CN111205223B - Quinoline derivatives, preparation method and application thereof - Google Patents

Abstract

The invention belongs to the technical field of insecticides and acaricides, and particularly relates to quinoline derivatives, and a preparation method and application thereof. Specifically disclosed is a compound represented by the formula (I) below or a salt thereof,

Description

Quinoline derivatives, preparation method and application thereof

Technical Field

The invention belongs to the technical field of insecticides and acaricides, and particularly relates to a quinoline derivative and a preparation method and application thereof.

Background

Pesticides refer to chemical agents used to control pests. Including organic insecticides (organochlorine, organophosphorus, organosulfur preparations and carbamates and pyrethroids), inorganic insecticides (inorganic arsenic, inorganic fluorine, inorganic sulfur preparations), botanical insecticides, mineral oil insecticides, microbial insecticides, and the like.

The pesticide plays an extremely important role in solving the problem of human grain in agricultural production increase. After world war ii, a batch of organochlorine acaricides appeared, but the resistance of harmful mites increased with increasing use time. The type of the current acaricide is greatly developed, the acaricidal activity is greatly improved, and some acaricides which are safe to predatory mites appear. The development trend of acaricides is toward acaricides and insecticides.

Patent document CN1688193A discloses a mixed composition for controlling parasites, which comprises quinoline compounds represented by the following general formula and a specific compound CK₁(Compound No. 61) CK₂(Compound No. 64):

however, the biological activity of the above compounds is still to be further improved.

The inventor of the present invention disclosed in the prior application CN108689928A that compounds of the following general formula and specific compounds CK₃(Compound No. 9) CK₄(Compound No. 32).

The inventors have further conducted intensive studies to find an insecticidal/acaricidal agent having more excellent properties.

Disclosure of Invention

In order to improve the above problems, the present invention provides a compound represented by the following formula (I), a stereoisomer, a racemate, a tautomer, a nitrogen oxide thereof, or a pharmaceutically acceptable salt thereof,

r is selected from-COR₁or-COOR₁；

Each one of which isR is₁Identical or different, independently of one another, from C_1-12An alkyl group;

R₂、R₃、R₄identical or different, independently of one another, from the group consisting of F, Cl, Br, I, C_1-12Alkyl, or C_1-12An alkoxy group;

x is selected from F, Cl, Br or I.

According to an embodiment of the present invention, in formula (I),

r is selected from-COR₁or-COOR₁；

Each R₁Identical or different, independently of one another, from C_1-4An alkyl group;

R₂、R₃、R₄identical or different, independently of one another, from F, Cl, Br, I or C_1-4An alkyl group;

x is selected from F or Cl.

According to an exemplary embodiment of the invention: in the formula (I)

R is selected from-COR₁or-COOR₁；

R₁Is selected from C_1-4An alkyl group;

R₂、R₃、R₄identical or different, independently of one another, from C_1-4An alkyl group;

x is selected from F or Cl.

By way of example, the compound of formula (I) is selected from the following compounds,

the invention also provides a preparation method of the compound shown as the formula (I), which comprises the following steps: reacting the compound shown in the formula (II) with the compound shown in the formula (III) or the compound R-L shown in the formula (III-1) to obtain the compound shown in the formula (I),

r, R therein₁、R₂、R₃、R₄X has the meaning as defined above and L is selected from leaving groups such as Cl, Br, I or F.

According to the production method of the present invention, the reaction may be carried out in a solvent; the solvent may be selected from one, two or more of aromatic hydrocarbon solvents, haloalkane solvents, nitrile solvents, ether solvents, amide solvents, for example, one, two or more selected from toluene, dichloromethane, 1, 2-dichloroethane, acetonitrile, tetrahydrofuran, N-dimethylacetamide, N-dimethylformamide, or dioxane.

According to the preparation method of the invention, the reaction temperature can be 0-120 ℃, for example 5-30 ℃.

According to the production method of the present invention, the reaction may be carried out in the presence of a base; the base is selected from organic base or inorganic base, and the organic base can be selected from organic amine such as triethylamine, pyridine and the like; the inorganic base may be one, two or more selected from sodium carbonate, potassium carbonate, sodium hydroxide, potassium tert-butoxide, sodium hydride or the like.

According to the preparation method of the present invention, the reaction can be carried out by a method described in patent documents CN108689928A, US 3244586A or CN1193017A, or other similar methods.

The compound represented by the formula (III) or the compound R-L represented by the formula (III-1) can be synthesized by a method reported in the literature or obtained by purchase.

According to an embodiment of the invention, the preparation process further comprises the preparation of a compound of formula (II) comprising the steps of:

a) reacting a compound shown in a formula (IV) with a compound shown in a formula (V) to obtain a compound shown in a formula (II),

wherein R is₂、R₃、R₄X has the definition as described above; r₅Is C_1-4Alkyl groups such as methyl, ethyl, and the like.

According to the invention, the reaction can be carried out with reference to the process described in patent document WO 2010007964.

The compounds of formula (V) can be synthesized by methods reported in the literature or obtained by purchase.

According to an embodiment of the invention, the preparation process further comprises the preparation of a compound of formula (IV) comprising the steps of:

b) reducing the compound shown in the formula (VI) to obtain a compound shown in a formula (IV);

wherein R is₄X has the definition as described above; r₅Is C_1-4Alkyl groups such as methyl, ethyl, and the like.

According to an embodiment of the present invention, the reaction can be carried out by referring to a method described in handbook of organic compound synthesis 2011 edition, or can be obtained by purchase.

According to an embodiment of the invention, the preparation process further comprises the preparation of a compound of formula (VI) comprising the steps of:

c) nitrifying a compound shown in a formula (VIII) to obtain a compound shown in a formula (VII), and esterifying to obtain a compound shown in a formula (VI);

wherein R is₄X has the definition as described above; r₅Is C_1-4Alkyl groups such as methyl, ethyl, and the like.

According to an embodiment of the invention, the reaction can be carried out as described in Tetrahedron Letters 56(2015) 2860-2862.

According to an embodiment of the present invention, the compound of formula (II) may also be prepared by a process comprising the steps of:

reacting the compound shown in the formula (IX) with the compound shown in the formula (X) to obtain a mixture shown in the formula (II) and the formula (II-I), and separating and purifying to obtain the compound shown in the formula (II).

Wherein R is₂、R₃、R₄X has the definition as described above; r₅Is C_1-4Alkyl groups such as methyl, ethyl, and the like.

According to an embodiment of the invention, said reaction can be described in WO2010151737 or in Journal of Medicinal Chemistry,49(21), 6351-6363; 2006.

The compounds represented by the formulae (IX) and (X) can be synthesized by methods reported in the literature or obtained by purchase.

The preparation of the compounds of the formula (I) and their starting materials here can be carried out, depending on the reaction conditions and the choice of starting materials which are suitable in each case, by replacing, for example, in a one-step reaction only one substituent by another substituent according to the invention or by replacing, in the same reaction step, a plurality of substituents by further substituents according to the invention.

If the individual compounds are not obtainable via the above routes, they can be prepared by derivatizing the other compounds or by routinely varying the synthetic routes described.

After completion of the reaction, the reaction mixture can be worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude product by chromatography, for example on alumina or silica gel.

The pharmaceutically acceptable salts of the compounds of formula (I) of the present invention can be prepared by known methods. For example by suitable acid treatment to give an acid addition salt of the compound of formula (I). The preparation method comprises the following steps: the pharmaceutically acceptable salts of the compounds of formula (I) can be conveniently obtained by reacting the compounds of formula (I) with an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, trifluoroacetic acid, malic acid or citric acid in a solvent such as water, diethyl ether or toluene.

The above preparation process can obtain isomer mixture of the compound of formula (I), and if desired, pure isomer can be separated by conventional method such as crystallization or chromatography.

All reactions described above may conveniently be carried out at atmospheric pressure or the autogenous pressure of the particular reaction, unless otherwise indicated.

The present invention also provides a pesticidal composition, such as an insecticidal and/or acaricidal composition, comprising, as an active ingredient, one, two or more of a compound represented by formula (I), a stereoisomer, a racemate, a tautomer, a nitrogen oxide, or a pharmaceutically acceptable salt thereof.

According to an embodiment of the invention, the active ingredient is present in the composition in an amount of 0.1 to 99.9% by weight, for example 0.5 to 99% by weight.

According to an embodiment of the invention, one, two or more agriculturally and/or forestry and/or hygienically acceptable carriers are also included in the composition.

According to an embodiment of the invention, the composition may be administered in the form of a formulation.

For example, the compounds of formula (I) as active ingredients are dissolved or dispersed in a carrier or formulated so as to be more easily dispersible for insecticidal and/or acaricidal use.

According to an embodiment of the invention, the formulation includes, but is not limited to, the following forms: wettable powder, oil suspension, water suspension, aqueous emulsion, aqueous solution, missible oil or microcapsule and the like.

According to embodiments of the invention, a liquid or solid carrier, and optionally a surfactant, may also be added to the composition.

The invention also provides application of one, two or more of the compounds shown in the formula (I), stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof as pesticides, such as insecticides and/or acaricides.

The invention also provides application of one, two or more of the compounds shown in the formula (I), stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof in preparation of pesticides, such as insecticides and/or acaricides.

The invention also provides a method for controlling pests and/or harmful mites, which comprises applying an effective amount of one, two or more of the compounds shown in the formula (I), stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof or applying the composition to a growth medium of the pests and/or the harmful mites.

According to an embodiment of the invention, the effective amount is from 10 to 1000 grams per hectare, preferably from 20 to 500 grams per hectare.

