Bicyclic compounds and their use as pest control agents

Abstract

The present invention provides novel bicyclic compounds of formula (I) wherein the definitions of A1, A2, A3, A4, A5, Z, D, R3, R8 and R8a are as described in the detailed description. It shows a high insecticidal efficiency. The invention also relates to a preparation method of the compound shown in the formula (I). The invention also relates to compositions, combinations, uses and methods of use of the compounds of formula (I). # imgabs0 #

Description

Technical Field

[0001] The present invention described herein relates to novel bicyclic compounds, and in particular, the present invention relates to compounds of formula (I), compositions containing the compounds and their use as pest control agents. Further, the present invention also relates to the preparation of these novel bicyclic compounds and their useful intermediates. Prior art

[0002] It is known from the prior art, such as PCT Patent Publication No. WO2018011111, PCT Patent Publication No. WO2016071499, PCT Patent Publication No. WO2015038503, PCT Patent Publication No. WO2016087363, PCT Patent Publication No. WO2016087368, PCT Patent Publication No. WO2016087421 and PCT Patent Publication No. WO2016087422, that specific substituted bicyclic compounds exhibit pest control properties.

[0003] The active compounds mentioned in the above prior art have disadvantages in some aspects. For example, they only show a narrow insecticidal activity spectrum, do not have a satisfactory pest control effect at a lower application rate, or do not show the desired fast-acting or long-lasting activity.

[0004] Therefore, there is a constant need for new pest control agents with enhanced insecticidal activity, wider efficacy spectrum, longer lasting activity, greater plant compatibility, greater environmental safety, better formulation performance, and lower risk of resistance development. Summary of the invention

[0005] The present invention relates to novel bicyclic compounds which are found to have advantageous effects over similar compounds reported in the literature, whether in terms of improved pest control activity, more favorable biological or environmental properties, wider application range or enhanced plant compatibility.

[0006] The novel bicyclic compounds of the present invention may also be used in combination with other biologically active compounds to enhance their efficacy, particularly against difficult to control insects.

[0007] Therefore, the present invention provides a novel bicyclic compound of formula (I),

[0008]

[0009] in,

[0010] Z is selected from a direct bond or -C(=O)-;

[0011] D is selected from the group consisting of D1, D2 and D3,

[0012]

[0013] Y represents O or NR 7 ;

[0014] A1, A2 and A3 are independently C or N;

[0015] A4 and A5 are independently C or N, provided that A4 and A5 cannot be N at the same time;

[0016] R 1 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, phenethyl and C2-C6 heterocyclyl;

[0017] R 2 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;

[0018] R 3 Selected from the group consisting of hydrogen, halogen, nitrile, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy and C1-C6 haloalkyl;

[0019] 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 ;

[0020] R c Selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C3-C8 cycloalkyl;

[0021] R d 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, C3-C6 cycloalkyl-C1-C4 alkyl;

[0022] or

[0023] R c and R dThe substituent and the atom to which it is attached or together with other atoms may form a 3-6 membered ring, wherein the other atom is selected from the group consisting of C, N, O, C(=O), C(=S) and S(O). 0-2 , the ring may be optionally substituted by one or more substituents selected from the group consisting of halogen, CN and C1-C6 alkyl;

[0024] R 5 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;

[0025] or

[0026] R 4 and R 5 The substituent and the atom to which it is attached or together with other atoms may form a 3-6 membered ring, wherein the other atom is selected from the group consisting of C, N, O, C(=O), C(=S) and S(O). 0-2 , the ring may be optionally substituted by one or more substituents selected from the group consisting of halogen, CN and C1-C6 alkyl;

[0027] 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 ;

[0028] R 7 is selected from the group consisting of: hydrogen, nitrile, 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 ;

[0029] R 8 and R 8a independently selected from the group consisting of hydrogen, halogen, nitrile, C1-C4 alkyl and C1-C4 haloalkyl;

[0030] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Each aliphatic group can be optionally replaced by R a One or more groups of R are substituted; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 The ring group may be optionally replaced by R b One or more groups of

[0031] R a Selected from the group consisting of halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl;

[0032] R b Selected from the group consisting of halogen, nitrile, 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;

[0033] or a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof.

[0034] In another embodiment, the present invention provides a composition comprising the compound of formula (I) or its salt, metal complex, stereoisomer, polymorph or N-oxide and at least one additional component selected from the group consisting of: a surfactant and an adjuvant.

[0035] In yet another embodiment, the present invention provides a composition, wherein the composition additionally comprises at least one biologically active compatible compound selected from the group consisting of fungicides, insecticides, nematicides, miticides, biopesticides, herbicides, plant growth regulators, biostimulants, antibiotics, fertilizers or nutrients.

[0036] In another embodiment, the present invention provides a method for preparing the compound of formula (I).

[0037] The present invention will be described in detail below.

[0038] Implementation

[0039] definition:

[0040] The definitions provided herein for the terms used in this specification are for illustrative purposes only and do not in any way limit the scope of the invention disclosed in this specification.

[0041] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains,” “containing,” “characterized by,” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitations expressly stated. For example, a composition, mixture, process, or method that comprises a list of elements is not necessarily limited to those elements but may include other elements not expressly listed or inherent to that composition, mixture, process, or method.

[0042] The conjunction "consisting of" excludes any unspecified components, steps, or ingredients. If it appears in a claim, it will prevent the claim from including materials other than those stated, except for impurities normally associated therewith. When the phrase "consisting of" appears in a sentence in the body of a claim, rather than immediately following the preamble, it limits only the components specified in that sentence; other components are not excluded from the claim as a whole.

[0043] The conjunction phrase "consisting essentially of" is used to define a composition or method that includes materials, steps, features, ingredients, or elements, except those disclosed herein, where these additional materials, steps, features, ingredients, or elements do not materially affect the basic and novel characteristics of the claimed invention. The term "consisting essentially of" occupies an intermediate position between "comprising" and "consisting of."

[0044] In addition, unless expressly stated to the contrary, "or" refers to an inclusive "or" rather than an exclusive "or". For example, a condition A "or" B is satisfied by any of the following situations: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and A and B are both true (or exist).

[0045] Similarly, the indefinite article "a" and "an" before the components or elements of the present invention are intended not to limit the instances (i.e., the number of occurrences) of the element or element. Therefore, "a" or "an" should be understood to include one or at least one, and the singular form of the element or element also includes the plural form, unless the number obviously refers to the singular.

[0046] As used herein, the term "invertebrate pest" or "invertebrates" includes pests such as arthropods, gastropods, and nematodes of economic importance. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, ball moles, and myriapods. The term "gastropod" includes snails, slugs, and other Stylommatophora. The term "nematode" refers to a living organism of the Phylum Nematoda. The term "helminths" includes roundworms, heartworms, herbivorous nematodes (Nematoda), flukes (Tematoda), acanthocephala (Acanthocephala), and tapeworms (Cestoda).

[0047] In the context of this specification, "invertebrate pest control" refers to the inhibition of invertebrate pest development (including mortality, reduced feeding and / or disruption of mating), and related terms are similarly defined.

[0048] The term "agronomic" refers to the production of field crops, such as for food, feed, and fiber, and includes the growing of corn, soybeans and other legumes, rice, cereals (e.g., wheat, oats, barley, rye, rice, corn), leafy vegetables (e.g., lettuce, cabbage and other cole crops), fruiting vegetables (e.g., tomatoes, peppers, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone fruit and citrus), small fruits (berries, cherries), and other specialty crops (e.g., canola, sunflower, olives).

