[1, 5-a]-containing thieno [2, 3-e] pyridine derivative and preparation method and application thereof

Abstract

The invention relates to a [1, 5-a] thieno [2, 3-e] pyridine-containing derivative as shown in a formula I or an agronomically acceptable salt thereof, a preparation method of the [1, 5-a] thieno [2, 3-e] pyridine-containing derivative and application of the [1, 5-a] thieno [2, 3-e] pyridine-containing derivative as a plant antibacterial agent, the bactericidal activity is reported for the first time, and part of compounds show excellent bactericidal activity. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the field of pesticide chemistry, and particularly relates to [1,5-a]thieno[2,3-e]pyridine derivatives and their preparation methods and uses. Background Art

[0002] In the field of agricultural production, pesticides, as a key means of preventing and controlling diseases, insects, and weeds, play a crucial role in ensuring stable agricultural production, enhancing agricultural economic benefits, maintaining ecological balance, and protecting human health. Discovering new action mechanisms and lead compounds of pesticides is an important link in the process of developing new pesticides. The discovery of new pesticide targets can provide a precise research direction for the development of new pesticides. Combining new pesticide targets with computer-aided drug design technologies can significantly improve the efficiency of developing new pesticides, such as computer-aided drug design and virtual screening. In addition, by expanding the scope of bioactivity screening, potential lead structures with pesticidal activity can be efficiently discovered, thereby improving the efficiency of pesticide development, which is of great significance for exploring new pesticidal action mechanisms.

[0003] In previous studies, it was found that a class of aryl-linked [1,5-a]thieno[2,3-e]pyridine derivatives have certain antidepressant activities, but the actual effects of most compounds are not ideal, and no agricultural bactericidal activities have been reported.

[0004] Based on this, the present invention further carried out bactericidal activity tests on some compounds. According to the stage results of the bactericidal activity tests, a new round of design and structural optimization of target compounds was carried out, and a series of linked [1,5-a]thieno[2,3-e]pyridine derivatives were obtained and systematically screened and evaluated for biological activities. Summary of the Invention

[0005] The purpose of the present invention is to provide a [1,5-a]thieno[2,3-e]pyridine derivative and its preparation method and use.

[0006] In the first aspect of the present invention, there is provided a compound represented by formula I, or its stereoisomer, or its agrochemically acceptable salt:

[0007]

[0008] Wherein, A, B, C, and D are independently selected from a carbon atom or a nitrogen atom, and at least three of A, B, C, and D are selected from nitrogen atoms;

[0009] R1 is selected from hydrogen, a C1-C6 straight-chain or branched-chain alkyl group, a C3-C6 cycloalkyl group, a C6-C 12 aryl group or a C6-C containing N, O, S atoms 12Heteroaryl; the C6-C 12 aryl or C6-C containing N, O, S atoms 12 The heteroaryl may be further optionally substituted by one, two, three independent R2,

[0010] wherein R2 is selected from hydrogen, halogen, C1-C6 alkyl, halogen-substituted C1-C6 alkyl, C1-C6 alkoxy, halogen-substituted C1-C6 alkoxy, hydroxy or C6-C 12 aryl;

[0011] Preferably, A, B, C and D are independently selected from nitrogen atoms; or A, C and D are selected from nitrogen atoms and B is selected from carbon atoms;

[0012] R1 is selected from C3-C6 cycloalkyl, C6-C 12 aryl or C6-C containing N, O, S atoms 12 heteroaryl; the C6-C 12 aryl or C6-C containing N, O, S atoms 12 heteroaryl may be further optionally substituted by one, two, three independent R2,

[0013] wherein R2 is selected from hydrogen, halogen, C1-C6 alkyl, halogen-substituted C1-C6 alkyl, C1-C6 alkoxy or C6-C 12 aryl;

[0014] More preferably, R1 is selected from C3-C6 cycloalkyl, C6-C 12 aryl or C6-C containing N, O, S atoms 12 heteroaryl; the C6-C 12 aryl or C6-C containing N, O, S atoms 12 heteroaryl may be further optionally substituted by one, two, three independent R2,

[0015] wherein R2 is selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, -CFH2, -CF2H, -CF3, -CH2CFH2, -CH2CF2H or -CH2CF3, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, phenyl or biphenyl;

[0016] Even more preferably, R1 is selected from cyclopropyl, phenyl or thienyl; the phenyl or thienyl may be further optionally substituted by one, two, three independent R2,

[0017] wherein R2 is selected from hydrogen, fluorine, chlorine, bromine, methyl, -CF3, methoxy or phenyl.

[0018] More preferably, A, B, C and D are independently selected from nitrogen atoms; or A, C and D are selected from nitrogen atoms and B is selected from carbon atoms;

[0019] R1 is selected from

[0020] Even more preferably, R1 is selected from

[0021] The specific compound of Formula I is:

[0022]

[0023] In a second aspect of the present invention, there is provided a pesticidal composition comprising at least one compound of Formula I as defined in any one of claims 1-5, or a stereoisomer thereof, or an agrochemically acceptable salt thereof and a carrier; the carrier being in liquid or solid form.

[0024] Furthermore, the use of the aforementioned compound of Formula I, or a stereoisomer thereof, or an agrochemically acceptable salt thereof or the aforementioned pesticidal composition in controlling plant fungal diseases, preferably, the plant fungal diseases are the pathogens of tomato early blight, Botrytis cinerea, peanut brown spot, Fusarium graminearum, the pathogen of apple ring rot, Rhizoctonia solani or Sclerotinia sclerotiorum.

[0025] In a third aspect of the present invention, there is provided a fungicide, characterized in that the fungicide contains a fungicidally effective amount of at least one of the aforementioned compound of Formula I, or a stereoisomer thereof, or an agrochemically acceptable salt thereof, and optionally contains excipients.

[0026] Preferably, the dosage form of the fungicide is selected from at least one of emulsifiable concentrate, suspension concentrate, wettable powder, powder, granule, aqueous solution, mother liquor and mother powder.

[0027] In a fourth aspect of the present invention, there is provided a method for controlling or preventing useful plants from being infected by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound having Formula I as defined above or a composition containing such a compound as an active ingredient is applied to the plant, a part thereof or its locus.

[0028] In a fifth aspect of the present invention, the synthetic route of the compound of Formula I is as follows:

[0029]

[0030] Synthetic route of compound of formula I: (i) NaOH, EtOH; reflux; (ii) CH3COOH, reflux; (iii) Meldrum’s acid, R1-CHO, CH3COOH, reflux; (iv) P2S5, CH3CN (v) NH2NH2·H2O, CH3OH, reflux; (vi) NaNO2, 5% HCl, 0-5 °C; (vii) HC(OC2H5)3, 100 °C.

