Bicyclic compounds and their use as pest control agents

Abstract

The present invention provides a novel bicyclic compound of formula (I). TIFF2025521090000140.tif3663 wherein A1, A2, A3, A4, A5, Z, D, R 3 , R 8 and R 8a are defined in the detailed description. The said compound shows a high insecticidal effect. The present invention also relates to a method for producing the compound of formula (I). The present invention further relates to compositions, combinations, uses and methods of application of the compound of formula (I).

Description

Technical Field

[0001] The present invention described in this specification relates to novel bicyclic compounds, and in particular, the present invention relates to compounds of formula (I), compositions containing these compounds, and their use as pest control agents. Furthermore, the present invention relates to the production of these novel bicyclic compounds and their useful intermediates.

Background Art

[0002] It is known from the prior art, for example, WO 2018 / 011111, WO 2016 / 071499, WO 2015 / 038503, WO 2016 / 087363, WO 2016 / 087368, WO 2016 / 087421 and WO 2016 / 087422 that certain substituted bicyclic compounds exhibit pest control properties.

[0003] The active compounds reported in the above prior art have drawbacks in several respects. For example, they show only a narrow spectrum of insecticidal activity, have no satisfactory pest control effect at low application rates, or do not show the desired quick-acting or long-lasting effect. Therefore, there is always a need for new pest control agents with improved insecticidal activity, expanded effective range, extended duration of activity, improved plant compatibility, improved environmental safety, improved formulation properties, reduced risk of resistance development, etc.

[0004] Summary: The present invention relates to novel bicyclic compounds that have been found to have advantageous effects over similar compounds reported in the literature in terms of improved pest control activity, more favorable biological or environmental properties, expanded range of application, or improved plant compatibility. The novel bicyclic compounds of the present invention can also be used in combination with other biologically active compounds, thereby improving the efficacy against insects that are particularly difficult to control. Therefore, the present invention provides novel bicyclic compounds of formula (I). [Chemical formula] In the formula, Z is selected from a direct bond or -C(=O)-; D is selected from the group consisting of D1, D2, and D3, [Chemical formula] Y represents O or NR 7 . A1, A2, and A3 are independently C or N; A4 and A5 are independently C or N, provided that A4 and A5 cannot be N simultaneously; R 1 is selected from the group consisting of C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, phenyl, benzyl, phenylethyl, and C2-C6 heterocyclyl; R 2 is selected from the group consisting of C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, and C3-C8 cycloalkyl-C1-C6 alkyl; R 3 is selected from the group consisting of hydrogen, halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, and C1-C6 haloalkyl; R 4 is selected from the group consisting of C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, and -NR c R d ; R c is selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, and C3-C8 cycloalkyl; Rd is selected from the group consisting of hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C3-C8 cycloalkyl, and C3-C6 cycloalkyl-C1-C4 alkyl; or R c and R d The substituents may, together with the atoms to which they are attached, or together with further atoms selected from the group consisting of C, N, O, C(=O), C(=S), and S(O), form a 3- to 6-membered ring, and optionally may be substituted by one or more substituents selected from the group consisting of halogen, CN, and C1-C6 alkyl; 0-2 R 5 is selected from the group consisting of C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, phenyl, benzyl, and C2-C6 heterocyclyl; or R 4 and R 5 The substituents may, together with the atoms to which they are attached, or together with further atoms selected from the group consisting of C, N, O, C(=O), C(=S), and S(O), form a 3- to 6-membered ring, and optionally may be substituted by one or more substituents selected from the group consisting of halogen, CN, and C1-C6 alkyl; 0-2 R 6 is selected from the group consisting of C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, phenyl, benzyl, C2-C6 heterocyclyl, and -NR c R d ; R 7 ​​is selected from the group consisting of hydrogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C1-C6 alkoxy, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, phenyl, benzyl, C2-C6 heterocyclyl, C2-C6 heterocyclyl-C1-C6 alkyl, -COR 5 -CONR c R d SCF3, and -SO2R 5 selected from the group consisting of; R 8 and R 8a are independently selected from the group consisting of hydrogen, halogen, cyano, C1-C4-alkyl and C1-C4-haloalkyl; wherein R 1 R 2 R 3 R 4 R 5 R 6 and R 7 each aliphatic group of may optionally be substituted with one or more groups of R a and the cyclic groups of R 1 R 2 R 3 R 4 R 5 R 6 and R 7 may optionally be substituted with one or more groups of R b wherein R a is selected from the group consisting of halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl; R b is selected from the group consisting of halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C 3- C8 cycloalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkoxy and C1-C6 haloalkoxy; Alternatively, a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof.

[0005] In another embodiment, the present invention provides a composition comprising a compound of formula (I), a salt, metal complex, stereoisomer, polymorph or N-oxide thereof, and at least one additional component selected from the group consisting of a surfactant and an adjuvant.

[0006] In yet another embodiment, the present invention further provides a composition comprising at least one bioactive compatible compound selected from the group consisting of a bactericide, an insecticide, a nematicide, an acaricide, a biopesticide, a herbicide, a plant growth regulator, a biostimulant, an antibiotic, a fertilizer or a nutrient.

[0007] In yet another embodiment, the present invention provides a method for producing a compound of formula (I). Hereinafter, the present invention will be described in detail.

[0008] Detailed description of the present invention: Definitions: The definitions provided herein for the terms used in this disclosure are for illustrative purposes only and are not intended to limit the scope of the invention disclosed in this disclosure. As used herein, the terms "comprise", "comprising", "include", "including", "has", "having", "contain", "containing", "characterized by", or any other variations thereof are intended to cover non-exclusive inclusion, subject to any explicitly stated limitations. For example, a composition, mixture, process, or method comprising a list of elements is not necessarily limited to only those elements, and may include other elements not explicitly recited or inherent to the composition, mixture, process or method. The transitional phrase "consisting of" excludes unspecified elements, steps or components. When recited in a claim, it usually prohibits including materials other than those recited, except for impurities associated therewith. When the phrase "consisting of" is recited in a clause of the claim body rather than immediately following the preamble, it limits only the elements recited in that clause. Other elements are not excluded from the entire claim. The transitional phrase "consisting essentially of" is used to define a composition or method that includes materials, steps, features, components or elements in addition to those literally disclosed, provided that these additional materials, steps, features, components or elements do not substantially affect the basic and novel features of the invention claimed. The term "consisting essentially of" lies midway between "comprising" and "consisting of". Further, unless the contrary is explicitly stated, "or" refers to the inclusive "or" rather than the exclusive "or". For example, the condition A "or" B is satisfied by any of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present). Also, the indefinite articles "a" and "an" before an element or component of the present invention are non-limiting with respect to the number of instances (i.e., occurrences) of the element or component. Thus, "a" or "an" should be interpreted to include one or at least one, and the singular word form of an element or component includes the plural as well, unless the number is clearly intended to be singular. As used herein, the terms "invertebrate pest" or "invertebrate" include arthropods, gastropods, and nematodes that are economically important as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs, and symphylans. The term "gastropod" includes snails, slugs, and other Stylommatophora. The term "nematode" refers to organisms of the phylum Nematoda. The term "helminth" includes roundworms, heartworms, phytophagous nematodes (Nematoda), trematodes (Tematoda), acanthocephalans, and cestodes (Cestoda). In the context of the present disclosure, the term "invertebrate pest control" means inhibiting the occurrence of invertebrate pests (including mortality, reduced feeding, and / or mating disruption), and related expressions are defined similarly. The term "agronomic" refers to the production of field crops such as food, feed, and fiber, including the cultivation of corn, soybeans and other legumes, rice, cereals (e.g., wheat, oats, barley, rye, rice, corn), leafy vegetables (e.g., lettuce, cabbage, and other vegetable crops), fruiting vegetables (e.g., tomatoes, peppers, eggplants, brassicas, cucurbits), potatoes, sweet potatoes, grapes, cotton, fruit trees (e.g., pomegranates, stone fruits, citrus), small fruits (berries, cherries), and other specialty crops (e.g., canola, sunflowers, olives). The term "non-agronomic" refers to non-field crops such as horticultural crops (e.g., ornamental plants grown in greenhouses, nurseries, or outdoors), residential, agricultural, commercial, and industrial structures, lawns (e.g., turfgrass, pastures, golf courses, lawns, sports fields), wood products, stored products, forestry and vegetation management, public health (i.e., humans), and animal health (e.g., pets, livestock, poultry, etc. for livestock, wildlife, etc. for non-livestock) applications.

[0009] Non-agricultural uses involve protecting animals from invertebrate parasitic pests by administering to the animal to be protected a pesticidally effective (i.e., biologically effective) amount of the compounds of the invention, typically in the form of a composition formulated for veterinary use. As referred to in this disclosure and the claims, the terms "parasiticidal" and "parasiticidally" refer to an observable effect on invertebrate parasitic pests for protecting animals from the pests. The parasiticidal effect is usually associated with reducing the occurrence or activity of the target invertebrate parasitic pests. Such effects on the pests include death, retarded growth, reduced mobility, reduced ability to remain on or in the host animal, reduced feeding, inhibition of reproduction, etc. These effects on invertebrate parasitic pests provide for the control (including prevention, reduction or elimination) of parasitic infestation or infection in the animals.

[0010] The compounds of this disclosure may exist in pure form or as mixtures of various possible isomeric forms such as stereoisomers or constitutional isomers. The various stereoisomers include enantiomers, diastereomers, chiral isomers, atropisomers, conformational isomers, rotational isomers, tautomers, optical isomers, polymorphs, and geometric isomers. Any desired mixtures of these isomers are included within the scope of the claims of this disclosure. Those skilled in the art will understand that a particular stereoisomer may be more active and / or exhibit beneficial effects when enriched relative to other isomers or separated from other isomers. Further, those skilled in the art know the processes or methods or techniques for separating, enriching, and / or selectively preparing said isomers.

[0011] Here, the meanings of various terms used in the description are explained. The term - "alkyl", used alone or in compound words such as "alkylthio" or "haloalkyl" or -N(alkyl) or alkylcarbonylalkyl or alkylsulfonylamino, includes straight-chain or branched C1-C 12It includes alkyl, preferably C1-C8 alkyl, more preferably C1-C6 alkyl. Representative examples of alkyl include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl, or various isomers. For example, when alkyl is at the end of a complex substituent such as alkylcycloalkyl, the first part of the complex substituent, such as cycloalkyl, can be mono- or polysubstituted independently, either the same or different, by alkyl. The same applies to complex substituents with other radicals at the end, such as alkenyl, alkynyl, hydroxyl, halogen, carbonyl, carbonyloxy, etc.

[0012] The term "alkenyl", used alone or in a compound word, refers to a straight-chain or branched C2-C 12It contains alkenes, preferably C2-C8 alkenes, more preferably C2-C6 alkenes. Representative examples of alkenes include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl and various isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. This definition applies to alkenyl as part of a complex substituent such as haloalkenyl, etc., unless otherwise defined specifically.

[0013] Non-limiting examples of alkynyl include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl, and various isomers. This definition applies to alkynyl as part of a complex substituent, such as haloalkynyl, unless otherwise specifically defined. The term "alkynyl" can also include moieties composed of multiple triple bonds, such as 2,5-hexadiynyl.

[0014] The term "cycloalkyl" means alkyl closed to form a ring. Non-limiting examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. This definition applies to cycloalkyl as part of a complex substituent, such as cycloalkylalkyl, unless otherwise specifically defined.

[0015] Terms such as "cycloalkoxy" and "cycloalkenyloxy" are similarly defined. Non-limiting examples of cycloalkoxy include cyclopropyloxy, cyclopentyloxy, and cyclohexyloxy. This definition applies to cycloalkoxy as part of a complex substituent, such as cycloalkoxyalkyl, unless otherwise specifically defined.

[0016] The term "halogen" includes fluorine, chlorine, bromine, or iodine, either alone or in a compound word such as "haloalkyl". Further, when used in a compound word such as "haloalkyl", the alkyl may be partially or fully substituted with the same or different halogen atoms. Non-limiting examples of "haloalkyl" include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 1,1-dichloro-2,2,2-trifluoroethyl, and 1,1,1-trifluoroprop-2-yl. This definition applies to haloalkyl as part of a complex substituent, such as haloalkylaminoalkyl, unless otherwise specifically defined.

[0017] The terms "haloalkenyl" and "haloalkynyl" are similarly defined, except that an alkenyl group and an alkynyl group are present as part of the substituent instead of an alkyl group.

[0018] The term "haloalkoxy" means a straight-chain or branched alkoxy group, where some or all of the hydrogen atoms of these groups may be replaced by halogen atoms as described above. Non-limiting examples of haloalkoxy include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, and 1,1,1-trifluoroprop-2-oxy. This definition applies to haloalkoxy as part of a complex substituent, such as haloalkoxyalkyl, unless otherwise specifically defined.

[0019] The term "haloalkylthio" means a straight-chain or branched alkylthio group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as described above. Non-limiting examples of haloalkylthio include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio, and 1,1,1-trifluoroprop-2-ylthio. This definition applies to haloalkylthio as part of a complex substituent, such as haloalkylthioalkyl, unless otherwise specifically defined.

[0020] The term "hydroxy" means -OH, amino means -NRR, where R can be any possible substituent such as H or alkyl. Carbonyl means -C(O)-, carbonyloxy means -OC(O)-, sulfinyl means SO, and sulfonyl means S(O)2.

[0021] The term "alkoxy", used alone or in combination, refers to C1-C 12 alkoxy, preferably C1-C8 alkoxy, more preferably C1-C6 alkoxy. Examples of alkoxy include methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy and various isomers thereof. This definition applies also to alkoxy as part of a complex substituent such as, for example, haloalkoxy, alkynylalkoxy etc., unless otherwise specifically defined.

[0022] The term "alkoxyalkyl" means an alkoxy substitution on alkyl. Non-limiting examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2.

[0023] The term "alkylthio" includes the following branched or straight-chain alkylthio moieties: for example, methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and 1-ethyl-2-methylpropylthio and various isomers thereof.

[0024] Halo-cycloalkyl, halo-cycloalkenyl, alkyl-cycloalkyl, cycloalkyl-alkyl, cycloalkoxy-alkyl, alkylsulfinyl-alkyl, alkylsulfonyl-alkyl, haloalkyl-carbonyl, cycloalkyl-carbonyl, haloalkoxyl-alkyl, etc. are defined in the same manner as the above examples. "Alkylamino", "dialkylamino", etc. are defined in the same manner as the above examples.

[0025] The term "carbocyclic ring" includes "aromatic carbocyclic ring systems" and "non-aromatic carbocyclic ring systems", or polycyclic or bicyclic (spiro, fused, bridged, non-fused) ring compounds, the rings of which can be aromatic or non-aromatic (wherein aromatic indicates that the Hückel's rule is satisfied and non-aromatic indicates that the Hückel's rule is not satisfied).

[0026] The term "hetero" related to a ring refers to a ring that may contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, where at least one ring atom is not carbon. However, each ring contains no more than 4 nitrogens, 2 oxygens, and 2 sulfurs.

[0027] The terms "heterocyclic ring" or "heterocycle" include "aromatic heterocyclic ring" or "heteroaryl ring system" and "non-aromatic heterocyclic ring system", or polycyclic or bicyclic (spiro, fused, bridged, non-fused) ring compounds where the ring may be aromatic or non-aromatic. The heterocycle contains at least one heteroatom selected from 0-2 N, O, S(O) * R * ), and C=NR * and may be replaced by, * where is an integer.

[0028] The term "non-aromatic heterocyclic ring" or "non-aromatic heterocyclic" means a saturated or partially unsaturated heterocyclic ring containing 1 to 4 heteroatoms from the group of oxygen, nitrogen and sulfur, having 3 to 15 members, preferably 3 to 10 members: in addition to carbon ring members, a monocyclic, bicyclic or tricyclic heterocyclic ring containing 1 to 3 nitrogen atoms and / or 1 oxygen atom or sulfur atom, or 1 to 2 oxygen atoms and / or sulfur atoms; when the ring contains a plurality of oxygen atoms, they are not directly adjacent; for example (but not limited to) oxetanyl, oxiranyl, aziridinyl, thietanyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, 1,2,4-oxadiazolidinyl, 1,2,4-thiadiazolidinyl, 1,2,4-triazolidin-1-yl, 1,2,4-triazolidin-3-yl, 1,2,3-triazolidinyl, 1,3,4-oxadiazolidinyl, 1,3,4-thiadiazolidinyl, 1,3,4-triazolidinyl, dihydrofuryl, dihydrothienyl, pyrrolinyl, isoxazolinyl, isothiazolinyl, dihydropyrazolyl, dihydrooxazolyl, dihydrothiazolyl, piperidinyl, pyrazinyl, morpholinyl, thiomorpholinyl, 1,3-dioxan-5-yl, tetrahydropyranyl, tetrahydrothienyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl and cycloserine. This definition applies to heterocyclyl as part of a complex substituent, such as heterocyclylalkyl, unless otherwise specifically defined.

[0029] The term "heteroaryl" or "aromatic heterocycle" means a 5- or 6-membered fully unsaturated monocyclic ring system containing 1 to 4 heteroatoms from groups of oxygen, nitrogen and sulfur. When the ring contains one or more oxygen atoms, they are not directly adjacent; 5-membered heteroaryl containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom: in addition to carbon atoms, it can contain 1 to 4 nitrogen atoms as ring members, or a 5-membered heteroaryl group containing 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom, for example (but not limited to) furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1,2,4-triazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,3,4-triazolyl, tetrazolyl; nitrogen-bonded 5-membered heteroaryl containing 1 to 4 nitrogen atoms, or benzo-fused nitrogen-bonded 5-membered heteroaryl containing 1 to 3 nitrogen atoms: in addition to carbon atoms, it contains 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms as ring members, and two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member may be bridged by a buta-1,3-diene-1,4-diyl group in which 1 or 2 carbon atoms may be substituted by nitrogen atoms, and a 5-membered heteroaryl group in which these rings are bonded to the backbone through one of the nitrogen ring members, for example 1-pyrrolyl, 1-pyrazolyl, 1,2,4-triazol-1-yl, 1-imidazolyl, 1,2,3-triazol-1-yl and 1,3,4-triazol-1-yl.

[0030] 6-membered heteroaryl containing 1 to 4 nitrogen atoms: A 6-membered heteroaryl group that can contain 1 to 3 and 1 to 4 nitrogen atoms, respectively, as ring members in addition to carbon atoms, such as (but not limited to) pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, and 1,2,4,5-tetrazin-3-yl; benzo-fused 5-membered heteroaryl containing 1 to 3 nitrogen atoms or 1 nitrogen atom and 1 oxygen or sulfur atom: such as (but not limited to) indolyl, benzimidazolyl, indazolyl, benzofuranyl, benzothiophenyl, benzothiazolyl, and benzoxazolyl; benzo-fused 6-membered heteroaryl containing 1 to 3 nitrogen atoms: such as (but not limited to) quinolinyl, isoquinolinyl, quinoxalinyl, phthalazinyl, quinazolinyl, and cinnolinyl.

[0031] The term "partially / fully saturated or unsaturated heterocycle" includes partially / fully saturated heterocycles or partially / fully unsaturated heterocycles. This definition applies, unless otherwise specifically defined, to heteroaryl as part of a complex substituent, such as heteroarylalkyl, etc.

[0032] Non-limiting examples of "alkylcarbonyl" include C(O)CH3, C(O)CH2CH2CH3, and C(O)CH(CH3)2. Non-limiting examples of "alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(=O), CH3CH2CH2OC(=O), (CH3)2CHOC(=O), and various butoxy or pentyloxycarbonyl isomers.

[0033] The term "amide" means A-R’C=ONR’’-B, where R’ and R’’ represent substituents, and A and B represent any groups. The term "thioamide" means A-R’C=SNR’’-B, where R’ and R’’ represent substituents, and A and B represent any groups.

[0034] The total number of carbon atoms in the substituent is indicated by the prefix "C i -C j ". Here, i and j are numbers from 1 to 18. For example, C1-C3 alkylsulfonyl represents from methylsulfonyl to propylsulfonyl. C2 alkoxyalkyl represents CH3OCH2. C3 alkoxyalkyl represents, for example, CH3CH(OCH3), CH3OCH2CH2 or CH3CH2OCH2. Also, C4 alkoxyalkyl represents various isomers of an alkyl group substituted with an alkoxy group containing a total of 4 carbon atoms. For example, it includes CH3CH2CH2OCH2 and CH3CH2OCH2. In the above description, when the compound of formula (I) is composed of one or more heterocycles, all substituents are bonded to these rings via any available carbon or nitrogen by substitution of hydrogen on carbon or nitrogen.

[0035] When the compound is substituted with a substituent having a suffix indicating that the number of such substituents can exceed 1, the substituents (when there are more than one of them) are independently selected from the defined group of substituents. Also, when the m suffix m of (R)

[0036] indicates an integer from 0 to 4, for example, the number of substituents can be selected from integers from 0 to 4.

[0037] The term "optionally substituted" is used interchangeably in this specification with the terms "substituted or unsubstituted" or "(un)substituted". Unless otherwise specified, an optionally substituted group can have substituents at each substitutable position of the group, and each substitution is independent of the others. An optionally substituted group can also have no substituents. Thus, the term "optionally substituted with one (or two or more) substituents" means that the number of substituents can vary from 0 to the number of positions available for substitution.

[0038] The term "(un)substituted" means that the group is unsubstituted or the group is independently substituted with a substituent selected from the group consisting of halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, NH(alkyl), N(alkyl)2 and -S(O) 0~2 and is independently substituted with a substituent selected from the group consisting of C1-C6 alkyl.

[0039] The term "aliphatic group", used alone or in a compound word, refers to a straight-chain or branched substituent, such as C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl 、 C 1- C6 haloalkyl, C2-C6 haloalkenyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkoxy or C1-C6 haloalkoxy; The term "cyclic group", used alone or in a compound word, includes a cyclic or group that is fully / partially saturated or unsaturated, such as cycloalkyl, phenyl, C2-C6 heterocyclyl, etc.

[0040] Embodiments herein and their various features and advantageous details are described with reference to non-limiting embodiments of the specification. Descriptions of well-known components and processing techniques are omitted so as not to unnecessarily obscure the embodiments herein. The examples used herein are only intended to facilitate an understanding of how the embodiments herein can be implemented and enable those skilled in the art to further implement the embodiments herein. Accordingly, these examples should not be construed as limiting the scope of the embodiments herein.

[0041] The description of specific embodiments sufficiently reveals the general nature of the embodiments of this specification, so that others, by applying current knowledge, can easily modify and / or adapt such specific embodiments for various uses without departing from the general concept, and thus such adaptations and modifications should be understood to be within the meaning and scope of equivalents of the disclosed embodiments, and it is also intended to be understood. The expressions or terms used in this specification are for the purpose of explanation and not for limitation. Therefore, although the embodiments of this specification are described from the perspective of preferred embodiments, those skilled in the art will recognize that the embodiments of this specification can be implemented with modifications within the spirit and scope of the embodiments described in this specification.

[0042] Any discussion of documents, acts, materials, devices, articles, etc. included in this specification is only for the purpose of providing a context for the disclosure. It is not admitted that any or all of these matters form part of the basis of the prior art or are common general knowledge in the field related to the disclosure that existed anywhere before the priority date of this application.