[0049] The term "non-agronomic" refers to crops other than agricultural crops, such as horticultural crops (e.g., greenhouse, nursery, or ornamental plants not grown in the field), residential, agricultural, commercial, and industrial structures, turf (e.g., turf farms, pastures, golf courses, lawns, athletic fields, etc.), wood products, stored products, agroforestry and vegetation management, public health (i.e., humans) and animal health (e.g., domesticated animals (e.g., pets, livestock, and poultry) and non-domesticated animals (e.g., wildlife) applications.

[0050] Non-agronomic applications include protecting animals from invertebrate parasitic pests by applying a parasiticidal effective (i.e., biologically effective) amount of the disclosed compounds to the animals to be protected, usually in the form of a composition formulated for veterinary use. As mentioned in the specification and claims of this case, the terms "parasiticidal" and "parasiticidally" refer to observable effects of protecting animals from pests on invertebrate parasitic pests. Parasiticidal effects generally involve reducing the occurrence or activity of target invertebrate parasitic pests. Such effects on pests include death, growth retardation, reduced activity or reduced ability to stay in or within the host animal, reduced feeding, and inhibited reproduction. These effects on invertebrate parasitic pests provide control (including prevention, reduction, or elimination) of parasitic infections or infestations of animals.

[0051] The compounds disclosed herein may exist as pure substances or as different possible isomeric forms or as optical isomers, such as stereoisomers, for example, racemic mixtures, individual stereoisomers or mixtures of structural isomers. Various stereoisomers include mirror image isomers, non-mirror image isomers, chiral isomers, atropisomers, conformational isomers, tautomers, optical isomers, polymorphs and geometric isomers. Any desired mixture of these isomers falls within the scope of the patent application herein. It will be understood by those with ordinary knowledge in the art that when a stereoisomer is enriched relative to other isomers or when it is separated from other isomers, it may be more active and / or may exhibit beneficial effects. In addition, those with ordinary knowledge in the art know the process or method or technology for separating, concentrating and / or selectively preparing the isomers.

[0052] The definitions of various terms used in the specification will now be explained.

[0053] The term "alkyl", whether used alone or in a compound form (e.g., "alkylthio" or "haloalkyl" or -N(alkyl) or alkylcarbonylalkyl or alkylsulfonamido), includes a straight-chain or branched C1 to C12 Alkyl, preferably C1 to C8 alkyl, more preferably C1 to C6 alkyl. Representative examples of alkyl include, but are not limited to, 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 different isomers. If the alkyl is at the end of the composite substituent, such as in an alkylcycloalkyl, the starting part of the composite substituent, such as a cycloalkyl, can be monosubstituted or polysubstituted by the alkyl group identically or differently and independently. The same also applies to composite substituents in which other groups, such as alkenyl, alkynyl, hydroxyl, halogen, carbonyl, carbonyloxy, etc., are located at the end.

[0054] The term "alkenyl", whether used alone or in compound form, includes straight-chain or branched C2-C 12 Olefins, more preferably C2-C8 olefins, and most preferably C2-C6 olefins. Representative examples of olefins 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, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl and different isomers. "Alkenyl" also includes polyenes, such as 1,2-propadienyl and 2,4-hexadienyl. Unless specifically defined elsewhere, this definition also applies to alkenyl as part of a composite substituent, such as alkenyl, etc.

[0055] Non-limiting examples of alkynes 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 different isomers. Unless specifically defined elsewhere, this definition also applies to alkynyl as part of a composite substituent, such as alkynyl, etc. The term "alkynyl" may also include moieties consisting of multiple triple bonds, such as 2,5-hexadiynyl.

[0056] The term "cycloalkyl" refers to an alkyl group that is closed to form a ring. Non-limiting examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. Unless specifically defined elsewhere, this definition also applies to cycloalkyl groups that are part of a composite substituent, such as cycloalkylalkyl, etc.

[0057] The terms "cycloalkoxy", "cycloalkenyloxy" and the like are defined similarly. Non-limiting examples of cycloalkoxy include cyclopropyloxy, cyclopentyloxy and cyclohexyloxy. Unless specifically defined elsewhere, this definition also applies to cycloalkoxy as part of a composite substituent, such as cycloalkoxyalkyl, etc.

[0058] The term "halogen", whether used alone or in a compound form (e.g., "haloalkyl"), includes fluorine, chlorine, bromine, or iodine. In addition, when used in a compound form such as "haloalkyl", the alkyl group may be partially or fully substituted with halogen atoms, which may be the same or different. 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-trifluoropropan-2-yl. This definition also applies to haloalkyl as part of a composite substituent, for example haloalkylaminoalkyl etc., unless specifically defined elsewhere.

[0059] The terms "haloalkenyl" and "haloalkynyl" are defined similarly, except that the alkenyl and alkynyl groups are present as part of the substituent group rather than the alkyl group.

[0060] The term "haloalkoxy" refers to a straight or branched alkoxy group, wherein some or all of the hydrogen atoms in these groups can be replaced by the above-mentioned halogen atoms. The 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-trifluoropropane-2-oxy. Unless specifically defined elsewhere, this definition also applies to the haloalkoxy group as a part of a composite substituent, such as haloalkoxyalkyl, etc.

[0061] The term "haloalkylthio" refers to straight-chain or branched alkylthio groups in which some or all of the hydrogen atoms in these groups may be substituted by the above-mentioned halogen atoms. 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-difluoroethylthio, 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-trifluoropropyl-2-thio. Unless specifically defined elsewhere, this definition also applies to haloalkylthio as part of a composite substituent, such as haloalkylthioalkyl, etc.

[0062] The term "hydroxy" refers to -OH, amine refers to -NRR, where R can be H or any possible substituent, such as alkyl. Carbonyl refers to -C(O)-, carbonyloxy refers to -OC(O)-, sulfinyl refers to SO, and sulfonyl refers to S(O)2.

[0063] The term "alkoxy", whether used alone or in compound form, includes C1 to C 12 The alkoxy group is preferably a C1 to C8 alkoxy group, and more preferably a C1 to C6 alkoxy group. Examples of alkoxy groups 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, hexyloxy, 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 different isomers. This definition also applies to alkoxy as part of a composite substituent, for example haloalkoxy, alkynylalkoxy etc., unless defined specifically elsewhere.

[0064] The term "alkoxyalkyl" refers to an alkoxy substitution on an alkyl group. Non-limiting examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2, and CH3CH2OCH2CH2.

[0065] The term "alkylthio" includes branched or straight chain alkylthio groups, for example, methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylethylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methyl The invention also comprises different isomers thereof, including 1,1-dimethylbutylthio, 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.

[0066] The definitions of halocycloalkyl, halocycloalkenyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkoxyalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, haloalkylcarbonyl, cycloalkylcarbonyl, haloalkoxyalkyl and the like are similar to the above examples.

[0067] The definitions of "alkylamino", "dialkylamino" and the like are similar to the above examples.

[0068] The term "carbocycle" includes "aromatic carbocycle systems" and "non-aromatic carbocycle systems" or polycyclic or bicyclic (spiro, fused, bridged, non-fused) ring compounds, wherein the rings may be aromatic or non-aromatic (where aromatic means satisfying Huckel's rule, and non-aromatic means not satisfying Huckel's rule).

[0069] The term "hetero" in relation to a ring refers to a ring in which at least one ring atom is not carbon and which may contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs.