[0031] The sixth aspect of the present invention provides the use of a combination of a compound of formula I of [1,5-a]thieno[2,3-e]pyridine derivatives and an insecticide in controlling pests of agricultural, forestry, and horticultural plants: The compound of formula I of [1,5-a]thieno[2,3-e]pyridine derivatives of the present invention is combined with any one or two of commercial insecticides to form an insecticidal composition for controlling pests of agricultural, forestry, and horticultural plants. The commercial insecticides are selected from: methoprene, diazinon, acetamiprid, emamectin benzoate, milbemycin, avermectin, spinosad, heptaflumethrin, chlorfluazuron, beta-cypermethrin, cypermethrin, lambda-cyhalothrin, deltamethrin, fenpropathrin, beta-cyfluthrin, lambda-trifluorochlorobenzyl cyhalothrin, permethrin, resmethrin, allethrin, bifenthrin, pyrethrin, ethofenprox, flumethrin, tau-fluvalinate, imidacloprid, nitenpyram, clothianidin, thiacloprid, thiamethoxam, clothianidin, dinotefuran, conidine, dacthal, diflubenzuron, chlorbenzuron, novaluron, lufenuron, flucycloxuron, flufenoxuron, noviflumuron, hexaflumuron, bistrifluron, flupyrazofos, tebufenozide, methoxyfenozide, halofenozide, chromafenozide, dichlorvos, quinalphos, pyridaphenthion, isoprocarb, carbaryl, pirimicarb, propoxur, isoprocarb, cartap hydrochloride, Bassa, fenobucarb, naphthylcarbamate, cartap hydrochloride, bromopropylate, hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, pymetrozine, spirodiclofen, spirotetramat, spiroethrin, azocyclotin, buprofezin, monosultap, bisultap, chlorantraniliprole, tetrachlorantraniliprole, flubendiamide, cyhalodiamide, cyantraniliprole, ethiprole, tolfenpyrad, bromfenozide, pyrafluprole, emamectin, viliprodan; The mass percentage content of the compound of formula I of [1,5-a]thieno[2,3-e]pyridine derivatives of the present invention in the insecticidal composition is 1% - 90%. The ratio of the compound of formula I of [1,5-a]thieno[2,3-e]pyridine derivatives of the present invention to the aforementioned commercial insecticides is 1%:99% to 99%:1% by mass percentage; The dosage forms processed from the insecticidal composition are selected from: seed treatment emulsion, emulsion in water, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisoned grain, block bait, granular bait, sheet bait, concentrated bait, slow-release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke cartridge, smoke stick, smoke tablet, smoke pill, gas generator, ointment, thermal fogging agent, cold fogging agent, aerosol, solid / liquid mixed preparation, liquid / liquid mixed preparation, solid / solid mixed preparation, medicated paint, particulate agent, tracking powder, oil suspension, oil-dispersible powder, thick gel, drenching agent, seed coating agent, smearing agent, film-forming oil agent, ultra-low volume liquid agent, vapor release agent;The plant pests applicable to the insecticidal composition are selected from: Spodoptera frugiperda, Tetranychus cinnabarinus, Locusta migratoria manilensis, Gastrimargus marmoratus, Oxya chinensis, Patanga japonica, Gryllotalpa unispina, Gryllotalpa orientalis, Thrips oryzae, Thrips tabaci, Thrips hawaiiensis, Haplothrips aculeatus, Haplothrips tritici, Trialeurodes vaporariorum, Bemisia tabaci, Nephotettix cincticeps, Cicadella viridis, Empoasca biguttula, Lycorma delicatula, Nilaparvata lugens, Sogatella furcifera, Laodelphax striatellus, Perkinsiella saccharicida, Aphis gossypii, Schizaphis graminum, Sitobion avenae, Myzus persicae, Melanaphis sacchari, Lipaphis erysimi, Icerya purchasi, Pseudaulacaspis pentagona, Unaspis yanonensis, Quadraspidiotus perniciosus, Ericerus pela, Ceroplastes rubens, Didesmococcus koreanus, Stephanitis nashi, Stephanitis typica, Anthocoris tenuis, Orius minutus, Leptocorisa acuta, Leptocorisa oratoria, Scotinophara lurida, Nezara viridula, Apolygus lucorum, Adelphocoris suturalis, Adelphocoris taeniophorus, Chrysopa pallens, Chrysopa formosa, Chrysopa sinica, Tinea granella, Tinea pellionella, Cnidocampa flavescens, Setora postornata, Thosea sinensis, Gelechia cerealella, Pectinophora gossypiella, Brachmia macroscopa, Plutella xylostella, Carposina sasakii, Leguminivora glycinivorella, Carposina sasakii, Spilonota lechriaspis, Homona coffearia, Adoxophyes cyrtosema, Chilo suppressalis, Etiella zinckenella, Ostrinia furnacalis, Tryporyza incertulas, Hellula undalis, Cnaphalocrocis medinalis, Proceras venosatus, Notarcha derogata, Dichocrocis punctiferalis, Mythimna separata, Spodoptera litura, Naranga aenescens, Anomis flava, Sesamia inferens, Helicoverpa armigera, Earias cupreoviridis, Agrotis ypsilon, Agrotis tokionis, Agrotis segetum, Lymantria dispar, Actias selene, Clanis bilineata, Parnara guttata, Pelopidas mathias, Papilio xuthus, Papilio polytes, Pieris rapae, Vanessa indica, Vanessa cardui, Epicauta gorhami, Calosoma maderae, Calosoma maximoviczi, Calosoma chinense, Pleonomus canaliculatus, Agriotes fuscicollis, Trogoderma granarium, Attagenus unicolor, Agrilus auriventris, Agrilus chrysoderes, Tenebrio molitor, Alphitobius diaperinus, Tribolium castaneum, Tribolium confusum, Anomala corpulenta, Holotrichia parallela, Holotrichia oblita, Apriona germari, Anoplophora chinensis, Apriona swainsoni, Aromia bungii, Colaphellus bowringi, Phyllotreta striolata, Callosobruchus chinensis, Bruchus pisorum, Bruchus rufimanus, Sitophilus zeamais, Sitophilus oryzae, Dolerus tritici, Hoplocampa pyricola, Ichneumon flavicinctus, Coccygomimus disparis, Charops bicolor, Campoletis chlorideae, Diadegma semiclausum, Contarinia tritici, Sitodiplosis mosellana, Pachydiplosis oryzae, Bactrocera minax, Bactrocera cucurbitae, Agromyza triticella, Liriomyza sativae, Melanagromyza sojae, Oscinella frit, Delia platura, Delia antiqua, Delia floralis, Exorista civilis, Zenillia dolosa, Mythimna separata; The plants applicable to the insecticidal composition are selected from: paddy rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, mulberry, peanut, rapeseed, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, Chinese cabbage, celery, Sichuan pickle, sugar beet, rapeseed, onion, garlic, watermelon, muskmelon, Hami melon, papaya, apple, citrus and peach tree, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.

