Spiro tetronic acid derivative as well as preparation and application thereof

Abstract

The invention relates to a spiro tetronic acid derivative as well as preparation and application thereof. Specifically, the invention relates to a spirocyclic tetronic acid derivative as shown in a formula (I), or an isotope labeled compound thereof, or an optical isomer, a geometric isomer, a tautomer or an isomer mixture thereof, or a pharmaceutically acceptable salt thereof, and processes for the preparation of said compounds and intermediates thereof and their use as pest control agents and / or microbiocides and / or herbicides. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the field of pesticides, and particularly relates to a spirocyclic tetronic acid derivative and its preparation and application. Background Art

[0002] Although there are various control measures for pests in current agriculture, new and more effective and reasonable compounds for killing pests are still being continuously explored and discovered. The present invention provides a new type of compound that can be further studied. Spirocyclic compounds have stood out among many pesticides due to their unique chemical structures, novel modes of action, excellent control effects, and low resistance development, and have become a hot topic in current pesticide development. Due to the frequent use of single pesticides, insects or weeds have developed resistance to existing pesticides, reducing the control effect of pesticides. In the field of plant protection, spirocyclic compounds have shown broad application and development prospects and can solve the increasingly serious problems of pesticide resistance. Therefore, spirocyclic compounds have opened up new horizons for the development of pesticide chemistry and provided new ways to find new pesticides with high efficiency and low toxicity. Summary of the Invention

[0003] The herbicidal and / or acaricidal and / or insecticidal efficacy and / or breadth of action and / or plant compatibility of known compounds - especially the plant compatibility with crop plants - are not always satisfactory. The object of the present invention is to provide a new class of spirocyclic tetronic acid derivatives and their preparation and application, and such compounds can achieve better control effects at lower doses.

[0004] In a first aspect, the present invention provides a compound of formula (I) as a spirocyclic tetronic acid derivative or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or mixture of isomers, or its agrochemically acceptable salt,

[0005]

[0006] wherein X1, X2, and X3 are each independently selected from hydrogen, halogen, hydroxyl, nitro, amino, cyano, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy;

[0007] W is selected from O, C-R1 or N-R2;

[0008] wherein R1, R2 are each independently selected from hydrogen, halogen, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6Alkoxy C 1-6 alkyl, C 3-8 cycloalkyl, C 3-8 heterocyclic group, C 6-12 aryl, C 3-8 heteroaryl, C 3-8 cycloalkyl C 1-3 alkyl, C 3-8 heterocyclic group C 1-3 alkyl, C 6-12 aryl C 1-3 alkyl, C 6-12 haloaryl C 1-3 alkyl or halo C 3-8 heteroaryl C 1-3 alkyl;

[0009] R3 is selected from the following substituents:

[0010] wherein, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 are each independently selected from C 1-6 alkyl, halo C 1-6 alkyl, C 3-8 cycloalkyl, C 6-12 aryl, C 1-6 alkyl - S - C 1-6 alkyl, C 6-12 aryl C 1-3 alkyl, C 6-12 aryl C 1-3 alkoxy;

[0011] In one embodiment of the present invention, wherein,

[0012] X1, X2, and X3 are each independently selected from hydrogen, halogen, hydroxyl, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy;

[0013] W is selected from O, C - R1 or N - R2;

[0014] wherein, R1, R2 are each independently hydrogen, halogen, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy, C 1-6 alkoxy C 1-6 alkyl, C 3-8 cycloalkyl, C 3-8 heterocyclic group, C6-12 Aryl, C 3-8 Heteroaryl, C 3-8 Cycloalkyl C 1-3 Alkyl;

[0015] R3 is selected from the following substituents:

[0016] Wherein, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 Are each independently selected from C 1-6 Alkyl, halo C 1-6 Alkyl, C 3-8 Cycloalkyl, C 6-12 Aryl, C 1-6 Alkyl - S - C 1-6 Alkyl, C 6-12 Aryl C 1-3 Alkyl, C 6-12 Aryl C 1-3 Alkoxy;

[0017] In one embodiment of the present invention, wherein,

[0018] X1, X2, and X3 are each independently selected from hydrogen, halogen, hydroxyl, C 1-3 Alkyl, C 1-3 Haloalkyl, C 1-3 Alkoxy, C 1-3 Haloalkoxy;

[0019] W is selected from O, C - R1 or N - R2;

[0020] Wherein, R1, R2 are each independently selected from hydrogen, halogen, C 1-3 Alkyl, halo C 1-3 Alkyl, C 1-3 Alkoxy, halo C 1-3 Alkoxy, C 1-3 Alkoxy C 1-3 Alkyl, C 3-6 Cycloalkyl, C 3-6 Heterocyclic group, C 6-10 Aryl, C 3-6 Heteroaryl, C 3-6 Cycloalkyl C 1-3 Alkyl;

[0021] R3 is selected from the following substituents:

[0022] Wherein, R4, R5, R6, R7, R8, R9, R 10 , R11 , R 12 are each independently selected from C 1-6 alkyl, halo C 1-6 alkyl, C 3-8 cycloalkyl, C 6-12 aryl, C 1-6 alkyl-S-C 1-6 alkyl, C 6-12 aryl C 1-3 alkyl, C 6-12 aryl C 1-3 alkoxy;

[0023] In one embodiment of the present invention, wherein,

[0024] X1, X2, and X3 are each independently selected from hydrogen, halogen, hydroxy, C 1-3 alkyl;

[0025] W is selected from O, C-R1 or N-R2;

[0026] wherein, R1, R2 are each independently selected from hydrogen, halogen, C 1-3 alkyl, halo C 1-3 alkyl, C 1-3 alkoxy, halo C 1-3 alkoxy, C 3-6 cycloalkyl, C 3-6 cycloalkyl C 1-3 alkyl;

[0027] R3 is selected from the following substituents:

[0028] wherein, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 are each independently selected from C 1-6 alkyl, halo C 1-6 alkyl, C 3-8 cycloalkyl, C 6-12 aryl, C 1-6 alkyl-S-C 1-6 alkyl, C 6-12 aryl C 1-3 alkyl, C 6-12 aryl C 1-3 alkoxy;

[0029] In one embodiment of the present invention, wherein,

[0030] X1, X2, and X3 are each independently selected from hydrogen, halogen, hydroxy, C 1-3 alkyl;

[0031] W is selected from O, C-R1 or N-R2;

[0032] wherein, R1 and R2 are each independently selected from hydrogen, halogen, C 1-3 alkyl, halo-C 1-3 alkyl, C 1-3 alkoxy, halo-C 1-3 alkoxy, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-3 alkyl;

[0033] R3 is selected from the following substituents:

[0034] In one embodiment of the present invention, wherein, the compound is preferably selected from:

[0035]

[0036]

[0037] For the sake of simplicity, the "spirocyclic tetronic acid derivative", "compound of formula (I)" or "compound of the present invention" described hereinafter may also cover any isotopically labeled compound of the compound of formula (I), or its optical isomers, geometric isomers, tautomers or mixtures of isomers, or its agrochemically acceptable salts.

[0038] The term "optical isomers" means that when a compound has one or more chiral centers, each chiral center can exist in the R configuration or the S configuration, and the various isomers thus formed are optical isomers. Optical isomers include all diastereoisomers, enantiomers, meso forms, racemates or mixtures thereof. For example, optical isomers can be separated by a chiral chromatographic column or by chiral synthesis.

[0039] The term "geometric isomers" means that when a double bond exists in a compound, the compound can exist as a cis isomer, a trans isomer, an E isomer and a Z isomer. Geometric isomers include cis isomers, trans isomers, E isomers, Z isomers or mixtures thereof.

