defined above, unless otherwise noted.
Further, the reaction may be carried out at normal pressure or high pressure, preferably at atmospheric pressure, and the post-treatment may be carried out according to a conventional method.
Further, the synthesis method of II is exemplified as follows:
further, the synthesis method of II "is exemplified as follows:
further, III is commercially available.
An insecticide comprising a compound represented by the formula (I) or a salt thereof as an active ingredient is suitable for controlling pests in soil in the fields of fruit trees, vegetables, other crops and ornamental plants.
Examples of pests to which the insecticide of the present invention can be applied include, but are not limited to, lepidopteran insects (Lepidoptera), such as Agrotis ypsilon, agrotis ypsum, kapok (Alabama argillacea), spodoptera littoralis (Angioptera virescens), argyresthia conjugella, spodoptera exigua (Autographa gamma), armyworm (Bupalustris), cacoecia murinana, capua reillulariana, cheimatobia brumata, picea verpa (Choristoneura fumiferana), choristoneura occidentalis, chilo suppressalis (Cirphosum), malus pumila (Cydia pomonella), pine moth (Dendrolimus pini), diahanitides, zea mays (Diatraea grandiosella), egyptian diamond back (Emeria insolana), nanmei corn borer (Elasmopalpus lignosellus), ligustrum lucidum (Eupoecilia ambiguella), evetria bolla, evetzia Feltia subterranea, heliothis armigera (Galleria mellonella), heliothis armigera (Grapholitha funebrana), heliothis armigera (Grapholitha molesta), heliothis armigera (Heliothis armigera), heliothis armigera (Heliothis virescens), heliothis zea (Heliothis zea), heliothis armigera (Heliluundalis), hibernia defoliaria, fangback white moth (Hyphantrichia sanguinea), malus pumila (Hyponomeutamarinlus), solanum lycopersicum (Keiferia lycopersicella), lambdina fiscellaria, spodoptera exigua (Laphygma exigua), phaeda (Leucoptera coffeella), leuconosteroides spinosa (Leucopia), lithocolletis blancardella, callicarpa vinifera (Lobesia botana), begonia (Loxostege sticticalis), lymantria dispar), fabricius (Lymantria monacha), fabricius, peach leaf moths (Lyonetia clerkella), yellow brown cabbage caterpillars (Malacosoma neustria), cabbage loopers (mamestraarassicae), yellow fir moths (Orgyia pseudotsugata), corn borers (Ostrinia nubilalis), small eye moths (panois flagera), cotton red bollworms (Pectinophora gossypiella), black-bone moths (Peridromasaucia), round palm moths (Phalera bucephala), potato moths (Phthorimaea operculella), citrus leaf moths (Phyllocnistis citrella), european butterflies (Pieris brasica), alfalfa noctuid (Plathypena scabra), plutella xylostella (Plutella xylostella), soybean moths (pseudoopsis luncis), rhyacionia frustrana, scrobipalpula absoluta, wheat moths (sitotragacerealela), grape leaf moths (Sparganothis pilleriana), spodoptera litura (spodoptera), sea ash moths (Spodoptera littoralis), prodenia litura (Spodoptera litura), thaumatopoea pityocampa, green oak moths (trichlida), trichosannthes (Zeiraphera canadensi);
beetles (Coleoptera), for example, the species of Amomum pyriformis (Agrilus sinuatus), amomum straight (Agriotes lineatus), amomum dulcis (Agriotes obscurus), amphimallus solstitialis, anisandrus dispar, amomum mexicam (Anthonomus grandis), amomum apple (Anthonomus pomorum), aphthona euphoridae, athous haemorrhoidalis, amomum betananus (Atomum lineis), amomum longum (Blastophagus piniperda), blitophaga undata, vicia faba (Bruchus rufimanus), pityrospermum peas (Bruchus pisorum), amomum European (Bruchus lentis), amomum apple (Byctiscus betulae), amomum betananum (Casssima) Cerotoma trifurcata, amomum aureobasilicum (Cetonia aureosa), amomum gracilomyces (Ceuthorrhynchus assimilis), withanum genkwa (Ceuthorrhynchus napi), amomum betananensis (Chaetocnema tibialis), amomum fasciatus (Confucus, amomum zetimum (Crioceris asparagi), ctricornutum longhorn beetle (Diabrotica longicornis), amomum longhorn beetle (5268), amomum tsetum roseum (52), leucas, leuca (52, leuca glabra (52) and Leuca (52), leuca glabra (52, leuca glabra (37), leucas well as, leuca (Leucum tsetum, leucum tsetum, leemanum, leucum tsetum, leucum 37) and Leucadenii (52., melanotus communis, oulmeyeriana (Meligethes aeneus), dahurian beetle (Melolontha hippocastani), aureobasidium (Melolontha melolontha), oulemaoryza (Oulmezzae), portugal beak (Ortiorrhynchus sulcatus), fragaria root beetle (Otiorrychusovatus), horseradish beetle (Phaedon cochleariae), phylobius pyri, phyllotretatarinowicepala, pogostemon She Sai (Phyllophaga sp.), fabricius rimonia, phylloperthiatus (Phyllotreta nemorum), soy light foot beetle (Phyllotreta virtuata), japanese beetle (Popillia japonica), pisum sativum (Sitona linetus) and Pogostemon (Sitophilus granaria);