[0032] The seventh aspect of the present invention provides the use of a combination of a compound of formula I of [1,5-a]thieno[2,3-e]pyridine derivatives and a fungicide in the control of plant diseases in agriculture, forestry and horticulture. The combination of the compound of formula I of [1,5-a]thieno[2,3-e]pyridine derivatives of the present invention and any one or two of commercial fungicides forms a fungicidal composition for controlling plant diseases in agriculture, forestry and horticulture. The commercial fungicides are selected from: benzothiadiazole, tiadinil, methythiohydantoin, isotianil, ribavirin, anthofen, ningnanmycin or salicylic acid, cymoxanil, thiram, zinc dimethyldithiocarbamate, mancozeb, fosetyl-aluminum, thiophanate-methyl, chlorothalonil, fenaminosulf, fenpropidin, thiophanate-methyl, thiofanate, metalaxyl-M, flumorph, dimethomorph, metalaxyl-M, benalaxyl-M, diclocymet, sulfetramide, mesosulfamide, thifluzamide, phthalide, cyproconazole, cyflufenamid, cyazofamid, cyanovirin-N, silthiofam, carboxin, oxycarboxin, mepronil, furametpyr, dimethomorph, thifluzamide, boscalid, pyraclostrobin, pyraziflumid, bixafen, fluopyram, fluxapyroxad, fluazaindolizine, propiconazole, isopropylthianil, fluxapyroxad, fluopyram, fluoxastrobin, pyribencarb, procymidone, iprodione, azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, trifloxystrobin, enestroburin, enoxastrobin, oxycarboxin, bactraconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, silthiofam, tebuconazole, tetraconazole, triadimenol, triazoxide, bitertanol, thiabendazole, tridemorph, tricyclazole, imazalil, imazalil-M, prochloraz, flutriafol, cyazofamid, fenamidone, oxpoconazole, oxadixyl, thiazolylamine, quintozene, octhilinone, benzyldithiocarbamate, dodemorph, buthiobate, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, cyprodinil, fluopyram, pyrimethanil, cyprodinil, fluopyram, pyrimethanil, chlorothalonil, isoprothiolane, iprobenfos, pyrazophos, tolclofos-methyl, blasticidin-S, kasugamycin, polyoxin, validamycin, jinggangmycin, streptomycin, metalaxyl, ofurace, benalaxyl, furalaxyl, carbendazim, benomyl, thiophanate-methyl, triadimefon, ethirimol, dimethirimol, ethirimol, captafol, captan, folpet, vinclozolin, fludioxonil, maneb, isoprothiolane, isoprobenfos, blasticidin-S, thiodiazole copper, Bordeaux mixture, copper sulfate, copper oxychloride,Cuprous oxide, copper hydroxide, metrafenone, tebuconazole, pyrifenox, phthalide, pyroquilon, spiroxamine, tricyclazole, triforine, dodine, guazatine, guazatine acetate, dichloran, benzovindiflupyr, tolylfluanid, indanofan, sodium thiram, cinidon-ethyl, probenazole, bronopol, methyl iodide, metam-sodium, dimefuron, dazomet, 1,3-dichloropropene, isopropyl 2,6-dichloronicotinate, allyl isothiazole; The total mass percentage of the [1,5-a]thieno[2,3-e]pyridine derivative in the fungicidal composition of the present invention is 1%-90% for the compound of formula I, and the amount percentage of the [1,5-a]thieno[2,3-e]pyridine derivative of formula I compound of the present invention to the aforementioned commercial fungicides is 1%:99% to 99%:1%; The dosage forms processed from the fungicidal composition are selected from: seed treatment emulsion, water emulsion, microemulsion, suspo-emulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisoned grain, block bait, granular bait, flake bait, concentrated bait, slow-release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke tablet, smoke pill, gas generator, ointment, thermal fogging agent, cold fogging agent, aerosol, solid / liquid mixture, liquid / liquid mixture, solid / solid mixture, medicated paint, particle agent, tracking powder, oil suspension, oil-dispersible powder, thick gel, drenching agent, seed coating agent, smearing agent, film-forming oil agent, ultra-low volume liquid agent, steam release agent; The plant diseases applicable to the fungicidal composition are selected from: rice seedling cottony rot, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber downy mildew, cucumber anthracnose; The plants applicable to the fungicidal composition are selected from: paddy rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, mulberry, peanut, rapeseed, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, Chinese cabbage, celery, mustard tuber, sugar beet, rapeseed, onion, garlic, watermelon, muskmelon, Hami melon, papaya, apple, citrus and peach tree, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.,

[0033] The eighth aspect of the present invention provides the use of a compound of formula I containing a [1,5-a]thieno[2,3-e]pyridine derivative in combination with an anti-plant virus agent in the prevention and control of virus diseases of agricultural, forestry and horticultural plants. The compound of formula I containing a [1,5-a]thieno[2,3-e]pyridine derivative of the present invention is combined with any one or two of the commercial anti-virus agents to form an anti-virus composition for the prevention and control of virus diseases of agricultural, forestry and horticultural plants. The commercial anti-virus agents are selected from: benzothiadiazole, tiadinil, isotianil, ribavirin, anthofine, ningnanmycin, methythiohydantoin or salicylic acid, peptidomycin, dichloroisonicotinic acid, allyl isothiazole, jinggangmycin, moroxydine hydrochloride; the total mass percentage content of the compound of formula I containing a [1,5-a]thieno[2,3-e]pyridine derivative in the anti-virus composition of the present invention is 1% - 90%, and the ratio of the compound of formula I containing a [1,5-a]thieno[2,3-e]pyridine derivative of the present invention to the aforementioned commercial anti-plant virus agent is 1%:99% to 99%:1% by mass percentage; the dosage forms processed from the anti-virus composition are selected from: seed treatment emulsion, water emulsion, microemulsion, suspension emulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisoned grain, block poison bait, granular poison bait, flake poison bait, concentrated poison bait, slow-release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, thermal fogging agent, cold fogging agent, aerosol, solid / liquid mixed preparation, liquid / liquid mixed preparation, solid / solid mixed preparation, medicated paint, particulate agent, tracking powder, oil suspension, oil-dispersible powder, thick glue agent, drenching agent, seed coating agent, smearing agent, film-forming oil agent, ultra-low volume liquid agent, steam release agent; the virus diseases prevented and controlled by the anti-virus composition are selected from: rice dwarf disease, yellow dwarf disease, stripe virus disease, tomato fern leaf virus disease, pepper mosaic virus disease, tobacco vein necrosis virus disease, maize dwarf mosaic disease, cauliflower mosaic virus, citrus virus disease, cymbidium mosaic virus, cymbidium ringspot virus; the plants for which the anti-virus composition is used for prevention and control are selected from: paddy rice, wheat, barley, oats, maize, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, mulberry, peanut, rapeseed, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, Chinese cabbage, celery, mustard tuber, sugar beet, rapeseed, onion, garlic, watermelon, melon, Hami melon, papaya, apple, citrus and peach tree, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.

[0034] The ninth aspect of the present invention provides the use of a compound of formula I containing a [1,5-a]thieno[2,3-e]pyridine derivative in combination with a miticide in the control of mite pests in agricultural, forestry, and horticultural plants. The compound of formula I containing a [1,5-a]thieno[2,3-e]pyridine derivative of the present invention is combined with any one or two of commercial miticides to form a miticidal composition for controlling mite pests in agricultural, forestry, and horticultural plants. The commercial miticides are selected from: dichlorvos, heptenophos, mevinphos, dibrom, pirimiphos-methyl, phosmet, ethion, phosphocarb, phosalone, pirimiphos-methyl, quinalphos, formothion, propaphos, phosmet, imidacloprid, fluvalinate, bifenthrin, cyhalothrin, beta-cyhalothrin, fenpropathrin, flucythrinate, tau-fluvalinate, brofluthrinate, bifenazate, carbaryl, butocarboxim, methiocarb, propoxur, carbofuran, benomyl, cloethocarb, butyl mercaptan, pyridaben, tebufenpyrad, fenpyroximate, clofentezine, propargite, hexythiazox, spirodiclofen, fluacrypyrim, chlorfenson, dicofol, fenbutatin oxide, pyridaben; the total mass percentage content of the compound of formula I containing a [1,5-a]thieno[2,3-e]pyridine derivative of the present invention in the miticidal composition is 1% - 90%, and the ratio of the compound of formula I containing a [1,5-a]thieno[2,3-e]pyridine derivative of the present invention to the commercial miticide is 1%:99% to 99%:1% by mass percentage; the dosage forms processed from the miticidal composition are selected from: seed treatment emulsion, aqueous emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisoned grain, block poison bait, granular poison bait, sheet poison bait, concentrated poison bait, slow-release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke tablet, smoke pill, gas generator, ointment, thermal fogging agent, cold fogging agent, aerosol, solid / liquid mixture, liquid / liquid mixture, solid / solid mixture, medicated paint, particulate agent, tracking powder, oil suspension, oil-dispersible powder, thick gel, drenching agent, seed coating agent, coating agent, film-forming oil agent, ultra-low volume liquid agent, steam release agent; the mite pests controlled by the miticidal composition are selected from: mite pests selected from Tetranychidae, Tenuipalpidae, Acaridae, Eriophyidae, Tetranychus, Eriophyidae. These mite pests are worldwide agricultural, forestry, horticultural, and sanitary mite pests;The plants to be controlled by the acaricidal composition are selected from: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, mulberry, peanut, rapeseed, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, Chinese cabbage, celery, Sichuan pickle, sugar beet, rapeseed, onion, garlic, watermelon, muskmelon, Hami melon, papaya, apple, citrus and peach tree, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.;