[0040] The term "tautomers" refers to isomers resulting from the rapid movement of a certain atom in a molecule between two positions. Those skilled in the art can understand that tautomers can be converted into each other and may coexist in a certain state at an equilibrium state.

[0041] Unless otherwise indicated, when referring to "spirocyclic quaternary ketonic acid derivatives", "compounds of formula (I)", or "compounds of the present invention" herein, it also encompasses isotopically labeled compounds obtained by replacing any atom in the compound with its isotopic atom. The present invention includes all pharmaceutically acceptable isotopically labeled compounds of the compounds of formula (I), wherein one or more atoms are replaced by atoms having the same atomic number but different atomic mass or mass number as the atoms usually found in nature.

[0042] Examples of isotopes suitable for inclusion in the compounds of the present invention include isotopes of hydrogen, such as 2 H(D) and 3 H(T), isotopes of carbon, such as 11 C, 13 C and 14 C, isotopes of chlorine, such as 37 Cl, isotopes of fluorine, such as 18 F, isotopes of iodine, such as 123 I and 125 I, isotopes of nitrogen, such as 13 N and 15 N, isotopes of oxygen, such as 15 O, 17 O and 18 O, and isotopes of sulfur, such as 35 S.

[0043] The isotopically labeled compounds of formula (I) can generally be prepared by conventional techniques known to those skilled in the art or by using appropriate isotopically labeled reagents in place of the previously used unlabeled reagents in a manner similar to the methods described in the examples and preparations attached herein.

[0044] The compounds of formula (I) can exist in the form of agrochemically acceptable salts, such as acid addition salts and / or base addition salts of the compounds of formula (I). Unless otherwise indicated, "agrochemically acceptable salts" as used herein include acid addition salts or base addition salts that can occur in the compounds of formula (I).

[0045] The agrochemically acceptable salts of the compounds of formula (I) include their acid addition salts and base addition salts. Suitable acid addition salts are formed from acids that form non-toxic salts. Examples thereof include, but are not limited to: acetates, adipates, aspartates, benzoates, benzenesulfonates, bicarbonates / carbonates, bisulfates / sulfates, borates, camphorsulfonates, citrates, cyclohexanesulfamates, ethanedisulfonates, formates, fumarates, glucoheptanoates, gluconates, glucuronates, hexafluorophosphates, 2-(4-hydroxybenzyl)benzoates, hydrochlorides / chlorides, hydrobromides / bromides, hydroiodides / iodides, 2-hydroxyethanesulfonates, lactates, malates, maleates, malonates, methanesulfonates, methyl sulfates, naphthalenecarboxylates, 2-naphthalenesulfonates, nicotinates, nitrates, oxalates, palmitates, phosphates / hydrogen phosphates / dihydrogen phosphates, pyroglutamates, glucuronates, stearates, salicylates, tannates, tartrates, toluenesulfonates and trifluoroacetates. Suitable base addition salts are formed from bases that form non-toxic salts. Examples thereof include, but are not limited to: aluminum, arginine, calcium, choline, diethylamine, diethanolamine, glycine, lysine, magnesium, meglumine, ethanolamine, potassium, sodium, tromethamine and zinc salts. Hemisalts of acids and bases, such as hemisulfates and hemicalcium salts, can also be formed. For a review of suitable salts, see Handbook of Pharmaceutical Salts: Properties, Selection and Use by Stahl and Wermuth (Wiley-VCH, 2002). Methods for preparing the agrochemically acceptable salts of the compounds described herein are known to those skilled in the art.

[0046] To avoid ambiguity, the terms used herein are defined below. Unless otherwise stated, the meanings of the terms used herein are as follows.

[0047] The term "hydroxy" means -OH; the term "amino" means -NH2; the term "nitro" means -NO2; the term "cyano" means -CN; the term "phenoxy" means -O-Phe; and the term "benzyloxy" means -O-CH2-Phe.

[0048] As used herein, the term "substituted" means that one or more (preferably 1 to 5, more preferably 1 to 3) hydrogen atoms in a group are independently replaced by the corresponding number of substituents.

[0049] As used herein, the term "each independently" means that when the number of substituents exceeds one, these substituents can be the same or different.

[0050] As used herein, the term "alkyl" refers to saturated aliphatic hydrocarbons, including straight-chain and branched-chain. In some embodiments, the alkyl group has 1-8, or 1-6, or 1-3 carbon atoms. For example, the term "C 1-8 alkyl" refers to a straight-chain or branched-chain radical having 1-8 carbon atoms. The term "C 1-8 alkyl" includes the terms "C 1-6 alkyl", "C1-C3 alkyl", and "C1-C4 alkyl" in its definition. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, isopentyl, neopentyl, (R)-2-methylbutyl, (S)-2-methylbutyl, 3-methylbutyl, 2,3-dimethylpropyl, 2,3-dimethylbutyl, hexyl, etc. The alkyl group may optionally be substituted with one or more (e.g., 1 to 5) suitable substituents.

[0051] As used herein, the term "haloalkyl" refers to an alkyl group having one or more halogen substituents (up to perhaloalkyl, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom). For example, the term "C 1- C6 haloalkyl" refers to a C 1- C6 alkyl group having one or more halogen substituents (up to perhaloalkyl, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom). As another example, the term "C 1- C4 haloalkyl" refers to a C 1- C4 alkyl group having one or more halogen substituents (up to perhaloalkyl, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom); the term "C 1- C3 haloalkyl" refers to a C 1- C3 alkyl group having one or more halogen substituents (up to perhaloalkyl, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom); and the term "C 1- C2 haloalkyl" refers to a C 1- C2 alkyl group (i.e., methyl or ethyl) having one or more halogen substituents (up to perhaloalkyl, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom). As yet another example, the term "C1 haloalkyl" refers to a methyl group having 1, 2, or 3 halogen substituents. Examples of haloalkyl groups include: CF3, C2F5, CHF2, CH2F, CH2CF3, CH2Cl, etc.

[0052] As used herein, the term "n-membered heterocycloalkyl" refers to a heterocycloalkyl having m ring-forming carbon atoms and (n - m) ring-forming heteroatoms selected from O, S, and N. For example, 4- to 7-membered heterocycloalkyls include, but are not limited to, oxetane, thiolane, azetidine, tetrahydrofuran, tetrahydrothiophene, pyrrolidine, tetrahydropyran, tetrahydrothiopyran, piperidine, morpholine, piperazine, oxepane, thiepane, and azepane. Additionally, the heterocycloalkyl may optionally be substituted with one or more suitable substituents.

[0053] In this text, the number ranges related to the number of substituents, the number of carbon atoms, and the number of ring atoms represent the individual listing of all integers within that range, and the range is only used as a simplified notation. For example, "1 - 4 substituents" means 1, 2, 3, or 4 substituents; "3 - 8 ring atoms" means 3, 4, 5, 6, 7, or 8 ring atoms. Therefore, the number ranges related to the number of substituents, the number of carbon atoms, and the number of ring atoms also cover any of its sub-ranges, and each sub-range is also considered to be disclosed herein.

[0054] The compounds of the present invention can be prepared in a variety of ways known to those skilled in the art of organic synthesis. Those skilled in the art can refer to the synthetic routes of the specific compounds in the specific examples of the present invention and appropriately adjust the reaction raw materials and reaction conditions to obtain the synthetic methods of other compounds.