The active substances according to the invention or the active substances to be used according to the invention are suitable, in view of good plant tolerance, favourable warm-blooded animal toxicity and good environmental compatibility, for protecting plants and plant organs, increasing harvest yields, improving the quality of the harvest and for controlling animal pests, especially pests, mites and the like which occur in agriculture, horticulture, animal husbandry, forestry, gardens and leisure facilities, in the protection of pests and materials in warehouses, and in the hygiene sector. They are preferably used as plant protection compositions. They are active against conventional sensitive and resistant species and against all or individual developmental stages. The pests and mites include but are not limited to:

arthropoda, in particular Arachnida, such as, for example, the genus Amycolatopsis (Acarus spp.), the genus Citrus gall (Aceraschedoni), the genus Dermatophagoides (Aculopsis sp.), the genus Acropyrium (Aculops spp.), the genus Acropyrium spp., the genus Bluella (Amblyomma spp.), the genus Tetranychus (Amphiyranthus flavus), the genus Argase (Arganella spp.), the genus Boophilus spp., the genus Brevurica (Brevipalpus spp.), the genus Bryopbiagrnaemophilus, the genus Bryopyratia (Bryopia spp.), the genus Deuteropyra (Bryopyratia spp.), the genus Detailus spp.), the genus Dermatophus (Dermatophus spp.), the genus Dermatophus spp., the genus Dermatophus spp (Hypoglyphosatus spp.), the genus Dermatophagoides (Hygrophytin), the genus Dermatophagoides (Hygrophytin), the genus Dermatophagoides), the genus Dermatophus spp.), the genus Dermatophagoides (Hygrophytylenchus spp.), the genus Dermatophus spp.), the genus Dermatophagoides (Hygrophytin (Dermatophus spp.), the genus Dermatophus spp, Venomous (Latrodectus spp.), Loxosceles spp, Tetranychus (Metatrenchus spp.), Neutratus, Nuphersa spp, Micronychus (Oligonchus spp.), Blastonella (Ornithodorous spp.), Ornithromycotus spp, Ornithronosus spp, Panonychus (Panonychus spp.), Phyllostachys citri (Phytocopterus spp.), Mitragus crenulata (Phytocopterus specvora), Tarsonemus laterosus (Polytarsonemus), Psortus (Psoroptes spp.), Phyllostachys flabellatus (Rhipicephalus spp.), Rhizopus spp., Rhizopus, Tetranychus (Rhynchus spp.), Tetranychus (Tetranychus spp.), Acarus sp., Tetranychus spus (Stepron spp.), Acarus sp., Tetranychus spp.), Tetranychus (Sterculia spyritus spp.), Acarus spp.);

coleoptera (Coleoptera) (beetle): bean species (Acanthoscelides spp.) (elephant), phaseolus vulgaris (Acanthoscelides obtectus) (common pisiform), Ceratoptera alba (Agrilus planipes) and Ceratopteris versicolor (Quadrifolia narrow Germin), Flammulina species (Agriotes spp.) (wireworm), Anoplophora glabripennis (Aphis longipes), Gomphytus species (Anthonoma spp.) (Arthrobacter flavidus), Gomphytus grandis (Anthronus grandis) (Arthrobacter asiaticus), Gomphytus species (Aphidius spp.) (Aprionus spp.) (Arthrospora), Cochlothiaoma sp. (Anacardia), Cochlothiajaponica (Aponia spp.) (grub), Cochlothuroides (Atacys specularis) (Black piss specula (Atanthus spec), Pieris versicolor (Pieris indica) (Pieris indica), Pieris indica (Pieris indica) (Pieris) and Pieris (Pieris indica) (Pieris chinensis (Pieris) of (Pieris) variety (Pieris illustrates (Pieris) and Pieris (Pieris) such as Pieris (Pieris sinensis (Pieris variety (Pieris) and Pieris (Pieris), Cacoesia species (Cacoesia spp.), Callosobruchus maculatus (Callosobruchus maculatus) (southern cowpea weevil), yellow spot dew nail (carpophilus humilis) (xerophys), tortoise shell (Cassida witta), longicorn seed (ccystron spp.), Ceratoma species (Ccrotoma spp.), Ceratoma spp (chrysomella (chromycosis), Ceratoma trifoliate (Ceratoma trifoliate) (Ceratoma), Calycoptera viridis species (Ceratoma spp.), elephant, Chinese cabbage turtle (Ceratonia rubra) (cabbage weevil), turnip elephant (Ceratonia rubra), European cabbage (Ceratoma) nose (cabbage sepedodes (cabbage) weevil), Japanese beetle (Ceratonia), Japanese cabbage (Ceratonia flava), European red cabbage (Ceratonia flavus) (cabbage beetle), European red cabbage (Ceratous flavus (Ceratodes (cabbage), European red cabbage (European red beetle) (European red beetle), European red cabbage (European red beetle) (European red beetle), European red beetle (European red beetle), red cabbage (European red cabbage) (European red cabbage), red cabbage (European red cabbage) and red cabbage (European red cabbage), red cabbage (red cabbage) are (European red cabbage (red cabbage) and red cabbage (red cabbage) are (red cabbage, red, Examples of such plants include, but are not limited to, Cryptolepis pusillus (Cryptolepis parvum), Cryptolepis pusillus (Cryptolepis granulosus), Cryptolepis species (Ctenora spp.) (nematodes), elephant species (Curculio spp.) (weevil), Rhinocephalus species (Cycleephora spp.) (Holotrichia dioides), Rhinocephalus pseudoptera (Cyclenophora spp.) (Holotrichia dioides), Rhinocephalus pseudoptera (Apolygus grandis), Rhinocephalus pseudoptera) (Rhinocephalus pseudoptera), Rhinocephalus pseudoptera (Deporus marginatus) (Rhinocephalus pseudoptera) (Mesorula-pectinifera), Rhinocephalus (Rhinocephalus pseudoptera), Rhinocephalus pseudoptera (Rhinocephalus) and Rhinocephalus pseudoptera (Membristylis), Rhinocephalus pseudoptera (Rhinocephalus) Pectinopsis), Rhinocephalus pseudoptera (Rhinocephalus) and Rhinocephalus (Pilus) Pilus chinensis (Membriae) or Rhinocephalus) Pilus (Pilus) Pilus chinensis), Rhinocarpus (Pilus) Pilus chinensis (Pilus) and Rhinocarpus) Pilus chinensis (Pilus) or Pilus chinensis (Pilus) Pilus chinensis) and Pilus chinensis (, Alfalfa leaf weevil (Hypera stictica) (alfalfa weevil), Hyperdos species (Hyperdoss spp.) (argentina stem weevil (Hyperodes weevil)), coffee berry silly (Hypertenemus hamhei) (coffee fruit beetle), scotland species (Ips spp.) (echinacea), tobacco beetle (Lasioderma serricorne) (tobacco beetle), potato beetle (leptotarsia decemlineata) (colorado potato beetle), lipogyne fuscus, lipogynogenes suturalis, rice water weevil (lissorophiura) and silphigenia species (lycopus purpurea), common tortoise (megalophora), meldonia terrestris (Messostrea), Messostressostrea purpurea (Messochloes), Messochloesophagus spp (Messochloes grandis), Messochlothria spp. (Messochloesophagus spp.) (Messoides), Messochloesophagus spp. (Messoides albugineus spp.) (Messoensis, Mesloe beetle spochloes spp.) (Messochloes variety (Mesloe beetle), Mesloe beetle Rhinoceros rhynchophylla (oriycetes rhynchophylla) (date palm beetle), commerical saw beetle (O ryzaephilus beetle) (market saw beetle), cercaria castanea (elephant), cercaria subulata (odontobrama subulata) (saw beetle), rhynchophylla species (oxiphys spp.) (elephant), black horn mud insect (ocellumeyoplus subulata) (orange foot mud insect (cerolate)), rice negative mud insect (ocelluma oryzae), rose short beak elephant species (pandomous spp.) (elephant), phyllopodium parvus (phyllopodium parvum), phyllopomorpha (phyllopomorpha subulata) (ostriatus subulata), phyllopomorpha parva (phyllopomorpha), picrorhiza (ostriatus subulata), picrorhiza kura (ostriatus parvus (ostriatus spp.) (ostriatus parva), picria parva (ostriata), picria subulata (ostriata) species (ostriatus parva (ostriatus sp.) (picea mangle), picea mangle) and picea mangle (picrorhiza) (picea mangle) species (picrorhiza, picea mangle (picror) of picrorhiza, picea mangle (picrorhiza, picea sp. (picea) of picea mangle (picea sp. (picea) of, Root gill species (rhizorgus spp.) (european scarab (european chafer), cryptorhynchophorus species (Rhynchophorus spp.) (elephant), silly species (Scolytus spp.) (wooddull moth), shonophorus species (shonophorus spp.) (cereal elephant), pisum sativum (Sitona linkuntze) (pea leaf weevil)), rice weevil species (Sitophilus spp.) (cereal weevil), rice weevil (Sitophilus grandis) (millworm (gramnevia)), rice weevil (Sitophilus oryzae) (rice weevil)), sitophilum (Stegobium) (drerberry), triphylum purpurum (brown) (larva), and pseudopterocarpus (brown beetle) (red beetle)), or brown beetle (red beetle) (red beetle)), or red beetle (red beetle) (red beetle).

Dermaptera (Dcrmaptcra) (earwigs).

Vein winged order (Dictyoptera) (cockroach): german cockroach (Blattella germanica) (German cockroach), Blatta orientalis (Blatta orientalis), Blatta palustris (cocitria pennymannica), Periplaneta americana (peritland americana) (americana), Blatta australiana (peritland australoache), Blatta australiana (Australia nckroloach), Periplaneta fusca (pcriparia) brown cockroach (brown cockroach), Periplaneta smokaria (perilanta fuliginosa) (black chest cockroach (smoothckn), and Blatta subclinica (brown cockroach)), Blatta green cockroach (brown cockroach), and Periplaneta fuliginosa (brown cockroach) (Periplaneta subclinica cockroach (brown cockroach)).