[0035] The tenth aspect of the present invention provides the use of the [1,5-a]thieno[2,3-e]pyridine derivative of formula I in the preparation of a pesticidal composition. The [1,5-a]thieno[2,3-e]pyridine derivative of formula I of the present invention is used to prepare a pesticidal composition, which composition contains the [1,5-a]thieno[2,3-e]pyridine derivative of formula I of the present invention as the active ingredient, and the mass percentage content of the active ingredient is 0.1% to 99.9%, and the mass percentage content of the solid or liquid auxiliary is 99.9% to 0.1%. In addition, it also contains a surfactant with an optional mass percentage content of 0 to 25%.

[0036] The eleventh aspect of the present invention provides the use of the [1,5-a]thieno[2,3-e]pyridine derivative of formula I in the preparation of a pesticidal compound composition. The [1,5-a]thieno[2,3-e]pyridine derivative of formula I of the present invention can be compounded with other commercial pesticides, namely insecticides, acaricides, fungicides, antiviral agents or plant activators, to prepare a pesticidal compound composition. The compound composition contains the [1,5-a]thieno[2,3-e]pyridine derivative of formula I of the present invention and the commercial pesticides, namely insecticides, acaricides, fungicides, antiviral agents or plant activators as the active ingredients. The ratio of the [1,5-a]thieno[2,3-e]pyridine derivative of formula I of the present invention to other commercial pesticides, namely insecticides, acaricides, fungicides, antiviral agents or plant activators, is 1%:99% to 99%:1% in mass percentage. The mass percentage content of the active ingredient is 0.1% to 99.9%, the solid or liquid auxiliary with a mass percentage content of 99.9% to 0.1%, and an optional surfactant with a mass percentage content of 0 to 25%.

[0037] The following are the explanations and descriptions of the terms and expressions of the present invention:

[0038] The compounds and derivatives provided in the present invention can be named according to the IUPAC (International Union of Pure and Applied Chemistry) or CAS (Chemical Abstracts Service, Columbus, OH) naming system.

[0039] Definitions of terms used in the present invention: Unless otherwise specified, the initial definitions provided for groups or terms herein apply to such groups or terms throughout the specification; for terms not specifically defined herein, meanings that can be given to them by those skilled in the art should be provided based on the disclosure and context.

[0040] "Substituted" means that a hydrogen atom in a molecule is replaced by other different atoms or molecules.

[0041] The minimum and maximum carbon atom contents in a hydrocarbon group are indicated by a prefix. For example, the prefix Ca~b alkyl indicates any alkyl group containing "a" to "b" carbon atoms. Thus, for example, "C1~4 alkyl" means an alkyl group containing 1 to 4 carbon atoms.

[0042] The term "alkyl" means a saturated hydrocarbon chain having a specified number of member atoms. For example, C1~6 alkyl means an alkyl group having 1 to 6 member atoms, such as 1 to 4 member atoms. The alkyl group can be straight-chain or branched-chain. Representative branched-chain alkyl groups have one, two, or three branches. The alkyl group can be optionally substituted with one or more substituents as defined herein. Alkyl includes methyl, ethyl, propyl (n-propyl and isopropyl), butyl (n-butyl, isobutyl, and tert-butyl), pentyl (n-pentyl, isopentyl, and neopentyl), and hexyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, etc. The term "C1-C3 alkyl" means a straight-chain or branched-chain saturated hydrocarbon group having 1-3 carbon atoms. The alkyl group can also be part of other groups, such as C1~C6 alkoxy.

[0043] The term "alkoxy" means O-alkyl. The term "C1-C8 alkoxy" means O-C1-C8 alkyl.

[0044] The term "C6-C 10 aryl" means a fully carbon monocyclic or fused polycyclic group having 6 to 10 carbon atoms and having a completely conjugated π electron system. Typically includes but is not limited to phenyl, naphthyl, biphenyl.

[0045] The term "heteroaryl" means a monocyclic or fused ring group containing one, two, three, or four ring heteroatoms selected from N, O, or S, with the remaining ring atoms being C, and further having a completely conjugated π electron system. The term "C6-C 12 heteroaryl" means a heteroaryl containing 3 to 10 carbon atoms in its ring. C3-C 10 heteroaryl includes but is not limited to pyrrolyl, furyl, thienyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyrimidinyl, pyridyl.

[0046] The term "halogen" is fluorine, chlorine, bromine, or iodine.

[0047] The term "haloalkyl" means that the hydrogen atoms in the alkyl group can be replaced by one or more halogen atoms. For example, C1-4 haloalkyl refers to an alkyl group containing 1-4 carbon atoms in which the hydrogen atoms are replaced by one or more halogen atoms.

[0048] The compounds of the present invention may contain asymmetric centers or chiral centers, and thus there are different stereoisomers. All stereoisomeric forms of the compounds of the present invention, including but not limited to, diastereomers, enantiomers, atropisomers, and mixtures thereof, such as racemic mixtures, form part of the present invention. Many organic compounds exist in optically active forms, i.e., they have the ability to rotate the plane of plane-polarized light. When describing an optically active compound, the prefixes D, L or R, S are used to denote the absolute configuration of the chiral center of the molecule. The chemical structures of these stereoisomers are the same, but their spatial structures are different. A particular stereoisomer may be an enantiomer, and a mixture of isomers is usually called a mixture of enantiomers. A 50:50 mixture of enantiomers is called a racemic mixture or racemate, which may result in no stereoselectivity or stereospecificity during a chemical reaction. The terms "racemic mixture" and "racemate" refer to a mixture of equimolar amounts of two enantiomers, lacking optical activity.

[0049] The term "agronomically acceptable salts" refers to acid and / or basic salts formed by the above compounds or their stereoisomers with inorganic and / or organic acids and bases, including zwitterionic salts (inner salts), and also including quaternary ammonium salts, such as alkylammonium salts. These salts can be directly obtained during the final isolation and purification of the compound. They can also be obtained by appropriately (e.g., equimolarly) mixing the above compounds, or their stereoisomers, with a certain amount of acid or base. These salts may form a precipitate in solution and be collected by filtration, or recovered after evaporation of the solvent, or prepared by lyophilization after reaction in an aqueous medium. The salts described in the present invention may be hydrochloride, sulfate, citrate, benzenesulfonate, hydrobromide, hydrofluoride, phosphate, acetate, propionate, succinate, oxalate, malate, fumarate, maleate, tartrate or trifluoroacetate salts of the compound.