[0055] Synthesis Scheme 1:

[0056]

[0057] The target compound I-1 can be prepared by Synthesis Scheme 1. Compound A reacts with the corresponding halide under basic conditions to obtain the target compound I-1.

[0058] Synthesis Scheme 2:

[0059]

[0060] The target compound I-2 can be prepared by Synthesis Scheme 2. Compound B reacts with M1, M2, and M3 in one-pot synthesis at 0 °C - RT to obtain C. Compound C undergoes ring closure under the action of a base at RT - 150 °C to obtain D. Compound D reacts with the corresponding halide under basic conditions to obtain the target compound I-2.

[0061] In addition, the present invention also lists multiple synthesized exemplary compounds. It should be understood that the scope of the present invention is not limited to the listed exemplary compounds, and the selection of each group of the compounds in the present invention can be combined arbitrarily without special limitation. The following are the characterization data of the exemplary compounds in the present invention:

[0062] Table 1 Compound Characterization Data

[0063]

[0064]

[0065]

[0066] In a second aspect, the present invention provides an insecticide composition comprising a compound of formula (I) or its isotopically labeled compound, or its optical isomer, geometric isomer, tautomer or isomer mixture, or its agrochemically acceptable salt, and an agrochemically acceptable carrier.

[0067] The agrochemically acceptable carrier can be an organic or inorganic inert carrier material. For example, suitable carriers include water, gelatin, gum arabic, magnesium stearate, talc, vegetable oil, polyalkylene glycol, petrolatum, mannitol, cellulose, cellulose derivatives, sodium saccharin, magnesium carbonate, brine, glycerol, ethanol, etc. In addition, the insecticide composition may further contain other additives, such as preservatives, stabilizers, emulsifiers, buffers, diluents, binders, wetting agents, lubricants, glidants, etc.

[0068] The dosage form of the insecticide composition of the present invention can be a liquid dosage form, a solid dosage form or a semi-solid dosage form, without particular limitation. In some embodiments, the dosage form of the insecticide composition is selected from powders, granules, liquids, suspensions or sprays, preferably wettable powders, wettable liquids, soluble powders, dispersible liquids, aqueous solutions, microemulsions, emulsifiable concentrates, emulsions in water, sprayable solutions, dispersible oil suspensions, microcapsule suspensions, water-dispersible granules, water-soluble granules, macrogranules, granules for broadcasting and soil application, aerosols, ultra-low volume agents and wax products.

[0069] The content of the compound of the present invention in its insecticide composition can be adjusted according to actual needs (such as dosage form, application method, application object, etc.), including but not limited to 0.001 mg / L - 10 mg / L, such as 0.001 mg / L, 0.01 mg / L, 0.1 mg / L, 0.5 mg / L, 1 mg / L, 2.5 mg / L, 5 mg / L or 10 mg / L.

[0070] The specific application frequency can be determined by those skilled in the relevant art, such as once a day, once every two days, once every three days, once every four days, once every five days, once every six days, twice a day, three times a day, etc.

[0071] In a third aspect, the present invention provides the use of a compound of formula (I), or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or a pesticidally acceptable salt thereof, in the preparation of an insecticide for pest control.

[0072] The compounds of the present invention are suitable for controlling pests or mites, that is, controlling pests or mites, where the pests or mites refer to harmful or unwanted insects or mites, especially harmful or unwanted insects or mites encountered in the fields of agriculture, forestry, storage protection, material protection and hygiene. The compounds of the present invention are active against both generally sensitive and resistant species and are effective at all stages of pest or mite development.

[0073] The present invention also relates to a method for controlling pests or mites, which method comprises applying a pesticidally effective amount of a compound of formula (I) to the location of the insects, the insect habitat, the pest habitat, the area to be protected, or directly onto the insects to be controlled. The compounds of the present invention can also be used to control other invertebrate pests or organisms.

[0074] Specifically, the insect habitat, pest habitat or mite habitat refers to the environment where the insects, pests or mites live or where their eggs are present, including the surrounding air, the food they eat or the objects they come into contact with. For example, by applying the active compound to the seeds of plants (before planting), to seedlings, or planted cuttings, leaves, stems, fruits, grains and / or roots, or to the soil or other growth media (before or after crop planting), insects or mites that eat, damage or come into contact with edible agricultural products, ornamental plants, turf, forage plants or other economically valuable plants can be controlled. It is also possible to protect these plants against diseases caused by viruses, fungi or bacteria by controlling sap-sucking pests such as whiteflies, planthoppers, aphids, etc. or mites such as Tetranychus urticae, Tetranychus cinnabarinus, etc. The plants include plants obtained by conventional propagation methods and also plants with insect or mite resistance, herbicide resistance, high yield / or other beneficial characteristics obtained by genetic modification using modern biotechnology. It is expected that these compounds can be applied to protect articles and / or places such as fabrics, paper, stored grains, seeds and other foods, houses, buildings, etc., by applying the compounds of the present invention onto or near these objects.

[0075] The inventors of the present invention have found that even when the compounds of the present invention are administered at a relatively low dose, they can still exhibit high control efficacy against pests, especially against pests belonging to Lepidoptera, Coleoptera, Homoptera, Hemiptera, Thysanoptera, Isoptera, Diptera, Hymenoptera, Mallophaga, Anoplura, Orthoptera, Blattodea, Siphonaptera, Acarina, Nematoda, etc. Therefore, in one embodiment of the present invention, the pests are selected from pests belonging to Lepidoptera, Coleoptera, Homoptera, Hemiptera, Thysanoptera, Isoptera, Diptera, Hymenoptera, Mallophaga, Anoplura, Orthoptera, Blattodea, Siphonaptera, Acarina, Nematoda. More specific pest classifications are as follows:

[0076] Lepidoptera: Helicoverpa spp., Spodoptera spp., Mythimna unipuncta, Agrotis ipsilon, Earias spp., Trichoplusia ni, Anticarsia gemmatalis, Rachiplusia nu, Plutella xylostella, Chilo spp, Scirpophaga incertulas, Sesamia inferens, Cnaphalocrocis medinalis, Ostrinia nubilalis, Cydia pomonella, Carposina niponensis, Adoxophyes orana, Archips argyrospilus, Pandemis heparana, Epinotia aporema, Eupoecilia ambiguella, Lobesia botrana, Polychrosis biteana, Pectinophora gossypiella, Pieris rapae, Phyllonorycter spp., Leucoptera malifoliella, Phyllocnistis citrella, Spodoptera exigua Hübner;

[0077] Coleoptera: Diabrotica spp., Leptinotarsa decemlineata, Oulema oryzae, Anthonomus grandis, Lissorhoptrus oryzophilus, Agriotes spp., Melanotus communis, Popillia japonica, Cyclocephala spp., Tribolium spp.;

[0078] Homoptera: Aphis spp., Myzus Persicae, Rhopalosiphum spp., Dysaphis plantaginea, Toxoptera spp., Aphis craccivora Koch, Macrosiphum euphorbiae, Aulacorthum solani, Sitobion avenae, Metopolophium dirhodum, Schizaphis graminum, Brachycolus noxius, Nephotettix spp., Nilaparvata lugens, Sogatella furcifera, Laodelphax striatellus, Bemisia tabaci, Trialeurodes vaporariorum, Aleurodes proletella, Aleurothrixus floccosus, Quadraspidiotus perniciosus, Unaspis yanonenses, Ceroplastes rubens, Aonidiella aurantii;

[0079] Hemiptera: Lygus spp., Eurygaster maura, Nezara viridula, Piezodorus guildingi, Leptocorisa varicornis, Cimex lectularius, Cimex hemipterus;