Diptera (Diptera) (flies): mosquito species (Aedes spp.) (mosquito), lucerne fly larvae (Agromyza frontella) (alfa blotcheminensis), agromyzis species ((Agromyza spp.) (leaf miner), trypetid species (anastrep spp.) (fruit fly), garleria persica (anastrep persica), garleria persica (garleria persica) (garleria persica (calibrella fufly), mosquito species (anophes spp.) (mosquito), fruit fly species (Bactrocera spp.) (fruit fly), melon fly (Bactrocera persica) (melon), citrus fruit fly (Bactrocera persica), mosquito species (deer spp.) (mosquito), midge fly larvae (sartoria midges) (sea fly), sea fly larvae (sea fly larvae) (deer spp.) (moth), sea fly larvae (bilobagrub) (biles persica), sea fly larvae (moth) and sea fly larvae (sea fly larvae) (moth larvae) (sea fly larvae) (moth larvae) (biles sp.) (3652) Leaf of rape mosquito (Dasineura brassicae) (cabbage mosquito), Dimochi species (Delia spp.), Grapholitha californica (Delia platura) (root maggot (seed corn flag)), Drosophila species (Drosophila spp.) (vinegar fly), Musca species (Fannia spp.) (housefly), yellow belly fly (Fannia canthus) (summer fly (litter fly)), Grey belly fly (grey belly fly) (Grey belly fly), Gasterophilus intestinalis (Gasterous intestinalis) (horse bot), Gracillia persea, Haematobia irutans (Haematobia irritans) (Hymenophila), Blastus species (Hymenophila maggot) (root maggot (skin maggot)), Musca (common fly) (Merista typhus (Musca), Musca melanogaster (Musca), Musca species (Merista spongia) and Musca (Musca), Musca fly (leaf fly) (Merista spossius), Musca fly (Musca fly) (Merista) and Musca (leaf), Musca fly (Musca) and Musca (Musca) are included in the genus, Musca variety (Musca) and Musca, Musca, The plant includes, but is not limited to, the species fall houseflies (Muscaa utumnalis) (fall flies (face flies)), houseflies (vusca domestica) (house flies)), sheep houseflies (oesterussovies) (sheep nose flies (skin bot flies)), european stem flies (ostrich flies) (sweden wheat stem flies), beet spring flies (Pegomyia beta) (spinach leaf flies (beet aircraft)), musca spp (P. horbia spp.), carrot stem flies (Psila rosa (carrot flies)), cherry fruit flies (cherry fruit flies), apple fruit flies (rhapontella (apple maggots)), red mud flies (sitophilus mosquitos) (yellow flies (cow yellow flies)), and cattle fly (stable flies) (cattle yellow flies) (horsefly species).

Hemiptera (Hemiptera) (stinkbug): apolygus lucorum (Acrosteronum hieron) (green stink bug), Oryza sativa (Blissus leucopterus) (long stink bug), Oryza sativa (Caloris norvegicus) (potato stink bug), Tropical stink bug (Cimex hemipterus) (tropical stink), stinkbug (Cimex leucopterus) (bed bug), Daghertussis fasciatus, Dichelops furcatus, Oryza sativa (Euonymus sutus), Edessa meditibetus (Euonymus), Oryza sativa (Leyopteris), Oryza sativa (Leiplus), Oryza sativa (Oryza sativa), Oryza sativa (Oryza sativa) and/Oryza sativa (Oryza sativa) for treating, Lygus hesperus (lygushineus) (western tarnished plant bug), hibiscus syriacus (macrocytoericcus hirsutus), neuroolpus longirostris, rice green bugs (Nezara viridula) (southern green stink bug), lygus planticola (phytolocoris spp.) (lygus), california blind bugs (phytoorius californicus), phytoorius relatus, pisoruszodorus guildingii, lygus tetragonorrhoea (Poiococcus lineus) (neurolylindus bug), Psychicola, Pseudactyla, Scotococcus and trypanosoma species (nose cone)/trypanosoma (nose cone).

Homoptera (Homoptera) (aphid, scale, whitefly, leafhopper): piper pisum (Acrythosiphopkinsum) (pea aphid)), Coccinum species (Adelges spp.) (adelg ds), Beeuglena brassicae (Aleurodes proteella) (Beeuglena cabbage whitefly), Aleurodicus spiralis (Aleuroderus di spores), Beeurothyrius filiformis (Aleurothrix luteus) (gloomy whitlys), Begonia alba (Aluaspis spp.), Amrasa biguella, Laodermata species (Aphrophophora ra spp.) (leafhopper)), Rhodococcus aurantii (Amadonis nigrella aurantii) (Begonia aphid), Begonia nilaparvata (Begonia), Begonia nilaparvata (Begoniothiaca), Begoniothiaspora (Begoniothiaspora aphid), Begoniothrix gloea (Begoniothrix), Begonia indica (Begoniothiaspora indica), Begonia indica (Begonia), Begoniothiaspora (Begonia), Begonia (Begonia), Begonioth (Begonia), Begonia) and Begonia (Begonia) Aphis viride (Begonia) are (Begonia), Begonia (Begoniothrix) species (Begonia), Begonia (Begonia, Begoniothrix) of Begonia (Begonia), Begonia, wheat-tail aphid (Brachycolus noxius) (Russian aphid), asparagus tubular aphid (brachycorythrix asparagi) (asparagus aphid), Brevennia rehi, cabbage aphid (brevicornus brassicae) (cabbage aphid), Ceroplastes sp (Ceroplastes spp.), red Ceroplastes (Ceroplastes rubens) (red wax scale), snow shield plant (chilblastes spp.) (scale), round shield plant (chrysomyrod plant sp.) (scale), soft wax plant (cocussp.) (pink leaf fly), red leaf plant (apple leaf plant), green leaf plant (apple leaf plant), apple leaf plant, apple, euphorbia magna (Macrosiphum eupatoria) (potato aphid), Myzus avenae (Malcoprinus grandiflorum) (English grazing), Long-pipe aphid (Macrosiphum rosa) (rose aphid), Tetranychus tetragonolobus (Macrostemma quadratus) (purple leaf cicada (ash leaf hopper)), Mahanarafrimota, Metaplexis tetragonolobus (Methodophyllum dirhodorium) (rose aphid), Midis locorins, Myzus persicae (Myzus persicae), Myzus nigra (Netephrix paraphyllus) (Phosphophylum), Phytophthora nigra (leaf aphid), Phytophthora nigra (leaf hopper), Phytophthora nigra grandis (leaf), Phytophthora nigra (leaf aphid), Phytophthora nigra (leaf aphid), Phytophus nigra (leaf), Phytophthora grandis (leaf, Phytophthora grandis (P. sp), Phytophthora grandis (Phoma) and Phytophthora grandis (Phoma) A (Phocticola (leaf, Phytophthora grandis (P. sp), Phytophthora grandis (P. grandis), Phytophthora grandis (P. sp), Phytophthora grandis (P The plant diseases of the species lecanicillium (Physioderma piceae) (sport scale), the species Leptococcus sp (Plasmococcus spp.), the species Leptococcus sp (Leptococcus spp.), the species Leptococcus sp (Pseudococcus spp.), the species Bectonus sp (Pseudococcus spp.), the species Leptococcus sp (Pseudococcus spp.), the species Phryptococcus sp), the species Leptococcus sp (Rhapococcus spp.), the species Leptococcus sp (Pseudomonadaceae spp.), the species Leptococcus sp (Phytophagus spp.), the species Leptococcus spp (Phytophagus spp.), the species Leptococcus spp (Pseudophaga (Pseudophagus spp.), the species Leptococcus spp (Phytophagus spp.), the species Leptococcus spp (Tripterus sp (Tripterus spp.), the species Leptococcus spp (Tripterus sp (Tripterus spp.), the species Leptococcus spp), the species Leptococcus sp (Tripterus sp (Tri, Whitefly species (Trialeurodes spp.) (whitefly), greenhouse whitefly (Trialeurodes vaporariorum) (greenhouses whitefly), brown wing whitefly (Trialeurodes abutiloneus) (bandtwing whitefly), cupula species (Unaspis spp.) (scale), arrowhead (Unaspis yanonensis) (arrowhead scale), and Zulia entreriana.

Hymenoptera (Hymenoptera) (ants, wasps and bees): incised leaf ant species (Acromyrmex spp.), Sinkiang leaf beehive (Athalia rosae), leaf ant species (Atta spp.) (Ieafcutting ants), black ant species (Camponotus spp.) (carpenter ant)), pine leaf bee species (Diprion spp.) (leaf bee (saw fly)), ant species (Formica spp.) (Ant), Argentina ant species (Iridogyrmex pollicis) (Argentina), Carcinia subnata (Monorium spp.) (Monocorium ant), Lectium little (Solidarium), Carcinia carota (Solidaceae) (Pharmata spp.)), New Aphyllum species (Neomerinum spp.) (Melisseria spp.) (Melissus spp.)), family bee species (Solidago spp.) (Melissus spp.) (Solidago spp.) (Solidago), and Sinomene bee species (Solidago), Sinomene (Solidago spp.) (Solidago sp.) (Melissus spp.) (Solidago) Wasp species (vespela spp.) (yellow jack) and trichogramma species (Xylocopa spp.) (carpenter bee).

Isoptera (Isoptera) (termites): coptotermes spp, Coptotermes curcus, Coptotermes curcumine, Coptotermes frutus, Coptotermes formosanus, Formosan subcoternum, Corniteus spp, Coptotermes formosanus, Coptotermes spp, Coptotermes formosanus, Coptotermes formotermes spp, Heterotermes spp, Coptotermes formotermes spp, Coptotermes formosanus spp, Coptotermes formosanus termes spp, Coptotermes formosanus spp, Coptotermes termes formosanus termes spp, Coptotermes termes, Reticulitermes banyulensis, Spodoptera grassland (Reticulitermes grassei), Reticulitermes flavipes (Reticulitermes f la vi pes) (eastern soil-dwelling termites), Reticulitermes flavenii (Reticulitermes hagenii), West soil-dwelling termites (Reticulitermes heperus) (West soil-dwelling termites), Moraxella (Reticulitermes santonensis), North-dwelling soil-dwelling termites (Reticulitermes speratus), Reticulitermes nigripes (Reticulitermes tibialis), Reticulitermes virginicus (Reticulitermes virginicus), Reticulitermes formosanus species (Schedorthes spp.) and Zootes spp.