[0050] Compounds of formula I are used in the relevant art, for example, as active ingredients for controlling phytopathogenic pests, or on inanimate materials for controlling spoilage microorganisms or organisms potentially harmful to humans. The novel compounds of formula I are characterized by excellent activity at low application rates, good plant tolerance and environmental friendliness. They have very useful therapeutic, prophylactic and systemic properties and can be used to protect cultivated plants. Compounds of formula I can be used to inhibit or destroy pests occurring on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different useful plant crops, while also protecting, for example, those later-growing plant parts from phytopathogenic microorganisms.

[0051] The term "plant" refers to all tangible parts of a plant, including seeds, seedlings, young trees, roots, tubers, stems, stalks, leaves and fruits.

[0052] Compounds of formula I can be the sole active ingredient of a composition, or, where appropriate, it can be mixed with one or more additional active ingredients (such as pest control agents, fungicides, synergists, herbicides or plant growth regulators). In some cases, the additional active ingredients can result in unexpected synergistic activity.

[0053] Examples of suitable additional active ingredients include acyclic amino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, aniline fungicides, antibiotic fungicides, etc.

[0054] A formulation, for example, a composition comprising a compound of formula I, and a solid or liquid adjuvant or a monomer for encapsulating the compound of formula I, can be prepared in a known manner, typically by intimately mixing and / or grinding the compound with extenders (such as solvents, solid carriers and, optionally, surface-active compounds (surfactants)).

[0055] Generally, the formulation comprises from 0.01% to 90% by weight of the active ingredient, from 0 to 20% of an agriculturally acceptable surfactant and 10% to 99.99% of a solid or liquid formulation inert agent and adjuvant.

[0056] The composition of the present invention can be used in any conventional form, for example, in the form of a two-pack, emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water-dispersible granule (WG), emulsifiable granule (EG), water-in-oil emulsion (EO), oil-in-water emulsion (EW), microemulsion (ME), oil-based suspension (OD), oil suspension (OF), oil-soluble liquid (OL), soluble concentrate (SL), ultra-low volume suspension (SU), ultra-low volume liquid (UL), technical material (TK), dispersible concentrate (DC), wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0057] Obviously, based on the above content of the present invention, according to the common general technical knowledge and conventional means in the art, without departing from the above basic technical idea of the present invention, various other forms of modifications, substitutions or changes can be made.

[0058] Advantageous technical effects of the present invention: 1. The present invention provides a class of [1,5-a]thieno[2,3-e]pyridine derivatives; the derivatives of the present invention can regulate the biological activities of agricultural, horticultural and sanitary and forestry plant pests and plant pathogens, and can be used for insecticidal, acaricidal, bactericidal, anti-plant virus and inducing plant disease resistance in the agricultural field, horticultural field and forestry field, and have good economic value and application prospects.

[0059] 2. Compounds of formula I-b, formula I-f, formula I-h, formula I-j, formula I-k, formula I-n, formula I-o, formula I-r and formula I-s exhibit high bactericidal activities and the agricultural bactericidal activities of [1,5-a]thieno[2,3-e]pyridine derivative of formula I are reported for the first time. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 : EC of compound I-f against Rhizoctonia solani 50 Test results;

[0061] Figure 2 : EC of compound I-k against Cercospora arachidicola 50 Test results. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0062] The present invention will be further illustrated by the following examples, but it is not intended to limit the present invention.

[0063] Intermediate Example 1: Preparation of Compound I-2

[0064] Methyl 3-aminothiophene-2-carboxylate (18.0 mmol), sodium hydroxide (36 mmol) and 40 mL of ethanol were added to a 100 mL round-bottom flask. Then the mixture was stirred at 80 °C for 12 h. The reaction progress was monitored by thin-layer chromatography (TLC). After the reaction was completed, the reaction solvent was removed under reduced pressure, and the crude product was crystallized with ethanol to obtain Intermediate I-2, a white solid, with a yield of 92%.

[0065] Example 1: Preparation of Compound I-r

[0066] 1. Preparation of Compound I-3

[0067] Compound I-2 (18.0 mmol) and 30 mL of acetic acid were added to a 100 mL round-bottom flask. Subsequently, Meldrum's acid (27.0 mmol) and 4-methylbenzaldehyde (19.8 mmol) were added, and the reaction was monitored by thin-layer chromatography (TLC). The resulting mixture was reacted at 90 °C for 10 h. After the reaction was completed, 50 mL of water was added to the reaction solution, and then the mixture was extracted three times with 100 mL of ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, and the filtrate was removed by a vacuum pump. The residue was purified by silica gel column chromatography using dichloromethane:methanol (v:v, 100:1) as the eluent to obtain Intermediate I-3 as a white solid, with a yield of 48%.

[0068] 2. Preparation of Compound I-4

[0069] In a 100 mL round-bottom flask, 100 mL of a mixed solvent of acetonitrile / triethylamine (volume ratio 3:1) was added. Under ice bath conditions, phosphorus pentasulfide (9 mmol) was added in portions. Subsequently, Intermediate I-3 (10 mmol) was added to the reaction solution, and the mixture was refluxed. After the reaction was completed, the solvent was removed by evaporation under reduced pressure, and the crude product was crystallized with dichloromethane to obtain Intermediate I-4, a yellow solid, with a yield of 70%.

[0070] 3. Preparation of Compound I-5

[0071] 5 mmol of Compound I-4 and 10.0 mmol of hydrazine hydrate were added to a round-bottom flask containing 20 mL of methanol and reacted at 70 °C for 1 h. After the reaction was completed, the solvent was removed by evaporation under reduced pressure, and then the crude product was recrystallized with methanol to obtain Intermediate I-5, a white solid, with a yield of 64%.

[0072] 4. Preparation of Compound I-r

[0073] The above intermediate I-5 (2.0 mmol) and 10 mL of triethyl orthoformate were added to a 50 mL round-bottom flask, and then reacted at 120 °C for 12 h. After the reaction was completed, triethyl orthoformate was removed under reduced pressure using a vacuum pump. 30 mL of water was added to obtain a solid residue, which was filtered and dried to obtain the crude product. It was purified by column chromatography (methanol / dichloromethane = 1:200) to obtain the target compound I-r, a yellow solid, yield: 17%, Mp: 86 - 90 °C. 1 H NMR (500 MHz, CDCl3) δ 8.48 (s, 1H), 7.32 (d, J = 5.4 Hz, 1H), 7.26 (s, 1H), 7.18 (s, 1H), 7.16 (d, J = 1.2 Hz, 2H), 7.15 (s, 1H), 4.45 (dd, J = 10.2, 6.5 Hz, 1H), 3.62 (dd, J = 16.1, 6.5 Hz, 1H), 3.38 (dd, J = 16.1, 10.3 Hz, 1H), 2.35 (s, 3H). 13 C NMR (126 MHz, CDCl3) δ 149.62 (s), 137.89 (s), 137.85 (s), 137.49 (s), 130.14 (s), 129.81 (s), 127.35 (s), 127.04 (s), 126.10 (s), 116.62 (s), 39.65 (s), 30.06 (s), 21.12 (s). ESI-HRMS calcd for C 15 H 13 N3S + ([M+H] + ): 268.0903; found: 268.0904.

[0074] Example 2: Preparation of Compound I-n

[0075] The same intermediate I-5 was prepared according to the same route as in Intermediate Example 1 and Example 1.