flies, mosquitoes (Diptera), such as Aedes aegypti (Aedes aegypti), aedes albopictus (Aedes albopictus), aedes Aedes albopictus (Aedes vexans), drosophila mexicana (), anopheles pentadactyla (), anopheles albopictus (), anopheles glabra (), anopheles albopictus (Amylanthus), anopheles parvus (), anopheles suis (Amylanthus), anopheles suis (), anopheles cinematopsis, anopheles cinerea (Amylantha), anopheles (Amylantha sinensis), anopheles (Amylantha), and anopheles anopheles tetranychus (), red head drosophila (), medfly in the middle sea (), myiasis chrysomyia (Chrysomyabezziana), deer fly (), chrysops sibactea, gall midge (), culex pipiens (Culex pipiens), macitermes (), kumquat (), kid's-tail (kid's-tail) and the like anopheles tetranychus (), red head fly (), midge fly (), maggot fly (chrysomyabenzziana), deer fly (), chrysops siplae, gall midge (), culex spinosa (Culex pipiens), mosquito maciter (), schlieren (Hypoderma lineata), leptoconops torrens, vegetable leaf miner (Liriomyza sativae), american leaf miner (Liriomyza trifolii), lucilia camprina, microcephala (Lucilia cuprina), lucilia sericata (Lucilia seriata), lycoria pectoralis, mansonitiatidlanus, eriobotrya sinensis (Mayetiola destructor), autumn fly (Musca austenitalis), musca domestica (Musca omestinica), musca humicola (Muscina stabulans), yangji fly (Oestrus), opomyza florum, european wheat straw fly (Oscinella frat), henbane spring fly (Pegomya hysocyami) Phorbia anti-quat, turnip fly (Phorbia brassicae), phorbia coarctata, phlebotomus argentipes, psorocollumbiae, psila rosae, psorophora discolor, prosimulium mixtum, cherry fruit fly (Rhagoletis cerasi), apple fruit fly (Rhagoletis pomonella), red tail meat fly (Sarcophaga), bot (Sarcophaga), simulium vittatum, stable stings fly (stomoxyscalcitans), tabanus bovines (Tabanus bovines), tabanus atlus, tabanus lineola, tabanus similis, tipula oleracea, and European mosquito (Tipula panudosa);
thrips (Thysanoptera), such as frankliniella occidentalis (Dichromothrips corbetti), dichromothrips ssp, tabaci (Frankliniella fusca), frankliniella occidentalis (Frankliniella tritici), platycodon grandiflorum (Scirtothrips citri), thrips oryzae (threps oryzae), thrips palmi (threps palmi) and Thrips tabaci (threps tabaci);
termites (Isoptera), such as Calotermes flavicollis, leucotermes flavovipes, heterotermes aureus, yellow limb termites (Reticulitermes flavipes), southern termites (Reticulitermes virginicus), european termites (Reticulitermes lucifugus), black termites (Reticulitermes santonensis), reticulitermes grassei, termes natalensis, and termite termites (Coptotermes formosanus);
cockroaches (Blattaria) -blattadea, such as german cockroaches (Blattella germanica), blattella asahinae, american cockroaches (Periplaneta americana), japanese cockroaches (periplaneta japonica), brown cockroaches (Periplaneta brunnea), periplaneta fuligginosa, australian cockroaches (Periplaneta australasiae), and oriental cockroaches (Blatta orientalis);
bed bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), such as Lygus lucorum (Acrosternum hilare), lygus lucorum (Blissus leucopterus), lygus lucorum (cyrtophyllus) et al, lygus lucorum (Dysdercus cingulatus), dysdercus intermedius, lygus maculatus (Eurygaster integriceps), lygus lucorum (Euschistus impictiventris), lygus lucorum (Leptoglossus phyllopus), lygus lucorum (Lygus lineolaris), lygus lucorum (lygustatensis), lygus lucorum (Nezara virdula), lygus lucorum (Piesma quadat), solubeainsonii, thyanta perditor, acyrthosiphon onobrychis, myzus persicae (Adelslarcis), aphidula nasturtii, myzus persicae (Aphis fasciae), aphis pomis (Aphis pomi), aphis gossypii (Aphis fasyi), aphis hypoyi) North American tea seed aphid (), aphis chneideri, coil (Aphis spirocola), aphis sambuci, pisum sativum (Acyrthosphonplus), potato aphid (), silver leaf whitefly (), , apricot tail aphid (), , cabbage aphid (), , fir cone aphid (), spruce cone aphid (Dreyfusia picea), judge tail aphid (), , dysphisuri, broad bean micro leafhopper (Empoasca fabae), peach tail aphid (), hyperamyzus slacto, wheat long pipe aphid (), big long pipe aphid (), white pipe, rosa tube aphid (Macrosiphon rosae), megoura vicae, aphis nidus Vespae (Melanaphis pyrarius), myzus persicae (Metopolophium dirhodum), allium fistulosum aphid (Myzus ascalonicusDonc), myzuscerasi Li Liuya (Myzus varians), nasonovia rib-nigri, rice planthoppers (Nilaparotalugens), aphis spinosa (Pemphigus bursarius), nilaparvata lugens (Perkinsiella saccharicida), bulletia negundo (Phonodon humuli), phyllon psy (Psyla mali), myzus persicae (Myzus virens), myzus virginiana, nasovia japonica, nitroselis japonica, nilaparvata lupulus, and Orchium spinosum pear psyllium (psylli), allium wintergreen moth aphid (Rhopalomyzus ascalonicus), corn aphid (Rhopalosiphum maidis), cereal spillway aphid (Rhopalosiphum padi), rhopalosiphum insertum, sapphis mala, sapphis mali, wheat binary aphid (Schizaphis graminum), schizoneura lanuginosa, sitobion avena, white fly (Trialeurodes vaporariorum), toxoptera aurantiiand, grape root nodule aphid (viteustifolii), cimex lectularius, cimex hepteus, reduvius senilis, triatoma spp, and Arilus crittatus;