Lepidoptera (Lepidoptera) (moths and butterflies): achoea janata, Trichosporon species (Adoxophyceae spp.), Trichosta gossypii (Adoxophyes orana), Gekko sp (Agrotis spp.), cutworm (Agrotis ipsilon) (Black cutworm), Alabama virescens (Alabama argillaceae) (Cotton leaf worm (cottonleaf worm), Amorbia cuneata, Amylosis tradiatricella (Na orange), Anacamptodia fectaria, Spodoptera punctata (Antarctica Lineata) (peach twig borreria), Heliothis virescens (Anomia sibirica), Pseudocera erecta (Ostrinia), Pseudocera kummer (Ostrinia), Pseudocera punctata (Ostrinia), Pseudocera kummer (Bodinia), Pseudocera armorida (Ostrinia), Spodoptera punctata (Ostrinia), Spodoptera frugiella punctifera (Ostrinia), Spodoptera (Ostrinia) and leaf (Ostrinia) varieties, Spodoptera (Ostrinia) and leaf The species of the genus Spodoptera (Caloptilia spp.) (Spodoptera exigua), Capua reticulana, peach fruit moth (Carposina nipponensis) (peach fruit moth)), Bombycis gramineus (Chilo spp.), mango transverse-thread Philippine moth (Chuumetia transversa) (mango shoot front borner), Rose color cabbage moth (Choristeurosaana) (oblitera) (obliquus)) and Spodoptera species (Chrysodexis p.)), rice leaf roller (Cnaphalous medius) (grass leaf roller)), Bean flour species of the genus Pieris (Colias spp.)), Yao-punctifera (Conmopora reticulata), Spodoptera litura (apple leaf moth) (apple moth), Spodoptera frugiperda (apple moth (Plutella), Spodoptera xylostella), Spodoptera litura (Spodoptera frugiperda (apple moth) (apple moth (Plutella), Spirochaeta (Spirochaeta.) (Chorista), Spodoptera frugiperda (Spodoptera), Spirochaeta) (apple moth (Plutella), Spirocha) (apple moth (Plutella) species (Plutella) and Spirochaeta (moth (Plutella) A) and Spirogra (Plutella) in the family of the family Choristocarpus (Plutella) species (Plutella) and Spiritis sinensis (Plutella) and Spirilis (Spirilis) of the family, Spiritis sinensis (Sporica) and Sporica) species (Sporina, the species Darna diducta, Diaphania sp (Diaphania spp.) (stem borer)), borer sp (diaphraea spp.) (stem borer)), borer (diaphraea saccharalis) (sungar borer), southwestern corn stalk (diaphraea grandiosella) (southwester cornborer), diamond-back seed (eared leaf borer), diamond-back seed (eared leaf spot.) (cotton bollworm), diamond-back (earia insulata) (egg yellow diamond-back borm), diamond-back diamond-worm (ear diamond-back) (egg diamond-back diamond), diamond-back (ear diamond-back) of (ear diamond-back) (egg white moth), diamond-back (egg), south phaea larva (stem borer), stem borer (yellow leaf borer), yellow meadow (yellow meadow), yellow meadow (stem borer, yellow borer), yellow meadow (stem borer), yellow borer (yellow borer) (egg borer) (yellow borer) (egg white borer) (egg borer) (yellow borer), yellow borer) (yellow borer), yellow borer (yellow borer) (yellow borer), yellow borer (yellow leaf borer), yellow, Examples of such insects include, but are not limited to, banana cutworm (eriotia thrax) (banana skipper), glossy privet (eupoiiliambiguaella) (grape berry moth)), oriental cutworm (Euxoa auricularis) (armychus), cutworm (cutworm), grapevine species (felis spp.) (rhizoctonia cutworm), hornworm species (Gortyna spp.) (stem borer), oriental moth (graphoworm molesta) (peach (apricot) fruit borer (oriental fruit moth)), trilobia (cabbage leaf moth) (soybean leaf borer (bean leaf moth)), budworm (cabbage moth)), budworm (helicopterocarpa sp.) (helicoptera), cotton bollworm (helicopterocarpa armigera) (corn borer), cotton bollworm (helicopterocarpa), cotton bollworm (helicopteria armyworm) (corn borer), cotton bollworm (cabbage moth) (corn borer), cotton bollworm (cabbage moth) (corn borer) and corn borer) (corn borer) corn borer (corn borer) or corn borer (corn borer) corn borer (corn borer) corn borer (corn borer, White-fin eggplant borer (Leucinodes orbornalis) (eggplantfront borre), spiderworm moth (Leuciptera malifoliella), fine moth species (Lithocolletis spp.), grape leaf roller moth (Lobesia borna) (grape fruit moth), Loxagra gruotis species (Loxagrutissp.) (Spodoptera frugiperda), soybean-line root cutting insect (Loxagrus albicans) (western bean fruit moth), gypsy moth (Lymantria dispar) (gypsy moth), peach leaf roller (Lyonetherella), apple leaf roller (apple leaf moth (apple leaf miner)), oil palm moth (Mahasa coreticum) (tomato leaf moth), cabbage (cabbage), cabbage (Mallotus leaf borer), cabbage moth (apple leaf borer) (cabbage caterpillar), cabbage caterpillar (apple leaf borer), cabbage (cabbage caterpillar), cabbage caterpillar (cabbage caterpillar), cabbage caterpillar (cabbage caterpillar) leaf borer (cabbage caterpillar), cabbage caterpillar (cabbage caterpillar, moth (cabbage caterpillar, moth) moth (cabbage caterpillar, rice stem borer, moth (cabbage caterpillar, moth (cabbage caterpillar, moth, cabbage caterpillar, moth, cabbage caterpillar, moth, european corn borer (Ostrinia nubilalis) (European corn borer)), Oxydia vesulia, Ostrinia (Pandemiscarana) (common grape leaf moth (common currant torrex)), Spodoptera frugiperda (Pandemia hepes) (brown apple torrex), Pneumoniella africana (Papilio demoduloca), Spodoptera litura (Pectinophora grandiflora) (red bell bollworm (pink bollworm)), Spodoptera species (Peridroma spp.) (root cutting insect), Philobium japonicum (Peridroma saucia) (variegated cutworm), Spodoptera coffea (Perileria lutea), Plutella xylostella (Plumbum xylostella), Plumbum xylostella (Plumbum xylostella) (white moth (Plumbum xylostella), Plumbum xylostella (Plumbum xylostella) (Pimenta) (Plumbum xylostella), Plumbum xylostella (Plumbum xylostella) and Plumbum xylostella (Plumbum xylostella) A), Grape berry moth (polychloris vironda) (grapple berry moth), orange fruit moth (Prays endoocta), olive moth (prasys oleae) (olive moth), armyworm species (pseudogleria spp.) (noctuid), pseudoglettia unipunctata (marchand), soybean looper (Pseudoplusia includens) (soybean looper), inchworm (rachidiana nu), striped rice borer (chilopossus), tryporyza incertulas (sciola incertulas), phomopsis armyworm (Sesamia spp.) (spongiosa), rice stem borer (Sesamia infusoriana) (pink riope), pink stem borer (sembrotica), Spodoptera spongiosa (spongiosa), Spodoptera frugiperda (spongiosa), Spodoptera frugium Spodoptera (Spodoptera spongiosa), Spodoptera frugium (Spodoptera spongiensis) (Spodoptera spongiosa), Spodoptera frugiperda (Spodoptera) and Spodoptera (Spodoptera) species (Spodoptera), Spodoptera armyworm (Spodoptera) are also included in the rice stem borer, Spodoptera) and rice stem borer (Spodoptera) are also included in, Spodoptera (Spodoptera) in the rice stem borer (Spodoptera) may be, Spodoptera (Spodoptera) and the rice stem borer (Spodoptera) may be, Spodopter, The species Heliothis virescens (Synanthon spp.) (root borer), Therla basilides, Thermia gemmatalis, Chlamydia armyworms (Teneola bisseliella) (webbingclotheshes moth), Trichoplusia ni (cab looper), Tomatomyza sativa (Tutsassolutita), Phlebia nidulans (Yonomeuta spp.), Cochlothuria coffea arabica (Zeuzearocoffea) (red branchborer), Zeuzera pyrina (Leopard moth (Leopboard moth)), and Spodoptera litura (Fabricius)).

Mallophaga ((Mallophaga) feather louse (chewing lice)): ovine feather louse (Bovicola ovis) (sheet biting louse), turkey short horn feather louse (chicken feather louse), and chicken feather louse (Menopon gallina) (common henhouse).

Orthoptera (Orthoptera) (grasshopper, locust and cricket): arana nigra (anacrus simplex) (Mormon horns (Mormon cricket)), mole cricket (Gryllotalpidae) (mole cricket)), eastern asia migratory locust (Locusta migratoria), grasshopper species (Melanoplus spp.) (grasshopper), acephala wing spurs (microcentrumretrierve) (angular winged katydia (grasshopper)), pterophora species (pterophora spp.) (pterophora, steleophaga egr, pterygrosaurus (scuddita) (forked tail bush (fork tailed butydia)), and tuberous ridge (vanilloida).

Phthiraptera (Phthiraptera) (sucking lice): the blood sucking lice species (haemattopinus spp.) (cattle and pig lice), sheep jaw lice (sheep lice), head lice (pedigree capitis) (body lice), human body lice (pedigree humanus (body lice) and crab lice (crab lice)).

Siphonaptera (daphnaptera) (fleas): ctenocephalides canis (dog flea), Ctenocephalides felis (cat flea) and human flea (Pulex irutans) (human flea).

Thysanoptera (thrips): frankliniella fusca (Frankliniella fusca) (tobaco third), Frankliniella occidentalis (western flower) Frankliniella hultrias (western flower), Frankliniella shultzii (Frankliniella williamsii) (corn Thrips), Frankliniella glasshouse Thrips (IIelothrips hamoralidis) (greenhous third), Riphisprothrips cruentus, Scirpus sp (Sciroththrips spp), Platycodon grandiflorum (Scirthricirris) (citrus trough), Frankliniella tabacum (Scirthrips spp), Talothriparia (yellow Thrips spp), and Throughthrips (Thripus spp).

Thysanoptera (Thysanura) (bristletail): chlamydomonas species (Lepisma spp.) (silverfish) and locusta species (Thermobia spp.) (locusta spp.).