[0076] Then, intermediate I-5 (1.5 mmol) was added to a round-bottom flask containing 10 mL of 5% hydrochloric acid, and the reaction system was cooled to 0 - 5 °C. Then, 1 mL of a 3.0 mol / L aqueous sodium nitrite solution was slowly added. The reaction was monitored by thin-layer chromatography (TLC). After the reaction was completed, the reaction solution was extracted three times with 50 mL of dichloromethane. The organic phase was dried over anhydrous sodium sulfate, and the filtrate was removed by vacuum pumping. The residue was purified by silica gel column chromatography using petroleum ether:ethyl acetate (v:v, 20:1) as the eluent to obtain the target compound I-n, a yellow solid; yield: 18%. Mp: 103 - 105 °C. 11H NMR (500 MHz, CDCl3) δ 7.56 (d, J = 5.4 Hz, 1H), 7.38 (d, J = 5.4 Hz, 1H), 7.18 (d, J = 8.0 Hz, 2H), 7.13 (d, J = 8.1 Hz, 2H), 4.56 (dd, J = 10.3, 7.1 Hz, 1H), 3.75 (dd, J = 16.7, 7.0 Hz, 1H), 3.50 (dd, J = 16.7, 10.4 Hz, 1H), 2.36 (s, 3H). 13 13C NMR (126 MHz, CDCl3) δ 150.10 (s), 138.26 (s), 137.25 (s), 131.12 (s), 130.47 (s), 129.98 (s), 127.27 (s), 126.71 (s), 117.55 (s), 39.50 (s), 29.21 (s), 21.13 (s). ESI-HRMS calcd for C 14 H 12 N4S + ([M+H] + ): 269.0856; found: 269.0857.

[0077] Example 3: Preparation of Compound I-m

[0078] Following the same route as in Example 2, Compound I-m was prepared as a yellow solid in 62% yield, Mp: 142 - 146 °C. 1 1H NMR (500 MHz, CDCl3) δ 7.57 (d, J = 5.4 Hz, 1H), 7.39 (d, J = 5.4 Hz, 1H), 7.29 - 7.25 (m, 1H), 7.15 (d, J = 7.6 Hz, 1H), 7.08 - 7.00 (m, 2H), 4.55 (dd, J = 10.2, 7.1 Hz, 1H), 3.76 (dd, J = 16.7, 7.1 Hz, 1H), 3.52 (dd, J = 16.7, 10.3 Hz, 1H), 2.35 (s, 3H). 13 13C NMR (126 MHz, CDCl3) δ 150.06 (s), 140.25 (s), 139.13 (s), 130.92 (s), 130.51 (s), 129.20 (s), 129.17 (s), 128.09 (s), 126.76 (s), 124.42 (s), 117.54 (s), 39.80 (s), 29.15 (s), 21.49 (s). ESI-HRMS calcd for C 14 H 12 N4S + ([M+H]+ ): 269.0856; found: 269.0856.

[0079] Example 4: Preparation of Compound I-o

[0080] Following the same preparation route as in Example 2, Compound I-o was prepared as a yellow solid, yield: 14%. Mp: 120 - 125 °C. 1 H NMR (500 MHz, CDCl3) δ 7.56 (d, J = 5.4 Hz, 1H), 7.42 (d, J = 5.4 Hz, 1H), 7.30 - 7.24 (m, 1H), 6.97 (dd, J = 5.1, 3.6 Hz, 1H), 6.92 (d, J = 3.4 Hz, 1H), 4.93 (dd, J = 8.9, 6.9 Hz, 1H), 3.82 (dd, J = 16.6, 6.8 Hz, 1H), 3.65 (dd, J = 16.6, 9.1 Hz, 1H). 13 C NMR (126 MHz, CDCl3) δ 149.69 (s), 142.81 (s), 130.21 (s), 130.18 (s), 127.24 (s), 126.96 (s), 125.72 (s), 125.53 (s), 117.66 (s), 34.92 (s), 29.81 (s). ESI-HRMS calcd for C 11 H8N4S2 + ([M + H] + ): 261.0263; found: 261.0265.

[0081] Example 5: Preparation of Compound I-p

[0082] Following the same preparation route as in Example 2, Compound I-p was prepared as a yellow solid, yield: 10%, Mp: 161 - 165 °C. 1 H NMR (500 MHz, CDCl3) δ 7.58 (dd, J = 8.5, 6.7 Hz, 5H), 7.45 (t, J = 7.6 Hz, 2H), 7.41 (d, J = 5.4 Hz, 1H), 7.37 (d, J = 7.3 Hz, 1H), 7.30 (d, J = 8.2 Hz, 2H), 4.65 (dd, J = 9.9, 7.1 Hz, 1H), 3.81 (dd, J = 16.7, 7.1 Hz, 1H), 3.57 (dd, J = 16.7, 10.0 Hz, 1H). 1313C NMR (126 MHz, CDCl3) δ 149.98 (s), 141.39 (s), 140.22 (s), 139.19 (s), 130.64 (s), 130.60 (s), 128.90 (s), 128.01 (s), 127.81 (s), 127.67 (s), 127.08 (s), 126.88 (s), 117.64 (s), 39.52 (s), 29.20 (s). ESI-HRMS calcd for C 19 H 14 N4S + ([M + H] + ): 331.1012; found: 331.1014.

[0083] Example 6: Preparation of Compound I-q

[0084] According to the same preparation route as in Example 2, Compound I-q was prepared as a yellow solid, yield: 19%, Mp: 68 - 72 °C. 1 1H NMR (500 MHz, CDCl3) δ 7.52 (d, J = 5.4 Hz, 1H), 7.37 (d, J = 5.4 Hz, 1H), 3.64 (dd, J = 16.6, 6.8 Hz, 1H), 3.27 (dd, J = 16.6, 10.7 Hz, 1H), 2.54 (td, J = 10.1, 6.9 Hz, 1H), 1.12 - 1.00 (m, 1H), 0.82 - 0.65 (m, 2H), 0.41 (ddq, J = 28.8, 9.4, 4.9 Hz, 2H). 13 13C NMR (126 MHz, CDCl3) δ 150.44 (s), 131.36 (s), 129.56 (s), 126.00 (s), 117.63 (s), 39.50 (s), 26.78 (s), 16.30 (s), 4.86 (s), 4.02 (s). ESI-HRMS calcd for C 10 H 10 N4S + ([M + H] + ): 219.0699; found: 219.0701.

[0085] Example 7: Preparation of Compound I-s

[0086] According to the same preparation route as in Example 1, Compound I-s was prepared as a yellow solid; yield: 31%. Mp: 196 - 200 °C. 11H NMR (500 MHz, CDCl3) δ 8.61 (s, 1H), 7.17 (d, J = 5.0 Hz, 1H), 7.09 (d, J = 5.3 Hz, 1H), 6.98 - 6.86 (m, 2H), 6.65 (d, J = 5.2 Hz, 1H), 4.60 (t, J = 6.6 Hz, 1H), 3.17 (dt, J = 15.0, 5.4 Hz, 1H), 3.05 (dd, J = 15.1, 7.5 Hz, 1H). 13 13C NMR (126 MHz, CDCl3) δ 149.77 (s), 149.74 (s), 145.19 (s), 145.12 (s), 134.91 (s), 125.83 (s), 123.59 (s), 123.55 (s), 123.29 (s), 123.00 (s), 116.83 (s), 36.37 (s), 33.36 (s), 33.29 (s). ESI - HRMS calcd for C 12 19H9N3S2 + ([M + H] + ): 260.0311; found: 260.0312.