[0043] The numerical values described in the specification and in the specification / claims may form an important part of the present invention, but any deviation from such numerical values, if such deviation follows the same scientific principles as the present invention disclosed in the present invention, shall be considered to be within the scope of the present invention. The compounds of the present invention can exist, where appropriate, as various possible isomeric forms, especially stereoisomers, such as E and Z, threo and erythro, and mixtures of optical isomers, and may also exist as mixtures of tautomers where appropriate. Both the E isomer and the Z isomer, as well as the threo isomer and the erythro isomer, and optical isomers, any desired mixtures of these isomers and possible tautomers are disclosed and claimed.

[0044] For the purposes of the present disclosure, the term "pest" includes, but is not limited to, fungi, stramenopiles (oomycetes), bacteria, nematodes, mites, ticks, insects and rodents.

[0045] The term "plant" is understood herein to mean all plants and plant populations such as desirable and undesirable wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants obtained by conventional breeding and optimization methods, or methods of biotechnology and genetic engineering, or combinations of these methods, and include genetically modified plants, and plant cultivars that are and are not protectable by plant breeder's rights.

[0046] In the present disclosure, the term "plant" includes organisms of the types exemplified by trees, shrubs, herbs, grasses, ferns, and mosses, and typically grows in a place, absorbs water and necessary substances through its roots, and synthesizes nutrients in its leaves by photosynthesis. Examples of "plants" for the purposes of the present invention include agricultural crops such as wheat, rye, barley, triticale, oats or rice; beet plants, such as sugar beet or fodder beet; pomaceous, stone fruit or soft fruit, such as the fruits and fruit trees of apple, pear, plum, peach, almond, cherry, strawberry, raspberry, blackberry or gooseberry; leguminous plants such as lentil, pea, alfalfa or soybean; oil plants such as rapeseed, mustard, olive, sunflower, coconut, cocoa bean, castor oil plant, oil palm, peanut or soybean; cucurbitaceous plants such as pumpkin, cucumber, melon; fiber plants such as cotton, flax, hemp, jute; citrus fruits and citrus trees such as orange, lemon, grapefruit, tangerine; horticultural plants, vegetables such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato, cucurbitaceous plants, pepper; lauraceous plants such as avocado, cinnamon, camphor; cucurbitaceous plants; oregano; energy and raw material plants such as cereals, maize, soybean, other leguminous plants, rapeseed, sugar cane, oil palm; tobacco; nuts; coffee; tea; cocoa; banana; pepper; vine plants (vine plants for edible grapes and grape juice); hop; turf; sweet leaf (also called stevia); natural rubber plants or ornamental and forestry plants such as flowers, shrubs, broad-leaved trees or evergreen trees, such as conifers; and plant propagation materials such as seeds, and crop materials of these plants are mentioned.

[0047] Preferably, plants for the purposes of the present invention include, but are not limited to, cereals, maize, rice, soybean and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus fruits and citrus trees, any horticultural plants, cucurbitaceous plants, oil plants, tobacco, coffee, tea, cocoa, sugar beet, sugar cane, cotton, potato, tomato, onion, pepper and vegetables, ornamental plants, any flower plants, and other plants for human and animal use.

[0048] The term "plant part" is understood to mean all parts and organs of a plant, both above and below ground. For the purposes of this disclosure, the term "plant part" includes, but is not limited to, cuttings, leaves, twigs, tubers, flowers, seeds, branches, roots including taproots, lateral roots, root hairs, root tips, root caps, rhizomes, cuttings, sprouts, fruits, fruit bodies, bark, stems, buds, accessory buds, meristems, nodes and internodes.

[0049] The term "locus thereof" includes the soil, the surroundings of the plant or plant part, and the devices or tools used before, during or after sowing / planting of the plant or plant part.

[0050] The application of the compounds of the present disclosure to plants or plant materials or the locus thereof in a composition optionally containing the compounds of the present disclosure or other compatible compounds includes applications by techniques well known to those skilled in the art including, but not limited to, spraying, coating, dipping, fumigating, impregnating, injecting and dusting.

[0051] The term "applied" means to physically or chemically adhere to the plant or plant part and includes impregnation.

[0052] The present invention relates to compounds of formula (I).

Chemical formula

Chemical formula

[0053] The following embodiments provide definitions (including preferred definitions) of substituents related to the compounds of formula (I) of the present invention. For any one of these substituents, any of the definitions shown below can be combined with the definitions of any of the other substituents shown below or elsewhere in this document.

[0054] In one embodiment, the present invention provides a compound of formula (I) wherein D is D1.

Chemical formula

[0055] In another embodiment, the present invention provides a compound of formula (I) wherein D is D2.

Chemical formula

[0056] In yet another embodiment, the present invention provides a compound of formula (I) wherein D is D3.

Chemical formula

[0057] In one embodiment, the present invention provides a compound of formula (I) which is represented by a compound of formula (Ia).

Chemical formula

[0058] In another embodiment, the present invention provides a compound of formula (I) which is represented by a compound of formula (Ib).

Chemical formula

[0059] In one embodiment, the group R of the compound of formula (I) 1 , R 2 , R 3, R 4 , R 5 , R 6 and R 7 are described as follows. R 1 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, benzyl, phenyl and C3-C6 heterocyclyl; preferably selected from C1-C6 alkyl, C3-C6 cycloalkyl, phenyl, benzyl, and 4-6 membered aromatic or non-aromatic heterocycles. R 2 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl; preferably C1-C6 alkyl, C3-C6 cycloalkyl-C1-C6 alkyl, more preferably C1-C6 alkyl; most preferably methyl or ethyl. R 3 is selected from the group consisting of hydrogen, halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy and C1-C6 haloalkyl; preferably hydrogen, halogen and cyano; C1-C3 alkyl, C1-C3 haloalkyl and C1-C3 alkoxy; more preferably hydrogen, fluorine, chlorine, methyl, ethyl, methoxy and CF3. R 4 is selected from the group consisting of C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl and -NR c R d ; preferably C1-C6 alkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C3-C6 cycloalkyl, -NR c R d and C1-C6 haloalkyl; more preferably C1-C6 alkyl, C3-C6 cycloalkyl and C1-C6 haloalkyl; Rc is selected from the group consisting of hydrogen, C1-C6 alkyl, and C3-C8 cycloalkyl; more preferably hydrogen or C1-C6 alkyl; R d is selected from the group consisting of C1-C6 alkyl, C1-C6-C3-C8 cycloalkyl-C1-C6 alkyl, phenyl, and C2-C6 heterocyclyl; preferably C1-C6 alkyl, C1-C6 haloalkyl, and C3-C8 cycloalkyl; or R c and R d substituents, together with the atoms to which they are attached, or together with further atoms selected from the group consisting of C, N, O, C(=O), C(=S), and S(O) 0-2 may form a 3- to 6-membered ring, and optionally may be substituted by one or more substituents selected from the group consisting of halogen, CN, or C1-C6 alkyl; R 5 is C 1- C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, phenyl, benzyl, and C2-C6 heterocyclyl; Optionally, R 4 and R 5 substituents, together with the atoms to which they are attached, or together with further atoms selected from the group consisting of C, N, O, C(=O), C(=S), and S(O) 0-2 may form a 4- to 6-membered ring, which optionally may be substituted by one or more substituents selected from the group consisting of halogen, CN, and C1-C6 alkyl; R 6 is selected from the group consisting of C1-C6 alkyl, C2-C6 alkenyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, and C2-C6 heterocyclyl; preferably C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, and C2-C6 heterocyclyl. R7 is selected from the group consisting of hydrogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C1-C6 alkoxy, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C2-C6 heterocyclyl and -COR 5 ; preferably hydrogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C8 cycloalkyl C2-C6 heterocyclyl and -COR 5 . R 8 and R 8a are independently selected from the group consisting of hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, phenyl and C2-C6 heterocyclyl; preferably hydrogen, halogen, cyano, C1-C6 alkyl and C1-C6 haloalkyl. Here, each aliphatic group of R 1 , R 2 , R 4 , R 5 , R 6 and R 7 may optionally be substituted with one or more R a groups, and the cyclic groups of R 1 , R 2 , R 3、 R 4 , R 5 , R 6 and R 7 may optionally be substituted with one or more R b groups. Ra is selected from the group consisting of halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl; R bis selected from the group consisting of halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C3-C8 cycloalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkoxy and C1-C6 haloalkoxy.

[0060] Furthermore, the embodiments of the present disclosure described herein can be combined in any way, and the description of variables in the embodiments relates not only to the compounds of formula (I) but also to the starting compounds and intermediate compounds useful for preparing the compounds of formula (I). In this sense, embodiments that can be combined according to the present invention are shown below: In one embodiment, the present invention provides a compound of formula (I), wherein D is D1; Z is a direct bond or -C(=O)-; preferably Z is a direct bond; R 3 is selected from the group consisting of hydrogen, halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl and C1-C6 alkoxy; R 4 is selected from the group consisting of C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl and -NR c R d ; wherein R c is selected from the group consisting of hydrogen or C1-C6 alkyl; R d is selected from the group consisting of hydrogen or C1-C6 alkyl; R 5 is selected from the group consisting of C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, phenyl, benzyl and C2-C6 heterocyclyl; or R 4 and R 5The substituents, together with the atoms to which they are attached, or together with further atoms selected from the group consisting of C, N, O, C(=O), C(=S), and S(O) 0-2 may form a 4- to 6-membered ring, and may optionally be substituted by one or more substituents selected from the group consisting of halogen, CN, and C1-C6 alkyl. Here, R 4 and R 5 each aliphatic group of may optionally be substituted by one or more R a groups, and the cyclic groups of R 4 and R 5 may optionally be substituted by one or more R b groups. R a is selected from the group consisting of halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl, and C2-C6 heterocyclyl; R b is selected from the group consisting of halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C 3- C8 cycloalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkoxy and C1-C6 haloalkoxy; R 8 and R 8a are independently selected from the group consisting of hydrogen, halogen, cyano, C1-C4-alkyl, and C1-C4-haloalkyl; A1, A2, A3, A4, A 5は、 are defined as above; or a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof is provided.

[0061] In another embodiment, the present invention provides a compound of formula (I). Here, D is D2; Z is a direct bond; R 3is selected from the group consisting of hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C1-C6 alkoxy; R 6 is selected from the group consisting of C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, -NR c R d , phenyl, benzyl and C2-C6 heterocyclyl; preferably, R 6 is selected from the group consisting of C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl and -NR c R d . Here, R c is selected from the group consisting of hydrogen or C1-C6 alkyl; R d is selected from the group consisting of hydrogen or C1-C6 alkyl; R 7 is independently selected from the group consisting of hydrogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C1-C6 alkoxy, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, phenyl, benzyl, C2-C6 heterocyclyl, C2-C6 heterocyclyl C1-C6 alkyl and -COR 5 ; preferably, R 7 is selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, -COR 5、 phenyl, benzyl, C2-C6 heterocyclyl and cyano; Here, R 5 is C 1- C6 alkyl and C 3- C8 cycloalkyl; Here, R 5、 R 6 and R 7Each aliphatic group may be optionally substituted with one or more R a groups; and R 5 , R 6 and R 7 The cyclic groups may be optionally substituted with one or more R b groups, where R a is selected from the group consisting of halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl; R b is selected from the group consisting of halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C 3- C8 cycloalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkoxy and C1-C6 haloalkoxy; A1, A2, A3, A 4、 and A5 are as defined above; or a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof is provided.

[0062] In yet another embodiment, the present invention provides a compound of formula (I). Here, D is D3; Z is a direct bond; R2 is C1-C6 alkyl; R 3 is selected from the group consisting of hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, and C1-C6 alkoxy; R1 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, phenyl, benzyl, phenylethyl and 4-6 membered heterocyclyl; R 1 Each aliphatic group of is one or more R a groups and R aOptionally substituted with a cyclic group and optionally substituted with one or more R b groups, where R a is selected from the group consisting of halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl; R b is selected from the group consisting of halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C3-C8 cycloalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkoxy and C1-C6 haloalkoxy; R 8 and R 8a are independently selected from the group consisting of hydrogen, halogen, cyano, C1-C4-alkyl and C1-C4-haloalkyl; or a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof is provided.

[0063] In one embodiment, the present invention provides a compound of formula (I), where R 1 The C2-C6 heterocyclyl group of the group is preferably a partially / fully saturated or unsaturated furyl, thienyl, pyrrolyl, isoxazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrazolyl, oxazolyl, imidazolyl, oxadiazolyl, triazolyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazinyl selected from.

[0064] In one embodiment, the present invention provides a compound of formula (I), where R 5 The C2-C6 heterocyclyl group of the group is preferably a partially / fully saturated or unsaturated furyl, thienyl, pyrrolyl, isoxazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrazolyl, oxazolyl, imidazolyl, oxadiazolyl, triazolyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazinyl selected from.

[0065] In one embodiment, the present invention provides a compound of formula (I), wherein R 6 The C2-C6 heterocyclyl of the group is preferably selected from oxetanyl, partially / fully saturated or unsaturated furyl, thienyl, pyrrolyl, isoxazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrazolyl, oxazolyl, imidazolyl, oxadiazolyl, triazolyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.

[0066] In one embodiment, the present invention provides a compound of formula (I), wherein R 7 The C2-C6 heterocyclyl of the group is preferably selected from partially / fully saturated or unsaturated furyl, thienyl, pyrrolyl, isoxazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrazolyl, oxazolyl, imidazolyl, oxadiazolyl, triazolyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.

[0067] In one embodiment, the present invention provides a compound of formula (I) wherein A1, A2, A3, A4 and A5 are each independently C. In another embodiment, the present invention provides a compound of formula (I) wherein A1, A2, A3 and A5 are each independently C and A4 is N. In yet another embodiment, the present invention provides a compound of formula (I) wherein A1, A2, A3 and A4 are each independently C and A5 is N. In yet another embodiment, the present invention provides a compound of formula (I) wherein A1, A2, A4 and A5 are each independently C and A3 is N. In yet another embodiment, the present invention provides a compound of formula (I) wherein A2, A3, A4 and A5 are each independently C and A1 is N. In yet another embodiment, the present invention provides a compound of formula (I) wherein A1, A3, A4 and A5 are each independently C and A2 is N. In yet another embodiment, the present invention provides a compound of formula (I) wherein A1 and A3 are independently N, and A2, A4 and A5 are independently C. In yet another embodiment, the present invention provides a compound of formula (I) wherein A2 and A3 are independently N, and A1, A4 and A5 are independently C. In yet another embodiment, the present invention provides a compound of formula (I) wherein A2 and A4 are independently N, and A1, A3 and A5 are independently C. In yet another embodiment, the present invention provides a compound of formula (I) wherein A1, A3 and A4 are independently N, and A2 and A5 are independently C. In yet another embodiment, the present invention provides a compound of formula (I) wherein A2, A3 and A4 are independently N, and A1 and A5 are independently C.

[0068] In a preferred embodiment, the present invention provides a compound of formula (I) wherein A1, A2, A3, A4 and A5 are independently C. In yet another preferred embodiment, the present invention provides a compound of formula (I) wherein A1, A2, A3 and A5 are independently C, and A4 is N. In yet another preferred embodiment, the present invention provides a compound of formula (I) wherein A1, A2, A4 and A5 are independently C, and A3 is N. In yet another preferred embodiment, the present invention provides a compound of formula (I) wherein A1, A2 and A5 are independently C; A3 and A4 are independently N. In yet another preferred embodiment, the present invention provides a compound of formula (I) wherein A2, A3, A4 and A5 are independently C, and A1 is N. In yet another preferred embodiment, the present invention provides a compound of formula (I) wherein A2, A3 and A5 are independently C; A1 and A4 are independently N. In one embodiment, the present invention provides a compound of formula (I) (wherein D is D1 and Z is a direct bond). In another embodiment, the present invention provides a compound of formula (I) (wherein D is D1 and Z is -C(=O)-). In one embodiment, the present invention provides a compound of formula (I) (wherein D is D2 and Z is a direct bond). In one embodiment, the present invention provides a compound of formula (I) (wherein D is D3 and Z is a direct bond). In one embodiment, the present invention provides a compound of formula (I) (wherein D is D1 or D2 and Y is O). In another embodiment, the present invention provides a compound of formula (I) (wherein D is D1 or D2 and Y is NR 7 ). In a preferred embodiment, the present invention provides a compound of formula (I) (wherein D is D1 or D2 and Y is O). In one embodiment, the present invention provides a compound of formula (I) wherein R1 is C1-C6 alkyl. In another embodiment, the present invention provides a compound of formula (I) wherein R1 is C1-C6 alkyl substituted by optionally substituted phenyl. Here, the optionally substituted substituent is selected from halogen, CN, methyl or methoxy.

[0069] In one embodiment, the present invention provides a compound of formula (I) wherein R 2 is C1-C6 alkyl. In a preferred embodiment, the present invention provides a compound of formula (I) wherein R 2 is methyl or ethyl. In one embodiment, the present invention provides a compound of formula (I) wherein R 3 is C1-C6 alkyl. In another embodiment, the present invention provides a compound of formula (I) wherein R 3 is C1-C6 haloalkyl. In yet another embodiment, the present invention provides a compound of formula (I) wherein R 3To provide a compound of formula (I) wherein is halogen. In yet another embodiment, the present invention provides a compound of formula (I) wherein R 3 is C1-C6 alkoxy. In a preferred embodiment, the present invention provides a compound of formula (I) wherein R 3 is CF3. In another preferred embodiment, the present invention provides a compound of formula (I) wherein R 3 is fluoro or chloro. In a preferred embodiment, the present invention provides a compound of formula (I) wherein R 4 is C1-C6 alkyl. In a preferred embodiment, the present invention provides a compound of formula (I) wherein R 4 is C1-C6 alkyl optionally substituted with R a wherein R a is selected from F, CN, methyl, ethyl, (n, iso)propyl, methoxy, CF3, cyclopropyl, C2-C6 heterocyclyl; In a preferred embodiment, the present invention provides a compound of formula (I) wherein R 5 is C1-C6 alkyl. In a preferred embodiment, the present invention provides a compound of formula (I) wherein R 5 is C1-C6 alkyl optionally substituted with R a wherein R a is selected from F, CN, methyl, ethyl, (n, iso)propyl, methoxy, CF3, cyclopropyl, C2-C6 heterocyclyl; In a preferred embodiment, the present invention provides a compound of formula (I) wherein R 6 is C1-C6 alkyl. In a preferred embodiment, the present invention provides a compound of formula (I) wherein R 6 is C1-C6 alkyl optionally substituted with R a wherein R a is selected from F, CN, methyl, ethyl, (n, iso)propyl, methoxy, CF3, cyclopropyl, C2-C6 heterocyclyl. In a preferred embodiment, the present invention relates to R 7 where R is C1-C6 alkyl, -COR 5 および and provides a compound of formula (I) wherein R is C2-C6 heterocyclyl. In one embodiment, R 8 and R 8a are independently selected from the group consisting of hydrogen, halogen, cyano, C1-C4 alkyl, and C1-C4 haloalkyl; In a preferred embodiment, the present invention provides a compound of formula (I) wherein R 8 and R 8a are independently selected from the group consisting of hydrogen, chloro, fluoro, cyano, methyl, ethyl, isopropyl, and CF3; In a preferred embodiment, the present invention provides a compound of formula (I) wherein C3-C6 cycloalkyl is selected from cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. Preferably, it is cyclopropyl or cyclobutyl. In a preferred embodiment, the present invention provides a compound of formula (I) wherein A1, A2, A3, A4, and A5 are independently C; or A1, A2, A3, and A5 are independently C and A4 is N; or A1, A2, A4, and A5 are independently C and A3 is N; or A1, A2, and A5 are independently C and A3 and A4 are independently N; or A2, A3, A4, and A5 are independently C and A1 is N; or A2, A3, and A5 are independently C and A1 and A4 are independently N.

[0070] The present invention also relates to a method for producing a compound of formula (I). The compounds of the present invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Those skilled in the art will understand that a particular stereoisomer can be more active and / or exhibit more beneficial effects when enriched with respect to other stereoisomers or separated from other stereoisomers. Furthermore, those skilled in the art know methods for separating, enriching, and / or selectively preparing said stereoisomers. The compounds of the present invention may exist as mixtures of stereoisomers, individual stereoisomers, or optically active forms.

[0071] When the compound of formula (I) appears as the cationic moiety of a salt or can form such a cationic moiety of a salt, each anionic moiety can be inorganic or organic. Alternatively, when the compound of formula (I) appears as the anionic moiety of a salt or can form such an anionic moiety of a salt, each cationic moiety can be inorganic or organic. Examples of inorganic anion moieties of salts include, but are not limited to, chloride, bromide, iodide, fluoride, sulfate, phosphate, nitrate, nitrite, bicarbonate, bisulfate. Examples of organic anion moieties of salts include, but are not limited to, formate, alkanoate, carbonate, acetate, trifluoroacetate, trichloroacetate, propionate, glycolate, thiocyanate, lactate, succinate, malate, citrate, benzoate, cinnamate, oxalate, alkyl sulfate, alkyl sulfonate, aryl sulfonate, aryl disulfonate, alkyl phosphonate, aryl phosphonate, aryl diphosphonate, p-toluenesulfonate, and salicylate. Examples of inorganic cation moieties of salts include, but are not limited to, alkali metals and alkaline earth metals. Examples of organic cation moieties of salts include, but are not limited to, cations derived from pyridine, methylamine, imidazole, benzimidazole, histidine, phosphazene, tetramethylammonium, tetrabutylammonium, choline and trimethylamine.

[0072] The metal ions in the metal complexes of the compounds of formula (I) are, in particular, metal ions of elements of Group 2, in particular calcium and magnesium, elements of Group 3 and Group 4, in particular aluminum, tin and lead, and elements of Transition Groups 1 to 8, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc and other elements. In particular, metal ions of elements of the fourth period and Transition Groups 1 to 8 are preferred. Here, the metals can exist in various valences that they can assume.

[0073] Another embodiment of the present invention discloses a composition having a compound of formula (I), a salt, a metal complex, a stereoisomer, a diastereoisomer, an enantiomer, a chiral isomer, an atropisomer, a conformational isomer, a rotational isomer, a tautomer, an optical isomer, a polymorph, a geometric isomer, or an N-oxide, and any other essential components such as an excipient, an inert carrier, or a surfactant, an additive, a solid diluent and a liquid diluent.

[0074] Compounds selected from formula (I) (including all stereoisomers, N-oxides and salts thereof) usually exist in one or more forms, and formula (I) includes all crystalline and amorphous forms of the compounds represented by formula (I). Amorphous forms include embodiments that are solids such as waxes and gums, as well as embodiments that are liquids such as solutions and melts. Crystalline forms include embodiments that essentially represent a single crystal form and embodiments that represent a mixture of polymorphs (i.e., different crystal forms). The term "polymorph" refers to specific crystal forms of a compound that can crystallize in different crystal forms, and these forms have different arrangements and / or conformations of molecules within the crystal lattice. Polymorphs can have the same chemical composition, but they can also differ in composition depending on the presence or absence of co-crystallized water or other molecules that can bind weakly or strongly within the lattice. Polymorphs can differ in chemical, physical and biological properties such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspension, dissolution rate and bioavailability. Those skilled in the art will understand that a polymorph of a compound represented by formula (I) can exhibit beneficial effects (e.g., suitability for the preparation of useful formulations, improvement in biological performance) compared to another polymorph or a mixture of polymorphs of the same compound represented by formula (I). The production and isolation of a specific polymorph of a compound represented by formula (I) can be achieved by methods known to those skilled in the art, including crystallization using a selected solvent and temperature.