From the order of Acarina (Acarina) (mites (mite) and cicadas (tick)): woodbee scutellariae (acarapis woodi) (parasitic mites in the trachea of bees), dermatophagoides (Acarus spp.) (food mites), Acarus macrorhynchophylla (Acarus srorona) (grain mite), mango bud mite (Aceria mangifera) (mango bud mite), acanthophyrus sp. (Acarus spp.), acanthophysalis scabrosoides (acanthophyceae), acanthophysalis lycopersici (acanthophysalis septemporosa) (tomato bud mite), acanthophysalis pelekasi, acanthophysalis citri (acanthophysalis peekatsi) (acanthophysalis peeka), acanthophysalis dermalis (acanthophysalis spindalii) (apple gall mite (decapili mite), american tick (acanthophysalis tick (mangifer sporus sp.), Chinese tick (amygdalus persicum), short tick (mangiferous tick (mangifer), or mangiferous tick (mangifer sp.), or mangiferous tick (mangiferous tick) and mangiferous tick (mangiferous tick) species), mangiferous tick (mangiferous tick) and mangiferous tick (mange sp.) including mangiferous tick (mange variety), mange sp.) including mange variety), mange variety (mange variety), mange variety (mange variety), mange variety (mang, House dust mite (Dermatophagoides pteronyssinus) (house dust mite), Tetranychus sp (Eotetranus spp.), hornbeam Tetranychus carpesii (Eotetranthus carpini (yellow spider mite), Tetranychus sp.), Gephyrus sp (Epithromyces sp.), Gephylus sp (Eriophenous spp.), hard tick sp (I.D.; es sp.), ticks (tick), Tetranychus sp (Notederus sp.), Microphyrus sp.), Microphycus sp. sp.Ohiophagus (Ochrophycus sp.), Tetranychus sp (Notoednes. cati), Microphycus sp (Oligonychus sp.), Calonychus (Ocynidae) coffee, Tetranychus parvus (Ocigo nuciferus), Tetranychus wintergreen (Oligonychus (Ochrotus) and Tetranychus (Ochrotus sp.), Tetranychus (Tetranychus urticae (Tetranychus), Tetranychus urticae (Tetranychus urticae) (Tetranychus sp.), Tetranychus urticae (Tetranychus), Tetranychus (Tetranychus) and Tetranychus (Tetranychus) or Tetranychus (Tetranychus) or Tetrasticus (Tetrasticus) or (Tetrasticus) or Tetrasticus (Tetrasticus) or Tetrasticus, Rhizomorpha species (rhizomorph spp.) (root mite (bulb mite)), Sarcoptes scabies (Sarcoptes scabies) (itch mite), coronaria avocado (tetragonophys perseafarae), Tetranychus species (Tetranychus spp.), Tetranychus urticae (Tetranychus urticae) (twospoked spider mite)) and Varroa destructor (Varroa destructor) (honey bee mite).

Nematoda (nematodes): the species Aphelenchoides (Aphelenchoides spp.) (bud and leaf and pine wood nematodes (bud and leaf & pine wood nematodes)), the species nematodiasis (Belonolaevis spp.) (sting nematodes), the species Cyclotella minor (Criconella spp.) (ring nematodes), the species Dirofilaria immitis (dog heartword), the species Ditylenchus spp. (stem and bulb nematodes), the species Trichophythora (Heterodera spp.) (Cytospora spp.), the species Heterocladia (Heterocladia zeyla) (maize nematodide), the species Melilodinia spp. (Hichlamyella spp.) (Neurospora spp.) (Melilotus spp.)), the species Heterocladospora spp. (Melilotus spp.)), the species Melilotus spp.) (Melilotus spp The species of the genus Rapholus (Rapholus spp.) (Burrowing nematode) and the species of the Leptochloa (Rotylenchus reniformis) (kidney-shaped nematode).

General class (general classes of insects): white pine worm (Scutigerella immaculata).

Owing to their positive properties, the compounds of the formula (I) can be used advantageously for protecting crops, domestic animals and livestock animals of agricultural and horticultural importance, as well as the environment customary for humans, against pests and/or mites.

The amount of the compound of formula (I) to be used to obtain the desired effect will vary depending on various factors such as the compound used, the crop to be protected, the type of pest, the extent of infection, the climatic conditions, the method of application and the dosage form employed.

The ingredients of the dosage forms or compositions described herein are selected in accordance with the physical properties of the active ingredient, the mode of application and environmental factors such as soil type, moisture and temperature.

Useful dosage forms include solutions such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspensions), and the like, which may optionally be viscous jellies. Useful dosage forms also include solids such as powders, granules, tablets, pills, films, and the like, which may be water dispersible ("wettable") or water soluble. The effective components can be microencapsulated and made into suspension or solid dosage form; in addition, the whole dosage form of the effective components can be encapsulated. The capsule can control or delay the release of the effective components. Sprayable formulations can be diluted in a suitable medium using spray volumes of about one to several hundred liters per hectare. The compositions in high concentrations are mainly used as intermediates for further processing.

Typical solid Diluents are described in Watkins et al, Handbook of Instrument standards and Cariers, 2nd Ed., Dorland Books, Caldwell, N.J.. Typical liquid diluents are described in Marsden, Solventsguide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers annular, Allured pub. Corp., Ridgewood, New Jersey, and Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended applications. All formulations may contain small amounts of additives to reduce foaming, coalescence, corrosion, microbial growth, etc., or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, sulfonated dialkyl succinates, alkyl sulfates, alkyl benzene sulfonates, organosilanes, N, N-dialkyl taurates, lignosulfonates, aldehyde condensates for naphthalenesulfonates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers.

Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starches, sugars, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate, liquid diluents include, for example, water, N-dimethylformamide, dimethylsulfone, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene, olive oil, castor oil, linseed oil, tung oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and cocoa oil, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, dodecanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the components. Powders and fines can be prepared by mixing and the suspending agents are generally prepared by wet milling, usually by grinding in a hammer mill or liquid energy mill; see, for example, U.S. Pat. No. 3060,084, granules and pellets are prepared by spraying the active substance onto freshly prepared granular carriers or by granulation techniques. See Browning, "Aggloration," Chemical Engineering, Decumber 4, 1967, pp147-48, Perry's Chemical Engineering's Handbook, 4TH Ed., McGraw-Hill, New York, 1963, Pages 8-57and following, and WO 91/13546. The preparation of pellets is described in U.S.4172714, water dispersible and water soluble granules are described in U.S.4144050, U.S.3920442 and DE 3246493 to prepare tablets as described in US 5180587, U.S.5232701 and U.S. 5208030. Films may be prepared by the methods described in GB2095558 and u.s.3299566.

More information on processing can be found in U.S.3,235,361, Col.6, line 16through Chol.7, line 19and EXAMPLES 10-41; U.S. Pat. No. 3,309,192, Col.5, line 43through Col.7, line 62and EXAMPLES 8, 12, 15, 39, 41, 52, 53, 58, 132, 138, 140, 162, 164, 166, 167and 169-182; U.S.2,891,855, col.3, line 66through col.5, line 17and Examples 1-4; klingman, Weed Control as a Science, John Wiley and Sons, inc., New York 1961, pp 81-96; and Hance et al, Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

Herein, for certain applications of the composition, for example in agriculture, one, two or more other bactericides, acaricides, herbicides, plant growth regulators or fertilizers and the like may be added to the insecticidal and/or acaricidal composition of the invention, whereby additional advantages and effects may be produced.

Definition and description of terms

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs. All patents, patent applications, and publications cited herein are incorporated by reference in their entirety unless otherwise indicated. If there are multiple definitions of terms herein, the definition in this section controls.

It is understood that reference may be made to (including Carey and Sundberg "ADVANCED ORGANIC CHEMISTRY 4)^THED. "Vols.A (2000) and B (2001), Plenum Press, New York). Unless otherwise indicated, conventional methods within the skill of the art are employed, such as mass spectrometry, NMR, IR and UV/Vis spectroscopy, and pharmacological methods. Unless a specific definition is set forth, the terms used herein in the pertinent description of analytical chemistry, organic synthetic chemistry, and pharmaceutical chemistry are known in the art. Standard techniques can be used in chemical synthesis, chemical analysis, pharmaceutical preparation, formulation and delivery, and treatment of patients. For example, the reaction and purification can be carried out using the manufacturer's instructions for use of the kit, or in a manner known in the art or as described herein. The techniques and methods described above can generally be practiced according to conventional methods well known in the art, as described in various general and more specific documents referred to and discussed in this specification. In the present specification, groups and substituents thereof may be selected by one skilled in the art to provide stable moieties and compounds. When a substituent is described by a general formula written from left to right, the substituent also includes chemically equivalent substituents obtained when a formula is written from right to left, as long as it complies with the valence rules. For example, CH₂O is equivalent to OCH₂The substitution position may be bonded with an oxygen atom or a carbon atom of a methylene group.

The term "C_1-12Alkyl is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 12 carbon atoms. Preferably "C_1-6Alkyl group and C_1-6Alkyl "denotes straight and branched chain alkyl groups having 1,2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a neopentyl group, a 1, 1-dimethylpropyl group, a 4-methylpentyl group, a 3-methylpentyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, a 3, 3-dimethylbutyl group, a 2, 2-dimethylbutyl group, a 1, 1-dimethylbutyl group, a 2, 3-dimethylbutyl group, a 1, 3-dimethylbutyl group or a 1, 2-dimethylbutyl group.

The term "C_1-12Alkoxy "denotes-O-C_1-12Alkyl radical, wherein C_1-12Alkyl groups have the above definitions.

The term "pharmaceutically acceptable salt" as used herein refers to salts that retain the biological potency of the free acid and free base of the specified compound, and that are biologically or otherwise non-adverse. The compound of the present application also includes pharmaceutically acceptable salts, such as nitrate, hydrochloride, sulfate, phosphate, acetate, trifluoroacetate, malate, citrate and the like, which can be generally used in the field of agriculture and horticulture. Pharmaceutically acceptable salts refer to the form in which the base group in the parent compound is converted to a salt. Pharmaceutically acceptable salts include, but are not limited to, inorganic or organic acid salts of basic groups such as amine (amino) groups. Pharmaceutically acceptable salts of the present application may be synthesized from the parent compound, i.e., the basic group of the parent compound is reacted with 1-4 equivalents of the acid in one solventAnd (4) reacting in the system. Suitable salts are listed in Remingtong's Pharmaceutical sciences, 17^thed., Mack Publishing Company, Easton, Pa.,1985, p.1418 and Journal of Pharmaceutical Science,66,2(1977), for example the hydrochloride salt.

"stereoisomers" as used herein refers to isomers resulting from the different arrangement of atoms in a molecule in space. The compounds of formula (I) contain asymmetric or chiral centers and, therefore, exist in different stereoisomeric forms. All stereostructures and mixtures of formula (I) are as such, including racemic mixtures, as part of the present application. Diastereomeric mixtures can be separated into the individual diastereomers, based on their different physicochemical properties, by well-known means, e.g., resolution of the enantiomers can be converted into the diastereomers by reaction with a suitable optically active substance (e.g., a chiral alcohol or Mosher's moylchloride), which can be separated and converted (e.g., hydrolyzed) into the corresponding individual isomers. Some of the compounds of formula (I) may be atropisomers (e.g., substituted aryl) are also part of this application. Enantiomers can also be separated using a chiral chromatography column. The compounds of formula (I) may exist in different tautomeric forms, which forms are included within the scope of the present application. For example, keto-enol and imine-enamine forms of the compounds.