[0070] The term "heterocycle" or "heterocyclic" includes "aromatic heterocycles" or "heteroaromatic ring systems" as well as "non-aromatic heterocycle systems" or polycyclic or bicyclic (spiro, fused, bridged, non-fused) ring compounds, wherein the rings may be aromatic or non-aromatic, wherein the heterocycle contains at least one selected from N, O, S(O) 0-2 The heteroatoms and / or carbon ring members of the heterocycle may be substituted by C(═O), C(═S), C(═CR*R*) and C═NR*, where * represents an integer.

[0071] The term "non-aromatic heterocycle" or "non-aromatic heterocyclic" refers to a saturated or partially unsaturated heterocycle of three to fifteen members, preferably three to ten members, containing one to four heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur, and being monocyclic, bicyclic or tricyclic, and containing, in addition to carbon ring members, one to three nitrogen atoms and / or one oxygen atom or sulfur atom or one or two oxygen atoms and / or sulfur atoms; if more than one oxygen atom is contained, they are not directly adjacent; for example (but not limited to) oxetanyl, oxiranyl, aziridinyl, thietanyl, tetrahydrofuranyl ( tetrahydrofuranyl), tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, 1,2,4-oxadiazolidinyl, l,2,4-thiadiazolidinyl, l,2,4-triazolidinyl 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, The term "heterocyclyl" refers to a group consisting of cyclohexyl, ...

[0072] The term "heteroaryl" or "aromatic heterocyclic" refers to a five- or six-membered, fully unsaturated monocyclic ring system containing 1 to 4 heteroatoms selected from O, N and S; if the ring contains more than one oxygen atom, they are not directly adjacent; a five-membered heteroaryl containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom: a five-membered heteroaryl, in addition to carbon atoms, may also contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom as ring members. 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 (tetrazolyl); nitrogen-bonded five-membered heteroaryl containing 1 to 4 nitrogen atoms, or benzo-fused nitrogen-bonded five-membered heteroaryl containing 1 to 3 nitrogen atoms: five-membered heteroaryl, in addition to carbon atoms, may also contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms as ring members, wherein 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 radical, wherein 1 or 2 carbon atoms may be replaced by nitrogen atoms, and wherein these rings are connected to the main chain via one of the nitrogen ring members, for example, but not limited to: 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.

[0073] Six-membered heteroaryl containing 1 to 4 nitrogen atoms: In addition to carbon atoms, six-membered heteroaryl groups may contain 1 to 3 and 1 to 4 nitrogen atoms as ring members, respectively, non-limiting examples: pyridyl, 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 five-membered heteroaryl containing 1 to 3 nitrogen atoms or 1 nitrogen atom and 1 oxygen or sulfur atom: non-limiting examples are indolyl, benzimidazolyl, indazolyl, benzofuranyl ( benzofuranyl), benzothiophenyl, benzothiazolyl and benzoxazolyl; benzo-fused six-membered heteroaryl containing 1 to 3 nitrogen atoms, non-limiting examples of which include quinolinyl, isoquinolinyl, quinoxalinyl, phthalazinyl, quinazolinyl and cinnolinyl.

[0074] The term "partially / fully saturated or unsaturated heterocycles" includes partially / fully saturated heterocycles and partially / fully unsaturated heterocycles.

[0075] This definition also applies to heteroaryl as part of a composite substituent, for example heteroarylalkyl etc., unless specifically defined elsewhere.

[0076] 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 different butoxy- or pentoxycarbonyl isomers.

[0077] The term "amide" refers to A-R'C=ONR"-B, wherein R' and R" represent substituents, and A and B represent any group.

[0078] The term "thioamide" refers to A-R'C=SNR"-B, wherein R' and R" represent substituents, and A and B represent any group.

[0079] The total number of carbon atoms in a substituent is indicated by the prefix "C i -C j ” represents, wherein i and j are numbers from 1 to 18. For example, C1-C3 alkylsulfonyl represents methylsulfonyl to propylsulfonyl; C2 alkoxyalkyl represents CH3OCH2; C3 alkoxyalkyl represents, for example, CH3CH(OCH3), CH3OCH2CH2 or CH3CH2OCH2; C4 alkoxyalkyl refers to various isomers of alkyl substituted with an alkoxy group containing a total of 4 carbon atoms, examples of which include CH3CH2CH2OCH2 and CH3CH2OCH2CH2. In the above description, when the compound of formula (I) consists of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacing the hydrogen on the carbon or nitrogen.

[0080] When the compound is substituted with the following substituents, and the substituents indicate that the number of substituents may exceed 1, then the substituents (when they exceed 1) are independently selected from the defined substituent group. In addition, when (R) m Subscript in m When representing an integer ranging from, for example, 0 to 4, the number of substituents may be selected from integers between 0 and 4, inclusive.

[0081] When a group contains a substituent which may be hydrogen, then the group is considered unsubstituted when the substituent is regarded as hydrogen.

[0082] As used herein, the term "optionally substituted" is used interchangeably with the term "substituted or unsubstituted" or the term "(un)substituted". Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other. An optionally substituted group may also have no substituents. Thus, the term "optionally substituted with one or more substituents" means that the number of substituents may vary from zero to the available number of substitutions.

[0083] The term (un)substituted means that the group is unsubstituted or the group is substituted independently by the group consisting of: halogen, nitrile, 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) 0-2C1-C6 alkyl.

[0084] The term "aliphatic group", whether used alone or in compound form, includes straight-chain or branched substituents such as C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkoxy or C1-C6 haloalkoxy;

[0085] The term "cyclic groups", whether used alone or in compound form, includes fully / partially saturated or unsaturated ring substituents or groups, such as cycloalkyl, phenyl, C2-C6 heterocyclyl, etc.

[0086] The embodiments herein and their various features and advantageous details are explained with reference to the non-limiting examples in 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 intended only to facilitate an understanding of the manner in which the embodiments herein may be practiced and to further enable one of ordinary skill in the art to practice the embodiments herein. Therefore, these examples should not be construed as limiting the scope of the embodiments herein.

[0087] The description of the specific embodiments will fully reveal the general nature of the embodiments herein, and others can easily modify and / or adapt them into specific embodiments for various applications by applying existing knowledge without departing from the general concepts, and therefore, such adaptations and modifications should and are intended to be understood within the meaning and scope of the disclosed embodiments. It should be understood that the wording or terms used herein are for description and not limitation. Therefore, although the embodiments herein are described in terms of preferred embodiments, those with ordinary knowledge in the art will recognize that the embodiments herein can be implemented with modifications within the spirit and scope of the embodiments described therein.

[0088] Any discussion of documents, acts, materials, devices, articles, etc. in the specification is intended only to provide a background to the present case. It should not be taken as an admission that any or all of these matters form part of the prior art base or were common knowledge in the field relevant to the present case as it existed anywhere before the priority date of the present case.

[0089] Although the values ​​mentioned in the description and the description / claims may constitute a key part of the present invention, any deviation from these values ​​shall still fall within the scope of the present invention if the deviation follows the same scientific principles as disclosed in the present invention. If appropriate, the compounds of the present invention may exist as mixtures of different possible isomeric forms, in particular stereoisomers, such as E and Z, threo and erythro, and optical isomers. But there are also tautomers if appropriate. Any desired mixtures of E and Z isomers, threo and erythro isomers and optical isomers as well as possible tautomeric forms are disclosed and claimed. .

[0090] The term "pest" for purposes herein includes, but is not limited to, fungi, stramenopiles (oomycetes), bacteria, nematodes, mites, ticks, insects, and rodents.