[0075] The present invention also relates to a composition for controlling or preventing insect and mite pests. The composition comprises a biologically effective amount of a compound of formula (I) and at least one additional component selected from the group consisting of surfactants and adjuvants.

[0076] Another embodiment of the present invention relates to making a compound of formula (I) or its N-oxide or salt into a conventional type of pesticidal composition such as a solution, emulsion, suspension, powder, dust, paste, granule, compress, capsule, and mixtures thereof. Examples of composition types include suspensions (e.g., SC, OD, FS), emulsifiable concentrates (e.g., EC), emulsions (e.g., EW, EO, ES, ME), capsules (e.g., CS, ZC), paste, lozenge, wettable powder or dust (e.g., WP, SP, WS, DP, DS), compress (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticides (e.g., LN), and gel formulations (e.g., GF) for the treatment of plant propagation materials such as seeds. These and other types of compositions are defined in the ‘Catalogue of pesticide formulation types and international coding system’, Technical Monograph No.2, 6th Edition, May 2008, CropLife International.

[0077] The above compositions are manufactured by known methods as described in Mollet and Grubemann, “Formulation Technology”, Wiley VCH, Weinheim, 2001; or Knowles, “New Developments in Crop Protection Product Formulation”, Agrow Reports DS243, T&F Informa, London, 2005. Examples of suitable adjuvants for the formulations and / or pesticidal compositions according to the present invention include solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration promoters, protective colloids, adhesives, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreezing agents, defoamers, colorants, tackifiers and binders.

[0078] Suitable solvents and liquid carriers in this context are, for example, water and organic solvents, such as medium to high boiling point mineral oil fractions, such as kerosene, diesel oil, oils derived from plants or animals; aliphatic, cyclic and aromatic hydrocarbons, such as toluene, paraffin, tetrahydronaphthalene, alkylated naphthalene; alcohols, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; dimethyl sulfoxide; ketones, such as cyclohexanone; esters, such as lactates, carbonates, fatty acid esters, γ-butyrolactone; fatty acids; phosphonates; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof. Suitable solid carriers or fillers are, for example, mineral soils, such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products derived from plants, such as cereal meal, bark meal, wood meal, coconut, and mixtures thereof.

[0079] Suitable surfactants are, for example, surface-active compounds such as anionic, cationic, non-ionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration promoters, protective colloids, or adjuvants. Examples of surfactants are described in McCutcheon’s, Vol.1: ‘Emulsifiers & Detergents’, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

[0080] Suitable anionic surfactants are, for example, alkali salts, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, α-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecyl benzenes, sulfonates of naphthalene and alkylnaphthalenes, sulfosuccinates or sulfosuccinate esters. Examples of sulfates are sulfates of fatty acids and oils, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, or sulfates of fatty acid esters. Examples of phosphates include phosphate esters. Examples of carboxylates include alkyl carboxylates, and carboxylated alcohols or alkylphenol ethoxylates.

[0081] Suitable nonionic surfactants are, for example, alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters alkoxylated with 1 to 50 equivalents. For alkoxylation, ethylene oxide and / or propylene oxide can be used, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homo- or copolymers of vinyl pyrrolidone, vinyl alcohol or vinyl acetate.

[0082] Suitable cationic surfactants are, for example, quaternary surfactants, such as quaternary ammonium compounds having one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are, for example, A-B or A-B-A type block polymers containing blocks of polyethylene oxide and polypropylene oxide, or A-B-C type block polymers containing alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are, for example, polyacids or polybases. Examples of polyacids are polyacrylic acid or alkali salts of polyacid comb polymers. Examples of polybases are polyvinylamine or polyethyleneamine.

[0083] Suitable adjuvants are compounds that have little or no pesticidal activity per se and improve the biological performance of the compound of formula (I) against the target. For example, surfactants, mineral oils or vegetable oils, and other auxiliaries. Further examples are described in Knowles, “Adjuvants and Additives”, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5.

[0084] Suitable thickeners are, for example, polysaccharides (such as xanthan gum, carboxymethyl cellulose), inorganic clays (organo-modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are, for example, isothiazolinone derivatives such as bronopol and alkylisothiazolinone and benzisothiazolinone. Suitable antifreeze agents are, for example, ethylene glycol, propylene glycol, urea and glycerin. Suitable defoamers are, for example, silicones, long-chain alcohols, and salts of fatty acids. Suitable colorants (e.g., red, blue, green) include, for example, pigments and water-soluble dyes with low water solubility. Examples include inorganic colorants (e.g., iron oxide, titanium oxide, hexacyanoferrate) and organic colorants (e.g., alizarin, azo, phthalocyanine colorants). Suitable tackifiers or binders are, for example, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylate, biogenic or synthetic waxes, and cellulose ethers.

[0085] Examples of the types of compositions and their preparations are as follows: i) Water-soluble concentrates (SL, LS) 10 to 60% by weight of the compound of formula (I) and 5 to 15% by weight of a wetting agent (e.g., alcohol alkoxylate) are dissolved in water and / or a water-soluble solvent (e.g., alcohols) to make 100% by weight. The active substance dissolves when diluted with water.

[0086] ii) Dispersible concentrates (DC) 5 to 25% by weight of the compound of formula (I) and 1 to 10% by weight of a dispersant (e.g., polyvinylpyrrolidone) are dissolved in an organic solvent (e.g., cyclohexanone) to make 100% by weight. A dispersion of the active substance is obtained when diluted with water.

[0087] iii) Emulsifiable concentrates (EC) 15 to 70% by weight of the compound of formula (I) and 5 to 10% by weight of an emulsifier (e.g., calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in a water-insoluble organic solvent (e.g., aromatic hydrocarbons) to make 100% by weight. An emulsion of the active substance is obtained when diluted with water.

[0088] iv) Emulsions (EW, EO, ES) 5 to 40% by weight of the compound of formula (I) and 1 to 10% by weight of an emulsifier (for example, calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20 to 40% by weight of a water-insoluble organic solvent (for example, aromatic hydrocarbons). This mixture is introduced into water to make 100% by weight using an emulsifying device to obtain a homogeneous emulsion. Dilution with water gives an emulsion of the active substance.

[0089] v) Suspensions (SC, OD, FS) In a stirred ball mill, 20 to 60% by weight of the compound of formula (I) is pulverized by adding 2 to 10% by weight of a dispersant and a wetting agent (for example, sodium lignosulfonate and alcohol ethoxylate), 0.1 to 2% by weight of a thickener (for example, xanthan gum), and 100% by weight of water to obtain a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance. In the FS type composition, up to 40% by weight of a binder (for example, polyvinyl alcohol) is added.

[0090] vi) Water-dispersible granules and water-soluble granules (WG, SG) 50 to 80% by weight of the compound of formula (I) is finely pulverized to 100% by weight by adding a dispersant and a wetting agent (for example, sodium lignosulfonate and alcohol ethoxylate), and is prepared as water-dispersible or water-soluble granules using industrial equipment (for example, extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.

[0091] vii) Water-dispersible powders and water-soluble powders (WP, SP, WS) 50 to 80% by weight of the compound of formula (I) is pulverized in a rotor-stator mill, 1 to 5% by weight of a dispersant (for example, sodium lignosulfonate), 1 to 3% by weight of a wetting agent (for example, alcohol ethoxylate), and a solid carrier (for example, silica gel) are added to make 100% by weight. Dilution with water gives a stable dispersion or solution of the active substance.

[0092] viii) Gels (GW, GF) 5 to 25% by weight of the compound of formula (I) is pulverized in a stirred ball mill, and 3 to 10% by weight of a dispersant (for example, sodium lignosulfonate), 1 to 5% by weight of a thickener (for example, carboxymethyl cellulose), and 100% by weight of water are added to obtain a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.

[0093] ix) Microemulsion (ME) 5 to 20% by weight of the compound of formula (I), 5 to 30% by weight of an organic solvent blend (for example, fatty acid dimethylamide and cyclohexanone), 10 to 25% by weight of a surfactant blend (for example, alcohol ethoxylate and arylphenol ethoxylate), and 100% by weight of water are added. Stirring this mixture for 1 hour spontaneously generates a thermodynamically stable microemulsion of the active substance.

[0094] x) Microcapsules (CS) An oil phase containing 5 to 50% by weight of the compound of formula (I), 0 to 40% by weight of a water-insoluble organic solvent (for example, aromatic hydrocarbon), and 2 to 15% by weight of an acrylic monomer (for example, methyl methacrylate, methacrylic acid, and di- or triacrylate) is dispersed in an aqueous solution of a protective colloid (for example, polyvinyl alcohol). As a result of radical polymerization, poly(meth)acrylate microcapsules are formed. Alternatively, an oil phase containing 5 to 50% by weight of the compound of formula (I), 0 to 40% by weight of a water-insoluble organic solvent (for example, aromatic hydrocarbon), and an isocyanate monomer (for example, diphenylmethane-4,4'-diisocyanate) is dispersed in an aqueous solution of a protective colloid (for example, polyvinyl alcohol). When a polyamine (for example, hexamethylenediamine) is added, polyurea microcapsules containing the active substance are formed. The amount of the monomer is 1 to 10% by weight. The % by weight relates to the total CS composition.

[0095] xi) Dustable powder (DP, DS) 1 to 10% by weight of the compound of formula (I) is finely pulverized and thoroughly mixed with a solid carrier (for example, finely divided kaolin) to make 100% by weight.

[0096] xii) Granules (GR, FG) 0.5 to 30% by weight of the compound of formula (I) is finely pulverized and combined with a solid carrier (e.g., silicate) to make 100% by weight. Granulation is achieved by extrusion, spray drying or fluidized bed.

[0097] xiii) Ultra-low volume liquid (UL) 1 to 50% by weight of the compound of formula (I) is dissolved in an organic solvent (e.g., aromatic hydrocarbon) to make 100% by weight. Composition types i) to xiii) may optionally contain further adjuvants such as 0.1 to 1% by weight of a bactericide, 5 to 15% by weight of an antifreeze, 0.1 to 1% by weight of an antifoaming agent, and 0.1 to 1% by weight of a colorant.

[0098] Another embodiment of the present invention provides a pesticidal composition containing the compound of formula (I), which pesticidal composition contains 0.01 to 95% by weight, preferably 0.1 to 90% by weight, more preferably 1 to 70% by weight, particularly 10 to 60% by weight of the active substance. The purity of the active substance is 90% to 100%, preferably 95% to 100% (by NMR spectrum).

[0099] Water-soluble concentrates (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually used for the purpose of treating plant propagation materials, especially seeds. The compositions of the present invention, after dilution 2 to 10 times, give an active substance concentration of 0.01 to 60% by weight, preferably 0.1 to 40% by weight in the ready-to-use product. It can be applied before or during sowing.

[0100] Methods for applying the compounds of formula (I) and their compositions to plant propagation materials, especially seeds, respectively, include dressing, coating, pelleting, spraying, dipping, and in-furrow application of the propagation materials. Preferably, the compound of formula (I) or its composition is applied to the plant propagation material in a manner that does not induce germination, such as by seed treatment, pelleting, coating, and spraying. When used for plant protection, the amount of the active substance applied ranges from 0.001 to 2 kg / ha, preferably from 0.005 to 2 kg / ha, more preferably from 0.05 to 0.9 kg / ha, especially from 0.1 to 0.75 kg / ha, depending on the type of desired effect. For the treatment of plant propagation materials such as seeds, for example, for spraying, coating, or dipping seeds, an amount of the active substance in the range of 0.1 to 1000 g, preferably 1 to 1000 g, more preferably 1 to 100 g, most preferably 5 to 100 g per 100 kg of the plant propagation material (preferably seeds) is generally required.

[0101] When used for the protection of materials or storage products, the amount of the active substance applied varies depending on the type of the application area and the desired effect. The amount usually applied for the protection of materials is 0.001 g to 2 kg, preferably 0.005 g to 1 kg of the active substance per cubic meter of the treated material. Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients, and other pesticides (e.g., herbicides, insecticides, fungicides, growth regulators, safeners) are not added as a premix to the active substance or the composition containing them, or, if appropriate, until immediately before use (tank mix). These agents can be mixed with the composition of the present invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0102] The user can usually apply the composition according to the present invention from a forward dosing device, a backpack sprayer, a spray tank, a sprayer, or an irrigation system. Usually, the pesticide composition is formulated to the desired application concentration using water, a buffer, and / or further adjuvants, and in this way, a ready-to-use spray liquid or the pesticide composition according to the present invention is obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters of the ready-to-use spray liquid are applied per hectare of the effective agricultural area.

[0103] According to one embodiment, the individual components of the composition according to the present invention, such as part of a kit or part of a two-component or three-component mixture, can be mixed by the user himself in the spray tank and, if necessary, further adjuvants can be added and used.

[0104] The compounds and compositions of the present invention are thus agriculturally useful for protecting field crops from phytophagous invertebrate pests and are also non-agriculturally useful for protecting other horticultural crops and plants from phytophagous invertebrate pests. This usefulness includes protecting crops and other plants (i.e., both agriculturally and non-agriculturally) containing genetic material introduced by genetic engineering (i.e., transgenic) or modified by mutagenesis to provide advantageous traits.

[0105] The compounds of the present invention are characterized by favorable metabolic and / or soil residue patterns and exhibit activity in controlling a spectrum of agricultural and non-agricultural invertebrates. The compounds of the present invention are valuable active ingredients, prophylactically and / or therapeutically, even at low concentration applications, in the field of pest control, can be used against pesticide-resistant pests such as insects, and / or have a highly favorable biocidal spectrum and are well tolerated by warm-blooded animal species, fish, and plants.

[0106] The compounds of the present invention are active against pests in economically important agriculture, forestry, greenhouses, seedbeds, ornamental plants, food and fiber, public health and animal health, domestic and commercial structures, and domestic and stored products. These include: larvae of Lepidoptera such as the corn earworm, tobacco budworm, loopers, and heliothines (e.g., fall armyworm (Spodoptera fugiperda J. E. Smith)), beet armyworm (Spodoptera exigua Hubner), black cutworm (Agrotis ipsilon Hufnagel), cabbage looper (Trichoplusia ni Hubner), tobacco budworm (Heliothis virescens Fabricius));Pyralidae borers, leaf beetles, webworms, cutworms, cabbageworms, skeletonizers (e.g., European corn borer (Ostrinia nubilalis Hubner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), sod webworm (Herpetogramma licarsisalis Walker)), Tortricidae leafrollers, budworms, seedworms, fruitworms (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruit moth (Grapholita molesta Busck)), many other economically important Lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus)); larvae and adults of Blattodea (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blatella gemnanica Linnaeus), brown-banded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), smokybrown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius));Larvae and adults that feed on the leaves of Coleoptera, including the following: Anthribidae, Curculionidae, weevils of the family Curculionidae (e.g., Anthonomus grandis Boheman, Lissorhoptrus oryzophilus Kuschel, Sitophilus granarius Linnaeus, Sitophilus oryzae Linnaeus), flea beetles of the family Chrysomelidae, cucumber beetles, rootworms, flea beetles, potato flea beetles, leaf beetles (e.g., Leptinotarsa decemLineata Say, Diabrotica virgifera LeConte, etc.), Japanese beetles and other beetles of the family Scarabaeidae (e.g., Popillia japonica Newman, Rhizotrogus majalis Razoumowsky, etc.), carpet beetles of the family Dermestidae, rice weevils of the family Dryophthoridae, flour beetles of the family Tenebrionidae, grain weevils of the family Silvanidae; Furthermore, it includes the following: adults and larvae of Dermaptera including earwigs of the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches mono Fabricius)); adults and larvae of Hemiptera and Homoptera, such as pests of the family Pentatomidae, cicadas of the family Cicadidae, leafhoppers of the family Cicadellidae (e.g., Empoasca spp., etc.), planthoppers of the families Delphacidae and Tropiduchidae, treehoppers of the family Membracidae, aphids of the family Aphididae, whiteflies of the family Aleyrodidae, scale insects of the family Coccidae, armored scales of the family Diaspididae, soft scales of the family Margarodidae, flat bugs of the family Aradidae, stink bugs of the family Pentatomidae, stink bugs of the family Blissidae (such as those of the genus Blissus, etc.) and other seed bugs, plant bugs of the family Miridae, stink bugs of the family Pentatomidae, red stink bugs of the family Pyrrhocoridae, and cotton stainers. It also includes adults and larvae of Acarina (mites), such as spider mites and spider mite families (e.g., European red mite (Panonychus ulmi Koch), two-spotted spider mite (Tetranychus urticae Koch), McDaniel spider mite (Tetranychus mcdanieli McGregor)), false spider mite family (e.g., citrus flat mite (Brevipalpus lewisi McGregor)), false spider mites and bud mites of the family Tenuipalpidae, other leaf-eating mites, and mites important for the health of humans and animals, namely, chilli thrips of the family Thripidae, follicle mites of the family Demodicidae, cereal mites of the family Glycyphagidae, mites of the family Ixodidae (e.g., blacklegged tick (Ixodes scapularis Say), Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), Lone Star tick (Amblyomma americanum Linnaeus)) and scab mites and itch mites of the families Psoroptidae, Pyemotidae, and Sarcoptidae, adults and larvae of Orthoptera including grasshoppers, locusts, and crickets (e.g., migratory grasshopper (e.g., Melanoplus sanguinipes Fabricius, M.Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locust (Schistocerca gregaria Forskal), migratory locust (Locusta migratoria Linnaeus), house cricket (Acheta domesticus Linnaeus), mole cricket (Gryllotalpa spp.), adults and larvae of Diptera, fruit flies, midges, Muscidae, flies (such as Oscinella frit Linnaeus), soil fleas, house flies (such as Musca domestica Linnaeus), lesser house flies (such as Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (such as Stomoxys calcitrans Linnaeus), face flies, stable flies, blow flies (such as Chiysomya spp., Phonnia spp.), other muscoid fly pests, horse flies (such as Tabanus spp.), bot flies (such as Gastrophilus spp., Oestrus spp.), cattle larvae (such as Hypoderma spp.), deer flies (such as Chrysops spp.), ked (such as Melophagus ovinus Linnaeus) and other Brachyceran, mosquitoes (such as Aedes spp., Anopheles spp., Culex spp.), black flies (such as Prosimulium spp., Simulium spp.), midges, biting midges, beetles, other nematodes, onion thrips (Thrips tabaci Lindeman) and other leaf-eating thrips, adults and larvae of Thysanoptera including other thrips, ants (such as Camponotus ferrugineus Fabricius, Camponotus pennsylvanicus De Geer, Monomorium pharaonis Linnaeus, Wasmannia auropunctata Roger, Solenopsis geminataHymenoptera pests including Fabricius, red imported fire ant (Solenopsis invicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechina longicornis Latreille), white ant (Tetramorium caespitum Linnaeus), cornfield ant (Lasius alienus Fδrster), odorous house ant (Tapinoma sessile Say), bees (including bumblebees), wasps, hornets; Isoptera pests include eastern subterranean termite (Reticulitermes flavipes Kollar), western subterranean termite (Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), Indian drywood termite (Incisitermes immigrans Snyder) and other economically important termites, Lepisma saccharina Linnaeus and Thermobia domestica Packard and other pests of the order Thysanura; Mallophaga pests include head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitszch), dog louse (Trichodectes cams De Geer), downy louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurystemus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus), and other blood-sucking and chewing parasitic lice attacking humans and animals, and Siphonaptera pests (Xenopsylla cheopis Rothschild, cat flea (Ctenocephalides felis Bouche), dog flea (Ctenocephalides canisCurtis), the chicken flea (Ceratophyllus gallinae Schrank), the sticktight flea (Echidnophaga gallinacea Westwood), the human flea (Pulex irritans Linnaeus), and other fleas that afflict mammals and birds. Other arthropod pests of interest include spiders of the order Araneae such as the brown recluse spider (Loxosceles reclusa Gertsch and Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and centipedes of the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus). Activities also include members of the Nematoda, Cestoda, Trematoda, and Acanthocephala, including economically important agricultural pests (such as the large intestinal roundworm of the genus Ascaris, the root-lesion nematode of the genus Pratylenchus, the stubby root nematode of the genus Trichodorus, etc.), but not limited to these. And pests that harm the health of animals and humans (such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc., all economically important flukes, tapeworms, and roundworms).

[0107] The compounds of the present invention are particularly active against homopterous pests including: Acyrthisiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov / Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (plum aphid), Lipaphis erysimi Kaltenbach (turnip aphid), Metopolophium dirrhodum Walker (cereal aphid), Macrosiphum euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peach potato aphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp.(Root aphids and gall midges), Rhopalosiphum Maidis Fitch (corn leaf aphid), Rhopalosiphum Padi Linnaeus (bird cherry-oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii, Boyer de Fonscolombe (black citrus aphid), and Toxoptera citiicida Kirkaldy (brown citrus aphid); Adelges spp. (adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisia tabaci Gennadius (tobacco whitefly, sweet potato whitefly), Bemisia argentifolii Bellows and Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citrus whitefly), Trialeurodes vaporariorum Westwood (greenhouse whitefly). Empoasca fabae Harris, (potato leafhopper), Laodelphax striatellus Fallen (small brown planthopper), Macrolestesquadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler (green rice leafhopper), Nephotettix nigropictus Stal (rice leafhopper), Nilaparvata lugens Stal (brown planthopper), Peregrinus Maidis Ashmead (corn planthopper), Sogatella furcifera Horvath (white-backed planthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocyba pomaria McAfee white apple leafhopper, Erythroneoura spp.(Grape leafhopper); Magicidada septendecim Linnaeus (Periodical cicada); Icery purchasi Maskell (Cottony cushion scale), Quadraspidiotus perniciosus Comstock (San Jose scale); Planococcus citri Risso (Citrus mealybug); Pseudococcus spp. (Other mealybug group), Cacopsylla pyricola Foerster (Pear psylla), Trioza diospyri Ashmead (Persimmon psylla).

[0108] The compounds of the present invention also have commercially important activity against members of the Lepidoptera (e.g., Alabama argillacea Hubner (cotton leafworm), Archips argyrospila Walker (fruit tree leafroller), A. rosana Linnaeus (European leafroller) and other Archips species, Chilo successalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoveipa armigera Hybner (American tobacco budworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (lawn webworm), Lobesia botrana Denis and Schifferπnyller (grape berry moth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (large white), Pieris rapae Linnaeus (small white), Spodoptera exigua Hubner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera fragiperda J. E.Smith (beetle), Trichoplusia ni Hybner (cabbage looper), and Tula absoluta Meyrick (tomato leafminer).

[0109] These compounds also act on the following Hemiptera insects: Acrostemum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus Say (chinch bug), Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaeffer (cotton stain bug), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp. (seed bug complex), Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois (plant bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatus Dallas (large milkweed bug), Pseudamoscelis seriatus Reuter (cotton fleahopper).

[0110] Other insect orders controlled by the compounds of the present invention include the following: Thysanoptera (e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirthothrips citri Moulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips), Thrips tabaci Lindeman (onion thrips)), and Coleoptera (e.g., Leptinotarsa decemLineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle), and wireworms of the genera Agriotes, Athous, and Limonius).