Advantageous effects

The compound of formula (I) shows good activity to various pests and mites in agriculture or other fields. Furthermore, these compounds can be used for the preparation of insecticides and/or acaricides because of their excellent control effect at very low doses.

In addition, the compound has simple preparation steps and high yield, thereby having good application prospect.

The inventors of the present invention have also found that the substituent at the 5-position and the X-substituent at the 6-position on the quinoline ring in the compound of formula (I) have a large influence on the activity of the compound, and thus the compound of the present invention exhibits an excellent controlling effect on bemisia tabaci, thrips occidentalis, and the like.

Detailed Description

The technical solution of the present invention will be further described in detail with reference to specific embodiments. The following examples are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

The following chromatographic conditions were used for the LC-MS detection analysis in the examples below:

a chromatographic column: agilent ZORBAX SB-C18150 mm X4.6 mm, 5 μm (i.d);

detection wavelength: 254 nm; flow rate: 0.8 mL/min; column temperature: 30 ℃;

gradient elution conditions:

time (min)	Methanol (%)	0.1 aqueous formic acid solution (% by volume)
			0.00	50	50
5.00	50	50
			15.00	90	10
20.00	90	10

Synthetic examples

Example 1: preparation of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-yl acetate (Compound 1)

The first step of reaction: preparation of 3-chloro-2-methyl-6-nitrobenzoic acid: 17.1g (0.1mol) of 3-chloro-2-methylbenzoic acid and 130g (1.3mol) of concentrated sulfuric acid were added to a three-necked flask at room temperature, stirred, and cooled to 0 ℃ in an ice bath. 7.7g (0.12mol) of fuming nitric acid is dripped into the mixture, and the temperature is maintained at 0-5 ℃. After 30min, the reaction was continued at 0 ℃ for 5 h. The reaction solution was added dropwise to 230ml of water at 0 ℃ and 20 min. White solid is separated out, filtered and dried in vacuum to obtain 18g of product with the yield of 83.7 percent. LC-MS [ M + H ]]⁺＝216.01、[M+Na]⁺＝237.99、[M+K]⁺＝253.96。

The second step of reaction: preparation of isopropyl 3-chloro-2-methyl-6-nitrobenzoate: 13g (0.06mol) of 3-chloro-2-methyl-6-nitrobenzoic acid, 10g (0.072mol) of potassium carbonate and 50ml of N, N-dimethylformamide are stirred at room temperature in a three-necked flask. To the above mixture was added in portions 12.5g (0.072mol) of iodoisopropane. After the addition, the reaction was continued for 3 hours at room temperature with stirring. 200ml of water was added to the above reaction solution. Ethyl acetate (3 × 80ml) was extracted and the organic phases combined. Washed with saturated saline (80 ml). Dried over anhydrous sodium sulfate. And (5) filtering. Vacuum concentrating to obtain 8.1g product with yield of 52%.

LC-MS[M+H]⁺＝258.06、[M+Na]⁺＝280.04、[M+K]⁺＝296.01。

The third step of reaction: preparation of isopropyl 6-amino-3-chloro-2-methylbenzoate: 16.8g (0.3mol) of iron powder, 0.024g of ammonium chloride, 40ml of ethanol and 8ml of water were put into a three-necked flask at room temperature, and a 20ml ethanol solution of 7.8g (0.03mol) of isopropyl 3-chloro-2-methyl-6-nitrobenzoate was added dropwise to the above mixture. Heated to reflux for 5 hours. The heating was stopped, the filtration was carried out, the ethanol was distilled off under reduced pressure, and 50ml of ethyl acetate and 20ml of water were added to the residue and washed once. The organic phase was dried over anhydrous sodium sulfate. Filtering, and concentrating the filtrate under reduced pressure. The methanol is recrystallized to obtain 4.3g of product with the yield of 62 percent.

LC-MS[M+H]⁺＝228.08、[M+Na]⁺＝250.06、[M+K]⁺＝266.03。

And a fourth step of reaction: preparation of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ol: 3.5g (0.015mol) of isopropyl 6-amino-3-chloro-2-methylbenzoate, 2.8g (0.03mol) of 3-pentanone and 2.2g (0.015mol) of zinc chloride were dissolved in 40ml of xylene in this order at room temperature. The temperature is raised to reflux, 1.5g (0.01mol) of zinc chloride is added into the reaction system, and the reaction is carried out for 30 hours. The reaction mixture was cooled to room temperature, 15ml of 15% dilute hydrochloric acid was added, suction filtration was carried out, the filter cake was washed with 35ml of methanol/water (1/1), and after drying, 2.1g of the product was obtained, yield 58%. LC-MS [ M + H ]]⁺＝236.09、[M+Na]⁺＝258.07、[M+K]⁺＝274.04。

The fifth step of reaction: preparation of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-yl acetate: 1.18g (0.005mol) of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a low-temperature bath. To the above mixture was added 0.48g (0.006mol) of acetyl chloride in portions, the temperature was maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 4 hours. To the reaction system was added 20ml of water, and extracted with ethyl acetate (3 × 10 ml). The organic layers were combined, washed with saturated brine (15ml), and dried over anhydrous magnesium sulfate. The organic phase is decompressed and desolventized, and the product is obtained by column chromatography (eluent: ethyl acetate: petroleum ether (1:6)) with the yield of 68 percent, wherein the weight of the product is 0.95 g.

LC-MS[M+H]⁺＝278.10、[M+Na]⁺＝300.08、[M+K]⁺＝316.05。

¹H-NMR (400MHz, solvent CDCl)₃)δ(ppm):7.92(1H,m),7.46(1H,dd),3.02(2H,q),2.67(3H,s),2.56(3H,s),2.52(3H,s),1.36(3H,t)。

Example 2: preparation of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ylpropionate (Compound 2)

1.18g (0.005mol) of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a low-temperature bath. To the above mixture was added in portions 0.6g (0.006mol) of propionyl chloride, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 5 hours. To the reaction system was added 20ml of water, and extracted with ethyl acetate (3 × 15 ml). The organic layers were combined, washed with saturated brine (20ml), and dried over anhydrous sodium sulfate. Filtering, desolventizing the filtrate under reduced pressure, and performing column chromatography (eluent: ethyl acetate: petroleum ether (1:5)) to obtain 0.9g of a product with the yield of 62%.

LC-MS[M+H]⁺＝292.11、[M+Na]⁺＝314.09、[M+K]⁺＝330.06。

¹H-NMR (400MHz, solvent CDCl)₃)δ(ppm):7.91(1H,m),7.47(1H,dd),3.02(2H,q),2.67(3H,s),2.56(3H,s),2.52(2H,q),1.36(3H,t),1.12(3H,t)。

Example 3: preparation of methyl 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ylcarbonate (Compound 9)

1.18g (0.005mol) of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a low-temperature bath. To the above mixture was added 0.58g (0.006mol) of methyl chloroformate in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 5 hours. To the reaction system was added 20ml of water, and extracted with ethyl acetate (3 × 15 ml). The organic layers were combined, washed with saturated brine (20ml), and dried over anhydrous sodium sulfate. Filtering, desolventizing the filtrate under reduced pressure, and performing column chromatography (eluent: ethyl acetate: petroleum ether (1:6)) to obtain 1.1g of a product with the yield of 72 percent. LC-MS [ M + H ]]⁺＝294.09、[M+Na]⁺＝316.07、[M+K]⁺＝332.04。

¹H-NMR (400MHz, solvent CDCl)₃)δ(ppm):7.98(1H,m),7.46(1H,t),3.98(3H,s),3.00(2H,q),2.67(3H,s),2.56(3H,s),1.36(3H,t)。

Example 4: preparation of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ylcarbonate ethyl ester (Compound 10)

1.18g (0.005mol) of 6-chloro-2-ethyl-3, 5-dimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a low-temperature bath. To the above mixture was added 0.65g (0.006mol) of ethyl chloroformate in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 5 hours. To the reaction system was added 20ml of water, and extracted with ethyl acetate (3 × 15 ml). The organic layers were combined, washed with saturated brine (20ml), and dried over anhydrous sodium sulfate. Filtering, desolventizing the filtrate under reduced pressure, and performing column chromatography (eluent: ethyl acetate: petroleum ether (1:6)) to obtain 1.05g of a product with the yield of 68 percent. LC-MS [ M + H ]]⁺＝308.11、[M+Na]⁺＝330.09、[M+K]⁺＝346.06。

¹H-NMR (400MHz, solvent CDCl)₃)δ(ppm):7.97(1H,m),7.46(1H,t),4.38(2H,q),3.00(2H,q),2.67(3H,s),2.56(3H,s),1.43(3H,t),1.36(3H,t)。

Example 5: preparation of methyl 2-ethyl-6-fluoro-3, 5-dimethylquinolin-4-ylcarbonate (Compound 35):

the first step of reaction: preparation of 3-fluoro-2-methyl-6-nitrobenzoic acid: 15.8g (0.1mol) of 3-fluoro-2-methylbenzoic acid and 130g (1.3mol) of concentrated sulfuric acid were added to a three-necked flask at room temperature, stirred, and cooled to 0 ℃ in an ice bath. 7.7g (0.12mol) of fuming nitric acid is dripped into the mixture, and the temperature is maintained at 0-5 ℃. After 30min, the reaction was continued at 0 ℃ for 5 h. Will reactThe solution is dropped into 220ml of water at the temperature of 0 ℃, and the dropping is finished after 30 min. White solid is separated out, filtered and dried in vacuum to obtain 17.1g of product with yield of 86%. LC-MS [ M + H ]]⁺＝200.04、[M+Na]⁺＝222.02、[M+K]⁺＝237.99。

The second step of reaction: preparation of isopropyl 3-fluoro-2-methyl-6-nitrobenzoate: 12g (0.06mol) of 3-fluoro-2-methyl-6-nitrobenzoic acid, 10g (0.072mol) of potassium carbonate and 50ml of N, N-dimethylformamide are stirred at room temperature in a three-necked flask. To the above mixture was added in portions 12.5g (0.072mol) of iodoisopropane. After the addition, the reaction was continued for 3 hours at room temperature with stirring. 200ml of water was added to the above reaction solution. Ethyl acetate (3 × 80ml) was extracted and the organic phases combined. Washed with saturated saline (80 ml). Dried over anhydrous sodium sulfate. Filtering, decompressing and concentrating the filtrate to obtain 8.6g of the product with the yield of 60 percent.