ants, bees, wasps, phyllostats (Hymenoptera), such as, for example, singapore (athaliarose), phyllostat (Atta cepalotes), atta capiguara, atta cepalotes, atta laevigata, atta robusta, atta sexdens, atta textana, lapa (crematoka), hopanada, holicopaminula, hoplocampa testudinea, black hair ants (Lasius niger), micromonomonomonomonospiralis, tropical fire ants (Solenopsis geminata), red fire ants (Solenopsis invicta), black fire ants (Solenopsis richteri), southern fire ants (Solenopsis xyloni), red ants (pogomyexbaatus), pogonomyrmex californicus, megacephalic ants (Pheidole megacephala), megacaryophyllata (Dasymutilla occidentalis), bumblebee (bumblena), megavesna (Vespa sqsa), paravespula vulgaris, paravespula germanica, 3765, and abrus (Campodontus floridanus), wasp and abrus (Campodontus floridanus);
cricket, grasshopper, locust (Orthoptera), such as living house Ai Xi (Acheta domestica), mole cricket (Gryllotalpa gryllotalpa), migratory locust (Locusta migratoria), black locust bifidus (melanoplus bivittatus), black locust rubrum (Melanoplus femurrubrum), black locust melanoplasmoschus (melanoplospost), black locust migratory (Melanoplus sanguinipes), black locust rubra (Melanoplus spretus), striped red locust (Nomadacris septemfasciata), desert locust america (Schistocerca americana), desert locust africana (Schistocerca gregaria), morgans locust (Dociostaurus maroccanus), court range (Tachycines asynamorus), small locust in caucasia (Oedaleus senegalensis), bologna locust (Zonozerus variegatus), hieroglyphus daganensis, kraussaria angulifera, italian locust (Calliptamus italicus), calamus (Chortoicetes terminifera) and brown locust (Locustana pardalina);
arachnoidea (Arachnoidea), such as arachnids (Acarina), e.g., soft ticks (Argasidae), hard ticks (Ixodidae) and sarcopticae (Sarcoptidae), such as long star ticks (Amblyomma americanum), tropical flower ticks (Amblyomma variegatum), ambryomma maculatum, bossima sharp ticks (Argas personas), niu Bishi (Boophilus annulatus), boophilus decoloratus, microcow ticks (Boophilus microplus), dermacentor silvarum, anchus angustifous (Dermacentor andersoni), dermata americana (Dermacentor variabilis), hyalomma truncatum, castor hard ticks (Ixodes ribus), ixodes rubicundus, black foot hard ticks (Ixodes scapularis), full ring hard ticks (Ixodes holocyclus), pacific hard ticks (Ixodes), ornithodorus moubata, ornithodorus hermsi, ornithodorus turicata, platycladus fowl spike (Ornithonyssus bacoti), tobinini, gallica, sheep scabies (Psoosis), phalophilus, and Phalophilus, such as Phalocrocis, and Phalocrocis (Rhipicephalus sanguineus, 6342, phalocrocis, and Phalops; the genus Acarina (Tarsonemidae), such as Phytonemus pallidus and Tarsonius paraplectania (Polyphagotarsonemus latus); acarina (Tenuipalpidae), such as Acarina rhodochrous (Brevipalpus phoenicis); tetranychidae, such as Tetranychus cinnabarinus (Tetranychus cinnabarinus), tetranychus (Tetranychus kanzawai), tetranychus urticae (Tetranychus parcificus), tetranychus gossypii (Tetranychus telarius) and Tetranychus urticae (Tetranychus urticae), tetranychus urticae (Pannychus ulmi), tetranychus kangarcinus (Pannychus citri) and Oligonychus pratensis; arachnids (Araneida), such as erythema Kou Zhu (Latrodectus mactans) and brown spider (Loxosceles reclusa);
fleas (Siphonaptera), such as cat fleas (Ctenocephalides felis), dog fleas (Ctenocephalides canis), rat fleas (Xenopsylla cheopis), itch causing fleas (Pulex iritans), skin penetrating daphnia (tunea penetrans), and fleas with diseases (Nosopsyllus fasciatus);
tuna, tuna (Thysanura), such as western tuna (Lepisma saccharina) and plagionella (Thermobia domestica), polyporus (cheilopoda), such as Scutigera coleoptrata, polyporus (biplopoda), such as Narceus spp,
octopus vulgaris (Dermaptera), such as Forficula auricularia (forficula auricularia), lice (Mao Shimu (Phyirastera)), such as human head lice (Pediculus humanus capitis), human lice (Pediculus humanus corporis), pubic lice (Pthirus pubis), bovine blood lice (Haematopinus eurysternus), porcine blood lice (Haematopinus suis), niu Eshi (Linognathus vituli), bovicobaboovis, chicken lice (Menopon gallina), menacanthus stramineus and Solenopotes capillatus;
the order of the Carthamus (Collembola), for example, the genus echinochloa (Onychurus).