[0111] In particular, the compounds of formula (I), their N-oxides, their stereoisomers, their polymorphs and their salts are particularly suitable for efficiently controlling the following pests: insects of the order Lepidoptera (Lepidoptera), such as Agrotis ipsilon, Agrotis segetum, Alabama argillacea, Anticalcia gemmatalis, Aoi gusa, Autographa gamma, Bucculatrix pyrivorella, Cacoecia murinana, Capua reticulana, Cimatobia brumata, Mythimna separata, Choristoneura fumiferana, Choristoneura occidentalis, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Earias vittella, Erasmopelpus lignosellus, Eupoecilia ambiguella, Eubolia bruniana, Feltia subterranea, Galleria mellonella, Grapholita funebrana, Grapholita molesta, Helicoverpa armigera, Helicoverpa virenscens, Helicoverpa zea, Hellula undalis, Hybernia defoliaria, Hyphantria cunea, Hypomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Rafiigma exigua, Kophobothra, Cobaea, Lithocolletis blancardella, Lobesia botrana, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalaena brassicae, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Platypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Termites, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera exigua, Thaumetopoea pityocampa, Tortrixviridana, Trichoplusia ni, and Zeiraphera canadensis, beetles (Coleoptera), for example, Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica undecimpunctata Diabrotica speciosa, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemLineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus combis, Meligethes aeneus, Melontha hippocastani, Melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchusovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona linearatus and Sitophilus granarius, flies, mosquitoes (Diptera), e.g. Aedes albopictus, Aedes aegypti, Aedes taeniorhynchus, Anastrepha ludens, Calliphora maculipennis, Calliphora vomitoria, Calliphora albimanus, Calliphora gambiae, Calliphora freeborni, Calliphora leucosphyrus, Calliphora minima, Calliphora quadrimaculatus, Calyptraea vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelatesspp., Hylemyia platura, Hypoderma lineata, Leptoconops torens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillans, Mayetiola destructor, autumn flies, domestic flies, Muscina stabulans, estrous eggs, Ophyra aenescens, Oscinella frit, Pegomya hispida, Forcipomyia antiquus, Forcipomyia brassicae, Forcipomyia coactata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, STOMOXYS calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa. Termites (Isoptera), e.g., Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes groundsei, Termes natalensis, Coptotermes formosanus; Cockroaches (Blattaria Blattodea), e.g., Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, Blattaorientalis; ants, bees, wasps, hornets (Hymenoptera), e.g., Attalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinaria, Lasius niger, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Vespa orientalis, Vespula squamosa, Paravespula vulgaris, Paravespula pensylvanica, Paravespula germanica, Dolichovespula maculata, Vespula crabro, Vespa basalis, Camponotus floridanus, Linepithema humile. Crickets, grasshoppers, locusts (Orthoptera), e.g., Acheta domesticus, Gryllotalpa spp., Locusta migratoria, Melanoplus bivitattus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachysporus acinaciformis, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, Locustana pardalina. Spiders (Araneida), e.g., Latrodectus mactans, and Loxosceles reclusa. Fleas (Siphonaptera), e.g., Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, Nosopsyllus fasciatus, Ceratophyllus spp., Lepisma saccharina and Thermobia domestica, Centipedes (Chilopoda), e.g., Scutigeraoleoptrata, Diplopoda, e.g., Narceus spp., Dermaptera, e.g., forficula auricularia, Phthiraptera, e.g., Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon allinae, Menacanthus strmineus, Solenopotes capillatus. Fleas (Siphonaptera), e.g., Ctenocephalides ssp.

[0112] It is also suitable for the control of the following nematodes: plant parasitic nematodes, such as root-knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other species of the genus Meloidogyne, cyst nematodes, Globodera rostochiensis, and other species of the genus Globodera, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other species of the genus Heterodera, seed gall nematodes, species of the genus Anguina, foliar nematodes, species of the genus Aphelenchoides, sting nematodes, Belonolaimus longicaudatus and other species of the genus Belonolaimus, pine wood nematode, Bursaphelenchus xylophilus and other species of the genus Bursaphelenchus, ring nematodes, species of the genus Criconema, Criconemella, Criconemoides, Mesocriconema, stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other species of the genus Ditylenchus, needle nematodes, species of the genus Dolichodorus.Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species, sheath nematodes and sheathoid nematodes, Hemicycliophora and Hemicriconemoides genera; Hirshmanniella genus; lance nematodes Hoploaimus genus; false root-knot nematodes Nacobbus genus; needle nematodes Longidorus elongatus and other Longidorus species; lesion nematodes Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; burrowing nematodes Radopholus similis and other Radopholus species; kidney-shaped nematodes Rotylenchus robustus and other Rotylenchus species; Scutellonema genus; stubby-root nematodes Trichodorus primitivus and other Trichodorus species, Paratrichodorus genus; stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species, citrus nematodes, Tylenchulus genus, dagger nematodes, Xiphinema genus, and other plant-parasitic nematode species.

[0113] The compounds of formula (I) and their salts are also useful for controlling the following spiders (Araneae): such as mites (Acarina), e.g., of the families Algidae, Ixodidae, and Sarcoptidae, Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes robicundus, Ornithodorus moubata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora, Eriophyes sheldoni, etc., Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus, Tenuipalpidae spp. such as Brevipalpus phoenicus. Tetranychidae genus such as Tetranychus cinnabarinus, Tetranychus kanzai, Tetranychus pacificus, Tetranychus telarius, Tetranychus urticae, Panonychus ulmi, Panonychus citri, Oligonychus pratensis, etc.

[0114] In a further embodiment, the present invention provides a compound of formula (I) as an effective and useful compound for controlling sucking or piercing insects, such as insects of the genus Thrips, Diptera and Hemiptera, in particular insects selected from the following species: Lepidoptera: Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips tabaci, Thrips palmi and Thrips setosus, Diptera: Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anastrepha ludens, Calliphora maculipennis, Calliphora vomitoria, Calliphora albimanus, Calliphora gambiae, Calliphora freeborni, Calliphora leucosphyrus, Calliphora minima, Calliphora quadrimaculatus, Calyptraea vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobiairritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillans, Maetiolus destructor, Ochlerotatus, Musca domestica, Musina stubrans, estrous eggs, Oplomyzus florum, Oscinella frit, Pegomya hispida, Forcipomyia antiquaa, Forcipomyia brassicae, Forcipomyia coactata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, STOMOXYS calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa, Hemiptera, especially aphids: Aphis craccivora, Adelges laricis, Aphis fabae, Aphis gossypii, Aphis pomi, Aphis grossulariae, Aphis spiraecola, Aphis sambuci, Aphis pisum, Aulacorthum solani, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerataphis gossypii, Ketocephalus fragaefolii, Cryptomyzus ribis, Drepanosiphum nordmannianae, Drepanosiphum pisi, Diuraphis radicola, Dysaulacorthum pseudosolani, Dysaphisplantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mara, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantii, and Viteus vitifolii.

[0115] In a preferred embodiment, the invention of the compounds of formula (I) is particularly useful for controlling, for example, the following: western flower thrips (Frankliniella occidentalis), potato leafhopper (Empoasca fabae), brown planthopper (Nilaparvata lugens), green leafhopper (Nephotettix virescens), cotton / melon aphid (Aphis gossypii), green peach aphid (Myzus persicae), tobacco / sweet potato whitefly (Bemisia tabaci), and silverleaf whitefly (Bemisia argentifolii).

[0116] In one embodiment, the present invention further relates to a composition comprising a biologically effective amount of a compound of formula (I) and at least one additional biologically active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers and nutrients. In the composition, the compound used in combination with the compound of formula (I) is also referred to as an active compatible compound.

[0117] Known and reported fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, biostimulants, antibiotics and nutrients can be combined with at least one compound of formula (I) of the present disclosure. For example, the fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, biostimulants, antibiotics, fertilizers and nutrients disclosed and reported in WO 2016 / 156129 and WO 2017 / 153200 can be combined with at least one compound of formula (I) of the present disclosure.

[0118] In some cases, combinations with other invertebrate pest control compounds or agents having a similar control spectrum but different modes of action are particularly advantageous for resistance management. Accordingly, the compositions of the present invention can further comprise a biologically effective amount of at least one additional invertebrate pest control compound or agent having a similar control spectrum but different modes of action. Contacting a plant protection compound (such as a protein) or a genetically modified plant engineered to express a plant locus with a biologically effective amount of the compound of the present invention can also provide broader plant protection and is advantageous for resistance management.

[0119] In one embodiment of the present invention, the biologically effective amount of the compound of formula (I) in the composition ranges from 0.1 to 99% by weight, preferably from 5 to 50% by weight, based on the total weight of the composition.

[0120] The present invention further relates to a method for controlling insects and mite pests, said method comprising contacting an insect and mite pest, their habits, breeding grounds, food supply, plants, seeds, soil, areas, materials or environments in which the insects and mite pests are growing or may grow, or materials, plants, seeds, soil, surfaces or spaces to be protected from pest attack or infestation, with a biologically effective amount of a compound or composition of the present invention.

[0121] Control of invertebrate pests and protection of agriculture, horticulture and specialty crops, animals and human health are achieved by applying one or more of the compounds of the present invention in an effective amount directly to the environment of the pests, the area to be protected or the pests to be controlled, including agricultural and / or non-agricultural infestation sites. Accordingly, the present invention further includes a method for controlling invertebrates inhabiting leaves and soil and protecting agricultural and / or non-agricultural crops, said method comprising contacting the invertebrates or their environment with a biologically effective amount of one or more of the compounds of the present invention, or a composition comprising at least one such compound, or a composition comprising an effective amount of at least one such compound and at least one additional biologically active compound or agent. A preferred method of contact is by spraying. Alternatively, a granular composition containing a compound of the present invention can be applied to the leaves or soil of plants. The compounds of the present invention are effective in delivery via plant uptake by contacting the plants with a composition containing the compound of the present invention applied as a soil perfusion of a liquid formulation, a granular formulation to the soil, a plug tray treatment, or a dipping of transplanted seedlings. Other methods of contact include the application of the compounds or compositions of the present invention by direct and residual spraying, aerial spraying, seed coating, microencapsulation, systemic uptake, bait, ear canal, bolus, nebulizer, fumigant, aerosol, dust, etc.

[0122] The compounds of the present invention can be incorporated into food consumed by invertebrates or into devices such as traps. Granules or baits containing 0.01 - 5% active ingredient, 0.05 - 10% humectant, and 40 - 99% plant powder are effective in controlling soil insects at very low application rates, particularly at doses of the active ingredient that are lethal by ingestion rather than by direct contact. The compounds of the present invention can be applied in pure form, but most often are applied as a formulation containing one or more compounds including suitable carriers, diluents, and surfactants, and may possibly be applied in combination with food, depending on the intended end use. Preferred methods of application include spraying an aqueous dispersion or purified oil solution of the compound. Combinations with spray oils, spray oil concentrates, spreaders, stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance the effectiveness of the compound.

[0123] The application rate required for effective control (i.e., the "biologically effective amount") depends on factors such as the species of invertebrate to be controlled, the life cycle of the pest, its life stage, its size, location, time, host crop or animal, feeding behavior, mating behavior, ambient humidity, temperature, etc. Under normal circumstances, a spraying rate of about 0.01 - 2 kg of active ingredient per hectare is sufficient to control pests in an agricultural ecosystem, although in some cases as little as 0.0001 kg per hectare may be sufficient or as much as about 8 kg may be required. For non-agricultural uses, effective application rates are in the range of about 1.0 - 50 mg per square meter, although in some cases as little as about 0.1 mg per square meter may be sufficient or as much as about 150 mg per square meter may be required. A person skilled in the art can readily determine the biologically effective amount required for the desired level of control of invertebrates.

[0124] Animal pests, namely insects, arachnids and nematodes, plants, the soil or water in which the plants are growing, can be brought into contact with a compound of formula (I), their N-oxides and salts, or a composition containing them, by any suitable method of application known in the art. Thus, "contact" includes both direct contact (applying the compound / composition directly to the animal pest or plant, usually to the leaves, stems or roots of the plant) and indirect contact (applying the compound / composition to the location of the animal pest or plant).

[0125] The compounds of the invention or insecticidal compositions containing them can be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, mites or arachnids, by bringing the plant / crop into contact with an insecticidally effective amount of at least one compound of the invention. Accordingly, the invention relates to a method for protecting crops from attack or infestation by insect and mite pests, which comprises bringing the crop into contact with a biologically effective amount of a compound or composition, isomer, polymorph, N-oxide or salt thereof of the invention. The compounds of the invention are used as such or in the form of a composition by treating plant propagation materials such as insects or plants, seeds, soil, surfaces, materials or rooms protected from insecticidal attack with an insecticidally effective amount of the active compound. Application can be carried out both before and after infection of plant propagation materials such as plants, seeds, soil, surfaces, materials or rooms by insects. Accordingly, the invention also relates to a method for protecting seeds from soil insects and the roots and shoots of seedlings from soil and leaf insects, which comprises bringing the compound or composition, N-oxide or salt thereof of the invention into contact with the seeds before sowing and / or before and after germination.

[0126] Furthermore, the invention relates to a method for treating or protecting animals from parasitism or infection by parasites, which comprises administering or applying orally, topically or parenterally to the animal a biologically effective amount of a compound or composition, isomer, polymorph, N-oxide or veterinarily acceptable salt thereof of the invention.

[0127] For use in the treatment of crop plants, the appropriate dosage (dosage of the effective dosage) of the compounds of the present invention ranges from 1 to 5000 g ai per hectare in agricultural or horticultural crops, preferably from 25 to 600 g per hectare, more preferably from 35 to 300 g per hectare.

[0128] The compounds and compositions of the present invention are particularly useful for controlling a number of insects occurring in various cultivated plants such as cereals, root vegetables, oil crops, vegetables, spices, ornamental plants, for example, seeds of durum and other wheat, barley, oats, rye, maize (feed maize and sugar maize / sweet corn and field corn), soybeans, oil crops, rape, cotton, sunflowers, bananas, rice, oilseed rape, cabbage rape, sugarcane, fodder beet, eggplant, potato, grass, turf, lawn, fodder grass, tomato, chives, pumpkin / squash, cabbage, iceberg lettuce, pepper, cucumber, melon, rape species, melon, beans, peas, garlic, onion, carrot, tuber plants such as potato, sugarcane, tobacco, grapes, petunia, geranium / perargonium, pansy and impatiens.

[0129] In particular, the compounds or compositions of the present invention are useful for the protection of agricultural crops such as cereals, maize, rice, soybeans and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus fruits and citrus trees, any horticultural plants, cucurbitaceae, gramineae plants, tobacco, coffee, tea, cocoa, sugar beet, sugarcane, cotton, potato, tomato, onion, pepper and other vegetables, and ornamental plants.

[0130] The present invention further relates to a method for producing a compound selected from formula (I). The compounds of the present invention are effective through both contact (via soil, glass, walls, mosquito nets, carpets, plant or animal parts) and ingestion (feed or plant parts).

[0131] The compounds of the present invention can also be applied to non-crop pests such as ants, termites, wasps, flies, mosquitoes, crickets or cockroaches and mite pests. For use against said non-crop pests, the compounds of the present invention are preferably used in a bait composition. The bait can be a liquid, solid or semi-solid preparation (e.g. gel). The solid bait can be shaped into various shapes and forms suitable for each use, e.g. granules, blocks, sticks, disks. The liquid bait can be filled into various devices, e.g. open containers, spraying devices, droplet sources, or evaporation sources, to ensure proper application. The gel can be based on an aqueous or oily matrix and can be formulated according to specific needs in terms of adhesiveness, water retention or aging properties.

[0132] The bait used in the composition is a product having sufficient attractiveness to stimulate insects such as ants, termites, wasps, flies, mosquitoes, crickets or cockroaches or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Feeding stimulants are selected from, for example, animal and / or plant proteins (meat, fish, blood meal, insect parts, egg yolk), animal and / or plant-derived fats and oils, or mono-, oligo- or poly-organic saccharides, especially sucrose, lactose, fructose, dextrose, glucose, starch, pectin, or molasses or honey, but are not limited thereto. Fresh or spoiled parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as feeding stimulants. Sex pheromones are known to be more specific to insects. Specific pheromones are described in the literature and are known to those skilled in the art. For use in bait compositions, typical contents of the active ingredient are from 0.001 to 15% by weight, preferably from 0.001 to 5% by weight of the active compound.

[0133] The formulations of the compounds of the present invention as aerosol (such as spray cans), oil spray or pump spray are very suitable for non-professional users for controlling pests such as flies, fleas, mites, mosquitoes or cockroaches. An aerosol formulation preferably comprises an active compound, a solvent such as a lower alcohol (e.g., methanol, ethanol, propanol, butanol), a ketone (e.g., acetone, methyl ethyl ketone), a paraffinic hydrocarbon having a boiling range of about 50 - 250 °C (e.g., kerosene), dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, an aromatic hydrocarbon such as toluene, xylene, water, further an emulsifier such as sorbitol monooleate, oleyl ethoxylate having 3 - 7 moles of ethylene oxide, an aliphatic alcohol ethoxylate, a perfume oil such as an ether oil, an ester of a medium fatty acid having a lower alcohol, an aromatic carbonyl compound, a stabilizer such as sodium benzoate if necessary, an amphoteric surfactant, a lower epoxide, triethyl orthoformate, and a propellant such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or a mixture of these gases if necessary.

[0134] The oil spray formulation differs from the aerosol formulation in that no propellant is used. When used in a spray composition, the content of the active ingredient ranges from 0.001 to 80% by weight, preferably from 0.01 to 50% by weight, and most preferably from 0.01 to 15% by weight.

[0135] The compounds of the present invention and their respective compositions can also be used in mosquito-repellent incense and fumigation coils, smoke cartridges, vaporizer plates or long-term vaporizers, and also in insect-repellent papers, insect-repellent pads or other heat-independent vaporizer systems.

[0136] The compounds of formula (I) and their respective compositions can be used to control insect-borne infections (such as malaria, dengue fever, yellow fever, lymphatic filariasis, leishmaniasis, etc.). Methods also include treating the surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing, mosquito nets, tsetse fly traps, etc. The pesticidal compositions for application to fibers, fabrics, knitted products, non-woven fabrics, net materials or foils and waterproof sheets preferably contain a mixture comprising a pesticide, optionally a repellent and at least one binder. For example, suitable repellents are N,N-diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3-cyclohexan-1-yl-carbonyl)-2-methylpiperidine, (2-hydroxymethylcyclohexyl)acetic acid lactone, 2-ethyl-1,3-hexanediol, indalone, methyl neodecanamide (MNDA), pyrethroids not used for insect control such as {(+ / -)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysanthemate (esbiothrin)}, limonene, eugenol, plant extracts derived from or identical to (+)-eucamalol (1), (-)-1-epieucamalol, etc., or crude plant extracts from plants such as Eucalyptus, Vitex rotundifolia, Cymbopogon martinii, Cymbopogon citratus (lemongrass), Cymbopogon nardus (citronella). Suitable binders are selected, for example, from vinyl esters of aliphatic acids (such as vinyl acetate, vinyl versatate, etc.), acrylic esters and methacrylic esters of alcohols such as butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate, mono- and diethylenically unsaturated hydrocarbons such as styrene, and polymers and copolymers of aliphatic dienes such as butadiene.

[0137] The impregnation of curtains and mosquito nets is generally carried out by immersing the fibrous material in an emulsion or dispersion of the pesticide or spraying them onto the net. The compounds and compositions of the present invention can be used to protect wooden materials such as trees, board fences, and railroad ties, as well as buildings such as houses, outdoors, and factories. They can also be used to protect building materials, furniture, leather, fibers, vinyl products, wires and cables, etc. from ants and / or termites, and to prevent ants and termites from harming crops or humans (e.g., when pests invade houses or public facilities). The compounds of the present invention are not only applied to the surrounding soil surface or subfloor soil to protect wooden materials, but also to the surface of subfloor concrete, floor columns, beams, wood products such as plywood and furniture, wood products such as particle board and half board, and vinyl products such as coated wires, vinyl sheets, and heat insulating materials such as styrofoam.

[0138] Seed treatment The present invention further relates to seeds containing an amount of the compound of the present invention in the range of from about 0.0001 to about 1% by weight of the seeds before treatment. The compounds of the present invention are particularly useful for protecting seeds from soil pests, and for protecting the roots and new shoots of plants resulting from soil pests and leaf insects. Protection of the resulting plant roots and new shoots is preferred. More preferred is protecting the new shoots of the resulting plants from boring insects and sucking insects, and most preferred is protection from aphids. Accordingly, the present invention includes a method for protecting seeds from insects, particularly soil insects, and for protecting the roots and shoots of seedlings from insects, particularly soil and leaf insects, said method comprising contacting the seeds with the compound of the present invention before and / or after sowing and / or before and / or after germination. Particularly preferred is a method in which the roots and shoots of the plant are protected, more preferably a method in which the shoots of the plant are protected from boring insects and sucking insects, and most preferably a method in which the shoots of the plant are protected from aphids.

[0139] The term "seed" includes, but is not limited to, all types of seeds and plant propagules such as seed pieces, suckers, bulbs, corms, fruits, tubers, grains, cuttings, cut new shoots, etc., and in preferred embodiments means true seeds.

[0140] The term "seed treatment" includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed broadcasting, seed soaking and seed pelleting. The present invention also includes seeds coated with or containing active compounds. The seeds can be coated with a seed coating composition containing the compounds of the present invention. For example, seed coating compositions reported in EP3165092, EP3158864, WO2016198644, WO2016039623, WO2015192923, CA2940002, US2006150489, US2004237395, WO2011028115, EP2229808, WO2007067042, EP1795071, EP1273219, WO200178507, EP1247436, NL1012918 and CA2083415 may be mentioned.

[0141] The term "coated and / or containing" generally means that most of the active ingredient is on the surface of the growth product at the time of application, but depending on the application method, most or a small part of the ingredient may penetrate into the growth product. When the growth product is (re)planted, it may absorb the active ingredient. Suitable seeds are seeds of cereals, root vegetables, oil crops, vegetables, spices, ornamentals, for example seeds of durum and other wheat, barley, oats, rye, maize (feed maize and sugar maize / sweet and field corn), soybeans, oil crops, rape, cotton, sunflower, banana, rice, oilseed rape, turnip rape, sugar cane, fodder beet, eggplant, potato, grass, forage, turf, lawn, grass, forage grass, tomato, chives, pumpkin / squash, cabbage, iceberg lettuce, pepper, cucumber, melon, rape seed, melon, bean, pea, garlic, onion, carrot, potato, sugar cane, tobacco, grape, petunia, geranium / pelargonium, pansy and tuber plants such as impatiens.

[0142] Furthermore, the compounds of the present invention can be used for treating seeds from plants that are resistant to the action of herbicides or fungicides or insecticides by breeding including genetic engineering methods. For example, the compounds of the present invention can be used for treating seeds from plants that are resistant to herbicides from the group consisting of sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium and similar active substances (see EP242236, EP242246, etc.) (see EP257993, US5013659), or can be used for genetically modified crops having the ability to produce Bacillus thuringiensis toxin (Bt toxin) that renders plants resistant to specific pests, such as cotton, etc. (EP142924, EP193259). Furthermore, the compounds of the present invention can be used for treating seeds from plants having modified properties compared to existing plants, which can be produced, for example, by traditional breeding methods and / or generation of mutants or recombinant procedures. For example, recombinant modification of crops aimed at modifying starch synthesized in plants (e.g., WO92 / 11376, WO92 / 14827, WO91 / 19806) or many cases of genetically modified crops having a modified fatty acid composition are described (WO91 / 13972).