[0080] Thysanoptera: Frankliniella occidentalis, Thrips spp., Scirtothrips dorsalis;

[0081] Isoptera: Reticulitermes flavipes, Coptotermes formosanus, Reticulitermes virginicus, Heterotermes aureus, Reticulitermes hesperus, Coptotermes frenchii, Shedorhinotermes spp., Reticulitermes santonensis, Reticulitermes grassei, Reticulitermes banyulensis, Reticulitermes speratus, Reticulitermes hageni, Reticulitermes tibialis, Zootermopsis spp., Incisitermes spp., Marginitermes spp., Macrotermes spp., Microcerotermes spp., Microtermes spp.;

[0082] Diptera: Liriomyza spp., Musca domestica, Aedes spp., Culex spp., Anopheles spp., Fannia spp., Stomoxys spp.;

[0083] Hymenoptera: Iridomyrmex humilis, Solenopsis spp., Monomorium pharaonis, Atta spp., Pogonomyrmex spp., Camponotus spp., Monomorium spp., Tapinoma sessile, Tetramorium spp., Xylocapa spp., Vespula spp., Polistes spp.;

[0084] Mallophaga: chewing lice;

[0085] Anoplura: sucking lice, Pthirus pubis, Pediculus spp.;

[0086] Orthoptera: Melanoplus spp., Locusta migratoria, Schistocerca gregaria, Gryllotalpidae (mole crickets);

[0087] Blattodea: cockroaches, Blatta orientalis, Blattella germanica, Periplaneta americana, Supella longipalpa, Periplaneta australasiae, Periplaneta brunnea, Parcoblatta pennsylvanica, Periplaneta fuliginosa, Pycnoscelus surinamensis;

[0088] Siphonaptera: Ctenophalides spp., Pulex irritans;

[0089] Acari: Tetranychidae, Eupodidae, Eriophyidae, Phytoseiidae, Acaridae, specifically including but not limited to Tetranychus spp., Panonychus spp., Tetranychus cinnabarinus, Eotetranychus carpini, Tetranychus urticae Koch., Phyllocoptruta oleivora, Aculus pelekassi, Brevipalpus phoenicis, Boophilus spp., Dermacentor variabilis, Rhipicephalus sanguineus, Amblyomma americanum, Ixodes spp., Notoedres cati, Sarcoptes scabiei, Dermatophagoides spp.;

[0090] Nematoda: Dirofilaria immitis, Meloidogyne spp., Heterodera spp., Hoplolaimus columbus, Belonolaimus spp., Pratylenchus spp., Rotylenchus reniformis, Criconemella ornata, Ditylenchus spp., Aphelenchoides besseyi, Hirschmanniella spp.

[0091] In another preferred embodiment of the present invention, the pests may be selected from alfalfa aphids, Tetranychus cinnabarinus, and Bemisia tabaci.

[0092] The active compounds / active compound combinations of the present invention can also be used as defoliants, desiccants, haulmkillers, and especially as herbicides. The term "weed" in the broadest sense should be understood to mean all plants that grow where they are not desired. Whether the substances of the present invention are used as non-selective or selective herbicides depends mainly on the application rate.

[0093] The active compounds of the present invention can be used against annual monocotyledonous or dicotyledonous broad-leaved weeds, grasses, and sedges, as well as any undesired crop plants. More specific classifications are shown below:

[0094] Dicotyledonous weeds: including annual weeds such as Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp., Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp., Eclipta spp., Sesbania spp., Aeschynomene spp., and Viola spp., Xanthium spp., and perennial weeds such as Convolvulus, Cirsium, Rumex, and Artemisia.

[0095] Monocotyledonous weeds: Avena spp., Alopecurus spp., Apera spp., Brachiaria spp., Bromus spp., Digitaria spp., Lolium spp., Echinochloa spp., Leptochloa spp., Fimbristylis spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp.; and perennial varieties, including Agropyron, Cynodon, Imperata and Sorghum.

[0096] Annual and perennial Cyperaceae weeds, including Cyperus species, such as Cyperus rotundus L., Cyperus esculentus L., Cyperus brevifolius H., Cyperus microiris Steud, Cyperus itria L., etc.

[0097] The active compounds of the invention are generally suitable for controlling / preventing the growth of undesired plants in the following crops: food crops, for example including:

[0098] Cereals (small-grain cereals) such as Triticum aestivum and wheat-like crops such as T. durum, T. monococcum, T. dicoccon and T. spelta, Secale cereale, Tritiosecale, Hordeum vulgare;

[0099] Zea mays; rice (Oryza, such as Oryza sativa and Oryza glaberrima);

[0100] Legumes (Fabaceae), such as soybean (Glycine max.), peanut (Arachis hypogaea), and leguminous crops such as peas (including Pisum sativum, pigeon pea, and cowpea), kidney beans (including Vicia faba, Vigna, and Phaseolus), and lentils (Lens culinaris var.);

[0101] Cruciferae, including canola (Brassica napus), rapeseed (Brassica napus), cabbage (B. oleracea var.), mustard (B. juncea), Chinese cabbage (B. campestris), spoon cabbage (B. narinosa), black mustard (B. nigra), and Mediterranean turnip (B. tournefortii); and turnip (Brassica rapa var.);

[0102] Other broad-leaved crops, such as sunflower, cotton, flax, linseed, sugar beet, potato, and tomato, etc.

[0103] When the compound / active compound conjugate of formula (I) of the present invention is used for soil and above-ground plant parts, it has strong herbicidal activity and a broad spectrum of action. To some extent, they are also suitable for selectively controlling monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both pre-emergence and post-emergence.

[0104] In another preferred embodiment of the present invention, the unwanted plants can be selected from annual monocotyledonous or dicotyledonous broad-leaved weeds, gramineous weeds, and sedges.

[0105] Those skilled in the art can understand that the definitions and preferences described in one aspect of the present invention are equally applicable to other aspects. Those skilled in the art can understand that the embodiments of various aspects of the present invention can be combined in various ways without departing from the subject and idea of the present invention, and these combinations are also included within the scope of the present invention. Detailed Embodiments

[0106] The compound of formula (I) of the present invention can be synthesized by various methods familiar to those skilled in the art of organic synthesis. Some exemplary synthetic methods of the compound of formula (I) are given in the following specific examples, and these methods are well-known in the field of synthetic chemistry. Obviously, referring to the exemplary schemes in this patent, those skilled in the art can easily design other synthetic routes of the compound of formula (I) by appropriately adjusting the reactants, reaction conditions, and protecting groups.

[0107] The present invention will be further described below in conjunction with embodiments; however, these embodiments do not limit the scope of the present invention. Unless otherwise stated, all reactants used in each embodiment are obtained commercially; the instruments and equipment used in synthetic experiments and product analysis and detection are all conventional instruments and equipment commonly used in organic synthesis.

[0108] Intermediate synthesis example:

[0109] Intermediate 1: 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-9-methyl-1,4-dioxa-9-azadispiro[4.2.4 8 .2 5 tetradec-11-en-10-one synthesis

[0110]

[0111] Step 1: Synthesis of benzyl (2-isocyano-2-methylpropyl) carbonate

[0112] Under the condition of -78 °C, n-BuLi (2.7 mol / L) (24 mL, 60 mmol) was slowly added to a solution of 4,4-dimethyl-2-oxazoline (4.96 g, 50 mmol) in THF (50 mL). After stirring for 1 h, benzyl chloroformate (8.5 g, 50 mmol) was slowly added. After stirring for 30 min, the solution was warmed to 25 °C. After the reaction was completed, it was quenched with saturated aqueous NH4Cl solution, filtered, the solvent was evaporated, and extracted three times with ethyl acetate, water and saturated aqueous NaCl solution, dried over anhydrous NaSO4, and then column chromatographed (PE:EA = 10:1). A yellow oily liquid (5.59 g, yield: 48%) was obtained.