[0091] The term "plant" is understood here to mean all plants and plant populations, for example desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnology and genetic engineering methods or a combination of these methods, including genetically modified plants, including plant cultivars that are protected and not protected by plant breeders' rights.

[0092] In this disclosure, the term "plant" includes living organisms such as trees, shrubs, herbs, grasses, ferns and mosses, which usually grow in one location, absorb water and necessary substances through their roots, and synthesize nutrients in their leaves by photosynthesis.

[0093] Examples of "plants" for the purposes of the present invention include, but are not limited to, crop plants (such as wheat, rye, barley, triticale, oats or rice); beets (such as sugar beets or fodder beets); fruits and fruit trees (such as pome, stone fruit or soft fruit (such as apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or currants)); leguminous plants (such as lentils, peas, alfalfa or soybeans); oil plants (such as rapeseed, mustard, olives, sunflowers, coconuts, cocoa beans, castor oil plants, oil palms, peanuts or soybeans); cucurbits (such as pumpkins, cucumbers or melons); fiber plants (such as cotton, flax, hemp or jute); citrus fruits and citrus trees (such as oranges, lemons, grapefruits or tangerines); any horticultural plant; vegetables (such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato, cucurbit or pepper); laurel (such as avocado, cinnamon or camphor); cucurbits; oil plants; energy and raw material plants (such as cereals, corn, soybeans, other legumes, rapeseed, sugar cane or oil palm); tobacco; nuts; coffee; tea; cocoa; bananas; peppers; grapevines (table grapes and grapevines for juice); hops; turf; sweet leaf (also known as stevia); natural rubber plants or ornamental and forestry plants (such as flowers, shrubs, broad-leaved trees or evergreen plants (such as conifers)); and plant propagation material (such as seeds) and crop material of these plants.

[0094] Preferably, plants used for the purpose of the present invention include, but are not limited to, cereals, corn, rice, soybeans and other legumes, fruits and fruit trees, grapes, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbits, oil plants, tobacco, coffee, tea, cocoa, sugar beets, sugar cane, cotton, potatoes, tomatoes, onions, peppers and vegetables, ornamental plants, any flowering plants and other plants used by humans and animals.

[0095] The term "plant parts" is understood to mean all parts and organs of plants above and below ground. For the purposes of this disclosure, the term plant parts includes, but is not limited to, cuttings, leaves, branches, tubers, flowers, seeds, branches, roots (including taproots, lateral roots, root hairs, root tips, root caps, rhizomes), branches, shoots, fruits, fruiting bodies, bark, stems, buds, auxiliary buds, meristems, nodes, and internodes.

[0096] The term "locus thereof" includes the soil, the surroundings of the plants or plant parts and equipment or tools used before, during or after sowing / planting the plants or plant parts.

[0097] The compounds of the present invention or compositions of the compounds of the present invention optionally containing other compatible compounds are applied to plants or plant materials or their loci, including application by techniques known to those skilled in the art, including but not limited to spraying, coating, dipping, fumigating, impregnating, injecting and dusting.

[0098] The term "applied" means attached to plants or plant parts by physical or chemical means including impregnation.

[0099] The present invention relates to a compound as shown in formula (I),

[0100]

[0101] in,

[0102] Z is selected from a direct bond or -C(=O)-;

[0103] D is selected from the group consisting of D1, D2 and D3,

[0104]

[0105] Y represents O or NR 7 ;

[0106] A1, A2 and A3 are independently C or N;

[0107] A4 and A5 are independently C or N, provided that A4 and A5 cannot be N at the same time;

[0108] R 1 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, phenethyl and C2-C6 heterocyclyl;

[0109] R 2 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;

[0110] R 3 Selected from the group consisting of hydrogen, halogen, nitrile, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy and C1-C6 haloalkyl;

[0111] R4 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 ;

[0112] R c Selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C3-C8 cycloalkyl;

[0113] R d 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, C3-C6 cycloalkyl-C1-C4 alkyl;

[0114] or

[0115] R c and R d The substituent and the atom to which it is attached or together with other atoms may form a 3-6 membered ring, wherein the other atom is selected from the group consisting of C, N, O, C(=O), C(=S) and S(O). 0-2 , the ring may be optionally substituted by one or more substituents selected from the group consisting of halogen, CN and C1-C6 alkyl;

[0116] 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

[0117] R 4 and R 5 The substituent and the atom to which it is attached or together with other atoms may form a 3-6 membered ring, wherein the other atom is selected from the group consisting of C, N, O, C(=O), C(=S) and S(O). 0-2 , the ring may be optionally substituted by one or more substituents selected from the group consisting of halogen, CN and C1-C6 alkyl;

[0118] 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 cR d ;

[0119] R 7 is selected from the group consisting of: hydrogen, nitrile, 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 ;

[0120] R 8 and R 8a are independently selected from the group consisting of: hydrogen, halogen, nitrile, 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 can be optionally replaced by R a One or more groups of R are substituted; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 The ring group may be optionally replaced by R b One or more groups of

[0121] R a Selected from the group consisting of halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl;

[0122] R b Selected from the group consisting of halogen, nitrile, 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;

[0123] or a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof.

[0124] The following examples provide definitions of substituents of compounds of formula (I) according to the present invention, including preferred definitions. For any one of these substituents, any definition given below can be combined with any definition of any other substituent given below or elsewhere in this document.

[0125] In one embodiment, the present invention provides a compound of formula (I), wherein D is D1,

[0126] Z, Y, R 3 , R 4 and R 5 As defined above.

[0127] In another embodiment, the present invention provides a compound of formula (I), wherein D is D2,

[0128] Z is a direct key, Y, R 3 , R 6 and R 7 As defined above.

[0129] In another embodiment, the present invention provides a compound of formula (I), wherein D is D3,

[0130] Z, R 1 , R 2 and R 3 As defined above.

[0131] In one embodiment, the present invention provides a compound of formula (I), represented by a compound of formula (Ia):

[0132]

[0133] Among them, A1, A2, A3, A4, A5, Z, D, R 3 , R 8 and R 8a As defined above.

[0134] In another embodiment, the present invention provides a compound of formula (I), represented by a compound of formula (Ib):

[0135]

[0136] Among them, A3 is C; A1, A2, A4, A5, Z, D, R 3 , R 8 and R 8a As defined above.

[0137] In one embodiment, the group R of the compound of formula (1) 1 , R2 , R 3 , R 4 , R 5 , R 6 and R 7 Described as:

[0138] R 1 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 heterocyclic group; preferably C1-C6 alkyl, C3-C6 cycloalkyl, phenyl, benzyl and 4-6 membered aromatic or non-aromatic heterocyclic group.

[0139] R 2 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.

[0140] R 3 Selected from the group consisting of: hydrogen, halogen, nitrile, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy and C1-C6 haloalkyl; preferably hydrogen, halogen and nitrile; C1-C3 alkyl, C1-C3 haloalkyl and C1-C3 alkoxy; more preferably hydrogen, fluorine, chlorine, methyl, ethyl, methoxy and CF3.