[0143] The seed treatment application of the compounds of the present invention is carried out by spraying or dusting the seeds before sowing of the plants and before germination of the plants.

[0144] Compositions particularly useful for seed treatment are, for example, as follows: A Soluble concentrates (SL, LS) B Emulsions (EW, EO, ES) C Suspensions (SC, OD, FS) D Water-dispersible granules and water-soluble granules (WG, SG) E Water-dispersible powders and water-soluble powders (WP, SP, WS) F Gel formulations (GF) G Dustable powders (DP, DS)

[0145] Conventional seed treatment formulations include, for example, flowable concentrates FS, solutions LS, dry treatment powders DS, water-dispersible powders WS for slurry treatment, water-soluble powders SS, and emulsions ES and EC, as well as gel formulations GF. These formulations can be applied to diluted or undiluted seeds. Application to seeds is carried out before sowing, either directly on the seeds or after pre-germinating the seeds.

[0146] In one embodiment, an FS formulation is used for seed treatment. Typically, an FS formulation can contain 1 - 800 g / l of active ingredient, 1 - 200 g / l of surfactant, 0 - 200 g / l of antifreeze, 0 - 400 g / l of binder, 0 - 200 g / l of pigment, and up to 1 liter of solvent, preferably water. In particular, an FS formulation of the compounds of the present invention for seed treatment usually contains 0.1 - 80% by weight (1 - 800 g / l) of active ingredient, 0.1 - 20% by weight (1 - 200 g / l) of at least one surfactant, for example, 0.05 - 5% by weight of wetting agent and 0.5 - 15% by weight of dispersant, up to 20% by weight, for example 5 - 20% of antifreeze, 0 - 15% by weight, for example 1 - 15% by weight of pigment and / or dye, 0 - 40% by weight, for example 1 - 40% by weight of binder (sticker / adhesive), optionally up to 5% by weight, for example 0.1 - 5% by weight of thickener, optionally 0.1 - 2% of defoamer, and optionally 0.01 - 1% by weight of biocide, preservatives such as antioxidants, and up to 100% by weight of filler / excipient.

[0147] The seed treatment formulation may further contain a binder and optionally a colorant. Binders can be added to improve the adhesion of the active substance to the treated seeds. Suitable binders are homopolymers and copolymers of alkylene oxides such as ethylene oxide or propylene oxide, polyvinyl acetate, polyvinyl alcohol, polyvinyl pyrrolidone and their copolymers, ethylene-vinyl acetate copolymers, acrylic homopolymers and copolymers, polyethylene amines, polyethylene amides and polyethylene pyrimidines, polysaccharides such as cellulose, tylose and starch, polyolefin homopolymers and copolymers such as olefin / maleic anhydride copolymers, polyurethanes, polyesters, polystyrene homopolymers and copolymers.

[0148] Optionally, colorants can also be included in the formulation. Colorants or dyes suitable for seed treatment formulations are Rhodamine B, C.I. Pigment Red 112, C.I. Solvent Red 1, Pigment Blue 15:4, Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 80, Pigment Yellow 1, Pigment Yellow 13, Pigment Red 112, Pigment Red 48:2, Pigment Red 48:1, Pigment Red 57:1, Pigment Red 53:1, Pigment Orange 43, Pigment Orange 34, Pigment Orange 5, Pigment Green 36, Pigment Green 7, Pigment White 6, Pigment Brown 25, Basic Violet 10, Basic Violet 49, Acid Red 51, Acid Red 52, Acid Red 14, Acid Blue 9, Acid Yellow 23, Basic Red 10, Basic Red 108.

[0149] An example of a gelling agent is carrageenan (Satiagel trademark). In the treatment of seeds, the applicable dosage of the compounds of the present invention is generally 0.1 g to 10 kg per 100 kg of seeds, preferably 1 g to 5 kg per 100 kg of seeds, more preferably 1 g to 1 kg per 100 kg of seeds, and particularly 1 g to 200 g per 100 kg of seeds. Accordingly, the present invention also provides seeds containing a compound of formula (I) as defined herein, or an agriculturally useful salt of formula (I). The amount of the compound of formula (I) or its agriculturally useful salt is generally 0.1 g to 10 kg per 100 kg of seeds, preferably 1 g to 5 kg per 100 kg of seeds, and particularly 1 g to 1 kg per 100 kg of seeds. For specific crops such as lettuce, the dosage can be higher.

[0150] Animal health The present invention also provides agricultural and / or veterinary compositions comprising at least one compound of the present invention. The present invention further relates to the use of a compound of the present invention, its N-oxide, or its veterinarily acceptable salt, or a composition of the present invention, in the manufacture of a medicament for treating or protecting animals from infestation or infection by insect and mite pests or parasites. The compounds of formula (I), their N-oxides and / or their veterinarily acceptable salts are also particularly suitable for use in controlling parasites in and on the bodies of animals. Accordingly, one of the objects of the present invention is to provide a new method for controlling parasites that parasitize in and on the bodies of animals. Another object of the present invention is to provide a safer insecticide for animals. Another object of the present invention is to provide an animal insecticide that can be used at a lower dosage than existing insecticides. Another object of the present invention is to provide an animal insecticide that can control parasites for a long period of time.

[0151] The present invention also relates to a composition comprising at least one insecticidally effective amount of a compound of formula (I), an N-oxide or its veterinarily acceptable salt, and an acceptable carrier, for controlling parasites in and on the bodies of animals. The present invention also provides a method for treating, controlling, preventing and protecting animals from infestation and infection by parasites. This method includes orally, topically or parenterally administering or applying to the animal a parasitically effective amount of a compound of the present invention or a composition containing the same.

[0152] The present invention also provides a method for producing a composition for treating, controlling, preventing or protecting an animal from infestation or infection by a parasite, which composition contains a parasitically effective amount of a compound of the present invention or a composition containing the same. The activity of the compounds against agricultural pests does not suggest their suitability for controlling internal and external parasites of animals, which requires, for example in the case of oral administration, being non-emetic at low doses, metabolic compatibility with animals, low toxicity and safe handling. Surprisingly, the compounds of the present invention have been found to be suitable for controlling internal and external parasites of animals.

[0153] The compounds of the present invention and compositions containing them are preferably used for controlling and preventing infestation and infection of animals including warm-blooded animals (including humans) and fish. They are suitable for controlling and preventing infestation and infection in, for example, mammals such as cattle, sheep, pigs, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, fur-bearing animals such as mink, chinchillas and raccoons, birds such as chickens, geese, turkeys and ducks, and fish such as freshwater and seawater fish such as trout, carp and eels.

[0154] The compounds of the present invention and compositions containing them are preferably used for controlling and preventing infestation and infection in domestic animals such as dogs or cats. Parasites in warm-blooded animals and fish include, but are not limited to, lice, biting lice, mites, nasal polyps, ked, biting flies, blowflies, flies, larvae of small flies, chiggers, fleas, mosquitoes and ticks.

[0155] The compounds of the present invention and compositions containing them are suitable for the systemic and / or non-systemic control of external and / or internal parasites. They can be active against all or some stages of development. The compounds of the present invention are particularly useful for the control of external parasites. The compounds of the present invention are particularly useful for controlling parasites of the following orders and species. Fleas (Siphonaptera), such as Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, Cockroaches (Blattaria·Blattidae), e.g., Blatta orientalis, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Blatta lateralis, Blatta asahinai, Blaberus discoidalis, Blaberus giganteus, and Blatta australasiae, Flies, Mosquitoes (Diptera) Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anastrepha ludens, Cochliomyia macellaria, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya megacephala, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, fertile eggs, Phlebotomus argentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, STOMOXYS calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, lice (Phthiraptera), e.g., head louse, body louse, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus, Solenopotes capillatus. Fleas and parasitic mites (Parasitiformes): fleas (Siphonaptera), e.g., flea Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhificephilus Sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorus turicata, and parasitic mites (Mesostigmata), e.g., mite Ornithonyssus bacoti and Dermanyssus gallinae, Actinedida (Prostigmata) and Acaridida (Astigmata), etc. Genus Acarapis, genus Kerectestheria, genus Ornithokerectestheria, genus Myobia, genus Psorergates, genus Demodex, genus Trombicula, genus Listrophorus, genus Acarus, genus Conoptes, genus Caloglyphus, genus Hypodectes, genus Pterolichus., genera Psoroptes, Chorioptes, Otodectes, Sarcoptes, Notoedres, Knemidocoptes, Cytodites, and Laminosioptes, true bugs (Heteroptera): Cimex lectularius, Cimex hemipterus, Reduvius senilis, genus Triatoma., Rhodnius ssp., Panstrongylus ssp., Arilus critatus, genus Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp, Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp. For example, genus Trinoton, genus Bovicola, genus Werneckiella, genus Lepikentron, genus Trichodectes, genus Felicola..

[0156] Roundworms and nematodes: Whipworms and Trichosyringida, e.g., Trichinella spp., (Trichuridae,) Trichuris spp., Capillaria spp., Rhabditida, e.g., Rhabditis spp., Strongyloides spp., Helicephalobus spp., Strongylida, e.g., Strongylus spp., Ancylostoma spp., Necator americanus, Bunostomum spp. (hookworms), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus, Dictyocaulus, Ancylostoma, Uncinaria, Globocephalus, Necator, Metastrongylus, Muellerius capillaris, Protostrongylus, Angiostrongylus, Parastrongylus.Aleurostrongylus abstrusus, and Dioctophyma renale, intestinal roundworms (Ascaridida), examples: Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Pascaris equorum, Enterobius vermicularis (threadworms), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi, Camallanida, examples: Dracunculus medinensis (Guinea worm) Spirurida, examples: Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habronema spp, Acanthocephala (spiny-headed worms), examples: Acanthocephalus spp., Macracanthorhynchus hirudinaceus, Oncicola spp, Planarians (Plathelminthes): Trematoda (flukes), examples: Faciola spp., Fascioloides magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria a lata, Paragonimus spp., and Nanocyetes spp, Cercomeromorpha, especially tapeworms, examples: genus Diphyllobothrium, genus Taenia, genus Echinococcus, genus Dipylidium caninum, genus Multiceps, genus Hymenolepis, genus Mesocestoides, genus Vampirolepis, genus Moniezia, genus Anoplocephala, genus Schyzometra, genus Anoplocephala, genus Hymenolepis.

[0157] The compounds of formula (I) and compositions containing them are particularly useful for controlling pests of Diptera, Siphonaptera and Acarina. Furthermore, the use of the compounds of formula (I) and compositions containing them for controlling mosquitoes is one embodiment of the present invention. The use of the compounds of the present invention and compositions containing them for controlling flies is another embodiment of the present invention. Furthermore, the use of the compounds of the present invention and compositions containing them for controlling fleas is yet another embodiment of the present invention. The use of the compounds of the present invention and compositions containing them for controlling mites is yet another embodiment of the present invention.

[0158] The compounds of the present invention are also particularly useful for controlling endoparasites (roundworm nematodes, spiny-headed worms, planarians). Administration can be carried out both prophylactically and therapeutically. The compounds of the present invention are administered directly or in the form of a suitable formulation, orally, topically / transdermally, or parenterally.

[0159] In the case of oral administration to warm-blooded animals, the compounds of the present invention can be formulated as animal feed, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. Furthermore, the compounds of the present invention can be administered to animals by incorporating them into drinking water. In the case of oral administration, the selected dosage form should provide the compounds of the present invention to the animal at 0.01 mg / kg body weight to 100 mg / kg body weight per day, preferably 0.5 mg / kg body weight to 100 mg / kg body weight. Alternatively, the compounds of the present invention can be administered to animals parenterally, for example, by intraluminal, intramuscular, intravenous or subcutaneous injection. The compounds of the present invention can be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of the present invention can be formulated into implants for subcutaneous administration. Furthermore, the compounds of the present invention can be administered to animals transdermally. In the case of parenteral administration, the selected dosage form should provide the compound of the present invention to the animal at a concentration of 0.01 mg / kg body weight to 100 mg / kg body weight per day.

[0160] The compounds of the present invention can also be applied topically to animals in the form of dips, powders, dusts, collars, medallions, sprays, shampoos, spot-ons and pour-ons, and also in the form of ointments or water-in-oil or oil-in-water emulsions. In the case of topical application, dips and sprays usually contain from 0.5 ppm to 5,000 ppm, preferably from 1 ppm to 3,000 ppm of the compound of the present invention. Furthermore, the compounds of the present invention can be formulated as ear tags for animals, especially quadrupeds such as cattle and sheep.

[0161] Suitable formulations are oral liquids, concentrated liquids for oral administration after dilution, liquids for use on the skin or in body cavities, pour-on formulations, solutions such as gels; emulsions and suspensions for oral or transdermal administration; semi-solid formulations; formulations in which the active compound is treated with an ointment base or a water-in-oil or oil-in-water emulsion base; solid formulations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and shaped articles containing the active compound.

[0162] Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizing agents as required. The solution is filtered and filled under sterile conditions.

[0163] Suitable solvents are physiologically acceptable solvents such as water, ethanol, butanol, alkanols such as benzyl alcohol, glycerol, propylene glycol, polyethylene glycol, N-methylpyrrolidone, 2-pyrrolidone, and mixtures thereof. The active compound can, if desired, be dissolved in a physiologically acceptable vegetable or synthetic oil suitable for injection. As solubilizers, solvents that promote the dissolution of the active compound in the main solvent or prevent precipitation are suitable. For example, polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan esters. As preservatives, benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol are suitable. Oral solutions are administered directly. Concentrates are diluted beforehand to the concentration for use and then administered orally. Oral solutions and concentrates are manufactured in the same manner as the above injection solutions according to the latest technology, and no sterilization operation is required. Solutions for use on the skin are dropped, applied, rubbed in, sprayed or atomized. Solutions for use on the skin are prepared according to the latest technology and according to the method described above for injection solutions, and no sterilization operation is required.

[0164] Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxyethanol, esters such as ethyl acetate or butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers, for example dipropylene glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylene carbonate and mixtures thereof.

[0165] It may be advantageous to add a thickening agent during preparation. Suitable thickening agents are inorganic thickening agents such as bentonite, colloidal silica, aluminum monostearate, cellulose derivatives, polyvinyl alcohol and their copolymers, and organic thickening agents such as acrylates and methacrylates.

[0166] The gel is applied or spread on the skin or introduced into the body cavity. The gel is prepared by treating a solution prepared as described for injection solutions with a sufficient amount of a thickening agent to obtain a transparent substance having an ointment-like consistency. The thickening agent used is the above-mentioned thickening agent.

[0167] The pore-on preparation is poured or sprayed onto a limited area of the skin. The active compound penetrates the skin and acts systemically. The pore-on preparation is prepared by dissolving, suspending or emulsifying the active compound in a suitable skin-compatible solvent or solvent mixture. Optionally, other adjuvants such as colorants, bioabsorption promoters, antioxidants, light stabilizers, adhesives, etc. are added.

[0168] Suitable solvents are water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and / or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, methylpyrrolidone, n-alkylpyrrolidones such as n-butylpyrrolidone or octylpyrrolidone, N-methylpyrrolidone, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1,3-dioxolane and glycerol formal.

[0169] Suitable colorants are all colorants that are permitted for use in animals and can be dissolved or suspended. Suitable absorption promoters are, for example, diffusion oils such as DMSO, isopropyl myristate, dipropylene glycol pelargonate, silicone oil, and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.

[0170] Suitable antioxidants are sulfites or metabisulfites, for example, potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.

[0171] Suitable light stabilizers are, for example, novan antisoelic acid. Suitable adhesives are, for example, natural polymers such as cellulose derivatives, starch derivatives, polyacrylates, alginates, gelatin. The emulsion can be administered orally, dermally or by injection. The emulsion is either of the water-in-oil or oil-in-water type. They are prepared by dissolving the active compound in either the hydrophobic or hydrophilic phase and homogenizing it with the solvent of the other phase with the aid of suitable emulsifiers and, if necessary, other auxiliaries such as colorants, absorption promoters, preservatives, antioxidants, light stabilizers, viscosity increasing substances.

[0172] Suitable hydrophobic phases (oils) are as follows: Liquid paraffin, silicone oil, sesame oil, almond oil, natural vegetable oils such as castor oil, synthetic triglycerides such as caprylic / capric acid diglyceride, triglyceride mixtures of vegetable fatty acids with a chain length of Cs-Ci2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids that may contain hydroxyl groups, mono- and diglycerides of Cs-do fatty acids, fatty acid esters such as ethyl stearate, di-n-butyl adipate, hexyl laurate, dipropylene glycol parargonate, esters of medium-chain branched fatty acids with saturated fatty alcohols having a chain length of C16-C18, isopropyl myristate, isopropyl palmitate, caprylic / capric acid esters of saturated fatty acids with a chain length of C12-C18, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, wax fatty acid esters such as ethyl lactate, synthetic duck uropygial gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and mixtures thereof. Suitable hydrophilic phases are water, alcohols such as propylene glycol, glycerol, sorbitol, and mixtures thereof.

[0173] Suitable emulsifiers are non-ionic surfactants such as polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether, amphoteric surfactants such as disodium N-lauryl-p-iminodipropionate and lecithin.

[0174] Suitable anionic surfactants are sodium lauryl sulfate, fatty alcohol ether sulfates, mono / dialkyl polyglycol ether orthotolyl phosphate monoethanolamine salts, and suitable cationic active surfactants are cetyltrimethylammonium chloride.

[0175] Suitable further auxiliaries are substances that increase the viscosity and stabilize the emulsion, such as carboxymethyl cellulose, methyl cellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinyl pyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycol, waxes, colloidal silica, or mixtures of the above substances.

[0176] The suspensions can be administered orally or topically / dermally. They are prepared by suspending the active compound in a suspending agent, optionally with the addition of other auxiliaries such as wetting agents, colorants, bioabsorption promoters, preservatives, antioxidants, light stabilizers, etc. Liquid suspensions are all homogeneous solvents and solvent mixtures. Suitable wetting agents (dispersants) are the above-mentioned emulsifiers. Other auxiliaries that may be mentioned are the above-mentioned ones. The semi-solid preparations can be administered orally or topically / dermally. They differ from the above-mentioned suspensions and emulsions only in having a higher viscosity. For the manufacture of solid preparations, the active compound is mixed with suitable excipients, auxiliaries are added if necessary, and it is made into the desired form.

[0177] Suitable excipients are all physiologically acceptable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, bicarbonates, aluminum oxide, titanium oxide, silicic acid, argillaceous earth, precipitated or colloidal silica, or phosphates. Organic substances are, for example, foods and feeds such as sugar, cellulose, skimmed milk powder, animal meal, cereal meal and flakes, starch.

[0178] Suitable auxiliaries are the above-mentioned preservatives, antioxidants and / or colorants. Other suitable auxiliaries are lubricants and lubricating agents such as magnesium stearate, stearic acid, talc, bentonite, disintegration promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.

[0179] Generally, the "parasite control effective amount" means the amount of the active ingredient necessary to achieve an observable effect on growth, including death, delay, prevention, removal and destruction of the target organisms, or reduction in occurrence and activity by other means. The parasite control effective amount can vary for the various compounds / compositions used in the present invention. The parasite control effective amount of the composition also varies depending on general conditions such as the desired parasite control effect and duration, the target species, the method of application, etc. The compositions that can be used in the present invention usually contain about 0.001 to 95% of the compounds of the present invention.

[0180] Generally, it is preferred to apply the compounds of the present invention in a total amount of 0.5 mg / kg to 100 mg / kg per day, preferably 1 mg / kg to 50 mg / kg. The ready-made preparations contain the compounds acting against parasites, preferably ectoparasites, at a concentration of 10 ppm to 80% by weight, preferably 0.1 to 65% by weight, more preferably 1 to 50% by weight, most preferably 5 to 40% by weight. The preparations contain the compounds acting against ectoparasites at a concentration of 0.5 to 90% by weight, preferably 1 to 50% by weight, and are diluted before use. Further, the preparations contain the compounds of the present invention against endoparasites at a concentration of 10 ppm to 2% by weight, preferably 0.05 to 0.9% by weight, particularly preferably 0.005 to 0.25% by weight. In one embodiment, the composition containing the compounds of the present invention is applied transdermally / topically.

[0181] In another embodiment, the topical application is carried out in the form of shaped articles containing the compounds such as collars, medallions, ear tags, bands for fixing to a part of the body, adhesive strips and foils. Generally, it is preferable to apply a solid preparation that releases the compound of the present invention in a total amount of 10 mg / kg to 300 mg / kg, preferably 20 mg / kg to 200 mg / kg, and most preferably 25 mg / kg to 160 mg / kg body weight to a treated animal for three weeks. For the production of molded articles, thermoplastic plastics and flexible plastics, as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethanes, polyacrylates, epoxy resins, celluloses, cellulose derivatives, polyamides and polyesters that are sufficiently compatible with the compounds of the present invention. A detailed list of plastics and elastomers as well as the production procedures for molded articles are shown, for example, in WO2003 / 086075.

[0182] Digital technology The compounds of the present invention can be used, for example, in combination with models incorporated into computer programs for site-specific crop management, satellite agriculture, precision agriculture or precision farming. Such models use data from various sources such as soil, climate, crops (species, growth stage, plant health, etc.), weeds (species, growth stage, etc.), diseases, pests, nutrients, water, moisture, biomass, satellite data, harvest, etc. to support site-specific management of agricultural sites for the purpose of optimizing profitability, sustainability and environmental protection. In particular, such models help to optimize agricultural decisions, control the accuracy of pesticide spraying and record the work performed.

[0183] As an example, when the model models the occurrence of pests and calculates that the threshold at which it is recommended to apply the compound of the present invention to the crop has been reached, the compound of the present invention can be applied to the crop according to an appropriate dosage system. Commercially available systems including agricultural models are, for example, The Climate Corporation's FieldScriptsTM, BASF's XarvioTM, John Deere's AGLogicTM, etc.

[0184] The compounds of the present invention can also be used in combination with smart spraying devices such as spot spraying or precision spraying devices attached to or housed within agricultural vehicles such as unmanned aerial vehicles (UAVs) such as tractors, robots, helicopters, airplanes, drones, etc. Such devices typically include an input sensor (such as a camera, etc.) and a processing unit configured to analyze the input data and provide a determination to apply the compounds of the present invention to crops (or weeds) in a specific and accurate manner based on the analysis of the input data. The use of such smart spraying devices typically also requires a position system (such as a GPS receiver) to identify the recorded data and to guide or control the agricultural vehicle. A geographic information system (GIS) for representing information on an understandable map and an appropriate agricultural vehicle for performing the necessary agricultural activities such as spraying are also required.

[0185] As an example, pests can be detected from images obtained by a camera. In one example, pests can be identified and / or classified based on the image. Such identification and / or classification can utilize image processing algorithms. Such image processing algorithms can utilize machine learning algorithms such as trained neural networks, decision trees, and artificial intelligence algorithms. In this way, the compounds described herein can be applied only when necessary.

[0186] Positive crop response: The compounds of the present invention not only effectively control insect and mite pests, but also enhance root growth, enhance resistance to drought, high salinity, high temperature, low temperature, frost or light irradiation, improve flowering, enhance nutrient utilization (such as improvement of nitrogen assimilation, etc.), produce high-quality plant products, increase the number of productive tillers, enhance resistance to pests, resulting in an increase in yield and showing a positive crop response.

[0187] General synthetic scheme: Next, the present invention will be described in more detail by the following examples, which are not intended to be limiting. [Chem.]