[0113] 1 1H NMR (500 MHz, CDCl3) δ 7.35 - 7.41 (m, 5H), 5.2 (s, 2H), 4.11 (s, 2H), 1.45 - 1.46 (m, 6H).

[0114] Step 2: Synthesis of benzyl (2-(8-(2-(4-chloro-2,6-dimethylphenyl)-N-methylacetamido)-1,4-dioxoaspirin[4.5]decane-8-carboxamido)-2-methylpropyl) carbonate

[0115] 1,4-Dioxoaspirin[4.5]dec-8-one (1 g, 6.42 mmol), methylamine hydrochloride (0.34 g, 5 mmol), Et3N (0.6 g, 6 mmol) and 2,2,2-trifluoroethanol (15 mL) were charged into a round-bottom flask, stirred at room temperature for 20 min, then cooled to 0 °C in an ice-water bath, and subsequently 2,6-dimethyl-4-chlorophenylacetic acid (0.86 g, 4.28 mmol) was added to the reaction solution. After stirring for 5 min, (2-isocyano-2-methylpropyl) benzyl carbonate (1 g, 4.28 mmol) was added dropwise. The mixture was warmed to 25 °C and stirred overnight. After the reaction was completed, the solvent was evaporated, dissolved in DCM, and washed 3 times with saturated NaHCO3. (DCM:MeOH = 50:1) Column chromatography was carried out. A yellow oily liquid (1.80 g, yield: 70%) was obtained.

[0116] 1 H NMR (500 MHz, CD3SOCD3) δ 7.42–7.35 (m, 5H), 7.03 (s, 2H), 6.76 (s, 1H), 5.12 (s, 2H), 4.17 (s, 2H), 3.84 (dd, J = 5.2, 3.5 Hz, 4H), 3.64 (s, 2H), 3.06 (s, 3H), 2.13 (d, J = 9.6 Hz, 6H), 2.01 (dd, J = 12.1, 5.9 Hz, 2H), 1.91–1.74 (m, 4H), 1.55–1.42 (m, 2H), 1.14 (s, 6H).

[0117] Step 3: Synthesis of 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-9-methyl-1,4-dioxo-9-azadispiro[4.2.4 8 .2 5 tetradec-11-ene-10-one

[0118] t-BuOK (0.74 g, 6.6 mmol) was added to 12 mL of DMF, stirred at 0 °C for 5 min, then a solution of benzyl carbonate (2-(8-(2-(4-chloro-2,6-dimethylphenyl)-N-methylacetamido)-1,4-dioxoaspirin[4.5]decane-8-carboxamido)-2-methylpropyl) (1.8 g, 3 mmol) in DMF (30 mL) was added dropwise, and the temperature was raised to 25 °C and stirred overnight. After the reaction was completed, the solvent was evaporated, neutralized with dilute acetic acid, and extracted and separated 3 times with ethyl acetate and water. (DCM:EA = 1:1) Column chromatography was carried out. A yellowish-white solid (0.46 g, yield: 41%) was obtained.

[0119] 11H NMR (500 MHz, CD3SOCD3) δ 10.92 (s, 1H), 7.13 (s, 2H), 3.97–3.84 (m, 4H), 2.73 (s, 3H), 2.19 (d, J = 13.1 Hz, 2H), 2.07 (s, 6H), 1.71 (d, J = 11.7 Hz, 2H), 1.58 (d, J = 11.8 Hz, 2H), 1.24 (s, 2H).

[0120] Intermediate Two: 11-(4-chloro-2,6-dimethylphenyl)-9-cyclopropyl-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4 8 .2 5 tetradec-11-en-10-one synthesis

[0121]

[0122] Step 1: Synthesis of benzyl carbonate (2-(8-(2-(4-chloro-2,6-dimethylphenyl)-N-cyclopropylacetamido)-1,4-dioxaspiro[4.5]decane-8-carboxamido)-2-methylpropyl)

[0123] Charge 1,4-dioxaspiro[4.5]dec-8-one (1 g, 6.42 mmol), cyclopropylamine (0.34 g, 5 mmol) and 2,2,2-trifluoroethanol (15 mL) into a round-bottom flask, stir it at room temperature for 20 min, then cool it to 0 °C in an ice-water bath, and subsequently add 2,6-dimethyl-4-chlorophenylacetic acid (0.86 g, 4.28 mmol) into the reaction solution. After stirring for 5 min, add (2-isocyano-2-methylpropyl) benzyl carbonate (1 g, 4.28 mmol) dropwise. Warm the mixture to 25 °C and stir overnight. After the reaction is completed, spin-dry the solvent, dissolve it with DCM, and wash it 3 times with saturated NaHCO3. (DCM:MeOH = 50:1) Column chromatography. Obtain a yellow oily liquid (1.57 g, yield: 58%).

[0124] 1 1H NMR (500 MHz, CD3SOCD3) δ 7.42–7.31 (m, 5H), 7.14 (s, 1H), 7.07 (s, 2H), 5.11 (s, 2H), 4.16 (s, 2H), 3.95 (s, 3H), 2.36 (t, J = 7.1 Hz, 4H), 2.19 (s, 6H), 1.93 (t, J = 7.1 Hz, 4H), 1.63 (d, J = 12.3 Hz, 2H), 1.48 (t, J = 10.7 Hz, 2H), 1.15 (s, 6H), 1.00 (d, J = 7.4 Hz, 2H), 0.83 (d, J = 2.4 Hz, 2H).

[0125] Step 2: Synthesis of 11-(4-chloro-2,6-dimethylphenyl)-9-cyclopropyl-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4 8 .2 5 tetradec-11-en-10-one

[0126] Add t-BuOK (1.14 g, 10.16 mmol) to 18 mL of DMF. After stirring at 0 °C for 5 min, add a solution of benzyl carbonate (2-(8-(2-(4-chloro-2,6-dimethylphenyl)-N-cyclopropylacetamido)-1,4-dioxoaspirin[4.5]decane-8-carboxamido)-2-methylpropyl) (2.89 g, 4.62 mmol) in DMF (46 mL), and then warm the mixture to 25 °C and stir overnight. After the reaction is completed, evaporate the solvent under reduced pressure, neutralize with dilute acetic acid, and extract with ethyl acetate and water three times by liquid separation. (DCM:EA = 3:1) Purify by column chromatography. Obtain a yellowish-white solid (0.50 g, yield: 27%). 1 H NMR (500 MHz, CD3SOCD3) δ 10.90 (s, 1H), 7.12 (s, 2H), 3.90 (dd, J = 13.9, 5.1 Hz, 4H), 2.23 (s, 1H), 2.05 (s, 6H), 1.72 (d, J = 13.1 Hz, 3H), 1.61 (d, J = 13.3 Hz, 3H), 1.24 (s, 2H), 0.80 (s, 2H), 0.71 (d, J = 4.8 Hz, 2H).