They are also suitable for controlling nematodes: plant parasitic nematodes such as root-knot nematodes, northern root-knot nematodes (Meloidogyne), southern root-knot nematodes (Meloidogyne incognita), java root-knot nematodes (Meloidogyne javanica) and other root-knot nematodes (Meloidogyne); cyst-forming nematodes, golden potato nematodes (globodendron stonensis) and other sacculus species (Globodera); grass Gu Bao cyst nematodes (Heterodera avenae), soybean cyst nematodes (Heterodera glycines), beet cyst nematodes (Heterodera schachtii), clover cyst nematodes (Heterodera trifolii) and other cyst nematodes (hetedodera); goiter seed, granatum (Anguina); stem and leaf nematodes, aphelenchoides (Aphelenchoides); spiny nematodes, weed spiny nematodes (belonolausoniudus) and other spiny nematodes (Belonolaimus); pine nematodes, pine wood nematodes (Bursaphelenchus xylophilus) and other Bursaphelenchus species (Bursaphelenchus); the species of the genus strongylus (cricondencma), the species of the genus strongylus (cricondencella), the species of the genus strongylus (cricondenchoides), the species of the genus strongylus (mesocrycronecma); corm nematodes, rotting nematodes (Ditylenchus destructor), sweet potato nematodes (Ditylenchus dipsaci) and other stem nematodes (Ditylenchus); trypanosoma, trypanosoma (dolichorrus); spiraling nematodes, heliocotylenchus multicinctus and other genera helicobacter; sheath and sheath nematodes, sheath and semi-round nematodes (Hemicelliophora) and Hemicentrotus (Hemicinecoat); the genus Trichinella (Hirshmanniella); crown nematodes, gun nematodes (Hoplolaimus); pseudoroot-knot nematodes, pearl nematodes (nacobus); needle nematodes, long-shank nematodes (Longidorus elongatus) and other long-shank nematodes (Longidorus); root rot nematodes, pratylenchus neglectus, piercing root rot nematodes (Pratylenchus), pratylenchus curvitatus, whole body nematodes (Pratylenchus goodeyi) and other root rot nematodes (Pratylenchus); radopholus, radopholus (Radopholus similis) and other Radopholus; reniform nematodes, spiral nematodes (Rotylenchus robustus) and other reniform nematodes (Rotylenchus); scutellonema genus; root-worm, prader (Trichodorus primitivus) and other Bursaphelenchus (Trichodorus); genus quasi-burring (Paratricrodorus); blocking long nematodes, purslane dwarfing nematodes (Tylenchorhynchus claytoni), cis-trans dwarfing nematodes (Tylenchorhynchus dubius) and other dwarfing nematodes (tyrenchonchus); citrus nematodes, hemipiercing nematodes (tyrencchulus); caenorhabditis, the genus caenorhabditis (Xiphinema); and other plant parasitic nematodes.
They can also be used for controlling arachnids (arachnidae), such as acarina (Acarina), for example Soft ticks, hard ticks and scabies, such as Alternaria longifolia (Amblyomma americanum), alternaria tropicalis (Amblyomma variegatum), rhaponticus aculeatus (Argas persicus), niu Bishi (Boophilus annulatus), boophilus decoloratus, rhapontici (Boophilus microplus), dermacentor silvarum, hyalomma truncatum, hard castor bean ticks (Ixodes), ixodes rubicundus, ornithodorus moubata, otobius megnini, dermatophagoides pteronyssinus (Dermanyssus gallinae), sheep scabies (Psorophtes ovis), rhipicephalus appendiculatus, rhipicephalus evertsi, human scabies (Sarcoptes scabiei), and goiter (Eriopyidae), such as Rhizopus apple (Aculus schlechtendali), phyllocoptrata oleivora and Eriophyes sheldoni; the genus Tetranychus (Tarsonemidae), such as Phytonemus pallidus and Tarsonemus lateral (Polyphago tarsonemuslatus); acarina (Tenuipalpidae), such as Acarina rhodochrous (Brevipalpus phoenicis); tetranychidae, such as Tetranychus cinnabarinus (Tetranychus cinnabarinus), tetranychus kanzawai, tetranychus pacificus (Tetranychus pacificus), tetranychus gossypii (Tetranychus telarius) and Tetranychus urticae (Tetranychus urticae), tetranychus urticae (Panonechus ulmi), tetranychus kangari (Panonechus citri) and oligonychus pratensis.