[0188] In one of the preferred embodiments, the compound of formula (I) (wherein D represents D1 and Z is a direct bond) is prepared by a metal-catalyzed cross-coupling reaction between a compound of formula A-1 (wherein LG represents a leaving group) and a compound of formula D 1- 1 according to the procedures described in document US20190297887 and further documents cited therein. The compound of formula D 1- 1 is commercially available or can be synthesized by the methods described in Chem Eur.J. 2021, 27, 17293-17321, European Journal of Medicinal Chemistry 2017,126, 225-245, Chem.Commun., 2017, 53, 348-351, J.Am.Chem.Soc.2020,142(36),15445-15453 and further documents cited therein. Unless otherwise specified, the definitions of each variable are as defined above for the compound of formula (I).

[0189] The C-N coupling reaction is usually carried out in the presence of a solvent, and the solvent that can be used for this reaction is not particularly limited as long as it does not adversely affect the reaction. For example, ethers such as dioxane, tetrahydrofuran, ethylene glycol, dimethyl ether and diethylene glycol dimethyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; N-amides such as N,N-dimethylformamide, N-dimethylacetamide and 1-methyl-2-pyrrolidone; alcohols such as methanol, ethanol, propanol, butanol, 2-propanol and 2-methyl-2-propanol; nitriles such as acetonitrile; or water or a mixture thereof serve this purpose. Preferred solvents include aromatic hydrocarbons such as toluene and xylene, and amides such as N,N-dimethylformamide, N,N-dimethylacetamide and 1-methyl-2-pyrrolidone, with N,N-dimethylformamide and toluene being most preferred. The reaction is carried out in the presence of a base selected from metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide and sodium tert-butoxide, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, potassium phosphate, potassium hydrogen phosphate and potassium hydride; and organic bases such as triethylamine, N,N-diisopropylethylamine and pyridine, but is not limited thereto. Preferred bases include metal alkoxides such as potassium tert-butoxide and sodium tert-butoxide.Examples of palladium catalysts that can be used in this reaction include inorganic palladium salts such as palladium-carbon and palladium chloride; organic palladium complexes such as palladium acetate; tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, 1,1'-bis(diphenylphosphino)phenylpalladium(II) chloride, and tris(dibenzylideneacetone)dipalladium(0); and polymer-immobilized organic palladium complexes such as polymer-supported bis(acetato)triphenylphosphine palladium(II) and polymer-supported di(acetato)dicyclohexylphosphine palladium(II), but are not limited thereto. More preferred palladium catalysts include palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, 1'-bis(diphenylphosphino)phenylpalladium(II) chloride, and tris(dibenzylideneacetone)dipalladium(0).Examples of ligands that can be used in this reaction include, but are not limited to, tris(o-tolyl)phosphine, tricyclohexylphosphine, tri-tert-butylphosphonium tetrafluoroborate, (oxydi-2,1-phenylene)bis[dicyclohexyl]phosphine, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl, (2-biphenyl)di-tert-butylphosphine, 2-(di-tert-butylphosphino)biphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl, 1,1'-ferrocenediyl-bis(diphenylphosphine), 2-di-tert-butylphosphino-2'-methylbiphenyl, 2-methyl-2'-dicyclohexylphosphinobiphenyl and [1,1'-biphenyl]-3-sulfonic acid, 2'-(dicyclohexylphosphino)-2,6-dimethoxynatrium salt, but are not limited thereto. Preferred ligands include 2-(di-tert-butylphosphino)biphenyl, 2-di-tert-butylphosphino-3, 4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl(oxydi-2,1-phenylene)bis[dicyclohexyl]phosphine, 1,1'-ferrocenediyl-bis(diphenylphosphine and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene. The reaction can be carried out at a temperature in the range of 0 to 200 °C, preferably in the range of 50 to 150 °C, for a period in the range of 30 minutes to 24 hours.

[0190] [Chem.]

[0191] In another preferred embodiment, the compound of formula (I) in which D represents D1 and Z is -C=O is prepared by a metal-catalyzed aminocarbonylation reaction or by an amide coupling reaction with a compound of formula A-1 (A-2 for amide coupling reactions) in which LG represents a leaving group and a compound of formula D 1- 1 according to the procedures described in WO2016144351, Chem. Eur. J. 2021, 27, 17293-17321 and further references cited therein. Compounds of formula D1-1 are commercially available or can be synthesized by the methods described in Chem. Eur. J. 2021, 27, 17293-17321, European Journal of Medicinal Chemistry 2017, 126, 225-245, Chem. Commun., 2017, 53, 348-351, J.Am.Chem. Soc. 2020,142, 36, 15445-15453 and further references cited therein. Unless otherwise stated, the definitions of each variable are as defined above for the compounds of formula (I).

[0192] The metal-catalyzed aminocarbonylation reaction as shown in Scheme 2 is carried out in the presence of a solvent such as, but not limited to, N-amide. For example, N,N-dimethylformamide, N-dimethylacetamide, and 1-methyl-2-pyrrolidone can be mentioned. N,N-dimethylformamide is a preferred solvent. The metal hexacarbonyl that functions as a "CO surrogate" in this reaction is selected from, but not limited to, molybdenum hexacarbonyl and tungsten hexacarbonyl. The reaction is carried out in the presence of a base selected from, but not limited to, metal hydrides such as sodium hydride, lithium hydride, and potassium hydride; metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; organic amine bases such as triethylamine, N,N-diisopropylethylamine, and 1,8-diazabicyclo[5.4.0]undec-7-ene; and preferably, organic amines such as N,N-diisopropylethylamine and 1,8-diazabicyclo[5.4.0]undec-7-ene. Examples of the catalyst that can be used in this reaction include, but are not limited to, organic palladium complexes such as polymer-supported bis(acetato)triphenylphosphine palladium(II), trans-di-μ-acetatobis[2-[bis(2-methylphenyl)phosphino]benzyl]dipalladium, and polymer-supported (acetato)dicyclohexylphosphine palladium(II). An example of the ligand used in this reaction is tri-tert-butylphosphonium tetrafluoroborate. This reaction is typically carried out in the temperature range of 0 to 200 °C, preferably 50 to 180 °C, for 30 minutes to 24 hours. This reaction can also be optionally carried out under microwave irradiation conditions.

[0193] The amid coupling reaction as shown in Scheme 2 is usually carried out in the presence of a solvent such as N-amides, for example, N,N-dimethylformamide, N-dimethylacetamide, and 1-methyl-2-pyrrolidone, but is not limited thereto. N,N-dimethylformamide is a preferred solvent. Further, these reactions are carried out in the presence of a base selected from organic amine bases such as triethylamine, N,N-diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, but is not limited thereto, and triethylamine and N,N-diisopropylethylamine are preferred bases. The coupling reagents that can be used in this reaction are N,N'-dicyclohexylcarbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methiodide, 1-hydroxybenzotriazole hydrate, 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate, and N-[(dimethylamino)-1H-1,2,3-triazolo-[4,5-b]pyridin-1-ylmethylene]-N-methylmethanaminium hexafluorophosphate N-oxide, but is not limited thereto. This reaction can be carried out at a temperature in the range of 0 to 200 °C, preferably 0 to 50 °C, and in the range of 30 minutes to 24 hours.

[0194]

Chemical formula

[0195] In another preferred embodiment, the compound of formula (I) (wherein D represents D1 and Z is -C=S) can be prepared in the presence of Lawesson's reagent under suitable thioacylation reaction conditions as described in Chem. Sci., 2021, 12, 6393 - 6405 and further references cited therein. Unless otherwise specified, the definitions of each variable are as defined above for the compounds of formula (I). The thioacylation reaction shown in Scheme 3 is carried out in the presence of a solvent such as aromatic hydrocarbons like benzene, toluene and xylene, but is not limited thereto. Preferably, it is carried out in toluene. This reaction can be carried out at a temperature in the range of 0 - 200 °C, preferably at a temperature of 50 - 150 °C, for a range of 30 minutes to 24 hours.

[0196]

Chemical formula

[0197] In another preferred embodiment, the compound of formula (I) (wherein D represents D3 and Z represents a direct bond) can be prepared by a metal - catalyzed cross - coupling reaction between a compound of formula A - 1 (wherein LG represents a leaving group) and an alkoxytriazolone of formula D 3- 1 according to the procedure described in US20190297887 and further references cited therein. The alkoxytriazolone of formula D 3- 1 is commercially available or can be synthesized by the methods described in US005606070A and further references cited therein. Unless otherwise specified, the definitions of each variable are as described above for the compounds of formula (I).

[0198] The reaction is carried out in the presence of a solvent such as, but not limited to, ethers such as dioxane, tetrahydrofuran, 2-methyl-tetrahydrofuran, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, aromatic hydrocarbons such as benzene, toluene and xylene; N-amides such as N,N-dimethylformamide, N-dimethylacetamide and 1-methyl-2-pyrrolidone; alcohols such as methanol, ethanol, propanol, butanol, 2-propanol, 2-methyl-2-propanol and 2-methyl-2-butanol; nitriles such as acetonitrile; and water or mixtures thereof. Preferred solvents include amides such as N,N-dimethylformamide, N,N-dimethylacetamide and 1-methyl-2-pyrrolidone and alcohols such as methanol, ethanol, propanol, butanol, 2-propanol, 2-methyl-2-butanol and 2-methyl-2-propanol, N,N-dimethylformamide, and 2-methyl-2-butanol and the like. Bases that can be used in this reaction include, but are not limited to, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide and sodium tert-butoxide, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, potassium phosphate, potassium hydrogen phosphate and potassium hydride, and organic bases such as triethylamine, N,N-diisopropylethylamine and pyridine, etc., but are not limited thereto. Preferred bases include phosphates such as sodium phosphate, potassium phosphate, potassium hydrogen phosphate, and carbonates such as sodium carbonate, potassium carbonate and cesium carbonate.

[0199] Here, carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate are more preferred bases. Palladium catalysts that can be used in this reaction include inorganic palladium salts such as palladium-carbon and palladium chloride; organic palladium complexes such as palladium acetate; tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, 1,1'-bis(diphenylphosphino)phenylpalladium(II) chloride, and tris(dibenzylideneacetone)dipalladium(0); and polymer-immobilized organic palladium complexes such as polymer-supported bis(acetato)triphenylphosphine palladium(II) and polymer-supported di(acetato)dicyclohexylphosphine palladium(II), but are not limited thereto. As the palladium catalyst, palladium catalysts such as palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, 1'-bis(diphenylphosphino)phenylpalladium(II) chloride, and tris(dibenzylideneacetone)dipalladium(0) are more preferred.

[0200] Examples of ligands that can be used in this reaction include, but are not limited to, tris(o-tolyl)phosphine, tricyclohexylphosphine, tri-tert-butylphosphonium tetrafluoroborate, (oxydi-2,1-phenylene)bis[dicyclohexyl]phosphine, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 5-(di-tert-butylphosphino)-1',3',5'-triphenyl-1'H-[1,4']bipyrazole, 5-(dicyclohexylphosphino)-1',3',5'-triphenyl-1'H-[1,4']bipyrazole, 5-[di(1-adamantyl)phosphino]-1',3',5'-triphenyl-1'H-[1,4']bipyrazole, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl, (2-biphenylyl)di-tert-butylphosphine, 2-(di-tert-butylphosphino)biphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl, 1,1'-ferrocenediyl-bis(diphenylphosphine), 2-di-tert-butylphosphino-2'-methylbiphenyl, 2-methyl-2'-dicyclohexylphosphinobiphenyl, [1,1'-biphenyl]-3-sulfonic acid, 2'-(dicyclohexylphosphino)-2,6-dimethoxy-sodium salt, and the like.Preferred ligands include 2-(di-tert-butylphosphino)biphenyl, 5-(di-tert-butylphosphino)-1’,3’,5’-triphenyl-1’H-[1,4’]bipyrazole, 5-(dicyclohexylphosphino)-1’,3’,5’-triphenyl-1’H-[1,4’]bipyrazole, 5-[1,4’]-1’,3’,5’-triphenyl-1’H-(di(1-adamantyl)phosphino, 1,1’-ferrocenediyl-bis(diphenylphosphine) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene. The reaction is carried out at a temperature in the range of 0 to 200 °C, preferably 50 to 150 °C, for a duration in the range of 30 minutes to 24 hours.

[0201]

Chemical Structure

[0202] In another preferred embodiment, the compound of formula (I) in which D represents D2, Z represents a direct bond, and R 7 represents hydrogen can be further derivatized at the imine-NH functional group using reactions such as N-(halo)alkylation, N-(hetero)arylation, N-acylation, N-amidization, N-halogenation, and N-cyanation, and can be formed according to appropriate methods described, for example, in European Journal of Medicinal Chemistry 2017, 126, 225-245, Org. Lett. 2015, 17, 12, 3166-3169, Tetrahedron Letters 56 (2015) 7056-7058, Eur. J. Org. Chem. 2012, 20, 3737-3741, and WO2019150219, and further references cited therein, to form a compound of formula (I) in which D represents D2, Z represents a direct bond, and R 7 represents its usual meaning other than hydrogen. Unless otherwise stated, the definitions of each variable are as defined above.

[0203]

Chemical Structure

[0204] In another preferred embodiment, various sulfur-containing representatives of the compounds represented by formula (I), such as, but not limited to, sulfoximines, sulffilimines, and sulfonedimides (wherein D represents D2, Z is a direct bond, and R7 is as defined above herein) can be prepared starting from the compounds of formula A-3 according to the procedures described in the literature, such as European Journal of Medicinal Chemistry 2017, 126, 225-245 and Chem. Commun., 2017, 53, 348-351, and further literature cited therein. Unless otherwise specified, the definitions of each variable are as defined above for the compounds of formula (I). The sulfoximines of formula (I) can be prepared starting from the sulfides of formula A-3 in the presence of ammonium carbamate and diacetoxyiodobenzene (see, for example, Angew. Chem. Int. Ed. 2016, 55, 7203-7207). Alternatively, the sulfoximine (I) can also be synthesized by the oxidation of sulffilimine (I) (see, for example, Chem. Rev. 1977, 77, 409-435). On the other hand, the sulffilimines of formula (I) can be obtained from the sulfides of formula (A-3) by an imination reaction using an electrophilic amination reagent, such as O-(mesitylsulfonyl)hydroxylamine (MSH) or O-(2,4-dinitrophenyl)hydroxylamine (DPH), according to the procedures described in the literature, such as Angew. Chem. Int. Ed. 2012, 51, 4440-4443 and further literature cited therein.The sulfimines of formula (I) can also be prepared by imination of the sulfoxides of formula (A-4) using either a) a Burgess-type reagent as described in the literature, for example Adv. Synth. Catal. 2013, 355, 3363-3368 and further literature cited therein, or b) rhodium-catalyzed conditions in the presence of an electrophilic amination reagent such as O-(mesitylsulfonyl)hydroxylamine (MSH) or O-(2,4-dinitrophenyl)hydroxylamine (DPH) as described in the literature, for example Chem. Commun., 2014, 50, 9687-9689 and further literature cited therein. The sulfondiimides of formula (I) can be synthesized using either a) direct imination of the sulfides of formula A-3 as described in the literature, for example Chem. Ber. 1984, 117, 2779-2784 and further literature cited therein, or b) imination of the sulfimines of formula (I) as described in the literature, for example Angew. Chem. Int. Ed. 2012, 51, 4440-4443 and further literature cited therein, or c) imination of the sulfiminium salts represented by formula A-5 using N-chlorosuccinimide and an amine as described in the literature, for example Angew. Chem. Int. Ed. 2012, 51, 4440-4443 and further literature cited therein.

[0205] According to the features of the present invention, the compounds of formula A-3 in which all substituents are as previously defined can be prepared by the methods shown in Scheme 7, Scheme 8, Scheme 9 or the methods disclosed in the experimental examples. Representative procedures are shown below. However, this disclosure should not be construed as limiting the scope of the present invention for synthesizing the compounds of formula A-3.

[0206]

Chemical formula

[0207] According to Scheme 7, the compound represented by formula A-3 can be prepared by a base-mediated metal-catalyzed C-S coupling reaction between the compound of formula A-1 and the thiol of formula R 6 SH, as described in WO2020257145 and further documents cited therein. The thiol of formula R 6 SH is commercially available. Unless otherwise stated, the definitions of the variables A1, A2, A3, A4, A 5、 R 3、 R 6 、R 8 and R 8a are as defined above. LG represents a leaving group such as halogen or tosylate.

[0208] General protocol for C-S coupling: The reaction is usually carried out in the presence of solvents such as ethers like dioxane, tetrahydrofuran, 2-methyl-tetrahydrofuran, methylene glycol dimethyl ether and diethylene glycol dimethyl ether; aromatic hydrocarbons like benzene, toluene and xylene; N-amides like N,N-dimethylformamide, N-dimethylacetamide and 1-methyl-2-pyrrolidone; alcohols like methanol, ethanol, propanol, butanol, 2-propanol, 2-methyl-2-propanol and 2-methyl-2-butanol; nitriles like acetonitrile; and water or mixtures thereof. Preferred solvents include amides such as N,N-dimethylformamide, N,N-dimethylacetamide and 1-methyl-2-pyrrolidone, and aromatic hydrocarbons such as benzene, toluene and xylene. N,N-dimethylformamide and toluene are the most preferred solvents. The reaction is carried out in the presence of a base selected without limitation from metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and sodium tert-butoxide, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, potassium phosphate, potassium hydrogen phosphate, and potassium hydride, and organic bases such as triethylamine, N,N-diisopropylethylamine and pyridine. Preferred bases include metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide, and carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate. Here, carbonates such as cesium carbonate and metal alkoxides such as sodium tert-butoxide and potassium tert-butoxide are most preferred.Palladium catalysts that can be used in this reaction include, for example, palladium-carbon; inorganic palladium salts such as palladium chloride; organic palladium complexes such as palladium acetate; organic palladium complexes such as tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, 1,1'-bis(diphenylphosphino)phenylpalladium(II) chloride and tris(dibenzylideneacetone)dipalladium(0); and polymer-immobilized organic palladium complexes such as polymer-supported bis(acetato)triphenylphosphine palladium(II) and polymer-supported di(acetato)dicyclohexylphosphine palladium(II). Palladium catalysts such as palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, 1'-bis(diphenylphosphino)phenylpalladium(II) chloride and tris(dibenzylideneacetone)dipalladium(0) are more preferred.The ligands that can be used in this reaction include, but are not limited to, tris(o-tolyl)phosphine, tricyclohexylphosphine, tri-tert-butylphosphonium tetrafluoroborate, (oxydi-2,1-phenylene)bis[dicyclohexyl]phosphine, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 5-(di-tert-butylphosphino)-1',3',5'-triphenyl-1'H-[1,4']bipyrazole, 5-(dicyclohexylphosphino)-1',3',5'-triphenyl-1'H-[1,4']bipyrazole, 5-[di(1-adamantyl)phosphino]-1',3',5'-triphenyl-1'H-[1,4']bipyrazole, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl, (2-biphenylyl)di-tert-butylphosphine, 2-(di-tert-butylphosphino)biphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl, 1,1'-ferrocenediyl-bis(diphenylphosphine), 2-di-tert-butylphosphino-2'-methylbiphenyl, 2-methyl-2'-dicyclohexylphosphinobiphenyl, [1,1'-biphenyl]-3-sulfonic acid, 2'-(dicyclohexylphosphino)-2,6-dimethoxysodium salt, but are not limited thereto.Preferred ligands include 2-(di-tert-butylphosphino)biphenyl, 5-(di-tert-butylphosphino)-1’,3’,5’-triphenyl-1’H-[1,4’]bipyrazole, 5-(dicyclohexylphosphino)-1’,3’,5’-triphenyl-1’H-[1,4’]bipyrazole, 5-[1,4’]-1’,3’,5’-triphenyl-1’H-bipyrazole, 1,1’-ferrocenediyl-bis(diphenylphosphine), and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene. The reaction is typically carried out in a temperature range of 0 to 200 °C, preferably 50 to 150 °C, for a duration in the range of 30 minutes to 24 hours.

[0209]

Chemical Structure

[0210] Alternatively, the compound of formula A-3 can also be prepared by following the above-mentioned “General Protocol for C-S Coupling” as shown in Scheme 8. The compound of formula A-1 and formula R 6 Appropriate metal thiolates of SM can afford the compound of formula A-3 as described in the literature of WO2020257145 and further literature cited therein. The formula R 6 The metal thiolate of SM can be, but is not limited to, sodium or potassium, and can be commercially available or generated in situ by treating the corresponding thiol with organic and inorganic bases. Unless otherwise stated, the definitions of variables A1, A2, A3, A4, A5, R 3 、R 6 、R 8 and R 8a are each as defined above. LG represents a leaving group such as halogen or tosylate.

[0211]

Chemical Structure

[0212] In a further embodiment of the present invention, the compound of formula A-3 has all substituents as defined above and can be prepared by the method shown in Reaction Scheme 9. The compound of formula A-1 is subjected to a metal-catalyzed C-S coupling reaction as described above in a general protocol for C-S coupling in the presence of a trialkylsilanethiol such as triisopropylsilanethiol to obtain a thiolsilyl compound of formula A-6 (Route-A). Then, to deprotect the thiolsilyl of formula A-6 to obtain a compound of formula A-7, suitable bases such as sodium carbonate, potassium carbonate, cesium carbonate, or metal hydride bases such as sodium hydride, potassium hydride, and a metal fluoride source, for example, cesium fluoride, sodium fluoride, or a reagent in which metal ions are exchanged by a tetraalkylammonium cation such as tetramethylammonium fluoride, tetrabutylammonium fluoride, etc. can be used, but are not limited thereto. For example, it is described in the document of WO2020257145 and further documents cited therein. The thiol of formula A-7 can also be obtained by a metal-catalyzed coupling reaction between the compound of formula A-1 and commercially available sodium sulfide (Na2S·9H2O) using a catalytic amount of 1,2-ethanedithiol (Route B; for example, Synlett 2017; 28(17) 2272-2276 and further documents cited therein). The thiol of formula A-7 can be further alkylated in the presence of a suitable inorganic and organic base and a suitable alkyl halide of formula R 6 X to obtain a compound of formula A-3. The alkyl halide of formula R 6 X is commercially available. Alternatively, the thiolsilyl compound of formula A-6 can be a suitable (hetero)aryl halide, or triflate, or of formula R 6In the presence of tosylate of X, using appropriate metal-catalyzed C-C cross-coupling reaction conditions, (hetero)arylation can be carried out to obtain the compound of formula A-3 as described in WO2011087712, WO2004087156 and further documents cited therein. Further, the compound of formula A-1 can undergo a metal-catalyzed C-S coupling reaction in the presence of a mercaptoester to obtain a sulfide of formula A-7a (Route-C) as described in the general protocol above (wherein R represents an alkyl group). By further devising a base-mediated retro-Michael reaction and subjecting it to various S-alkylations using appropriate alkyl halides, in-situ metal sulfides can be generated to obtain various A-3 sulfides as described in J. Med. Chem. 2020, 63, 2308-2324 and the documents cited herein. Unless otherwise specified, the definitions of each variable are as defined above. X represents a leaving group such as halogen, triflate, mesylate or tosylate.