[0127] Intermediate 3: 11-(4-chloro-2,6-dimethylphenyl)-9-(cyclopropylmethyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4 8 .2 5 tetradec-11-en-10-one

[0128]

[0129] Use a method similar to that for synthesizing Intermediate 2. The yield is 43%. 1 H NMR (500 MHz, CD3SOCD3) δ 10.88 (s, 1H), 7.12 (s, 2H), 3.89 (dd, J = 12.4, 5.2 Hz, 4H), 3.07 (d, J = 6.7 Hz, 2H), 2.14 (s, 3H), 2.07 (s, 6H), 1.68 (s, 2H), 1.60 (d, J = 9.0 Hz, 2H), 1.39 (s, 2H), 1.11 (s, 1H), 0.44–0.42 (m, 2H), 0.27–0.24 (m, 2H).

[0130] Compound synthesis examples:

[0131] Example 1: Synthesis of 11-(4-chloro-2,6-dimethylphenyl)-9-methyl-10-oxo-1,4-dioxa-9-azadipyro[4.2.4 8 .2 5 tetradec-11-ene-12-dimethylaminosulfonate (Compound 1)

[0132]

[0133] Dissolve solid 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-9-methyl-1,4-dioxo-9-azadipyrrolo[4.2.4 8 .2 5 tetradec-11-en-10-one (0.15 g, 0.4 mmol) in 5 mL of acetonitrile, add dimethylaminosulfonyl chloride (0.03 g, 0.2 mmol) and Et3N (0.65 g, 6.4 mmol), heat to 50 °C and reflux, stir overnight. After the reaction, extract and separate with DCM and water 3 times. Dry with anhydrous Na2SO4. (DCM:EA = 3:1) Column chromatography. Then crystallize with n-hexane solution to obtain a white solid (0.044 g, yield: 45%).

[0134] Example 2: Synthesis of 11-(4-chloro-2,6-dimethylphenyl)-9-cyclopropyl-12-hydroxy-1,4-dioxo-9-azadipyrrolo[4.2.4 8 .2 5 tetradec-11-en-10-one (Compound 5)

[0135]

[0136] Adopt a method similar to that of Synthesis Example 1, and replace the reaction substrate with Intermediate II. The yield is 46%.

[0137] Example 3: Synthesis of 11-(4-chloro-2,6-dimethylphenyl)-9-(cyclopropylmethyl)-10-oxo-1,4-dioxo-9-azadipyro[4.2.48.25]tetradec-11-ene-12-dimethylaminosulfonate (Compound 8)

[0138]

[0139] Adopt a method similar to that of Synthesis Example 1, and replace the reaction substrate with Intermediate III. The yield is 41%.

[0140] Example 4: 11-(4-chloro-2,6-dimethylphenyl)-9-methyl-10-oxo-1,4-dioxa-9-azadispiro[4.2.4 8 .2 5 tetradec-11-en-12-yl (1S,3R)-3-((Z)-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane-1-carboxylate (Compound 2) synthesis

[0141]

[0142] (1S,3R)-3-((Z)-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane-1-carboxylic acid (0.12 g, 0.48 mmol) and N-methylimidazole (0.1 g, 1.2 mmol) were added dropwise to a solution of TsCl (0.1 g, 0.48 mmol) in acetonitrile (5 mL) under an argon atmosphere. After stirring at 0 °C for 1 h, a solution of 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-9-methyl-1,4-dioxo-9-azadispiro[4.2.4 8 .2 5 tetradec-11-en-10-one (0.15 g, 0.4 mmol) in acetonitrile was added dropwise, and the temperature was then raised to 25 °C and the reaction was carried out overnight. After the reaction was completed, it was quenched with water and extracted and separated with ethyl acetate and water 3 times. (DCM:EA = 3:1) Column chromatography was performed. Then, crystallization was carried out with a n-hexane solution to obtain a white solid (0.101 g, yield: 42%).

[0143] Example 5: 11-(4-chloro-2,6-dimethylphenyl)-9-methyl-12-(2-oxo-2-phenylethoxy)-1,4-dioxo-9-azadispiro[4.2.4 8 .2 5 tetradec-11-en-10-one (Compound 3) synthesis

[0144]

[0145] The product 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-9-methyl-1,4-dioxo-9-azadispiro[4.2.4 8 .2 511-Tetradecen-10-one (0.15 g, 0.4 mmol), K2CO3 (0.08 g, 0.6 mmol), NaI (0.006 g, 0.04 mmol) and 2-bromoacetophenone (0.12 g, 0.6 mmol) were placed in a flask, and then 8 mL of acetonitrile was added. The mixture was heated under reflux at 80 °C overnight. After the reaction was completed, DCM and water were added for extraction three times. (DCM:EA = 3:1) Column chromatography was performed. After evaporation to dryness, recrystallization was carried out with a n-hexane solution to obtain an orange-yellow solid (0.06 g, yield: 32%).

[0146] Example 6: Synthesis of ethyl 1-((11-(4-chloro-2,6-dimethylphenyl)-9-methyl-10-oxo-1,4-dioxa-9-azadipyro[4.2.4 8 .2 5 tetradec-11-en-12-yl)oxy)carbonate (Compound 4)

[0147]

[0148] The product 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-9-methyl-1,4-dioxo-9-azadipyrrolo[4.2.4 8 .2 5 tetradec-11-en-10-one (0.15 g, 0.4 mmol) (0.15 g, 0.4 mmol), K2CO3 (0.08 g, 0.6 mmol), NaI (0.006 g, 0.04 mmol) and 1-chloroethyl methyl carbonate (0.08 g, 0.6 mmol) were placed in a flask, and then 8 mL of acetonitrile was added. The mixture was heated under reflux at 80 °C overnight. After the reaction was completed, DCM and water were added for extraction three times. (DCM:EA = 3:1) Column chromatography was performed. After evaporation to dryness, recrystallization was carried out with a n-hexane solution to obtain a yellowish-green viscous liquid (0.07 g, yield: 36%).

[0149] Example 7: Synthesis of 11-(4-chloro-2,6-dimethylphenyl)-9-methyl-10-oxo-1,4-dioxa-9-azadiphospha[4.2.4 8 .2 5 tetradec-11-en-12-yl (tert-butoxycarbonyl)glycinate (Compound 12)

[0150]

[0151] Put Boc-glycine (0.37 g, 2.12 mmol) into a flask, add redistilled THF (10 mL) under a nitrogen atmosphere, and then slowly dropwise add propyl chloroformate (0.23 g, 1.91 mmol). During stirring, slowly dropwise add DCM (0.26 g, 2.54 mmol), and then react at 0 °C to 5 °C for 2 h. Then add Et3N (0.06 g, 0.64 mmol) to supplement the solid 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-9-methyl-1,4-dioxa-9-aza-diiso[4.2.4 8 .2 5 tetradec-11-en-10-one (0.2 g, 0.529 mmol) was dissolved in redistilled DCM (5 mL) and added to the reaction solution, and then stirred at room temperature for 2 days. After the reaction was completed, EA and water were added for extraction 3 times. (DCM:EA = 3:1) Column chromatography. After rotary evaporation, a white solid A1 (52 mg, yield: 24%) was obtained.

[0152] Example 8: Synthesis of 11-(4-chloro-2,6-dimethylphenyl)-9-methyl-10-oxo-1,4-dioxa-9-aza-dipyro[4.2.4 8 .2 5 tetradec-11-en-12-yl (tert-butoxycarbonyl)phenylalanine (Compound 13)

[0153]

[0154] Using a method similar to that of Synthesis Example 12, the reaction substrate was changed to N-Boc-DL-phenylalanine, and the yield was 31%.