The plant object used for the insecticide of the present invention is not particularly limited; mention may be made of, for example, cereals (e.g., rice, barley, wheat, rye, oat, corn, sorghum, etc.), beans (soybean, bean, broad bean, pea, peanut, etc.), fruit trees/fruits (apple, citrus, pear, grape, peach, japanese apricot, cherry, walnut, apricot, banana, strawberry, etc.), vegetables (cabbage, tomato, spinach, broccoli, lettuce, onion, welsh onion, green pepper, etc.), root vegetables (carrot, potato, sweet potato, radish, lotus root, turnip, etc.), industrial crops (cotton, hemp, paper mulberry, roses, rape, beet, hops, sugarcane, sugar beet, olive, rubber, coffee, tobacco, tea, etc.), berries (pumpkin, cucumber, watermelon, melon, etc.), pastures (grasses, milo, alfalfa, grass, bentgrass, etc.), spices, etc., crops (lavender, rosemary, thyme, pepper, thyme, celery, flowers, chrysanthemum, etc.), flowers, roses, etc.
Advantageous effects
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
by chemical modification and molecular design of the compound with the metadiamide structure, the structure of ether is introduced into N of the amide group, so that a series of compounds which are more efficient and can be used for agricultural or forestry disinsection and have excellent activity are obtained, and particularly, the compounds have quick-acting and lasting disinsection activity at low dosage.
Embodiments of the invention
The technical solutions in the embodiments of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
By comprehensively considering the economy, diversity and bioactivity of the synthesized compounds, it is preferred that some of the compounds are listed in the following table. Specific compound structures are shown in tables 1 to 2, and specific compound physical property data are shown in table 3. The compounds of tables 1-3 are only for better illustration of the present invention and are not meant to limit the present invention, and those skilled in the art should not understand that the scope of the above subject matter of the present invention is limited to the following compounds.
In the structure shown in formula I, X 1 F, X of a shape of F, X 2 For H, the specific structure is shown in Table 1:
TABLE 1 Structure of Compounds of formula I
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In the structure shown in formula I, X 1 Is CN, X 2 For H, the specific structure is shown in Table 2:
TABLE 2 Structure of Compounds of formula I
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In the structure shown in formula I, X 1 H, X of a shape of H, X 2 For F, the specific structure is shown in Table 3:
TABLE 3 Structure of Compounds of formula I
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TABLE 4 Table 4 1 H NMR data
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The process for preparing the compounds of the present invention is illustrated in the following schemes and examples. The starting materials are commercially available or can be prepared by methods known in the literature or as shown in detail. Those skilled in the art will appreciate that other synthetic routes may also be used to synthesize the compounds of the present invention. Although specific starting materials and conditions in the synthetic routes have been described below, they may be readily replaced with other similar starting materials and conditions, and modifications or variations of the preparation methods of the present invention, such as various isomers of the compounds, are included within the scope of the present invention. In addition, the preparation methods described below may be further modified in accordance with the present disclosure using conventional chemical methods well known to those skilled in the art. For example, protection of the appropriate groups during the reaction, and the like.
Example 1
Preparation of Compound I-1:
(1) Preparation of 2-bromo-4- (heptafluoropropane-2-yl) -6- (trifluoromethyl) aniline:
FeSO was added to a dry 500mL single-necked flask 4 ·7H 2 O (11.68 g,0.042 mol) is dissolved in 42mL of water, 240mL of DMSO, O-trifluoromethylaniline (19.33 g,0.12 mol) and 2-heptafluoroiodopropane (46.18 g,0.156 mol) are sequentially added under stirring at room temperature, 12mL of concentrated sulfuric acid is dropwise added, 28mL of hydrogen peroxide is slowly dropwise added, LC-MS monitoring reaction is carried out after the dropwise addition is completed, 120mL of saturated saline solution and 300mL of ethyl acetate are added after the reaction is completed, the organic phase is collected, anhydrous sodium sulfate is dried, filtered, concentrated under reduced pressure and dissolved in 200mL of DMF, NBS (23.50 g,0.13 mol) is added, stirring is carried out for 1h at 60 ℃, 100mL of saturated sodium chloride aqueous solution is added after the reaction is completed, 150mL of dichloromethane is used for extraction three times, the organic phase is combined, anhydrous sodium sulfate is dried, concentrated under reduced pressure, and the product is separated through column chromatography (leaching solution is petroleum ether: ethyl acetate=50:1), thus obtaining the target product (32.08 g, the yield is 81%) as yellow oily liquid).