[0141] R 4 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;

[0142] R c Selected from the group consisting of: hydrogen, C1-C6 alkyl, C3-C8 cycloalkyl; more preferably hydrogen or C1-C6 alkyl;

[0143] R dSelected from the group consisting of: C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, phenyl and C2-C6 heterocyclyl; preferably C1-C6 alkyl, C1-C6 haloalkyl and C3-C8 cycloalkyl; or

[0144] R c and R d The substituent and the atom to which it is attached or together with other atoms may form a 3-6 membered ring, wherein the other atom is selected from the group consisting of C, N, O, C(=O), C(=S) and S(O). 0-2 , the ring may optionally be one or more

[0145] Substituted with a substituent selected from the group consisting of halogen, CN or C1-C6 alkyl;

[0146] R 5 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;

[0147] Optionally, R 4 and R 5 The substituent and the atom to which it is attached or together with other atoms may form a 4-6 membered ring, wherein the other atom is selected from the group consisting of C, N, O, C(=O), C(=S) and S(O). 0-2 , the ring may be optionally substituted by one or more substituents selected from the group consisting of halogen, CN and C1-C6 alkyl;

[0148] R 6 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.

[0149] R 7 is selected from the group consisting of hydrogen, nitrile, 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, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C8 cycloalkyl, C2-C6 heterocyclyl and -COR5 .

[0150] R 8 and R 8a Independently selected from the group consisting of: hydrogen, halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, phenyl and C2-C6 heterocyclyl; preferably hydrogen, halogen, nitrile, C1-C6 alkyl and C1-C6 haloalkyl.

[0151] Among them, R 1 , R 2 , R 4 , R 5 , R 6 and R 7 Each aliphatic group can be optionally replaced by R a and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 The ring group may be optionally replaced by R b One or more groups of

[0152] R a Selected from the group consisting of halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl;

[0153] R b Selected from the group consisting of halogen, nitrile, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-

[0154] C6 haloalkyl, C2-C6 haloalkenyl, C3-C8 cycloalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkoxy and C1-C6 haloalkoxy.

[0155] Furthermore, the embodiments described in the present disclosure may be combined in any manner, and the description of the variables in the embodiments relates not only to the compound of formula (I) but also to the starting compound and the intermediate compound that can be used to prepare the compound of formula (I).

[0156] In this sense, embodiments that can be combined according to the present invention are as follows:

[0157] In one embodiment, the present invention provides a compound of formula (I), wherein

[0158] D is D1;

[0159] Z is a direct bond or -C(=O)-; preferably Z is a direct bond;

[0160] R 3 is selected from the group consisting of hydrogen, halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl and C1-C6 alkoxy; R 4 Selected from the group consisting of C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl and -NR c R d ;

[0161] Among them, R c Selected from the group consisting of: hydrogen or C1-C6 alkyl;

[0162] R d Selected from the group consisting of: hydrogen or C1-C6 alkyl;

[0163] 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

[0164] R 4 and R 5 The substituent and the atom to which it is attached or together with other atoms may form a 4-6 membered ring, wherein the other atom is selected from the group consisting of C, N, O, C(=O), C(=S) and S(O). 0-2 , the ring may be optionally substituted with one or more substituents selected from the group consisting of halogen, CN and C1-C6 alkyl.

[0165] Among them, R 5 , R 6 and R 7 Each aliphatic group can be optionally replaced by R a and R 4 and R 5 The ring group may be optionally replaced by R b One or more groups of

[0166] R a Selected from the group consisting of halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl;

[0167] R bSelected from the group consisting of halogen, nitrile, 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;

[0168] R 8 and R 8a independently selected from the group consisting of hydrogen, halogen, nitrile, C1-C4 alkyl and C1-C4 haloalkyl;

[0169] A1, A2, A3, A4, A5 are as defined above;

[0170] or a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof.

[0171] In another embodiment, the present invention provides a compound of formula (I), wherein,

[0172] D is D2;

[0173] Z is a direct key;

[0174] R 3 Selected from the group consisting of hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C1-C6 alkoxy;

[0175] R 6 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 heterocyclic group; preferably R 6 Selected from the group consisting of C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl and -NR c R d ;

[0176] Among them, R c Selected from the group consisting of: hydrogen or C1-C6 alkyl;

[0177] R d Selected from the group consisting of: hydrogen or C1-C6 alkyl;

[0178] R 7independently selected from the group consisting of hydrogen, nitrile, 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 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 heterocyclic group and nitrile group;

[0179] Among them, R 5 Selected from the group consisting of: C1-C6 alkyl and C3-C8 cycloalkyl;

[0180] Among them, R 5 , R 6 and R 7 Each aliphatic group can be optionally replaced by R a One or more groups of R are substituted; and R 5 , R 6 and R 7 The ring group may be optionally replaced by R b One or more groups of

[0181] R a Selected from the group consisting of halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl;

[0182] R b Selected from the group consisting of halogen, nitrile, 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;

[0183] A1, A2, A3, A4 and A5 are as defined above;

[0184] or a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof.

[0185] In another embodiment, the present invention provides a compound of formula (I), wherein,

[0186] D is D3;

[0187] Z is a direct key;

[0188] R 2 is a C1-C6 alkyl group;

[0189] R 3 Selected from the group consisting of hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C1-C6 alkoxy;

[0190] R 1 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, phenethyl and 4-6 membered heterocyclyl;

[0191] R 1 Each aliphatic group can be optionally replaced by R a One or more groups of R are substituted; and R 1 The ring group may be optionally replaced by R b One or more groups of

[0192] R a Selected from the group consisting of halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl;

[0193] R b Selected from the group consisting of halogen, nitrile, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-

[0194] C6 haloalkyl, C2-C6 haloalkenyl, C3-C8 cycloalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkoxy and C1-C6 haloalkoxy;

[0195] R 8 and R 8a independently selected from the group consisting of hydrogen, halogen, nitrile, C1-C4 alkyl and C1-C4 haloalkyl;

[0196] or a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof.

[0197] In one embodiment, the present invention provides a compound of formula (I), wherein R 1The C2-C6 heterocyclic group 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.

[0198] In one embodiment, the present invention provides a compound of formula (I), wherein R 5 The C2-C6 heterocyclic group 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.

[0199] In one embodiment, the present invention provides a compound of formula (I), wherein R 6 The C2-C6 heterocyclic group 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.

[0200] In one embodiment, the present invention provides a compound of formula (I), wherein R 7 The C2-C6 heterocyclic group 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.

[0201] In one embodiment, the present invention provides a compound of formula (I), wherein A1, A2, A3, A4 and A5 are independently C.

[0202] In another embodiment, the present invention provides a compound of formula (I), wherein A1, A2, A3 and A5 are independently C, and A4 is N.

[0203] In yet another embodiment, the present invention provides a compound of formula (I), wherein A1, A2, A3 and A4 are independently C, and A5 is N.

[0204] In yet another embodiment, the present invention provides a compound of formula (I), wherein A1, A2, A4 and A5 are independently C, and A3 is N.

[0205] In yet another embodiment, the present invention provides a compound of formula (I), wherein A2, A3, A4 and A5 are independently C, and A1 is N.

[0206] In yet another embodiment, the present invention provides a compound of formula (I), wherein A1, A3, A4 and A5 are independently C, and A2 is N.

[0207] In 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.

[0208] In 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.

[0209] In 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.

[0210] In 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.

[0211] In 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.

[0212] In a preferred embodiment, the present invention provides a compound of formula (I), wherein A1, A2, A3, A4 and A5 are independently C.

[0213] In 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.

[0214] In 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.

[0215] In another preferred embodiment, the present invention provides a compound of formula (I), wherein A1, A2 and A5 are independently C and A3 and A4 are independently N.

[0216] In 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.

[0217] In another preferred embodiment, the present invention provides a compound of formula (I), wherein A2, A3 and A5 are independently C and A1 and A4 are N.

[0218] In one embodiment, the present invention provides a compound of formula (I), wherein D is D1, and Z is a direct bond.