[0155] Example 9: Synthesis of 11-(4-chloro-2,6-dimethylphenyl)-9-methyl-10-oxo-1,4-dioxa-9-aza-dipyro[4.2.4 8 .2 5 Synthesis of tetradec-11-en-12-yl acryloyl acetate (Compound 20)

[0156]

[0157] In a nitrogen environment, put N-acetyl-DL-leucine (0.08 g, 0.64 mmol) into a flask. After adding redistilled DCM (10 mL) at -5°C to 0°C, slowly drip thionyl chloride (0.15 g, 1.27 mmol), and stir at room temperature for 5 h. After the reaction is completed, rotary evaporate the solvent and extract with DCM and water. A viscous liquid is obtained. In a nitrogen atmosphere, slowly add DIPEA (0.27 g, 2.12 mmol) and the viscous liquid dissolved in redistilled DCM to the reaction solution of solid 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-9-methyl-1,4-dioxo-9-azadicyclo[4.2.4 8.2

[0158] ]-tetradec-11-en-10-one (0.2 g, 0.529 mmol) dissolved in redistilled DCM (5 mL) in sequence, and then stir at 0°C for 2 h. After the reaction is completed, add DCM and water for extraction 3 times. (DCM:EA:PE = 1:1:1) Column chromatography. After rotary evaporation, a white solid (0.11 g, yield: 32%) is obtained.

[0158] Example 10: Synthesis of 11-(1H-indol-1-yl)-9-methyl-10-oxo-1,4-dioxo-9-azadipyrrolo[4.2.4 8 8 .2 5 tetradec-11-en-12-yl propyl carbonate (Compound 21)

[0159]

[0160] Step 1: Synthesis of 12-hydroxy-11-(1H-indol-1-yl)-9-methyl-1,4-dioxo-9-azadicyclo[4.2.4 8.2

[0158] ]-tetradec-11-en-10-one

[0161] Add t-BuOK (0.8 g, 7.16 mmol) to 12 mL of DMF. After stirring at 0°C for 5 min, drip a solution of 2-(8-(2-(1H-indol-1-yl)-N-methylacetamido)-1,4-dioxoaspirin[4.5]decane-8-carboxamido)-2-methylpropyl benzyl carbonate (1.88 g, 3.25 mmol) in DMF (32 mL), and then raise the temperature to 25°C and stir overnight. After the reaction is completed, rotary evaporate the solvent, neutralize with dilute acetic acid, and then extract and separate with DCM and water 3 times. (DCM:EA = 3:1) Column chromatography. A yellowish-white solid (0.19 g, yield: 16%) is obtained.

[0162] Step 2: 11-(1H-indol-1-yl)-9-methyl-10-oxo-1,4-dioxo-9-azadipyrrolo[4.2.4 8 8 .2 5Synthesis of Propyl Tetradec-11-ene-12-yl Carbonate

[0163] Dissolve solid 12-hydroxy-11-(1H-indol-1-yl)-9-methyl-1,4-dioxo-9-aza-dicyano[4.2.48.25]tetradec-11-en-10-one (0.20 g, 0.56 mmol) in 7 mL of DCM, add propyl chloroformate (0.14 g, 1.13 mmol) and Et3N (0.14 g, 1.35 mmol), and stir at room temperature overnight. After the reaction is completed, extract and separate with DCM and water three times. Remove the solvent by vacuum distillation. (DCM:EA = 5:1) Column chromatography. Then crystallize with n-hexane solution to obtain a yellowish-white solid (0.12 g, yield: 46%).

[0164] Biological Activity Test

[0165] In this example, the insecticidal activities of the exemplary compounds against Aphis craccivora, Tetranychus cinnabarinus, and Bemisia tabaci, as well as the herbicidal activities against Amaranthus retroflexus and Eclipta prostrata, were tested.

[0166] The specific implementation process is as follows:

[0167] 1. Preparation of medicaments:

[0168] Preparation of insecticidal activity medicaments: Dissolve the original drug in 5 ml of acetone, and prepare a 500 mg / L liquid medicine with 0.1% Triton water. On this basis, dilute it with 0.1% Triton water to the required concentration of the liquid medicine for standby.

[0169] Preparation of herbicidal activity medicaments: Dissolve the original drug in N,N-dimethylformamide containing 1% Tween-80 emulsifier to prepare a 1.0% mother liquor, and then dilute it with distilled water for standby.

[0170] 2. Test method: See the specific test.

[0171] 3.1 Activity test against Aphis craccivora

[0172] Spraying method: The test was carried out by the in vivo potted plant spraying method. Plant broad beans in small flower pots with a diameter of 7 cm, one plant per pot. When the bud length is about 3 cm and the leaves have not yet unfolded, spread white sand around the broad bean plants, introduce 25 - 40 second-instar Aphis craccivora, and spray with a laryngeal sprayer, 2.5 ml. Investigate the number of dead and live insects 72 h after the application. The test concentrations are 100 mg / L and 10 mg / L respectively.

[0173] Among some of the tested compounds, compounds 1, 2, 3, 4, 5, 6, 7, 12, 14, 15, 16, 19, and 21 showed significant control effects against Aphis craccivora at a concentration of 100 mg / L, and the mortality rates were all 100%.

[0174] Among the tested compounds, Compounds 1, 2, 3, 4, 5, 6, 7, 12, 14, 15, 16, 19, and 21 showed significant control efficacy against Aphis medicaginis at a concentration of 10 mg / L, with a mortality rate > 90%.

[0175] 3.2. Activity Test against Tetranychus cinnabarinus

[0176] Leaf-dipping method: Using the semi-living plant leaf dipping method, select broad bean potted plants with consistent growth, cut off part of the broad bean plants with leaves, carefully transfer 20 - 30 adult Tetranychus cinnabarinus mites onto the broad bean leaves, immerse all the broad bean leaves in the prepared liquid medicine for 10 seconds, take them out, dry them, place them in a 10 mL glass bottle containing water, and place the glass bottle in an insect rearing cage (30 cm * 30 cm * 30 cm). Place the insect rearing cage in a light incubator at 25°C with a light cycle of (16 / 8 h) and observe the survival of Tetranychus cinnabarinus after 96 hours. Each treatment has 3 replicates, and a solvent without the medicine is set as a control. The test concentrations are 500 mg / L and 50 mg / L respectively.

[0177] Among the tested compounds, Compounds 1, 2, 3, 4, 5, 6, 7, 12, 14, 15, 16, 19, and 21 showed significant control efficacy against Tetranychus cinnabarinus at a concentration of 500 mg / L, with a mortality rate of 100% for all.

[0178] Among the tested compounds, Compounds 1, 2, 3, 4, 5, 6, 7, 12, 14, 15, 16, 19, and 21 showed significant control efficacy against Tetranychus cinnabarinus at a concentration of 50 mg / L, with a mortality rate > 70%.

[0179] 3.3. Activity Test against Bemisia tabaci

[0180] Leaf-dipping method: Using the living plant leaf dipping method, select cotton potted plants with consistent growth, wrap the soil in the flower pot with plastic sheeting, immerse all the cotton leaves in the liquid medicine for 10 seconds, take them out, dry them, and place them in an insect rearing cage (30 cm * 30 cm * 30 cm). Carefully transfer 20 - 30 Bemisia tabaci into the insect rearing cage. Place the insect rearing cage in an observation room at 25°C with a light cycle of (16 / 8 h) for cultivation. Observe the survival of Bemisia tabaci after 96 hours. Each treatment has 3 replicates, and a solvent without the medicine is set as a control. The test concentration is 200 mg / L.

[0181] Among the tested compounds, Compounds 1, 2, 3, 4, 5, 6, 7, 12, 14, 15, 16, 19, and 21 showed significant control efficacy against Bemisia tabaci at a concentration of 200 mg / L, with a mortality rate > 70%.