[0213]

Chemical formula

[0214] According to Scheme 10, the present invention provides a method for selective C-H functionalization at R of the central pyrazole ring of formula A-1. Here, the same R 8 represents hydrogen, and all other variables have their usual meanings. In the presence of N-chlorosuccinimide (NCS), A-1 can selectively undergo chlorination at R in the central pyrazole ring to form the compound of formula A-1. Here, pyrazole-R 8 represents Cl. Further, the same R of A-1 8 8 represents Cl. Further, the same R of A-1 8Hydrogen can also be alkylated in two consecutive steps. First, perform a similar R8 iodination in the presence of N-iodosuccinimide, and then carry out a metal-catalyzed Suzuki coupling reaction in the presence of various alkylboronic acids represented by the formula R8B(OH)2 to form the compound of formula A-1. Here, pyrazole-R8 represents different alkyl groups (For a comprehensive overview of C-H functionalization in IndazoleR8, see Org. Biomol. Chem., 2022, 20, 7746).

[0215]

Chemical formula

[0216] In a further embodiment according to Scheme 11, the present invention provides a process for preparing a compound of formula A-2, wherein all substituents are as defined above. A compound of formula A-1 (wherein A1, A2, A3, A4, A5, R3, R8 and R8a have the normal meanings defined above and LG represents a leaving group, preferably a halogen) can be converted to a carboxylic acid of formula A-2 according to the procedures described in WO2016144351 and further documents cited therein. The metal hexacarbonyl acting as the "CO source" in this reaction is selected from, but not limited to, molybdenum hexacarbonyl and tungsten hexacarbonyl. The reaction is carried out in the presence of bases such as metal hydrides such as sodium hydride, lithium hydride and potassium hydride, metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; organic amine bases such as triethylamine, N,N-diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene; and organic amines such as N,N-diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, although not limited to these. Catalysts that can be used in this reaction include, but are not limited to, organic palladium complexes such as polymer-supported bis(acetato)triphenylphosphine palladium(II), trans-di-μ-acetatobis[2-[bis(2-methylphenyl)phosphino]benzyl]dipalladium, and polymer-supported di(acetato)dicyclohexylphosphine palladium(II). Examples of ligands that can be used in this reaction are selected from, but not limited to, tritert-butylphosphonium tetrafluoroborate. This reaction is typically carried out in the temperature range of 0 to 200 °C, preferably 50 to 180 °C, for 30 minutes to 24 hours. This reaction can also optionally be carried out under microwave irradiation conditions.

[0217]

Chemical formula

[0218] According to Scheme 12, the present invention provides a method for preparing a compound of formula A-1 from a substituted benzaldehyde of formula E-1, where A1, A2, A 3、 R 8および R 8a are as described above. LG and LG 1 represent leaving groups, preferably halogen substituents. The appropriately substituted benzaldehyde of formula E-1 can undergo a nucleophilic substitution reaction either at room temperature or at a high temperature in the presence of a nucleophilic organic or inorganic azide to obtain an aryl azide of formula C-1. The aryl azide having formula C-1 can further react with a heteroaryl amine of formula B-1, where A4, A5 and R3 are as described above, and perform an in situ cyclization at a high temperature to form an imine intermediate that gives the desired bicyclic product of formula A-1 (see, for example, WO2016144351). However, depending on the nature of the substrate, such a high-temperature in situ cyclization method may pose further problems. To avoid this, a low-temperature Cu / ligand-mediated method for cyclizing C-2 can be implemented as described in Chem. Commun., 2011, 47, 10133 - 10135 and the references cited therein (Step 3).

[0219]

Chemical formula

[0220] Alternatively, the compound of formula A-1 can be prepared as described in Scheme 13. A substituted benzaldehyde of formula E-1 (wherein A1, A 2、 A 3、 R 8および R 8a are as described above, and LG and LG 1 represent leaving groups, preferably halogen substituents) is reacted with a heteroaryl amine of formula B-1 (wherein A4, A5 and R 3is reacted with either at room temperature or at elevated temperature as described above to produce an imine of Formula C-3. The imine of Formula C-3 can undergo an initial intermolecular substitution reaction and subsequently an intramolecular cyclization reaction in the presence of a nucleophilic organic or inorganic azide, either at room temperature or at elevated temperature, to produce a bicyclic product of Formula A-1 (see, for example, WO2016144351).

[0221] [Chemical Formula]

[0222] Alternatively, the compound of Formula A-1 can be prepared as described in Scheme 14. A suitably substituted 2-nitrobenzaldehyde of Formula E-2 (wherein A1, A 2、 A 3、 R 8および R 8a is as described above) can be reacted with a heterocyclic amine of Formula B-1 (wherein A4, A5 and R 3 is as described above) to produce imine C-4. Thus, in the presence of a suitable phosphorus(III) reagent, such as triethyl phosphite, a bicyclic compound of Formula A-1 (see, for example, US2019029788) can be obtained by reductive cyclization in a second reaction step at elevated temperature. Several alternative reductive cyclization methods are available and can be carried out as shown in Org. Lett. 2014, 16, 3114-3117 and the references cited therein. In one embodiment, the present invention provides a method for the preparation of a compound of Formula (I) (wherein D is D1 or D3), comprising the following steps: i Reacting a compound of Formula (A-1) with a compound of Formula (D 1-1 ) or (D 3-1 ) to obtain a compound of Formula (I) (wherein Z is a direct bond); [Chemical Formula] or i Reacting a compound of Formula (A-2) with a compound of Formula (D 1-1) or a compound of formula (D 3-1 ) to react with a compound to obtain a compound of formula (I) (wherein Z is a -C(=O)- bond);

Chemical formula

[0223] i React a compound of formula (A-1) with a compound of formula R 6 SH to obtain a compound of formula (A-3) (wherein Z is a direct bond);

Chemical formula

Chemical formula

[0224] In one embodiment, the present invention provides a method for producing a compound of formula (I) wherein D is D2. Step ii can be carried out in a single step as described below. ii Convert the compound of formula (A-3) to a compound of formula (I) by O- and NH-transfer using a suitable oxidizing agent and N source,

Chemical formula

[0225] In one embodiment, the present invention provides a method for producing a compound of formula (I) (wherein D is D2), and step ii can be carried out in two steps as described below. ii Oxidize the compound of formula (A-3) using a suitable oxidizing reagent to obtain a compound of formula (A-4). This compound is further converted to a compound of formula (I) by imination using a suitable N source or imination reagent.

Chemical formula

Chemical formula

[0226] Here, LG represents a leaving group, and A1, A2, A3, A4, A5, R 3 , R 6 , R 7、 R 8および R 8a are the same as those described in claim 1. Suitable oxidizing agents in step (ii) are: H2O2; H2O2, FeCl3 (catalyst); H2O2, molybdenum(VI) oxide cerium(IV) oxide (catalyst); H2O2, trifluoromethanesulfonic acid, sodium tungstate (Na2WO4); m-chloroperbenzoic acid; sodium periodate; phenyl(III) iodide diacetate (PIDA); hydrochloric acid or acetic acid, hydrogen peroxide; peracetic acid; triphenylmethyl hydroperoxide, catalyst: bis(acetylacetonato) dioxomolybdenum; H2O2, tetraphenylphosphonium bromide (PB-7-23-111’1’2)-diaquaoxodiperoxomolybdenum 1H-imidazolium, 1,3-bis[(1S)-1-carboxy-2-methylpropyl]-, inner salt; 2-(1-hydroperoxy-1-methylethyl)furan, catalyst: diethyl tartrate, titanium isopropoxide; H2O2, catalyst: tantalum pentachloride; tert-butyl hydroperoxide; oxygen, catalyst: nitrogen dioxide; oxygen, catalyst: nitrosyl tetrafluoroborate; tert-butyl hypochlorite; chlorotrimethylsilane, H2O2; tetrabutylammonium nitrate, catalyst: cupric nitrate, tetracarbonylbis(triphenylphosphine)molybdenum; or H2O2, zirconium chloride (ZrCl4).

[0227] Suitable N sources or imination reagents for step ii are selected from the following. Ammonium carbamate; sodium azide, sodium bicarbonate, [Chemical formula] ; FeSO4, phenanthroline and MeCN (0.4 mL); sodium azide, concentrated H2SO4; trifluoroacetamide, MgO, Rh2(OAc)4, PhI(OAc)2; (O-(mesitylsulfonyl)hydroxylamine); Ph-I=N-Ts (Ts = toluenesulfonyl); Ph-I=N-Ns (Ns = N-alkylnitrobenzenesulfonamide); Ph-I=N-Ses (2-(trimethylsilyl)ethanesulfonyl); or Rh2(esp)2 and O-(2,4-dinitrophenyl)hydroxylamine.

[0228] In one embodiment, the oxidizing agent and the N source or iminoating reagent can be used either in one pot or individually in a stepwise reaction. In one embodiment, the oxidizing agent and the N source or iminoating reagent can be used individually or in combination thereof. Without further elaboration, it is believed that one skilled in the art, using the preceding description, can utilize the present invention to its fullest extent.

[0229] Chemical experimental examples: The following experimental examples illustrate methods and processes for producing the compounds of the present invention without limiting the present invention, and include the best mode contemplated by the inventors for practicing the present invention.

[0230] Experimental procedures: Example 1: Synthesis of isopropyl ((2-(pyrimidin-5-yl)-2H-indazol-5-yl)imino)(3,3,3-trifluoropropyl)-λ 6 -sulfanone 101

Chemical formula

[0231] Table 1: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 1. Note: For certain substrates, better results were observed when cesium carbonate (Cs2CO 3) or tribasic potassium phosphate (K3PO 4) was used.

Table 1-1

Table 1-2

Table 1-3

Table 1-4

Table 1-5

Table 1-6

Table 1-7

Table 1-8

Table 1-9

Table 1-10

Table 1-11

Table 1-12

Table 1-13

Table 1-14

Table 1-15

Table 1-16

Table 1-17

Table 1-18

Table 1-19

Table 1-20

Table 1-21

Table 1-22

Table 1-23

Table 1-24

Table 1-25

Table 1-26

Table 1-27

Table 1-28

Table 1-29

Table 1-30

Table 1-31

Table 1-32

Table 1-33

Table 1-34

Table 1-35

Table 1-36

Table 1-37

Table 1-38

Table 1-39

[0232] Example 2: Synthesis of N-(dimethyl(oxo)-λ 6 -sulfanelylidene)-2-(pyridin-3-yl)-2H-indazole-4-carboxamide 92

Chemical formula

[0233] Table 2: Representative compounds of the present disclosure were prepared according to the method described in Example 2.

Table 2

[0234] Example 3: N-(ethyl(isopropyl)(oxo)-λ6 Synthesis of N-(ethyl(isopropyl)(oxo)-λ-sulfanediylidene)-2-(pyridin-3-yl)-2H-indazole-5-carboxamide 105 [Chemical formula] A solution of 2-(pyridin-3-yl)-2H-indazole-5-carboxylic acid (0.1 g, 0.418 mmol) and ethyl(imino)(isopropyl)-λ-sulfanone (0.057 g, 0.418 mmol) in dimethylformamide (DMF) (2 mL) was treated with 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU) (0.159 g, 0.418 mmol) and N-ethyl-N-(propan-2-yl)propan-2-amine (DIPEA) (0.110 mL, 0.627 mmol), and stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was quenched by adding water (5 mL) and extracted with ethyl acetate (2 × 25 mL). The combined organic layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure to give an oily residue. This residue was purified by CombiFlash® chromatography (normal phase; isocratic elution with 100% ethyl acetate) to afford the desired N-(ethyl(isopropyl)(oxo)-λ-sulfanediylidene)-2-(pyridin-3-yl)-2H-indazole-5-carboxamide 105 (80 mg, 0.224 mmol, 53.7% yield). 6 -sulfanediylidene)-2-(pyridin-3-yl)-2H-indazole-5-carboxamide 105(80mg, 0.224mmol, yield 53.7%) was obtained. 6 -sulfanediylidene)-2-(pyridin-3-yl)-2H-indazole-5-carboxamide 105(80mg, 0.224mmol, yield 53.7%) was obtained.

[0235] Table 3: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 3. [Table 3]

[0236] Example 4: Synthesis of N,N4-trimethyl-N'-(2-(pyridin-3-yl)-2H-indazol-5-yl)benzenesulfonimidamide 93 [Chemical formula] A solution of 5-bromo-2-(pyridin-3-yl)-2H-indazole (0.27 g, 0.985 mmol) and N,N,N-trimethylbenzenesulfonimidamide (0.195 g, 0.985 mmol) in toluene (5 mL) was treated with tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba) 3) (0.045 g, 0.049 mmol), (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) (Xantphos) (0.057 g, 0.098 mmol) and sodium tert-butoxide (0.095 g, 0.985 mmol), and irradiated with microwave (MW) at 120 °C for 1 hour. After completion of the reaction, the reaction mixture was quenched by adding water (10 mL) and extracted with ethyl acetate (2 × 25 mL). The combined organic layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain an oily residue. This residue was purified by CombiFlash® chromatography to obtain N,N,N-trimethyl-N'-(2-(pyridin-3-yl)-2H-indazol-5-yl)benzenesulfonimidamide 93 (133 mg, 0.340 mmol, yield 34.5%).

[0237] Table 4: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 4.

Table 4

[0238] Example 5: Synthesis of 5-methoxy-4-methyl-2-(2-(pyridin-3-yl)-2H-indazol-5-yl)-2,4-dihydro-3H-1,2,4-triazol-3-one 110

Chem.

[0239] Table 5: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 5.

Table 5-1

Table 5-2

[0240] Example 6: Synthesis of 4-ethyl-2-(2-(5-fluoropyridin-3-yl)-2H-indazol-4-yl)-5-methoxy-2,4-dihydro-3H-1,2, 4-triazol-3-one 130

Chemical formula

[0241] Table 6: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 6. [Table 6-1] [Table 6-2] [Table 6-3] [Table 6-4] [Table 6-5] [Table 6-6] [Table 6-7] [Table 6-8] [Table 6-9]

[0242] Example 7: Synthesis of (Cyclopropylmethyl)(imino)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 -sulfanone 450 [Chemical Structure] Step 1: Synthesis of 5-((cyclopropylmethyl)thio)-2-(pyrimidin-5-yl)-2H-indazole To a stirred solution of 5-bromo-2-(pyrimidin-5-yl)-2H-indazole (15 g, 54.5 mmol) in toluene (200 mL) under a N2 atmosphere were added Xantphos (9.46 g, 16.36 mmol) and sodium tert-butoxide (10.48 g, 109 mmol), and the reaction mixture was degassed with nitrogen for 15 minutes. Tris(dibenzylideneacetone)dipalladium (9.99 g, 10.90 mmol) and cyclopropylmethanethiol (5.77 mL, 65.4 mmol) were added, and the resulting mixture was heated at 110 °C for 18 hours. After completion of the reaction, the mixture was filtered through celite and washed with ethyl acetate. The filtrate was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude semi-solid. Purification by CombiFlash® chromatography gave 5-((cyclopropylmethyl)thio)-2-(pyrimidin-5-yl)-2H-indazole (15 g, 53.1 mmol, 97% yield). Step 2: Synthesis of (Cyclopropylmethyl)(imino)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 -sulfanone 450 To a stirred solution of 5-((cyclopropylmethyl)thio)-2-(pyrimidin-5-yl)-2H-indazole (15 g, 53.1 mmol) in methanol (230 mL) was added ammonium carbamate (18.66 g, 239 mmol) at 0 °C. The reaction mixture was brought to room temperature (2 (5 °C) and stirred at this temperature for 1 hour. The reaction mixture was cooled again to 0° 0 °C, and (diacetoxyiodo)benzene (PIDA, 37.6 g, 117 mmol) was added. The resulting solution was stirred at 25 °C for 16 hours. After completion of the reaction, methanol was concentrated under reduced pressure, and the crude residue was diluted with a minimum amount of water (1×50 mL). This solution was further acidified with concentrated hydrochloric acid (pH = 1 - 2), and the aqueous layer was extracted with ethyl acetate (3×200 mL) to remove residual nonpolar organic impurities. The aqueous layer was basified with sodium bicarbonate solution (pH = 8) and extracted with chloroform (3×250 mL). The combined organic layers were further washed with brine solution (1×250 mL), dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude solid. This crude solid was further triturated with methyl tert-butyl ether to obtain (cyclopropylmethyl)(imino)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 -sulfanone 450 (10 g, 31.9 mmol, 60% yield).

[0243] Table 7: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 7.

Table 7-1

Table 7-2

[0244] Example 8: Synthesis of (cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 -sulfanone 468

Chemical formula

[0245] Step 1: Synthesis of methyl 3-((2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)thio)propanoate To a degassed solution of 5-bromo-2-(5-fluoropyridin-3-yl)-2H-indazole (10 g, 34.2 mmol) in toluene (150 mL) were added Xantphos (9.90 g, 17.12 mmol), N,N-diisopropylethylamine (11.93 mL, 68.5 mmol), tris(dibenzylideneacetone)dipalladium (9.40 g, 10.27 mmol), and methyl 3-mercaptopropanoate (4.55 mL, 41.1 mmol) under a N2 atmosphere, and the resulting reaction mixture was heated at 110 °C for 16 h. After completion of the reaction, the mixture was cooled to room temperature, filtered through celite, and washed with ethyl acetate. The filtrate was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude residue, which was purified by CombiFlash® chromatography to give the desired methyl 3-((2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)thio)propanoate (10 g, 30.2 mmol, 88% yield) as a pale yellow solid.

[0246] Step 2: Synthesis of 5-((cyclobutylmethyl)thio)-2-(5-fluoropyridin-3-yl)-2H-indazole Methyl 3-((2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)thio)propanoate (4 g, 12.07 mmol) was added to a stirred solution of sodium hydride (60% dispersed in mineral oil, 0.966 g, 24.14 mmol) in N,N-dimethylformamide (20 mL) at 0 °C and stirred for 0.5 h. Then, (bromomethyl)cyclobutane (2.71 mL, 24.14 mmol) was added at the same temperature, and the resulting reaction mixture was stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was quenched with water (100 mL) and extracted with ethyl acetate (3×100 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the crude compound 5-((cyclobutylmethyl)thio)-2-(5-fluoropyridin-3-yl)-2H-indazole (3.5 g, 11.17 mmol, 93% yield). This was used directly in the next step.

[0247] Step 3: Synthesis of (cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 -sulfanone 468 To a stirred solution of 5-((cyclobutylmethyl)thio)-2-(5-fluoropyridin-3-yl)-2H-indazole (3.78 g, 12.06 mmol) in methanol (50 mL) was added ammonium carbamate (4.24 g, 54.3 mmol) at 0 °C, and the mixture was stirred at 25 °C for 0.5 h. Iodobenzene diacetate (8.55 g, 26.5 mmol) was added portionwise at 0 °C, and the mixture was stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, neutralized with sodium hydrogen carbonate, and extracted with dichloromethane (3×50 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude solid. The crude compound was purified by CombiFlash® chromatography to obtain (cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 -sulfanone 468 (2.3 g, 6.68 mmol, 55% yield).

[0248] Table 8: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 8. [Table 8-1] [Table 8-2] [Table 8-3] [Table 8-4]

[0249] Example 9: Synthesis of (cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)((6-(trifluoromethyl)pyrazin-2-yl)imino)-λ 6 -sulfanone 473 [Chemical formula] (cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 -sulfanone (300 mg, 0.871 mmol) in a degassed solution of toluene (10 mL) was added sodium tert-butoxide (184 mg, 1.916 mmol), Xantphos (252 mg, 0.436 mmol), 2-chloro-6-(trifluoromethyl)pyrazine (0.159 mL, 1.307 mmol) and tris(dibenzylideneacetone) dipalladium (239 mg, 0.261 mmol), and the resulting reaction mixture was stirred under reflux conditions for 16 hours. After completion of the reaction, the reaction mixture was filtered through Celite and washed with additional volumes of ethyl acetate (3X10 mL). The combined supernatant was concentrated under reduced pressure to give a crude residue, which was purified by preparative HPLC to give the desired (cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)((6-(trifluoromethyl)pyrazine-2-yl)imino)-λ 6- Sulfanone 473 (130 mg, 0.265 mmol, yield 30.4%) was obtained.

[0250] Table 9: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 9. [Table 9-1] [Table 9-2]

[0251] Example 10: Synthesis of N-((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(oxo)-λ 6 - sulfanelylidene)acetamide 472 [Chemical formula] To a stirred solution of (cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 - sulfanone (250 mg, 0.726 mmol) in dichloromethane (6 mL) was added pyridine (0.088 mL, 1.089 mmol), and the resulting reaction mixture was stirred for 10 minutes. The reaction mixture was 0° cooled to C, and acetyl chloride (0.057 mL, 0.798 mmol) was added to the reaction mixture stirred at 25 °C for 16 hours. After completion of the reaction, the reaction mixture was poured into water (10 mL), and the aqueous layer was extracted with dichloromethane (3 X 20 mL). The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude solid. The crude compound was purified by preparative HPLC to obtain the desired N-((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(oxo)-λ 6 - sulfanelylidene)acetamide 472 (110 mg, 0.285 mmol, yield 39.2%).

[0252] Table 10: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 10. [Table 10-1] [Table 10-2] [Table 10-3] [Table 10-4] [Table 10-5] [Table 10-6] [Table 10-7] [Table 10-8] For fluorinated acyl analogs, the corresponding acid anhydrides were used.

[0253] Example 11: Synthesis of N-((Cyclopropylmethyl)(oxo)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 -sulfanediyl)-3,3-difluorocyclobutane-1-carboxamide 429 [Chemical formula] (Cyclopropylmethyl)(imino)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ in N,N-dimethylformamide (3 mL) 6- To a stirred solution of sulfanone (250 mg, 0.798 mmol), 3,3-difluorocyclobutane-1-carboxylic acid (130 mg, 0.957 mmol) and 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (455 mg, 1.197 mmol) were added at 25 °C. Next, N,N-diisopropylethylamine (0.278 mL, 1.596 mmol) was added and the resulting mixture was stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was quenched by adding water (10 mL), extracted with ethyl acetate (3 X 25 mL), and washed with brine (1 X 25 mL). The organic layer was further dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude gum. The crude compound was purified by preparative HPLC to give the desired N-((cyclopropylmethyl)(oxo)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 - sulfanelylidene)-3,3-difluorocyclobutane-1-carboxamide 429 (88 mg, 0.204 mmol, 26% yield).

[0254] Table 11: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 11. [Table 11-1] [Table 11-2] [Table 11-3] [Table 11-4] [Table 11-5]

[0255] Example 12: (2-(5-Fluoropyridin-3-yl)-2H-indazol-5-yl)(isopropyl)(methylimino)-λ 6-Sulfanone 407 Synthesis

Chem.

[0256] Table 12: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 12.

Table 12-1

Table 12-2

[0257] Example 13: (Cyclobutylmethyl)(ethylimino)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)-λ 6 -Sulfanone 471 Synthesis

Chem.

[0258] Table 13: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 13.

Table 13-1

Table 13-2

Table 13-3

Table 13-4

Table 13-5

[0259] Example 14 Synthesis of N-(isopropyl(oxo)(2-(pyridin-3-yl)-2H-indazol-5-yl)-λ 6 -sulfanenediamide 392

Chem.

[0260] Table 14: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 14.

Table 14

[0261] Example 15: ((2,2-Difluoroethyl)imino)(isopropyl)(2-(pyridin-3-yl)-2H-indazol-4-yl)-λ 6 -sulfanone 424 synthesis

Chem.

[0262] Table 15: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 15.