[0087] Example 8: Preparation of Compound I - t

[0088] According to the same preparation route as in Example 1, Compound I - t was prepared as a yellow solid; yield: 37%. Mp: 130 - 134 °C. 1 1H NMR (500 MHz, CDCl3) δ 8.52 (s, 1H), 7.58 (d, J = 7.8 Hz, 5H), 7.44 (t, J = 7.6 Hz, 3H), 7.36 (t, J = 6.0 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H), 7.20 (d, J = 5.3 Hz, 1H), 4.54 (dd, J = 9.6, 6.6 Hz, 1H), 3.67 (dd, J = 16.1, 6.5 Hz, 1H), 3.46 (dd, J = 16.1, 9.8 Hz, 1H). 13 13C NMR (126 MHz, CDCl3) δ 141.07 (s), 140.38 (s), 139.82 (s), 137.55 (s), 130.28 (s), 129.61 (s), 128.86 (s), 127.87 (s), 127.86 (s), 127.55 (s), 127.09 (s), 126.29 (s), 116.68 (s), 39.63 (s), 30.02 (s). ESI - HRMS calcd for C 20 19H 15 N3S+ ([M+H] + ): 330.1060; found: 330.1061.

[0089] Example 9: Preparation of Compound I-u

[0090] Following the same preparation route as in Example 1, Compound I-u was prepared as a yellow solid; yield: 10%. Mp: 110 - 114 °C. 1 H NMR (500 MHz, CDCl3) 10.45 - 10.21 (m, 0.5H), 8.51 - 8.47 (m, 0.5H), 7.43 - 7.34 (m, 2H), 7.31 (dd, J = 10.4, 5.5 Hz, 0.5H), 7.23 (dd, J = 8.6, 5.2 Hz, 0.5H), 7.17 - 6.99 (m, 3H), 5.35 - 5.29 (m, 1H), 4.50 - 4.29 (m, 1H), 3.84 - 3.66 (m, 1H), 3.60 - 3.41 (m, 0.5H), 3.32 - 3.25 (m, 0.5H). 1313C NMR (126 MHz, CDCl3) δ 163.44 (s), 163.38 (s), 163.00 (s), 162.87 (d, J = 2.6 Hz), 161.45 (d, J = 8.5 Hz), 160.92 (s), 160.90 (s), 159.70 (s), 159.67 (s), 151.40 (s), 151.12 (s), 149.25 (s), 149.10 (s), 139.11 (s), 139.09 (s), 138.90 (s), 138.88 (s), 136.06 (s), 136.04 (s), 136.02 (s), 135.99 (s), 133.58 (s), 133.46 (s), 131.95 (s), 131.87 (s), 131.71 (s), 131.47 (s), 130.20 (s), 130.12 (s), 129.29 (s), 129.22 (s), 129.14 (s), 129.07 (s), 128.81 (s), 128.79 (s), 128.75 (s), 128.72 (s), 125.99 (s), 125.95 (s), 124.56 (s), 124.42 (s), 123.26 (s), 123.17 (s), 117.11 (s), 117.08 (s), 116.26 (s), 116.25 (s), 116.09 (s), 116.07 (s), 115.92 (s), 115.87 (s), 115.75 (s), 115.70 (s), 39.36 (s), 39.33 (s), 38.95 (s), 38.60 (s), 35.20 (s), 35.10 (s), 30.34 (s), 30.30 (s), 29.72 (s). ESI-HRMS calcd for C 14 H 10 FN3S + ([M + H] + ): 272.0652; found: 272.0653.

[0091] Example 10: Preparation of Compound I-v

[0092] Following the same preparation route as in Example 1, Compound I-v was prepared as a yellow solid; yield: 24%. Mp: 171 - 176 °C. 11H NMR (500 MHz, CDCl3) δ 10.45 (d, J = 12.5 Hz, 0.5H), 8.44 (s, 0.5H), 7.43 - 7.34 (m, 1H), 7.29 - 7.25 (m, 0.5H), 7.11 (dd, J = 19.0, 5.3 Hz, 0.5H), 3.63 - 3.46 (m, 0.5H), 3.45 - 3.23 (m, 1H), 3.16 - 3.06 (m, 0.5H), 3.04 - 2.94 (m, 0.5H), 2.45 - 2.23 (m, 0.5H), 1.36 - 1.23 (m, 1H), 1.05 - 0.91 (m, 0.5H), 0.81 - 0.56 (m, 2H), 0.45 - 0.26 (m, 2H). 13 13C NMR (126 MHz, CDCl3) δ 159.62 (s), 159.59 (s), 151.80 (s), 151.58 (s), 149.65 (s), 149.46 (s), 133.69 (s), 133.63 (s), 132.52 (s), 132.26 (s), 131.99 (s), 129.20 (s), 125.09 (s), 125.05 (s), 124.29 (s), 124.19 (s), 121.98 (s), 121.92 (s), 117.29 (s), 117.18 (s), 40.27 (s), 40.00 (s), 39.66 (s), 39.63 (s), 36.05 (s), 36.00 (s), 28.27 (s), 28.14 (s), 19.74 (s), 19.66 (s), 16.03 (s), 15.83 (s), 6.11 (s), 6.01 (s), 5.63 (s), 5.60 (s), 4.82 (s), 4.79 (s), 3.99 (s), 3.87 (s). ESI - HRMS calculated for C 11 H 11 N3S + ([M + H] + ): 218.0747; found: 218.0747.

[0093] Effect Example 1

[0094] The bactericidal or bacteriostatic activity of the [1,5 - a]thieno[2,3 - e]pyridine derivative of Formula I of the present invention was determined by the mycelial growth rate method. The mycelial growth rate method is a bactericidal virulence assay method that determines the bacteriostatic ability of a medicament by the growth rate of pathogenic bacteria mycelia on a culture medium containing different concentrations of the medicament. The specific steps are as follows:

[0095] (1) Preparation of drug-containing plates. Take 10 mg of the compound to be tested, dissolve it in 400 μL of N,N-dimethylformamide, and make up the volume to 20 mL with a sterile aqueous solution containing 0.1% (mass fraction) of Tween 80 emulsifier to obtain a test drug solution with a concentration of 500 μg / mL. Prepare the drug-containing medium in a laminar flow hood. Pipette 4 mL of the test drug solution into a sterilized 50 mL centrifuge tube, add 36 mL of Potato dextrose agar (PDA) medium and mix well, then pour it into a sterilized petri dish. After cooling, it is the culture medium plate containing 50 μg / mL of the test drug. Use the PDA medium added with the corresponding volume of N,N-dimethylformamide and sterile water containing 0.1% Tween 80 as the control.

[0096] (2) Preparation of fungal discs. Inoculate the long-term preserved strain onto the drug-free PDA medium and activate it 1 - 2 times. After good growth, use a punch with a diameter of 4 mm to cut fungal discs at the outer 1 / 3 of the colony.

[0097] (3) Inoculation of fungal discs. Use an inoculation needle to transfer the fungal disc to the center of the drug-containing plate, with the aerial hyphae side facing down. Seal it with a sealing film and place it in an incubator at a temperature of 24 ± 1°C for inverted culture. Each treatment has 3 replicates.

[0098] (4) Data investigation. When the colonies of the blank control are close to the edge of the petri dish, measure the colony diameter twice using the "cross method", and use the average value to represent the colony size.