LC-MS[M+H]⁺＝242.09、[M+Na]⁺＝264.07、[M+K]⁺＝280.04。

The third step of reaction: preparation of isopropyl 6-amino-3-fluoro-2-methylbenzoate: 16.8g (0.3mol) of iron powder, 0.024g of ammonium chloride, 40ml of ethanol and 8ml of water were put into a three-necked flask at room temperature, and a solution of 7.2g (0.03mol) of 3-fluoro-2-methyl-6-nitrobenzoic acid isopropyl ester in 20ml of ethanol was added dropwise to the above mixture. Heated to reflux for 5 hours. The heating was stopped, the filtration was carried out, the ethanol was distilled off under reduced pressure, and 50ml of ethyl acetate and 20ml of water were added to the residue and washed once. The organic phase was dried over anhydrous sodium sulfate. Filtering, and concentrating the filtrate under reduced pressure. The methanol is recrystallized to obtain 4.3g of product with the yield of 68 percent.

LC-MS[M+H]⁺＝212.11、[M+Na]⁺＝234.09、[M+K]⁺＝250.06。

And a fourth step of reaction: preparation of 2-ethyl-6-fluoro-3, 5-dimethylquinolin-4-ol: 3.2g (0.015mol) of isopropyl 6-amino-3-fluoro-2-methylbenzoate, 2.8g (0.03mol) of 3-pentanone and 2.2g (0.015mol) of zinc chloride were dissolved in 40ml of xylene in this order at room temperature. The temperature is raised to reflux, 1.5g (0.01mol) of zinc chloride is added into the reaction system, and the reaction is carried out for 30 hours. Cooling the reaction mixture to room temperature, adding 15ml 15% dilute hydrochloric acid, filtering, washing the filter cake with 35ml methanol/water (1/1), drying to obtain 1.8g product, and collectingThe rate was 56%. LC-MS [ M + H ]]⁺＝220.12、[M+Na]⁺＝242.1、[M+K]⁺＝258.07。

The fifth step of reaction: preparation of methyl 2-ethyl-6-fluoro-3, 5-dimethylquinolin-4-ylcarbonate: 1.1g (0.005mol) of 2-ethyl-6-fluoro-3, 5-dimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a low-temperature bath. To the above mixture was added 0.58g (0.006mol) of methyl chloroformate in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 4 hours. To the reaction system was added 20ml of water, and extracted with ethyl acetate (3 × 12 ml). The organic layers were combined, washed with saturated brine (15ml), and dried over anhydrous sodium sulfate. Filtering, and removing the solution from the filtrate under reduced pressure. Column chromatography (eluent: ethyl acetate: petroleum ether (1:6)) gave 1.06g, 76% yield.

LC-MS[M+H]⁺＝278.12、[M+Na]⁺＝300.1、[M+K]⁺＝316.07。

¹H-NMR (400MHz, solvent CDCl)₃)δ(ppm):7.83(1H,m),7.16(1H,t),3.97(3H,s),3.00(2H,q),2.65(3H,s),2.56(3H,s),1.36(3H,t)。

Example 6: preparation of ethyl 2-ethyl-6-fluoro-3, 5-dimethylquinolin-4-ylcarbonate (Compound 36):

1.1g (0.005mol) of 2-ethyl-6-fluoro-3, 5-dimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ in a low-temperature bath. To the above mixture was added 0.68g (0.006mol) of ethyl chloroformate in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 4 hours. To the reaction system was added 20ml of water, and extracted with ethyl acetate (3 × 12 ml). The organic layers were combined, washed with saturated brine (15ml), and dried over anhydrous sodium sulfate. Filtering, and removing the solution from the filtrate under reduced pressure. Column chromatography (eluent: ethyl acetate: petroleum ether (1:6)) gave 1.1g, 75% yield.

LC-MS[M+H]⁺＝292.14、[M+Na]⁺＝314.12、[M+K]⁺＝330.09。

¹H-NMR (400MHz, solvent CDCl)₃)δ(ppm):7.82(1H,m),7.15(1H,t),4.36(2H,q),3.00(2H,q),2.65(3H,s),2.56(3H,s),1.43(3H,t),1.36(3H,t)。

Example 7: preparation of methyl 6-fluoro-2, 3, 5-trimethylquinolin-4-ylcarbonate (Compound 43)

The first step of reaction: preparation of 6-fluoro-2, 3, 5-trimethylquinolin-4-ol: 3.2g (0.015mol) of isopropyl 6-amino-3-fluoro-2-methylbenzoate, 4.4g (0.03mol) of ethyl 2-methylacetoacetate and 6g of polyphosphoric acid were successively charged into a three-necked flask at room temperature. The temperature is increased to 150 ℃ and the reaction is carried out for 2 h. The reaction solution is cooled to 60 ℃, poured into 75ml of saturated sodium carbonate solution, fully and uniformly mixed, and solid is separated out. And (5) carrying out suction filtration, and carrying out vacuum drying on a filter cake. Column chromatography (eluent: ethyl acetate: petroleum ether (1: 4)) gave 1.4g, 46% yield.

LC-MS[M+H]⁺＝206.1、[M+Na]⁺＝228.08、[M+K]⁺＝244.05。

The second step of reaction: preparation of methyl 6-fluoro-2, 3, 5-trimethylquinolin-4-ylcarbonate: 1.05g (0.005mol) of 6-fluoro-2, 3, 5-trimethylquinolin-4-hydroxy and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ by a cold bath. To the above mixture was added 0.58g (0.006mol) of methyl chloroformate in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 4 hours. To the reaction system was added 20ml of water, and extracted with ethyl acetate (3 × 12 ml). The organic layers were combined, washed with saturated brine (15ml), and dried over anhydrous sodium sulfate. Filtering, and removing the solution from the filtrate under reduced pressure. Column chromatography (eluent: ethyl acetate: petroleum ether (1:5)) gave 1.05g, 80% yield.

LC-MS[M+H]⁺＝264.11、[M+Na]⁺＝286.09、[M+K]⁺＝302.06。

¹H-NMR (400MHz, solvent CDCl)₃)δ(ppm):7.85(1H,m),7.17(1H,t),3.97(3H,s),2.91(3H,s),2.65(3H,s),2.56(3H,s)。

Example 8: preparation of 6-fluoro-2, 3, 5-trimethylquinolin-4-yl carboxylic acid ethyl ester (Compound 44)

1.05g (0.005mol) of 6-fluoro-2, 3, 5-trimethylquinolin-4-ol and 1.12g (0.01mol) of potassium tert-butoxide were dissolved in 15ml of N, N-dimethylacetamide in this order and cooled to 10 ℃ with a low-temperature bath. To the above mixture was added 0.65g (0.006mol) of ethyl chloroformate in portions, the temperature being maintained below 20 ℃. After the addition, the reaction was carried out at room temperature for 4 hours. To the reaction system was added 20ml of water, and extracted with ethyl acetate (3 × 12 ml). The organic layers were combined, washed with saturated brine (15ml), and dried over anhydrous sodium sulfate. Filtering, and removing the solution from the filtrate under reduced pressure. Column chromatography (eluent: ethyl acetate: petroleum ether (1:6)) gave 1.08g, 78% yield.

LC-MS[M+H]⁺＝278.12、[M+Na]⁺＝300.1、[M+K]⁺＝316.07。

¹H-NMR (400MHz, solvent CDCl)₃)δ(ppm):7.81(1H,m),7.16(1H,t),4.36(2H,q),2.92(3H,s),2.65(3H,s),2.57(3H,s),1.44(3H,t)。

The present invention also synthesizes the following compounds by reference to the methods in the above examples:

formulation examples

In the following examples, all percentages are by weight and all dosage forms are prepared using conventional methods.

Example 9:

in this example, the compound obtained in the above example is used to prepare a wettable powder, which is specifically prepared by using the following raw material compositions in proportion:

950.0% of compound, 4.0% of dodecylphenol polyethoxy glycol ether, 6.0% of sodium lignosulfonate, 8.0% of sodium aluminosilicate and 32.0% of montmorillonite (calcined).

Example 10:

in this example, granules were prepared using the compounds obtained in the above examples, specifically using the following raw material compositions:

3520.0% of compound, 2.0% of sodium dodecyl sulfate as other components, 6.0% of calcium lignosulfonate, 10.0% of potassium chloride, 1.0% of polydimethylsiloxane and soluble starch to make up to 100%.

Example 11:

in this example, the compound obtained in the above example is used to prepare an extruded pellet, specifically using the following raw material composition:

3630.0% of compound, 9.0% of anhydrous calcium sulfate, 4.0% of crude calcium lignosulfonate, 1.0% of sodium alkyl naphthalene sulfonate and 56.0% of calcium/magnesium bentonite.

Example 12:

in this example, the compound obtained in the above example is used to prepare emulsifiable concentrate, and specifically, the emulsifiable concentrate is prepared by using the following raw material compositions:

4425.0% of compound, 15060% of solvent, PEG 4005% of Rhodacal 70/B3% of Rhodameen RAM/77%.

Example 13:

in this example, the compound obtained in the above example is used to prepare an aqueous suspension, specifically, the following raw material composition is used to prepare the aqueous suspension:

6630.0%, POE polystyrene phenyl ether sulfate 5.0%, xanthan gum 0.5%, polyethylene glycol 5%, triethanolamine 1%, sorbitol 0.5% and water to 100.0%.

Biological activity assay

Example 14:

1. determination of insecticidal Activity

In this example, several insects were tested for insecticidal activity using the compounds prepared in the above examples.

And (3) testing the insecticidal activity: the test method is that a test compound sample is dissolved by a suitable solvent (the kind of the solvent is acetone, methanol, DMSO, etc., and is selected according to the dissolving capacity of the solvent on the sample) to prepare a test solution with a required concentration. The test cell consisted of a small open container containing 12-15 day old radish plants. The plants were pre-infested by placing 30-40 pests on a leaf of the test plant that was cut from a cultivated plant (leaf cutting method). As the leaves dehydrate, the pests move on the test plants. After pre-dip dyeing, the soil of the test cell was covered with a layer of sand.