(2) Preparation of N- (2-bromo-4- (heptafluoropropane-2-yl) -6- (trifluoromethyl) phenyl) -2-fluoro-3-nitrobenzamide:
in a dry 500mL single-neck flask was added 2-fluoro-3-nitrobenzoic acid (20.35 g,0.11 mol), dissolved in 200mL dichloromethane, and 4 drops of DMF was added dropwise, oxalyl chloride (16.76 g,0.132 mol) was slowly added dropwise under ice-water bath, stirred at room temperature for 3h, LC-MS monitored reaction, after the reaction was completed, concentrated under reduced pressure, and dissolved in 20mL acetonitrile for use. The product of the first step was added to a dry 500mL single-neck flask, dissolved with 200mL acetonitrile, KI (3.87 g,0.023 mol) was added, a 2-fluoro-3-nitrobenzoyl chloride acetonitrile solution was slowly added dropwise to the reaction system under stirring at room temperature, stirring was carried out for 20h at 85 ℃, the reaction was monitored by lc-MS, after the reaction was completed, the reaction was concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=5:1) to obtain the objective product (37.94 g, yield: 68%) as a yellow oily liquid.
(3) Preparation of 3-amino-N- (2-bromo-4- (heptafluoropropane-2-yl) -6- (trifluoromethyl) phenyl) -2-fluorobenzamide:
stannous chloride dihydrate (44.68 g, 0.198mol) was added to a dry 500mL single-necked flask, dissolved in concentrated hydrochloric acid, and the second-step product was dissolved in 80mL methanol and added dropwise to the reaction system. The reaction mixture was heated to 60 ℃ and reacted for 3h, the reaction was monitored by lc-MS, after the reaction was completed, the PH was adjusted to 8-9 with aqueous sodium hydroxide solution, a large amount of solids were precipitated, filtered off with suction, concentrated under reduced pressure, extracted with ethyl acetate, dried, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=4:1) to give the desired product (33.08 g, yield 92%) as a yellow solid.
(4) Preparation of N- (2-bromo-4- (fluoropropane-2-yl) -6- (trifluoromethyl) phenyl) -2-fluoro-3- (methoxymethyl) amino) benzamide:
a dry 500mL single-neck flask was charged with the third step (5.44 g,0.01 mol), dissolved in DMF, added with potassium carbonate (2.76 g,0.02 mol), and bromomethyl ether (1.87 g,0.015 mol) with stirring at room temperature, heated to 100deg.C after the addition, reacted for 6h, monitored by LC-MS, after the reaction was completed, extracted three times with ethyl acetate, concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=2:1) to give the desired product (4.32 g, 73.4% yield) as a yellow solid.
(5) Preparation of Compound I-1:
compound intermediate III-1 (1.85 g,0.013 mol), toluene (35 mL) were added to a dry 100mL single-necked flask, compound intermediate II-1 (7.06 g,0.012 mol) was added with stirring at room temperature, the reaction mixture was heated to 90 ℃, the reaction was monitored by lc-MS, after the reaction was completed, concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=5:1) to give the objective product I-1 (5.18 g, 62.4%). 1 H NMR(500MHz,Chloroform-d)δ8.42-8.30(m,1H),8.08(s,1H),8.02-7.7.91(d, J＝2.0Hz,1H),7.88-7.82(d,J＝2.2Hz,1H),7.79-7.67(m,3H),7.63-7.58(m,1H),7.42-7.35(m,3H),5.31(s,2H),3.67(s,3H).
Example 2
Preparation of Compound I-27:
(1) Preparation of N- (2-bromo-4- (fluoropropane-2-yl) -6- (trifluoromethyl) phenyl) -2-fluoro-3- (methoxyethyl) amino) benzamide:
a dry 500mL single-neck flask was charged with the product of the third step of example 1 (5.44 g,0.01 mol), dissolved in DMF, potassium carbonate (2.76 g,0.02 mol) was added with stirring at room temperature and chloromethyl ether (1.42 g,0.015 mol), heated to 100deg.C after the addition, reacted for 6h, monitored by LC-MS, after the reaction was completed, extracted three times with ethyl acetate, concentrated under reduced pressure, and the product was isolated by column chromatography (eluent: petroleum ether: ethyl acetate=2:1) to give the desired product (4.03 g, 66.9% yield) as a yellow solid.
(2) Preparation of Compound I-27:
compound intermediate III-27 (2.72 g,0.016 mol), toluene (30 mL) was added to a dry 100mL single-necked flask, compound intermediate II-2 (9.05 g,0.015 mol) was added with stirring at room temperature, the reaction mixture was heated to 90 ℃, the reaction was monitored by lc-MS, after the reaction was completed, concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=5:1) to give the objective product I-27 (7.34 g, 67%). 1 H NMR(500MHz,Chloroform-d)δ8.21(s,4H),8.08(m,2H),8.02-7.94(d,J＝2.0 Hz,1H),7.92-7.86(d,J＝2.2Hz,1H),7.75-7.63(m,1H),7.51-7.39(m,1H),5.44(s,2H),3.62-3.51(m,2H),1.18(t,J＝6.2Hz,3H).