[0219] In another embodiment, the present invention provides a compound of formula (I), wherein D is D1, and Z is -C(=O)-.

[0220] In one embodiment, the present invention provides a compound of formula (I), wherein D is D2, and Z is a direct bond.

[0221] In one embodiment, the present invention provides a compound of formula (I), wherein D is D3, and Z is a direct bond.

[0222] In one embodiment, the present invention provides a compound of formula (I), wherein D is D1 or D2, and Y is O.

[0223] In one embodiment, the present invention provides a compound of formula (I), wherein D is D1 or D2, and Y is NR 7 .

[0224] In a preferred embodiment, the present invention provides a compound of formula (I), wherein D is D1 or D2, and Y is O.

[0225] In one embodiment, the present invention provides a compound of formula (I), wherein R 1 It is a C1-C6 alkyl group.

[0226] In another embodiment, the present invention provides a compound of formula (I), wherein R 1 is C1-C6 alkyl substituted by an optionally substituted phenyl group; wherein the optional substituent is selected from halogen, CN, methyl or methoxy.

[0227] In one embodiment, the present invention provides a compound of formula (I), wherein R 2 It is a C1-C6 alkyl group.

[0228] In a preferred embodiment, the present invention provides a compound of formula (I), wherein R 2 It is methyl or ethyl.

[0229] In one embodiment, the present invention provides a compound of formula (I), wherein R 3 It is a C1-C6 alkyl group.

[0230] In another embodiment, the present invention provides a compound of formula (I), wherein R 2 It is a C1-C6 haloalkyl group.

[0231] In another embodiment, the present invention provides a compound of formula (I), wherein R 3 It is a halogen.

[0232] In another embodiment, the present invention provides a compound of formula (I), wherein R 3 It is a C1-C6 alkoxy group.

[0233] In a preferred embodiment, the present invention provides a compound of formula (I), wherein R 3 It is CF3.

[0234] In another preferred embodiment, the present invention provides a compound of formula (I), wherein R 3 is fluorine or chlorine.

[0235] In a preferred embodiment, the present invention provides a compound of formula (I), wherein R 4 It is a C1-C6 alkyl group.

[0236] In a preferred embodiment, the present invention provides a compound of formula (I), wherein R 4 is a C1-C6 alkyl group, optionally with R a Substitution, where R a Selected from F, CN, methyl, ethyl, (n-, iso-)propyl, methoxy, CF3, cyclopropyl, C2-C6 heterocyclyl;

[0237] In a preferred embodiment, the present invention provides a compound of formula (I), wherein R 5 It is a C1-C6 alkyl group.

[0238] In a preferred embodiment, the present invention provides a compound of formula (I), wherein R 5 is a C1-C6 alkyl group, optionally with R a Substitution, where R a Selected from F, CN, methyl, ethyl, (n-, iso-)propyl, methoxy, CF3, cyclopropyl, C2-C6 heterocyclyl;

[0239] In a preferred embodiment, the present invention provides a compound of formula (I), wherein R 6 It is a C1-C6 alkyl group.

[0240] In a preferred embodiment, the present invention provides a compound of formula (I), wherein R 6 is a C1-C6 alkyl group, optionally with R a Substitution, where R a Selected from F, CN, methyl, ethyl, (n-, iso-)propyl, methoxy, CF3, cyclopropyl, C2-C6 heterocyclyl.

[0241] In a preferred embodiment, the present invention provides a compound of formula (I), wherein R 7 C1-C6 alkyl, -COR 5 and a C2-C6 heterocyclic group.

[0242] In one embodiment, R 8 and R 8aIndependently selected from the group consisting of: hydrogen, halogen, nitrile, C1-C4 alkyl, C1-C4 haloalkyl;

[0243] In a preferred embodiment, the present invention provides a compound of formula (I), wherein R 8 and R 8a independently selected from the group consisting of hydrogen, chlorine, fluorine, nitrile, methyl, ethyl, isopropyl and CF3;

[0244] In a preferred embodiment, the present invention provides a compound of formula (I), wherein the C3-C6 alkyl group is selected from cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Preferably, cyclopropyl or cyclobutyl.

[0245] 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.

[0246] The present invention also relates to a method for preparing the compound of formula (I).

[0247] The compounds of the present invention may exist as one or more stereoisomers. Different stereoisomers include mirror image isomers, diastereomers, atropisomers, and geometric isomers. One of ordinary skill in the art will appreciate that one stereoisomer may be more active and / or may exhibit more beneficial effects when enriched relative to other stereoisomers or when separated from other stereoisomers. In addition, one of ordinary skill in the art knows how to separate, enrich, and / or selectively prepare the stereoisomers. The compounds of the present invention may exist as a mixture of stereoisomers, a single stereoisomer, or as an optically active form.

[0248] In the case where the compound of formula (I) appears as the cationic part of the salt or can form such a cationic part of the salt, the corresponding anionic part can be inorganic or organic. Alternatively, in the case where the compound of formula (I) appears as the anionic part of the salt or can form such an anionic part of the salt, the corresponding cationic part can be inorganic or organic. Examples of inorganic anionic parts of salts include, but are not limited to, chloride, bromide, iodide, fluoride, sulfate, phosphate, nitrate, nitrite, bicarbonate and bisulfate. Examples of organic anionic parts of salts include, but are not limited to, formates, alkanoates, carbonates, acetates, trifluoroacetates, trichloroacetates, propionates, glycolates, thiocyanates, lactates, succinates, malates, citrates, benzoates, cinnamates, oxalates, alkyl sulfates, alkyl sulfonates, aryl sulfonates, aryl disulfonates, alkyl phosphonates, aryl phosphonates, aryl diphosphonates, p-toluene sulfonates and salicylates. Examples of inorganic cationic parts of salts include, but are not limited to, alkali metals and alkaline earth metals. Examples of organic cationic portions of the salt include, but are not limited to, cations derived from pyridine, methylamine, imidazole, benzimidazole, histidine, phosphazene, tetramethylammonium, tetrabutylammonium, choline, and trimethylamine.

[0249] The metal ions in the metal complexes of the compounds of formula (I) are in particular ions of elements of the second main group, in particular ions of calcium and magnesium, ions of elements of the third and fourth main groups, in particular ions of aluminum, tin and lead, and elements of the first to eighth transition groups, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc, etc. Particularly preferred are metal ions of elements of the fourth period and of the first to eighth transition groups. Here, the metals may be present in the various valences they may assume.

[0250] Another embodiment of the present invention discloses a compound of formula (I), a salt thereof, a metal complex, a stereoisomer, a diastereomer, a mirror image isomer, a chiral isomer, a rotational isomer, a tautomer, an optical isomer, a polymorph, a geometric isomer or an N-oxide thereof, and a composition containing an excipient, an inert carrier or any other necessary ingredients (such as a surfactant, an additive, a solid diluent and a liquid diluent).