Table 15

[0263] Compounds of formula A-1, A-2 or A-3 are synthesized according to general formula 6-14 described in the specification. In particular, compounds of formula A-1 (wherein A1, A2 and A3 represent C) are synthesized according to the procedure described in WO201614435, and compounds of formula A-1 (wherein one of A1, A2 and A3 represents N) are synthesized according to the procedure described below. Reaction scheme: Example - 16:

Chemical formula

Chemical formula

[0264] 5-Bromo-2-(pyridin-3-yl)-2H-pyrazolo[4,3-b]pyridine:

Chem.

[0265] As described herein, the compounds of formula (I) exhibit insecticidal activity against a number of insects attacking important crops. The activity of the compounds of the present invention was evaluated in the following tests: Biological Example: Example A: Bemisia tabaci For the test, the leaf immersion method was used. The required amount of the compound was weighed and dissolved in a tube containing a solvent solution. The tube was placed in a vortex at 2000 rpm to mix properly and diluted to the test concentration with a 0.01% Triton-X solution. The leaves of Brassica were immersed in the compound solution for 10 seconds. After air-drying in the shade for 20 minutes, with the abaxial side of the leaf facing up, they were placed in 4 ml of solidified 1% agar solution in the cap of each container. A known number of newly emerged adult Bemisia tabaci were collected using an improved aspirator and released into a perforated container with the cap containing the treated leaves. The containers were placed in a plant growth chamber at a temperature of 2 5° °C and a relative humidity of 70%. Observations of dead adults, dying adults, and living adults were recorded 72 hours after release. The mortality rate was calculated by combining dead adults and dying adults, and the results were compared with those of the untreated control. Compounds 1, 9, 11, 18, 25, 28, 29, 30, 31, 32, 33, 34, 38, 43, 48, 65, 66, 68, 71, 72, 73, 74, 77, 78, 79, 86, 87, 93, 101, 104, 108, 109, 110, 116, 119, 122, 123, 124, 126, 135, 184, 186, 193, 213, 214, 215, 216, 218, 219, 220, 221, 222, 223, 224, 226, 227, 228, 231, 236, 237, 238, 239, 240, 241, 248, 249, 250, 254, 255, 278, 287, 288, 289, 290, 291, 292, 293, 294, 296, 306, 307, 308, 309, 310, 311, 312, 313, 314, 337, 354, 355, 358, 368, 369, 383, 385, 386, 387, 389, 391, 397, 406, 408, 410, 418, 419, 421, 446, 447, 450, 455, 457, 458, 461, 462, 463, 465, 466, 467, 470, 474, 475, 478, 479, 480, 482, 554, 557, 561 and 580 showed a mortality rate of 70% or more at 300 ppm.

[0266] Example B: Myzus persicae The leaf dip method was used for the test. The required amount of the compound was weighed and dissolved in a tube containing a solvent solution. The tube was placed in a vortex at 2000 rpm to mix properly and diluted to the desired test concentration with a 0.01% Triton-X solution. The leaves of Capsicum annuum were immersed in the compound solution for 10 seconds, air-dried for 20 minutes, and then placed with the abaxial side up in a single cell of a bioassay tray containing 4 ml of solidified 1% agar solution. A known number of Popillia japonica larvae collected in a petri dish were released into the cells together with the treated leaves and covered with a perforated lid to enhance air permeability. The trays were stored in a plant growth chamber at a temperature of 2 5° °C and a relative humidity of 70%. Observations of dead, dying, and surviving larvae were recorded 72 hours after release. The mortality rate was calculated by combining dead and dying larvae and compared with the untreated control. Compounds 1, 2, 3, 25, 28, 29, 32, 41, 64, 70, 71, 73, 88, 89, 90, 92, 99, 102, 110, 112, 119, 123, 124, 136, 137, 138, 146, 147, 148, 156, 168, 180, 193, 216, 217, 218, 224, 236, 237, 238, 239, 240, 248, 249, 250, 254, 255, 256, 287, 288, 290, 291, 306, 312, 314, 337, 354, 383, 386, 387, 388, 389, 390, 397, 406, 419, 455, 456, 457, 458, 460, 461, 478, 479, 480, 482, 483, 484, 485, 486, 487, 488, 490, 491, 492, 557, 558, 560, 564, 567, 569 and 581 showed a mortality rate of 70% or more at 300 ppm.

[0267] Example C: Nilaparvata lugens The seedling immersion method was used for the test. The required amount of the compound was weighed and dissolved in a test tube containing a solvent solution. After applying a vortex at 2000 rpm to the test tube to mix properly, it was diluted to the test concentration with a 0.01% Triton-X solution. Paddy field seedlings were immersed in the compound solution for 10 seconds, air-dried for 20 minutes, and then the seedlings were placed in a glass test tube with the roots kept in water. Fifteen third-instar larvae of Nilaparvata lugens were released into each test tube, and the test tubes were placed at a temperature of 2 5°C. It was stored in a plant growth chamber with a relative humidity of 75%. The observations of dead, dying, and surviving larvae were recorded 72 hours after release. The mortality rate was calculated by combining the dead and dying larvae, and the results were compared with those of the untreated control. Compounds 1 23 4 5 7 8 9 11 12 13 14 16 19 20 21 23 26 27 28 29 30 32 33 38 41 42 51 64 71 72 73 78 86 87 92 93 104 105 111 112 113 114 115 125 126 127 137 146 147 148 152 153 155 181 193 194 202 206 236 238 240 331 337 343 347 354 355 356 357 358 359 360 367 385 386 387 388 389 391 392 394 396 397 402 406 417 419 446 447 450 454 457 461 462 464 470 471 474 and 475 recorded a mortality rate of over 70% at 300 ppm.

[0268] The invention has been described with reference to certain preferred embodiments, but other embodiments will be apparent to those skilled in the art upon examination of the specification.

Claims

1. Compound of formula (I), 【Chemistry 1】 During the ceremony, Z is selected from direct bonds or -C (=O)-; D is D １ , D ２ and D ３ Selected from the group consisting of, 【Chemistry 2】 ； Y is O or NR ７ Represents; A １ A ２、 and A ３ is independently C or N; A ４ and A ５ are independently C or N, but both A ４ and A ５ cannot both be N at the same time; R １ C １ -C ６ Alkyl, C ２ -C ６ Alkenil, C ２ -C ６ Alkinyl, C １ -C ６ Haloalkyl, C ３ -C ８ Cycloalkyl, C ３ -C ８ Cycloalkyl-C １ -C ６ Alkyl, phenyl, benzyl, phenylethyl and C ２ -C ６ Selected from a group consisting of heterocyclines; R ２ C １ -C ６ Alkyl, C ２ -C ６ Alkenil, C ２ -C ６ Alkinyl, C １ -C ６ Haloalkyl and C ３ -C ８ Cycloalkyl-C １ -C ６ Selected from the group consisting of alkyl groups; R ３ These are hydrogen, halogen, cyano, and C １－ C ６ Alkyl, C ２ -C ６ Alkenil, C ２ -C ６ Alkinyl, C ３ -C ６ Cycloalkyl, C １ -C ６ Alkoxy, and C １ -C ６ Selected from the group consisting of haloalkyls; R ４ C １ -C ６ Alkyl, C ２ -C ６ Alkenil, C ２ -C ６ Alkinyl, C １ -C ６ Haloalkyl, C ２ -C ６ Haloalkenil, C ３ -C ８ Cycloalkyl, C ３ -C ８ Cycloalkyl-C １ -C ６ Alkyl and -NR ｃ R ｄ Selected from the group consisting of; R ｃ is hydrogen, C １ -C ６ Alkyl, C １ -C ６ Haloalkyl and C ３ -C ８ Selected from the group consisting of cycloalkyl groups; R ｄ is selected from the group consisting of hydrogen, C １ -C ６ -alkyl, C ２ -C ６ -alkenyl, C ２ -C ６ -alkynyl, C １ -C ６ -haloalkyl, C ２ -C ６ -haloalkenyl, C ３ -C ８ -cycloalkyl, C ３ -C ６ -cycloalkyl-C １ -C ４ -alkyl; or R ｃ and R ｄ Substituents are attached to the atom they are bonded to, or to C, N, O, C(=O), C(=S), and S(O). ０－２ They may form a 3- to 6-membered ring together with further atoms selected from the group consisting of, optionally, halogens, CN, and C １ -C ６ It may be substituted with one or more substituents selected from the group consisting of alkyl groups; R ５ C １ -C ６ Alkyl, C １ -C ６ Haloalkyl, C ３ -C ８ Cycloalkyl, C ３ -C ８ Cycloalkyl-C １ -C ６ Alkyl, C ２ -C ６ Alkenil, C ２ -C ６ Haloalkenyl, phenyl, benzyl, and C ２ -C ６ Selected from a group consisting of heterocyclines; or R ４ and R ５ Substituents are attached to the atom they are bonded to, or to C, N, O, C(=O), C(=S), and S(O). ０－２ They may form a 3- to 6-membered ring together with further atoms selected from the group consisting of, optionally, halogens, CN and C １ -C ６ It may be substituted with one or more substituents selected from the group consisting of alkyl groups; R ６ C １ -C ６ Alkyl, C ２ -C ６ Alkenil, C ２ -C ６ Alkinyl, C １ -C ６ Haloalkyl, C ２ -C ６ Haloalkenil, C ３ -C ８ Cycloalkyl, C ３ -C ８ Cycloalkyl-C １ -C ６ Alkyl, phenyl, benzyl, C ２ -C ６ Heterocyclines and -NR ｃ R ｄ Selected from the group consisting of; R ７ is hydrogen, cyano, C １ -C ６ Alkyl, C ２ -C ６ Alkenil, C ２ -C ６ Alkinyl, C １ -C ６ Haloalkyl, C ２ -C ６ Haloalkenil, C １ -C ６ Alkoxy, C ３ -C ８ Cycloalkyl, C ３ -C ８ Cycloalkyl-C １ -C ６ Alkyl, phenyl, benzyl, C ２ -C ６ Heterocyclyl, C ２ -C ６ Heterocyclyl-C １ -C ６ Alkyl, -COR ５ , -CONR ｃ R ｄ SCF ３ , and -SO ２ R ５ Selected from the group consisting of; R ８ and R ８ａ These are independently hydrogen, halogen, cyano, and C １ -C ４ - Alkyl, C １ -C ４ - Selected from the group consisting of haloalkyl groups; R １ , R ２ , R ３ , R ４ , R ５ , R ６ and R ７ Each aliphatic group may have one or more R groups. ａ It may be substituted with the base; R １ , R ２ , R ３、 R ４ , R ５ , R ６ and R ７ The cyclic group of can be any one or more R ｂ It may be substituted with the base, here, R ａ These are halogen, cyano, and C １ -C ６ Alkyl, C １ -C ６ Haloalkyl, C ３ -C ８ Cycloalkyl, C １ -C ６ Alkoxy, C １ -C ６ Alkylthio, phenyl and C ２ -C ６ Selected from a group consisting of heterocyclines; R ｂ These are halogen, cyano, and C １ -C ６ Alkyl, C ２ -C ６ Alkenil, C ２ -C ６ Alkinyl, C １ -C ６ Haloalkyl, C ２ -C ６ Haloalkenil, C ３ -C ８ Cycloalkyl, C １ -C ６ Alkylthio, C １ -C ６ Haloalkylthio, C １ -C ６ Alkoxy and C １ -C ６ Selected from the group consisting of haloalkoxys; Alternatively, its salts, stereoisomers, tautomers, polymorphs, metal complexes, or N-oxides.

2. D is D １ The compound of formula (I) as described in claim 1.

3. D is D ２ The compound of formula (I) as described in claim 1.

4. D is D ３ The compound of formula (I) as described in claim 1.

5. A compound of formula (I) according to any one of claims 1 to 4, wherein Z is a direct bond.

6. D is D １ It is; Z is either a direct bond or -C (=O)-; R ３ However, hydrogen, halogen, cyano, C １ -C ６ Alkyl, C １ -C ６ Haloalkyl and CC １ -C ６ Selected from the group consisting of alkoxys; R ４ However, C １ -C ６ Alkyl, C ３ -C ８ Cycloalkyl, C ３ -C ８ Cycloalkyl-C １ -C ６ Alkyl and -NR ｃ R ｄ Selected from the group consisting of; Here, R ｃ However, hydrogen or C １ -C ６ Selected from the group consisting of alkyl groups; R ｄ However, hydrogen or C １ -C ６ Selected from the group consisting of alkyl groups; R ５ However, C １ -C ６ Alkyl, C １ -C ６ Haloalkyl, C ３ -C ８ Cycloalkyl, C ３ -C ８ Cycloalkyl-C １ -C ６ Alkyl, phenyl, benzyl, and C ２ -C ６ Selected from the group consisting of heterocyclines: or R ４ and R ５ Substituents, together with the atom to which they are bonded, or C, N, O, C(=O), C(=S), and S(O) ０－２ They may form a 4- to 6-membered ring together with further atoms selected from the group consisting of, optionally, halogens, CN, and C １ -C ６ It may be substituted with one or more alkyl groups; Here, R ４ and R ５ Each aliphatic group may optionally have one or more R ａ It may be substituted with R ４ and R ５ The cyclic group of the compound may optionally be one or more R ｂ It may be substituted with the base; R ａ However, halogen, cyano, C １ -C ６ Alkyl, C １ -C ６ Haloalkyl, C ３ -C ８ Cycloalkyl, C １ -C ６ Alkoxy, C １ -C ６ Alkylthio, phenyl, and C ２ -C ６ Selected from a group consisting of heterocyclines; R ｂ However, halogen, cyano, C １ -C ６ Alkyl, C ２ -C ６ Alkenil, C ２ -C ６ Alkinyl, C １ -C ６ Haloalkyl, C ２ -C ６ Haloalkenil, C ３ -C ８ Cycloalkyl, C １ -C ６ Alkylthio, C １ -C ６ Haloalkylthio, C １ -C ６ Alkoxy and C １ -C ６ Selected from the group consisting of haloalkoxys; R ８ and R ８ａ However, independently, hydrogen, halogen, cyano, C １ -C ４ - Alkyl, and C １ -C ４ - Selected from the group consisting of haloalkyl groups; A １ A ２ A ３ A ４ , and A ５ However, it is the same as that defined in claim 1; A compound of formula (I) as described in claim 1, or a salt, stereoisomer, tautomer, polymorph, metal complex, or N-oxide thereof.

7. D is D ２ Z is a direct bond; R ３ However, hydrogen, halogen, C １ -C ６ Alkyl, C １ -C ６ Haloalkyl and C １ -C ６ Selected from the group consisting of alkoxys; R ６ However, C １ -C ６ Alkyl, C ３ -C ８ Cycloalkyl, C ３ -C ８ Cycloalkyl-C １ -C ６ Alkyl and -NR ｃ R ｄ Selected from the group consisting of; Here, R ｃ However, hydrogen or C １ -C ６ Selected from the group consisting of alkyl groups; R ｄ However, hydrogen or C １ -C ６ Selected from the group consisting of alkyl groups; R ７ However, hydrogen, C １ -C ６ Alkyl, C １ -C ６ Haloalkyl, C ３ -C ８ Cycloalkyl, C ３ -C ８ Cycloalkyl-C １ -C ６ Alkyl, -COR ５ phenyl, benzyl, C ２ -C ６ Selected from the group consisting of heterocyclyls and cyanos; Here, R ５ However, C １ -C ６ Alkyl and C ３ -C ８ Selected from the group consisting of cycloalkyl groups; Here, R ５ , R ６ and R ７ Each aliphatic group may optionally have one or more R groups. ａ It may be substituted with R ５ , R ６ and R ７ The cyclic group of the compound may optionally consist of one or more R groups. ｂ It may be substituted with the base, R ａ However, halogen, cyano, C １ -C ６ Alkyl, C １ -C ６ Haloalkyl, C ３ -C ８ Cycloalkyl, C １ -C ６ Alkoxy, C １ -C ６ Alkylthio, phenyl and C ２ -C ６ Selected from a group consisting of heterocyclines; R ｂ However, halogen, cyano, C １ -C ６ Alkyl, C ２ -C ６ Alkenil, C ２ -C ６ Alkinyl, C １ -C ６ Haloalkyl, C ２ -C ６ Haloalkenil, C ３ -C ８ Cycloalkyl, C １ -C ６ Alkylthio, C １ -C ６ Haloalkylthio, C １ -C ６ Alkoxy and C １ -C ６ Selected from the group consisting of haloalkoxys; R ８ and R ８ａ However, independently, hydrogen, halogen, cyano, C １ -C ４ - Alkyl and C １ -C ４ - Selected from the group consisting of haloalkyl groups; A １ A ２ A ３ A ４ , and A ５ However, it is the same as that defined in claim 1; A compound of formula (I) as described in claim 1, or a salt, stereoisomer, tautomer, polymorph, metal complex, or N-oxide thereof.

8. D is D ３ Z is a direct bond; R １ However, C １ -C ６ Alkyl, C ２ -C ６ Alkenil, C ２ -C ６ Alkinyl, C １ -C ６ Haloalkyl, C ３ -C ６ Cycloalkyl, C ３ -C ６ Cycloalkyl-C １ -C ６ Alkyl, phenyl, benzyl, phenylethyl and C ２ -C ６ Selected from heterocyclines; Here, R １ Each aliphatic group may optionally have one or more R groups. ａ It may be substituted with R １ The cyclic group of the compound may optionally consist of one or more R groups. ｂ It may be substituted with the base, R ａ However, halogen, cyano, C １ -C ６ Alkyl, C １ -C ６ Haloalkyl, C ３ -C ８ Cycloalkyl, C １ -C ６ Alkoxy, C １ -C ６ Alkylthio, phenyl and C ２ -C ６ Selected from a group consisting of heterocyclines; R ｂ However, halogen, cyano, C １ -C ６ Alkyl, C ２ -C ６ Alkenil, C ２ -C ６ Alkinyl, C １ -C ６ Haloalkyl, C ２ -C ６ Haloalkenil, C ３ -C ８ Cycloalkyl, C １ -C ６ Alkylthio, C １ -C ６ Haloalkylthio, C １ -C ６ Alkoxy and C １ -C ６ Selected from the group consisting of haloalkoxys; R ２ However, C １ -C ６ It is alkyl; R ３ However, hydrogen, halogen, C １ -C ６ Alkyl, C １ -C ６ Haloalkyl and C １ -C ６ Selected from the group consisting of alkoxys; R ８ and R ８ａ These are independently hydrogen, halogen, cyano, and C １ -C ４ Alkyl and C １ -C ４ Selected from the group consisting of haloalkyls; A １ A ２ A ３ A ４ and A ５ However, it is the same as that defined in claim 1; A compound of formula (I) as described in claim 1, or a salt, stereoisomer, tautomer, polymorph, metal complex, or N-oxide thereof.

9. A １ A ２ A ３ A ４ and A ５ C is independent of A １ A ２ A ３ and A ５ C is independent of A ４ is N; or A １ A ２ A ４ and A ５ C is independent of A ３ is N; or A １ A ２ and A ５ C is independent of A ３ and A ４ N is independent of A ２ A ３ A ４ and A ５ C is independent of A １ is N; or A ２ A ３ and A ５ C is independent of A １ and A ４ A compound of formula (I) according to claim 1, wherein A is independently N; or A5 is N and A1, A2, A3 and A4 are independently C; or A2 is N and A1, A3, A4 and A5 are independently C; or A2 and A4 are independently N and A1, A3 and A5 are independently C.

10. D is D １ or D ３ A method for producing the compound of formula (I) or a salt thereof, a metal complex, a stereoisomer, a polymorph, or an N-oxide according to claim 1, comprising the following steps: i. Compound of formula (A-1) １－ 1) or (D ３－ By reacting it with compound (1), we obtain the compound of formula (I), where Z is a direct bond; 【Transformation 3】 or i. Compound of formula (A-1) １－ 1) or (D ３－ 1) is reacted with the compound of formula (I) to obtain the compound of formula (I), where Z is a -C (=O)- bond; 【Chemistry 4】 In the formula, LG represents a leaving group, and A １ A ２ A ３ A ４ A ５ , R １ , R ２ , R ３ , R ４ , R ５ , R ８ and R ８ａ The definition is the same as that defined in claim 1.

11. D is D ２ A method for producing the compound of formula (I) according to claim 1, or a salt, metal complex, stereoisomer, polymorph, or N-oxide thereof, comprising the following steps: i. Compound of formula (A-1) ６ It is reacted with a compound of SH to obtain the compound of formula (A-3), where Z is a direct bond; 【Transformation 5】 ii. The compound of formula (A-3) is converted to the compound of formula (I) by (O) and (N) rearrangement using an appropriate oxidizing agent and N source to obtain the compound of formula (I). 【Transformation 6】 Here, A １ A ２ A ３ A ４ A ５ , R ３ , R ６ , R ７ , R ８ and R ８ａ The definition is the same as that defined in claim 1.

12. A composition comprising at least one additional component selected from the group consisting of the compound of formula (I) described in claim 1, a salt thereof, a metal complex, a stereoisomer, a polymorph or N-oxide thereof, and surfactants and auxiliaries.

13. The composition according to claim 12, wherein the composition further comprises at least one biocompatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, biostimulants, antibiotics, fertilizers, or nutrients.

14. The composition according to claim 12, wherein the compound of formula (I) is present in an amount ranging from 0.1 to 99% by weight of the total weight of the composition.

15. A combination comprising a biologically effective amount of the compound of formula (I) described in claim 1 and at least one additional biocompatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, biostimulants, antibiotics, fertilizers, and nutrients.

16. A method for controlling insects and mites, comprising contacting a biologically effective amount of a compound of formula (I) described in claim 1, its salts, stereoisomers, polymorphs, metal complexes, or N-oxides with insects and mites, their habitats, breeding grounds, food sources, plants, seeds, soil, areas where insects and mites grow or are likely to grow, materials or environments, or materials, plants, seeds, soil, surfaces or spaces that are protected from pest attack or invasion.

17. The method involves contacting a crop with a compound of formula (I) as described in claim 1, its salt, stereoisomer, polymorph, metal complex, or N-oxide. Methods for protecting crops from attacks or invasions by insect and mite pests.

18. The method according to claim 16, wherein the method comprises applying an effective dose of the compound of formula (I) to an agricultural or horticultural crop in an amount ranging from 1 to 5,000 gai per hectare.

19. The method comprises contacting seeds before sowing and / or before germination with a compound of formula (I) described in claim 1, its salt, stereoisomer, polymorph, metal complex, or N-oxide. A method for protecting seeds, plants and plant parts from soil insects, as well as seedling roots and shoots from soil and leaf insects.

20. Use of the compound of formula (I) described in claim 1, or its salts, metal complexes, N-oxides, stereoisomers, and polymorphs, for the control of insect and mite pests in agricultural crops, horticultural crops, households, and vectors, as well as for the control of animal parasites.

21. The use of the compound of formula (I) according to claim 20, wherein the crop is grain, maize, sorghum, bajra, rice, soybeans, oilseeds and other legumes, fruits and fruit trees, grapes, nuts and nut trees, citrus fruits and citrus trees, any ornamental plant, cucurbits, oily plants, tobacco, coffee, tea, cocoa, sugar beets, sugarcane, cotton, potatoes, tomatoes, onions, peppers, and other vegetables and ornamental plants.

22. Seeds comprising the compound of formula (I) according to claim 1, a salt thereof, a metal complex thereof, an N-oxide, a stereoisomer, or a polymorph, wherein the amount of the compound of formula (I) in the seed is in the range of 0.0001 to 1% by weight.

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