Example 3
Preparation of Compound I-97:
(1) Preparation of 2, 6-dibromo-4- (heptafluoropropane-2-yl) aniline:
FeSO was added to a dry 500mL single-necked flask 4 ·7H 2 O (19.46 g,0.07 mol) is dissolved in 40mL of water, 350mL of DMSO,2, 6-dibromoaniline (50.18 g,0.2 mol) and 2-heptafluoroiodopropane (69 g,0.25 mol) are added in sequence, 40mL of hydrogen peroxide is slowly added dropwise at room temperature, stirring is carried out at room temperature, LC-MS monitoring reaction is carried out, after the reaction is finished, 250mL of saturated saline solution and 400mL of ethyl acetate are added for extraction for 4 times, an organic phase is collected, anhydrous sodium sulfate is dried, filtered and subtractedThe product was isolated by column chromatography (petroleum ether: ethyl acetate=50:1) to give the desired product (72.72 g, 87.2% yield) as a yellow solid.
(2) Preparation of 3-amino-N- (2, 6-dibromo-4- (heptafluoropropane-2-yl) phenyl) -2-fluorobenzamide preparation of N- (2, 6-dibromo-4- (perfluoropropyl-2-yl) phenyl) -2-fluoro-3-nitrobenzamide:
in a dry 500mL single-neck flask was added 2-fluoro-3-nitrobenzoic acid (38.72 g,0.209 mol), dissolved in 300mL dichloromethane, and 4 drops of DMF was added dropwise, oxalyl chloride (29.21 g,0.23 mol) was slowly added dropwise under ice-water bath, stirred at room temperature for 3h, LC-MS monitored reaction, after the reaction was completed, concentrated under reduced pressure, and dissolved in 30mL acetonitrile for use. The product of the first step was added to a dry 500mL single-neck flask, dissolved with 300mL acetonitrile, KI (6.97 g,0.042 mol) was added, a 2-fluoro-3-nitrobenzoyl chloride acetonitrile solution was slowly added dropwise to the reaction system under stirring at room temperature, stirring was performed for 20h at 85 ℃, the reaction was monitored by lc-MS, after the reaction was completed, the reaction was concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=5:1) to obtain the objective product (91.4 g, yield: 91.3%) as a yellow solid.
(3) Preparation of 3-amino-N- (2, 6-dibromo-4- (heptafluoropropane-2-yl) phenyl) -2-fluorobenzamide:
stannous chloride dihydrate (107.79 g,0.478 mol) was added to a dry 500mL single-necked flask, dissolved in concentrated hydrochloric acid, and the second-stage product was dissolved in 150mL methanol and added dropwise to the reaction system. The reaction mixture was heated to 60 ℃ and reacted for 3h, the reaction was monitored by lc-MS, after the reaction was completed, the PH was adjusted to 8-9 with aqueous sodium hydroxide solution, a large amount of solids were precipitated, filtered off with suction, concentrated under reduced pressure, extracted with ethyl acetate, dried, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=4:1) to give the desired product (82.3 g, yield 93.3%) as a yellow solid.
(4) Preparation of N- (2, 6-dibromo-4- (heptafluoropropane-2-yl) phenyl) -2-fluoro-3- (methoxymethyl) amino) benzamide:
a dry 500mL single-neck flask was charged with the third step (5.54 g,0.01 mol), dissolved in DMF, potassium carbonate (2.76 g,0.02 mol) was added with chloromethyl methyl ether (1.21 g,0.015 mol) under stirring at room temperature, heated to 100deg.C after the addition, reacted for 6h, monitored by LC-MS, after the reaction was completed, extracted three times with ethyl acetate, concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=2:1) to give the desired product (4.24 g, yield 71.2%) as a yellow solid.
(5) Preparation of Compound I-97:
compound intermediate III-97 (3.5 g,0.022 mol), toluene (50 mL) were added to a dry 100mL single-necked flask, compound intermediate II-4 (11.96 g,0.02 mol) was added with stirring at room temperature, the reaction mixture was heated to 90 ℃, the reaction was monitored by lc-MS, after the reaction was completed, concentrated under reduced pressure, and the product was separated by column chromatography (eluent: petroleum ether: ethyl acetate=5:1) to obtain the objective product I-97 (8.99 g, 62.3%). 1 H NMR(500MHz,Chloroform-d)δ9.36-9.24(d,J＝1.9Hz,1H),8.54(s,1H), 8.31-8.25(m,1H),8.10(m8.17-8.09,1H),7.89(s,2H),7.82-7.73(m,1H),7.47-7.39(m,1H),7.22(t,J＝8.1Hz,1H),5.24(s,2H),3.67(s,3H).
Example 4
Preparation of the preparation:
1. soluble liquid: 10-50% of the compound of formula (I) and 5-20% of a wetting agent are dissolved in water and/or a water-soluble solvent added to 100% to give the product.
2. Emulsifiable concentrate: 15-70% of the compound of formula (I) and 5-10% of an emulsifier are dissolved in a water-insoluble organic solvent added to 100% to give the product.