[0251] Compounds selected from formula (I) (including all stereoisomers, N-oxides and salts thereof) generally exist in more than one form, and thus formula (I) includes all crystalline and non-crystalline forms represented by compounds of formula (I). Non-crystalline forms include embodiments of solids (e.g. waxes and gums) and embodiments of liquids (e.g. solutions and melts). Crystal forms include embodiments representing substantially single crystal types and embodiments representing mixtures of polymorphs (i.e., different crystal forms). The term "polymorph" refers to a specific crystalline form of a compound that can crystallize in different crystalline forms, which have different molecular arrangements and / or stereo configurations in the crystal lattice. Although polymorphs may have the same chemical composition, their composition may also differ due to the presence or absence of co-crystallization water or other molecules, which may be weakly or strongly bound to the crystal lattice. The chemical, physical and biological properties of polymorphs (e.g., crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspension, dissolution rate and bioavailability) may differ. Those of ordinary skill in the art will appreciate that a polymorph of a compound represented by formula (I) may exhibit beneficial effects (e.g., suitability for preparing useful formulations, improved biological performance) relative to another polymorph or mixture of polymorphs of a compound represented by formula (I). The preparation and separation of a specific polymorph of a compound represented by formula (I) may be achieved by methods known to those of ordinary skill in the art, including, for example, crystallization using a selected solvent and temperature.

[0252] The present invention also relates to a composition for controlling or preventing insect and acarid pests, comprising a biologically effective amount of a compound of formula (I) and at least one additional component selected from surfactants and adjuvants.

[0253] Another embodiment of the present invention is a compound of formula (I) or its N-oxide or salt thereof prepared as a conventional type of agricultural chemical composition, such as: solution, emulsion, suspension, powder, powder, paste, granule, compressed preparation, capsule and mixtures thereof. Examples of composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or powders (e.g. WP, SP, WS, DP, DS), compressed preparations (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticide preparations (e.g. LN) and gel preparations for treating plant propagation materials such as seeds (e.g. GF). These and other composition types are defined in "Catalogue of pesticide Formulation types and international coding system, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International".

[0254] The above compositions are prepared in a known manner, for example as described in "Formulation Technology, Wiley VCH, Weinheim, 2001" by Mollet and Grubemann; or in "New Developments in Crop Protection Product Formulation, Agrow Reports DS243, T&F Informa, London, 2005" by Knowles. Examples of suitable adjuvants for the formulations and / or agrochemical compositions according to the invention are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, humectants, insect repellents, attractants, feeding stimulants, extenders, bactericides, antifreeze agents, defoamers, colorants, tackifiers and adhesives.

[0255] Suitable solvents and liquid carriers herein are, for example, water and organic solvents, such as medium to high boiling point mineral oil fractions, such as kerosene, diesel; vegetable oils or animal oils; aliphatic, cyclic and aromatic hydrocarbons, such as toluene, paraffin, tetralin, alkylated naphthalene compounds; alcohols, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; ethylene glycol; dimethyl sulfoxide (DMSO); ketones, such as cyclohexanone; esters, such as lactic acid esters, carbonates, fatty acid esters, γ-butyrolactone; fatty acids; phosphates; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof. Suitable solid carriers or fillers are mineral earths, for example silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, for example cellulose, starch; fertilizers, for example ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products of plant origin, for example cereal flour, bark flour, wood flour, nut shell flour and mixtures thereof.

[0256] Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes and mixtures thereof. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids or adjuvants. Examples of surfactants are listed in "McCutcheo N's, Vol. 1: Emulsifiers & Detergents, McCutcheo N's Directories, Glen Rock, USA, 2008" (International Edition or North American Edition).

[0257] Suitable anionic surfactants are, for example, alkali metal salts, alkaline earth metal salts or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, α-olefinsulfonates, ligninsulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalene, sulfonates of decyl and tridecylbenzene, sulfonates of naphthalene and alkylnaphthalene, sulfosuccinates or sulfosuccinamates. 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 are phosphate esters. Examples of carboxylates are alkylcarboxylates and carboxylated alcohols or alkylphenol ethoxylates.

[0258] 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 that have been alkoxylated with 1 to 50 equivalents, such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters. Ethylene oxide and / or propylene oxide can be used for the alkoxylation reaction, preferably ethylene oxide.

[0259] Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerides or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polysaccharides. Examples of polymeric surfactants are homopolymers or copolymers of vinyl pyrrolidone, vinyl alcohol or vinyl acetate.

[0260] Suitable cationic surfactants are, for example, quaternary surfactants, such as quaternary ammonium compounds with 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, AB or ABA type block polymers comprising polyethylene oxide and polypropylene oxide blocks, or ABC type block polymers comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are, for example, polyacids or polybases. Examples of polyacids are alkali metal salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.

[0261] Suitable adjuvants are compounds which themselves have negligible or even no insecticidal activity, which improve the biological performance of the compounds of formula (I) on the target. Adjuvants are, for example, surfactants, mineral or vegetable oils and other auxiliaries. Further examples are listed in "Knowles, Adjuvants and added, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5".

[0262] Suitable thickeners are, for example, polysaccharides (eg, trisaccharide, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates.

[0263] Suitable fungicides are, for example, bronopol and isothiazolinone derivatives, such as alkylisothiazolinones and benzisothiazolinones.

[0264] Suitable antifreeze agents are, for example, ethylene glycol, propylene glycol, urea and glycerol.

[0265] Suitable antifoams are, for example, silicone compounds, long-chain alcohols and salts of fatty acids.

[0266] Suitable colorants (for example red, blue or green) are, for example, low water-soluble pigments and water-soluble dyes. Examples are inorganic colorants (such as iron oxide, titanium oxide, hexacyanoferric acid) and organic colorants (such as alizarin, azo and phthalocyanine colorants).

[0267] Suitable tackifiers or adhesives are, for example, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological or synthetic waxes and cellulose ethers.

[0268] The types of compositions and their preparation methods are as follows:

[0269] i) Water-soluble concentrates (SL, LS)

[0270] 10-60 wt% of the compound of formula (I) and 5-15 wt% of a wetting agent (e.g., an alcohol alkoxy compound) are dissolved in a mixture of 100% by weight.

[0271] wt% water and / or water-soluble solvents (such as alcohols). The active substance dissolves when diluted with water.

[0272] ii) Dispersible Concentrate (DC)

[0273] 5-25 wt% of the compound of formula (I) and 1-10 wt% of a dispersant (eg polyvinyl pyrrolidone) are dissolved in an organic solvent (eg cyclohexanone) added to 100 wt%, and diluted with water to obtain a dispersion of the active substance.

[0274] iii) Emulsifiable concentrates (EC)

[0275] 15-70 wt% of the compound of formula (I) and 5-10 wt% of an emulsifier (such as calcium dodecylbenzenesulfonate and ethoxylated castor oil) are dissolved in a water-insoluble organic solvent (such as aromatic hydrocarbon) added to 100 wt%. The active substance emulsion is obtained by diluting with water.

[0276] iv) Emulsion (EW, EO, ES)

[0277] 5-40 wt% of the compound of formula (I) and 1-10 wt% of an emulsifier (e.g. calcium dodecylbenzenesulfonate and ethoxylated castor oil) are dissolved in 20-40 wt% of a water-insoluble organic solvent (e.g. aromatic hydrocarbon). Then, the mixture is added to 100 wt% of water by using an emulsifier to form a uniform emulsion. The mixture is diluted with water to obtain an emulsion of the active substance.

[0278] v) Suspension (SC, OD, FS)

[0279] 20-60 wt% of the compound of formula (I) is added with 2-10 wt% of a dispersant and wetting agent (e.g. sodium lignin sulfonate and alcohol ethoxylate), 0.1-2 wt% of a thickener (e.g. Sanxian gum) and water up to 100 wt% and ground in a stirred ball mill to obtain a good suspension of the active substance. Dilution with water gives a stable suspension of the active substance. For FS type compositions, a maximum of 40 wt% of a binder (e.g. polyvinyl alcohol) is added.