[0182] In addition, in the following test examples, the exemplary compounds of the present invention also have the effect of controlling weeds simultaneously, and the effect is significant.

[0183] 3.4. Activity Tests on *Amaranthus retroflexus* and *Eclipta prostrata*

[0184] Pot experiment method: The target weeds for testing were *Amaranthus retroflexus* and *Eclipta prostrata*. Take flowerpots with an inner diameter of 7.5 cm, fill them with a composite soil (vegetable garden soil: seedling substrate, 1:2, v / v) to 3 / 4 of the pot, directly sow the above two weed targets (germination rate ≥ 85%), cover with 0.2 cm of soil, and wait until the weeds grow to about the three-leaf stage for standby. After applying each compound at a dose of 200 g a.i. / ha in an automatic spray tower (model: 3WPSH 700E), move the weeds into the greenhouse for cultivation after the liquid medicine on the leaf surface has dried. Investigate the activity (%) of the weeds 30 days later.

[0185] The control effects of Compounds 1, 3, 4, 5, 6, 7, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 of the present invention on *Amaranthus retroflexus* were > 70% at a dose of 200 g a.i. / ha.

[0186] The control effects of Compounds 4, 7, 12, 13, 14, 15, 16, 17, 18, 19, 20 of the present invention on *Eclipta prostrata* were > 70% at a dose of 200 g a.i. / ha.

[0187] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all fall within the protection scope of the present invention.

Claims

1. A compound of formula (I) which is a spirocyclic tetronic acid derivative or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or a pesticidally acceptable salt thereof, Among them, X1, X2, and X3 are each independently selected from hydrogen, halogen, hydroxy, nitro, amino, cyano, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy; W is selected from O, C-R1 or N-R2; Among them, R1 and R2 are each independently selected from hydrogen, halogen, C 1-6 alkyl, halo-C 1-6 alkyl, C 1-6 alkoxy, halo-C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 3-8 cycloalkyl, C 3-8 heterocyclic group, C 6-12 aryl, C 3-8 heteroaryl, C 3-8 cycloalkyl-C 1-3 alkyl, C 3-8 heterocyclic group-C 1-3 alkyl, C 6-12 aryl-C 1-3 alkyl, C 6-12 haloaryl-C 1-3 alkyl or halo-C 3-8 heteroaryl-C 1-3 alkyl; R3 is selected from the following substituents: Among them, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 are each independently selected from C 1-6 alkyl, halo C 1-6 alkyl, C 3-8 cycloalkyl, C 6-12 aryl, C 1-6 alkyl-S-C 1-6 alkyl, C 6-12 aryl C 1-3 alkyl, C 6-12 aryl C 1-3 alkoxy group.

2. The compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or a pesticidally acceptable salt thereof according to claim 1, wherein, X1, X2, and X3 are each independently selected from hydrogen, halogen, hydroxy, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy; W is selected from O, C-R1 or N-R2; wherein, R1 and R2 are each independently hydrogen, halogen, C 1-6 alkyl, halo-C 1-6 alkyl, C 1-6 alkoxy, halo-C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 alkyl, C 3-8 cycloalkyl, C 3-8 heterocyclic group, C 6-12 aryl, C 3-8 heteroaryl, C 3-8 cycloalkyl-C 1-3 alkyl; R3 is selected from the following substituents: Among them, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 are each independently selected from C 1-6 alkyl, halo C 1-6 alkyl, C 3-8 cycloalkyl, C 6-12 aryl, C 1-6 alkyl-S-C 1-6 alkyl, C 6-12 aryl C 1-3 alkyl, C 6-12 aryl C 1-3 alkoxy group.

3. The compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or a pesticidally acceptable salt thereof according to claim 1, wherein, X1, X2, and X3 are each independently selected from hydrogen, halogen, hydroxy, C 1-3 alkyl, C 1-3 haloalkyl, C 1-3 alkoxy, C 1-3 haloalkoxy; W is selected from O, C-R1 or N-R2; wherein, R1 and R2 are each independently selected from hydrogen, halogen, C 1-3 alkyl, halo-C 1-3 alkyl, C 1-3 alkoxy, halo-C 1-3 alkoxy, C 1-3 alkoxy-C 1-3 alkyl, C 3-6 cycloalkyl, C 3-6 heterocyclic group, C 6-10 aryl, C 3-6 heteroaryl, C 3-6 cycloalkyl-C 1-3 alkyl; R3 is selected from the following substituents: Among them, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 are each independently selected from C 1-6 alkyl, halo C 1-6 alkyl, C 3-8 cycloalkyl, C 6-12 aryl, C 1-6 alkyl-S-C 1-6 alkyl, C 6-12 aryl C 1-3 alkyl, C 6-12 aryl C 1-3 alkoxy group.

4. The compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or a pesticidally acceptable salt thereof according to claim 1, wherein, X1, X2, and X3 are each independently selected from hydrogen, halogen, hydroxy, C 1-3 alkyl; W is selected from O, C-R1 or N-R2; wherein, R1 and R2 are each independently selected from hydrogen, halogen, C 1-3 alkyl, halo-C 1-3 alkyl, C 1-3 alkoxy, halo-C 1-3 alkoxy, C 3-6 cycloalkyl, C 3-6 cycloalkyl-C 1-3 alkyl; R3 is selected from the following substituents: Among them, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 are each independently selected from C 1-6 alkyl, halo C 1-6 alkyl, C 3-8 cycloalkyl, C 6-12 aryl, C 1-6 alkyl-S-C 1-6 alkyl, C 6-12 aryl C 1-3 alkyl, C 6-12 aryl C 1-3 alkoxy group.

5. The compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or a pesticidally acceptable salt thereof according to claim 1, wherein: X1, X2, and X3 are each independently selected from hydrogen, halogen, hydroxyl, C 1-3 alkyl; W is selected from O, C-R1 or N-R2; Among them, R1 and R2 are each independently selected from hydrogen, halogen, C 1-3 alkyl, halo C 1-3 alkyl, C 1-3 alkoxy, halo C 1-3 alkoxy, C 3-6 cycloalkyl, C 3-6 cycloalkyl C 1-3 alkyl; R3 is selected from the following substituents:

6. A composition for controlling pests, microorganisms and / or unwanted plant growth, which comprises the compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or a pesticidally acceptable salt thereof according to any one of claims 1-5, and a pesticidally acceptable carrier.

7. The composition according to claim 6, wherein the dosage form is selected from powder, granule, liquid, suspension or spray, preferably wettable powder, wettable liquid, soluble powder, dispersible liquid, aqueous solution, microemulsion, emulsifiable concentrate, emulsion in water, sprayable solution, dispersible oil suspension, microcapsule suspension, water dispersible granule, water soluble granule, macrogranule, granule for broadcasting and soil application, aerosol, ultra-low volume agent and wax product.

8. Use of the compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or a pesticidally acceptable salt thereof according to any one of claims 1-5 in the preparation of a composition for controlling pests, microorganisms and / or unwanted plant growth.

9. The use according to claim 8, wherein the pests are selected from pests belonging to Lepidoptera, Coleoptera, Homoptera, Hemiptera, Thysanoptera, Isoptera, Diptera, Hymenoptera, Mallophaga, Anoplura, Orthoptera, Blattodea, Siphonaptera, Acarina, Nematoda.

10. The use according to claim 8, wherein the unwanted plants are selected from annual monocotyledonous or dicotyledonous broad-leaved weeds, gramineous weeds and sedges.

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