3. Aqueous emulsion: 5-40% of a compound of formula (I) and 1-10% of an emulsifier are dissolved in 20-40% of a water-insoluble organic solvent. The mixture was introduced into 100% water by means of an emulsifying machine and made into a homogeneous emulsion to obtain the product.
4. Suspending agent: crushing 20-60% of the compound of formula (I) in a stirred ball mill in the presence of 2-10% of dispersant and 1-5% of wetting agent, 0.1-5% of thickener and 100% of water to obtain an active substance suspension.
5. Water dispersible granule: grinding 50-80% of the compound of formula (I) with the addition of dispersant and wetting agent to 100% and preparing it into water dispersible granule by means of industrial production equipment.
All the above are weight percentages.
Example 5
Biological activity evaluation: chilo suppressalis (Chilo suppressalis)
After dissolving the test compound in N, N-dimethylformamide, it was diluted to a desired concentration with water containing 0.1% Tween-80. The indoor biological measurement adopts a leaf dipping method. Selecting healthy and consistent Chilo suppressalis 3-instar larvae, immersing fresh cane shoot slices in the liquid medicine for 10 seconds by using tweezers, taking out, naturally airing the liquid medicine, placing the cane shoot slices in culture dishes filled with moisturizing filter paper, repeating each treatment for 4 times for 20-head Chilo suppressalis 3-instar larvae, and taking blank treatment as a control. The treated test insects are placed in an artificial intelligent culture room with the temperature of 25+/-1 ℃ and the illumination time of L, D=16h and 8h and the relative humidity of 60 percent for feeding. The death rate (integer reserved) was calculated by investigating the number of dead chilo suppressalis 2 days after the drug.
The activity is as follows:
1-6, 9-11, 13-21, 24-35, 38-45, 49-56, 59-80, 83-93, 95-102, 104-108, 111-118, 120, 127-138, 140-142, 144-149, 154, 156, 158, 160, 163-166, 168-174, 176, 178, 180, 182-184, 187-195, 197-200, 202-213, 216-219, 222-226, 229-233, 235-240, 243-247, 247-253, 255-289, 291, 293-298, 302-324, 326-335, 337-340, 343-345, 349-353, 355-360, 362-370, 373-378, 381, 383-385, 387-388, 390-408, 411-417 at a concentration of 5 ppm.
The control effect in CK1-18 is more than 90 percent: CK4, CK5, CK8, CK10, CK11, CK12, CK13, CK14, CK16.
The above compounds were subjected to low concentration activity assay with a part of the compounds of the present invention, and the results were as follows:
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the above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be included within the scope of the present invention.

Claims (4)

1. An aryl substituted meta-diamide compound or a salt thereof which is acceptable as a pesticide, wherein the structural formula of the compound is any one of the following compounds:
。
2. an insecticidal composition comprising an pesticidally effective amount of at least one of the aryl substituted isopolyamide compounds of claim 1 or a pesticidally acceptable salt thereof.
3. A method for controlling plant pests, which comprises applying a pesticidally effective amount of at least one of the aryl-substituted metadiamides of claim 1 or their pesticidally acceptable salts or the pesticidal composition of claim 2 to crops or pests and/or their habitat.
4. Use of an aryl-substituted meta-diamide compound of claim 1 or at least one of its salts as pesticidally acceptable or of the pesticidal composition of claim 2 for controlling plant pests.
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WO2010013567A1 (en) * 2008-08-01 2010-02-04 三井化学アグロ株式会社 Amide derivative, pest control agent containing the amide derivative and pest controlling method
CN102119143A (en) * 2008-08-13 2011-07-06 三井化学Agro株式会社 Amide derivative, pest control agent containing the amide derivative and use of the pest control agent
CN109497062A (en) * 2018-06-26 2019-03-22 上海泰禾国际贸易有限公司 One inter-species diamide compound and its preparation method and application
CN110194726A (en) * 2018-05-11 2019-09-03 沈阳化工大学 A kind of benzamide compound and its application
CN112457288A (en) * 2019-09-06 2021-03-09 沈阳中化农药化工研发有限公司 Piperine acid derivative and application thereof
CN115925576A (en) * 2021-12-22 2023-04-07 浙江宇龙药业有限公司 Heptafluoroisopropyl-containing bisamide compound and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
WO2010013567A1 (en) * 2008-08-01 2010-02-04 三井化学アグロ株式会社 Amide derivative, pest control agent containing the amide derivative and pest controlling method
CN102112437A (en) * 2008-08-01 2011-06-29 三井化学Agro株式会社 Amide derivative, pest control agent containing amide derivative and pest controlling method
CN102119143A (en) * 2008-08-13 2011-07-06 三井化学Agro株式会社 Amide derivative, pest control agent containing the amide derivative and use of the pest control agent
CN110194726A (en) * 2018-05-11 2019-09-03 沈阳化工大学 A kind of benzamide compound and its application
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CN115925576A (en) * 2021-12-22 2023-04-07 浙江宇龙药业有限公司 Heptafluoroisopropyl-containing bisamide compound and preparation method and application thereof

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