[0099] (5) Data analysis. Substitute the data into the growth rate calculation formula to calculate the mycelial growth inhibition rate of different compounds. The test strains are the genera of most typical plant pathogens actually occurring in the fields of agricultural production in China, and their codes and names are as follows: A.s: Alternaria solani, the causal agent of early blight of tomato; B.c: Botrytis cinerea, the causal agent of gray mold of cucumber; C.a: Cercospora arachidicola, the causal agent of brown spot of peanut; F.g: Fusarium graminearum, the causal agent of head blight of wheat; P.p: Physalospora piricola, the causal agent of ring rot of apple; R.s: Rhizoctonia solani, the causal agent of sheath blight of rice; S.s: Sclerotinia sclerotiorum, the causal agent of sclerotinia rot of rapeseed.

[0100] The formula for calculating the mycelial growth inhibition rate is as follows:

[0101]

[0102] Table 1 Antibacterial Activity of Thieno[2,3-e]pyridine Derivatives of Formula I Containing [1,5-a] in the Present Invention (Inhibition Rate / % at 50 μg / mL)

[0103]

[0104]

[0105] Note: Pathogenic bacteria of early blight of tomato, A. solani (A.s); Botrytis cinerea, B. cinerea (B.c); Cercospora arachidicola, C. arachidicola (C.a); Fusarium graminearum, F. graminearum (F.g); Pathogenic bacteria of ring rot of apple, P. piricola (P.p); Rhizoctonia solani, R. solani (R.s); Sclerotinia sclerotiorum, S. sclerotiorum (S.s)

[0106] Using commercial agents thifluzamide and prothioconazole as positive controls. The in vitro bactericidal activity results at a concentration of 50 μg / mL in Table 1 show that the target compounds I-a to I-v in the present invention all have a certain degree of in vitro bactericidal activity against the seven pathogenic fungi tested. The inhibitory effects of some compounds on pathogenic fungi are shown in the accompanying drawings of the specification Figure 1 - Figure 2 。

[0107] For A. solani, the inhibition rates of I-e, I-f, I-h, I-j, I-l, I-n and I-o are between 64% and 87%, showing bactericidal activity equivalent to or better than that of thifluzamide (67%). For B. cinerea, compounds I-f, I-j, I-e, I-r and I-v show inhibitory effects exceeding 75%, among which the bactericidal activity of I-j is 89%, superior to that of thifluzamide (32%). For C. arachidicola, although the bactericidal activity of the target compounds is not as good as that of prothioconazole (97%) and thifluzamide (100%), some of these compounds still show good bactericidal activity. Among them, the bactericidal activities of I-h, I-k and I-n are 89%, 89% and 81% respectively. The inhibition rates of I-b, I-f, I-k, I-o and I-s on R. solani are between 71% and 80%, indicating that they show good bactericidal activity against this pathogen. For S. sclerotiorum, the inhibition rates of 4 compounds exceed 75%, among which the bactericidal activities of I-h and I-k are 90% and 91% respectively, superior to that of thifluzamide (15%) and equivalent to that of prothioconazole (95%).

[0108] In summary, compounds I-b, I-f, I-h, I-j, I-k, I-n, I-o, I-r and I-s exhibit high bactericidal activity, and the agricultural bactericidal activity of [1,5-a]thieno[2,3-e]pyridine derivatives of formula I is reported for the first time.

[0109] As described above, the above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. A compound of formula I, or a stereoisomer thereof, or an agrochemically acceptable salt thereof: in, A, B, C and D are independently selected from carbon atoms or nitrogen atoms, and at least three of A, B, C and D are selected from nitrogen atoms; R1 is selected from hydrogen, C1-C6 straight or branched alkyl, C3-C6 cycloalkyl, C6-C 12 Aryl or C6-C containing N, O, S atoms 12 Heteroaryl; the C6-C 12 Aryl or C6-C containing N, O, S atoms 12 The heteroaryl group may be further optionally substituted by one, two, or three independent R2 groups. R2 is selected from hydrogen, halogen, C1-C6 alkyl, halogen-substituted C1-C6 alkyl, C1-C6 alkoxy, halogen-substituted C1-C6 alkoxy, hydroxyl or C6-C 12 Aryl.

2. The compound according to claim 1, or its stereoisomer, or its agrochemically acceptable salt, characterized in that: in, A, B, C and D are independently selected from nitrogen atoms; or A, C and D are selected from nitrogen atoms, and B is selected from carbon atoms; R1 is selected from C3-C6 cycloalkyl, C6-C 12 Aryl or C6-C containing N, O, S atoms 12 Heteroaryl; the C6-C 12 Aryl or C6-C containing N, O, S atoms 12 The heteroaryl group may be further optionally substituted by one, two, or three independent R2 groups. R2 is selected from hydrogen, halogen, C1-C6 alkyl, halogen-substituted C1-C6 alkyl, C1-C6 alkoxy or C6-C 12 Aryl; Preferably, R1 is selected from C3-C6 cycloalkyl, C6-C 12 Aryl or C6-C containing N, O, S atoms 12 Heteroaryl; the C6-C 12 Aryl or C6-C containing N, O, S atoms 12 The heteroaryl group may be further optionally substituted by one, two, or three independent R2 groups. The R2 is selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, -CFH2, -CF2H, -CF3, -CH2CFH2, -CH2CF2H or -CH2CF3, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, phenyl or biphenyl; More preferably, R1 is selected from cyclopropyl, phenyl or thienyl; the phenyl or thienyl may be further optionally substituted by one, two or three independent R2, The R2 is selected from hydrogen, fluorine, chlorine, bromine, methyl, -CF3, methoxy or phenyl.

3. The compound according to any one of claims 1 to 2, or its stereoisomer, or its agrochemically acceptable salt, characterized in that: in, A, B, C and D are independently selected from nitrogen atoms; or A, C and D are selected from nitrogen atoms, and B is selected from carbon atoms; The R1 is selected from 4. The compound according to claim 3, or its stereoisomer, or its agrochemically acceptable salt, characterized in that: The R1 is selected from 5. The compound according to any one of claims 1 to 3, or its stereoisomer, or its agrochemically acceptable salt, characterized in that: The compound described in formula I is specifically:

6. A pesticide composition comprising at least one compound of formula I according to any one of claims 1 to 5, or a stereoisomer thereof, or an agrochemically acceptable salt thereof and a carrier; the carrier is in liquid or solid form.

7. Use of the compound of formula I according to any one of claims 1 to 5, or its stereoisomer, or its agrochemically acceptable salt or the pesticide composition according to claim 6 in preventing and controlling plant fungal diseases, preferably, the plant fungal diseases are the pathogenic bacteria of tomato early blight, Botrytis cinerea, peanut brown spot pathogen, Fusarium graminearum, the pathogenic bacteria of apple ring rot, Rhizoctonia solani or Sclerotinia sclerotiorum.

8. A fungicide, characterized in that: The bactericide contains a bactericidal effective amount of the compound of formula I according to any one of claims 1 to 5, or at least one of its stereoisomers, or its agrochemically acceptable salts, and optionally contains auxiliary materials.

9. The fungicide according to claim 8, characterized in that The dosage form of the fungicide is selected from at least one of emulsifiable concentrate, suspension, wettable powder, dust, granule, aqueous solution, mother solution and mother powder.

10. A method for controlling or preventing infection of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula I according to any one of claims 1 to 5 or a composition comprising such a compound as active ingredient is applied to the plants, parts thereof or the locus thereof.

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