The test method is as follows: the test was repeated three times, and after spraying the formulated test compound, each test unit was allowed to dry for 1 hour, and then a black mesh cap was placed on top. The test cells were kept in a growth chamber at 25 ℃ and 70% relative humidity for 6 days. The mortality rate (mortality) of the insects was then visually evaluated for each test unit, by calculating,

(1) test results for the control of myzus persicae by exemplary example Compounds

At a dose of 400ppm, the compounds with the lethality rate of more than 80% to the green peach aphids comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 100ppm, the compounds with the lethality rate of more than 80% to the green peach aphids comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 25ppm, the compounds with the lethality rate of more than 80% to the green peach aphids comprise: 9. 10, 11, 12, 13, 14, 15, 16, 19, 35,36, 37, 38, 39, 40, 41, 42, 43, 57, 66, 69.

(2) Test results for exemplary example Compounds against Bemisia tabaci

At a dose of 400ppm, the compounds with the fatality rate of more than 80% to bemisia tabaci are as follows: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 100ppm, the compounds with the fatality rate of more than 80% to bemisia tabaci are as follows: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 25ppm, the compounds with a mortality rate of more than 80% to bemisia tabaci are: 9. 10, 11, 12, 13, 14, 15, 16, 19, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 57, 66, 69, 77, 79.

(3) Test results for the control of Aphis gossypii by exemplary example Compounds

At a dose of 400ppm, the compounds with the lethality rate of more than 80% to cotton aphid comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 100ppm, the compounds with the lethality rate of more than 80% to cotton aphid comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 25ppm, the compounds with a lethality rate of more than 80% to Aphis gossypii have the following characteristics: 9. 10, 11, 12, 13, 14, 15, 16, 19, 35,36, 37, 38, 39, 40, 41, 42, 43, 57, 66, 69.

(4) Test results for controlling frankliniella occidentalis by exemplary example Compounds

At a dose of 400ppm, the compounds with the fatality rate of more than 80 percent to frankliniella occidentalis have the following characteristics: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 100ppm, the compounds with the fatality rate of more than 80 percent to frankliniella occidentalis have the following characteristics: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 25ppm, the compounds with the fatality rate of more than 80 percent to frankliniella occidentalis have the following characteristics: 9. 10, 11, 12, 13, 14, 15, 16, 19, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 57, 59, 66, 69, 77, 79.

(5) Test results for exemplary example Compounds against Plutella xylostella

At a dose of 400ppm, the compounds with the lethality rate of more than 80 percent to the plutella xylostella comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 100ppm, the compounds with the fatality rate to plutella xylostella of more than 80 percent are: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 25ppm, the compounds with a mortality rate of more than 80% to plutella xylostella are: 9. 10, 11, 12, 13, 14, 15, 16, 17, 35,36, 37, 38, 39, 40, 41, 42, 66, 69, 77, 79.

(6) Test results of the exemplary embodiment Compounds for controlling Pieris rapae

At a dose of 400ppm, the compounds with a fatality rate of more than 80% to pieris rapae are: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 100ppm, the compounds with a fatality rate of more than 80% to pieris rapae are: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 25ppm, the compounds with a fatality rate of more than 80% to pieris rapae are: 9. 10, 11, 12, 13, 14, 15, 16, 17, 19, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 57, 59, 66, 69.

(7) Exemplary example Compounds control armyworm test results

At a dose of 400ppm, the compounds with a lethality rate of more than 80% to armyworm are: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 100ppm, the compounds with a lethality rate of more than 80% to armyworm are: 1.8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 25ppm, the compounds with a lethality of more than 80% to armyworm are: 9. 10, 11, 12, 13, 16, 35,36, 37, 38, 39, 40, 41, 42, 66, 69, 77, 79.

(8) Exemplary example Compounds control Prodenia litura test results

At a dose of 400ppm, the compounds with the mortality rate of prodenia litura of more than 80 percent comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 100ppm, the compounds with a mortality rate of more than 80% to prodenia litura comprise: 9. 10, 11, 12, 13, 14, 15, 16, 19, 20, 26, 27, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 25ppm, the compounds with a mortality rate of more than 80% to prodenia litura comprise: 9. 10, 11, 12, 13, 16, 35,36, 37, 38, 39, 40, 41, 42.

(9) Test results for exemplary example Compounds to control Chilo suppressalis

At a dose of 400ppm, the compounds with the lethality rate of more than 80 percent to chilo suppressalis comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 100ppm, the compounds with the lethality rate of more than 80 percent to chilo suppressalis comprise: 9. 10, 11, 12, 13, 14, 15, 16, 35,36, 37, 38, 39, 40, 41, 42, 66, 69, 77, 79;

at a dose of 25ppm, the compounds with the lethality rate of more than 80 percent to chilo suppressalis comprise: 9. 10, 11, 12, 16, 35,36, 37, 38, 39, 40, 42.

(10) Test results for the control of rice leaf rollers by exemplary example Compounds

At a dose of 400ppm, the compounds with the lethality rate of more than 80 percent to rice leaf roller comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 100ppm, the compounds with the lethality rate of more than 80 percent to rice leaf roller comprise: 1.4, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 25ppm, the compounds with the lethality rate of more than 80 percent to rice leaf roller comprise: 9. 10, 11, 12, 13, 14, 15, 16, 17, 35,36, 37, 38, 39, 40, 41, 42, 66, 69, 77, 79.

(11) Test results for controlling brown planthopper with exemplary example compounds

At a dose of 400ppm, the compounds with the fatality rate of more than 80% to brown planthopper comprise: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 100ppm, the compounds with the fatality rate of more than 80 percent to brown planthopper comprise: 1. 2,8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 25ppm, the compounds with the fatality rate of more than 80% to brown planthopper comprise: 9. 10, 11, 12, 13, 14, 15, 16, 19, 35,36, 37, 38, 39, 40, 41, 42, 43, 66, 69, 77, 79.

2. Acaricidal Activity assay

In this example, several mite-killing activity tests were carried out using the compounds prepared in the above examples.

The test method is as follows: dissolving a compound sample to be detected with a suitable solvent (the kind of the solvent is acetone, methanol, DMSO, etc., and is selected according to the dissolving capacity of the solvent on the sample), and preparing the solution to be detected with the required concentration. The double-sided adhesive tape is cut into 2-3 cm long pieces, the pieces are attached to one end of a microscope slide, paper pieces on the adhesive tape are removed by tweezers, female adult mites which are consistent in size, bright in body color and lively in action are selected by a zero-number brush pen, the backs of the female adult mites are adhered to the double-sided adhesive tape (paying attention to the fact that the female adult mites do not stick to the mite feet, the mite beards and a mouth tool), 4 lines of the double-sided adhesive tape are adhered to each piece, and 10 heads of the double.

The test method is as follows: the test was repeated three times, and after 4 hours in a biochemical incubator at a temperature of (25+1) ° c and a relative humidity of about 85%, the dead or inactive individuals were removed by binocular observation. Soaking one end of the glass sheet with the mites into the liquid medicine, slightly shaking for 5s, taking out, and quickly sucking away the mites and the redundant liquid medicine around the mites with absorbent paper. Placing in the biochemical incubator, examining the result by using binoculars after 24h, touching the mite body by using a writing brush, and calculating the mortality rate by taking the mite with enough immobility as death. The mortality rate was calculated as follows:

the following results were obtained for the Tetranychus cinnabarinus part:

at a dose of 400ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 1. 2, 4, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 26, 27, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 46, 50, 51, 57, 59, 61, 63, 66, 69, 77, 79;

at a dose of 100ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 1. 9, 10, 11, 12, 13, 15, 16, 35,36, 37, 38, 39, 40, 41, 42, 43, 66, 69, 77, 79;

at a dose of 25ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 9. 11, 12, 16, 35,36, 37, 38, 39, 42, 43.

3. Test results for exemplary example compounds and control agents

This example was conducted to test the activity of exemplary compounds of the examples versus a control agent (control agent CK was prepared by itself according to the literature)₁、CK₂、CK₃And CK₄). The test results are shown in the following table.

In addition to the compounds listed in the above table, other exemplary compounds of the present invention have better control activity against pests and mites than the control agents. Therefore, the compound shown as the formula (I) shows good activity to various pests and mites in the agricultural field.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A compound represented by the following formula (I) or a pharmaceutically acceptable salt thereof,

r is selected from-COR₁or-COOR₁；

Each R₁Identical or different, independently of one another, from C_1-6An alkyl group;

R₂、R₃、R₄identical or different, independently of one another, from C_1-6An alkyl group;

x is selected from F, Cl, Br or I.

2. The compound of claim 1, or a pharmaceutically acceptable salt thereof, wherein in formula (I)

R is selected from-COR₁or-COOR₁；

Each R₁Identical or different, independently of one another, from C_1-4An alkyl group;

R₂、R₃、R₄identical or different, independently of one another, from C_1-4An alkyl group;

x is selected from F or Cl.

3. The compound of claim 1, or a pharmaceutically acceptable salt thereof, wherein in formula (I)

R is selected from-COR₁or-COOR₁；

Each R₁Identical or different, independently of one another, from C_1-4An alkyl group;

R₂、R₃、R₄identical or different, independently of one another, from C_1-4An alkyl group;

x is selected from F or Cl.

4. The compound of claim 1, or a pharmaceutically acceptable salt thereof, wherein the compound of formula (I) is selected from the group consisting of,

5. a process for the preparation of a compound of formula (I) as claimed in any one of claims 1 to 4, comprising the steps of: reacting the compound shown in the formula (II) with the compound shown in the formula (III) or the compound R-L shown in the formula (III-1) to obtain the compound shown in the formula (I),

r, R therein₁、R₂、R₃、R₄X has the meaning as claimed in any of claims 1 to 4, L is selected from Cl, Br or I.

6. The process of claim 5, further comprising the step of preparing a compound of formula (II) comprising:

reacting a compound shown in a formula (IV) with a compound shown in a formula (V) to obtain a compound shown in a formula (II),

wherein R is₂、R₃、R₄X has the definition as set forth in any one of claims 1 to 4; r₅Is C_1-4An alkyl group.

7. A pesticidal composition comprising, as an active ingredient, a compound represented by the formula (I) or a pharmaceutically acceptable salt thereof as claimed in any one of claims 1 to 4.

8. Use of a compound of formula (I) or a pharmaceutically acceptable salt thereof as claimed in any one of claims 1 to 4 in the preparation of a pesticide.

9. Use according to claim 8, wherein the pesticide is selected from insecticides and/or acaricides.