[0280] vi) Water dispersible granules and water soluble granules (WG, SG)

[0281] 50-80 wt% of the compound of formula (I) is added to 100 wt% of a dispersant and a wetting agent (e.g. sodium lignin sulfonate and alcohol ethoxylate) for fine grinding, and prepared into water-dispersible or water-soluble granules by technical equipment (e.g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.

[0282] vii) Water dispersible powders and water soluble powders (WP, SP, WS)

[0283] 50-80 wt% of the compound of formula (I) is ground in a rotor-stator grinder with the addition of 1-5 wt% of a dispersant (e.g. sodium lignin sulfonate), 1-3 wt% of a wetting agent (e.g. alcohol ethoxylate) and up to 100 wt% of a solid carrier (e.g. silica gel). Dilution with water gives a stable dispersion or solution of the active substance.

[0284] viii) Gel (GW, GF)

[0285] 3-10 wt% of a dispersant (e.g. sodium lignin sulfonate), 1-5 wt% of a thickener (e.g. carboxymethyl cellulose) and up to 100 wt% of water are added to 5-25 wt% of the compound of formula (I) and ground in a stirred ball mill to obtain a good suspension of the active substance. The mixture is diluted with water to obtain a stable suspension of the active substance.

[0286] ix) Microemulsion (ME)

[0287] 5-20 wt% of the compound of formula (I) is added to 5-30 wt% of an organic solvent mixture (e.g., fatty acid dimethylamide and cyclohexanone), 10-25 wt% of a surfactant mixture (e.g., alcohol ethoxylate and arylphenol ethoxylate) and water up to 100 wt%. The mixture is stirred for 1 hour to spontaneously produce a thermodynamically stable microemulsion of the active ingredient.

[0288] x) Microcapsules (CS)

[0289] An oil phase comprising 5-50 wt% of a compound of formula (I), 0-40 wt% of a water-insoluble organic solvent (e.g., aromatic hydrocarbons) and 2-15 wt% of an acrylic monomer (e.g., methyl methacrylate, methacrylic acid, and diacrylate or triacrylate) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). The free radical polymerization reaction results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound of formula (I) of the present invention, 0-40 wt% of a water-insoluble organic solvent (e.g., aromatic hydrocarbons) and an isocyanate monomer (e.g., diphenylmethene-4,4'-diisocyanatae) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). The addition of a polyamine (e.g., hexamethylenediamine) results in the formation of polyurea microcapsules. The amount of the monomer is 1-10 wt%. The weight percentage is related to the total CS composition.

[0290] xi) Powderable powder (DP, DS)

[0291] 1-10 wt% of a compound of formula (I) is finely ground and intimately mixed with up to 100 wt% of a solid carrier (eg finely divided kaolin).

[0292] xii) Granules (GR, FG)

[0293] 0.5-30 wt% of a compound of formula (I) is finely ground and combined with up to 100 wt% of a solid carrier (eg a silicate). Granulation is achieved by extrusion, spray drying or fluidized bed.

[0294] xiii) Ultra Low Volume Liquids (UL)

[0295] 1-50 wt% of the compound of formula (I) is dissolved in an organic solvent (eg aromatic hydrocarbon) added to 100 wt%.

[0296] Composition types i) to xiii) may optionally comprise further adjuvants, for example 0.1-1 wt % of a bactericide, 5-15 wt % of an antifreeze agent, 0.1-1 wt % of an antifoaming agent and 0.1-1 wt % of a colorant.

[0297] Another embodiment of the present invention provides an agrochemical composition containing a compound of formula (I), which comprises 0.01% to 95%, preferably 0.1% to 90%, more preferably 1% to 70%, and especially 10% to 60% of active substance by weight. The active substance is used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

[0298] 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 gel preparations (GF) are generally used for treating plant propagation materials (especially seeds). After two to ten times dilution, the composition has an active substance concentration of 0.01 to 60% by weight, preferably 0.1 to 40% by weight in a ready-to-use formulation. It can be applied before or during sowing.

[0299] The method of applying the compound of formula (I) and its composition to plant propagation materials, especially seeds, includes: dressing, coating, granulation, dusting, soaking and in-furrow application. Preferably, the compound of formula (I) and its composition are applied to plant propagation materials by a method that does not induce germination (e.g., by dressing, granulation, coating and dusting).

[0300] When used in plant protection, the amount of active substance applied is, depending on the type of effect desired, 0.001 to 2 kg per hectare, preferably 0.005 to 2 kg per hectare, more preferably 0.05 to 0.9 kg per hectare, in particular 0.1 to 0.75 kg per hectare.

[0301] For the treatment of plant propagation material, such as seeds, for example by dusting, coating or soaking the seeds, 0.1 to 1000 g, preferably 1 to 1000 g, more preferably 1 to 100 g, and more preferably 5 to 100 g of active ingredient per 100 kg of plant propagation material, preferably seeds, is generally necessary.

[0302] When used to protect materials or store products, the amount of active substance used depends on the type of application and the desired effect. The amount usually used for material protection ranges from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg of active substance per cubic meter of treated material.

[0303] Different types of oils, wetting agents, adjuvants, fertilizers or micronutrients and additional pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) can be added to the active substance or the composition comprising the active substance as a premix or, if appropriate, not until just before use (tank mix). These agents can be mixed with the composition according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0304] The user usually applies the agricultural composition of the present invention from a pre-dose device, a backpack sprayer, a spray tank, an aircraft spray or an irrigation system. Typically, the agricultural composition is made of water, a buffer and / or other adjuvants to the desired application concentration to obtain the ready-to-use spray liquid or agricultural composition of the present invention. Typically, 20 to 2000 liters, preferably 50 to 400 liters of the ready-to-use spray liquid are applied per hectare of agricultural useful area.

[0305] According to one embodiment, the individual components of the composition according to the invention, for example parts of a kit or parts of a binary or ternary mixture, can be mixed by the user himself in a spray can or other auxiliary equipment, if appropriate.

[0306] The compounds and compositions of the invention are therefore useful agronomically for protecting crops from phytopathogenic invertebrate pests and non-agronomically for protecting other horticultural crops and plants from phytopathogenic invertebrate pests. Such applications include protecting crops and other plants (i.e. agronomic and non-agronomic) containing genetic material introduced by genetic engineering (i.e. gene transfer) or modified by mutagenesis to provide advantageous traits.

[0307] The compounds of the invention are characterized by a good metabolism and / or soil residual pattern and show activity against a range of agronomic and non-agronomic invertebrate pests. The compounds of the invention are active ingredients of preventive and / or therapeutic value in the field of pest control and can be used to control insecticide-resistant pests (e.g., insects) and / or have a very favorable biocidal spectrum even at low application rates and are well tolerated by warm-blooded animals, fish and plants.

[0308] The compounds of the invention exhibit activity against economically important agronomic, forest, greenhouse, nursery, ornamental, food and fiber, public and animal health, domestic and commercial structure, household and stored product pests. These pests include larvae of the Lepidoptera, such as armyworms, cutworms, loopers, and heliothines of the family Noctuidae (e.g., fall armyworm, Spodoptera fugiperda JESmith, beet armyworm, Spodoptera exigua Hubner, black cutworm, Agrotis ipsilon Hufnagel, cabbage looper, Trichoplusia ni Hubner, tobacco budworm, Heliothis virescens Fabricius); borers, casebearers, webworms, coneworms, cabbageworms, and skeletonizers from the family Pyralidae (e.g., European corn borer, corn borer (Ostrinia nubilalis Hubner), navel orange borer (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), sod worm (Herpetogramma licarsisalis Walker); leaf rollers, budworms, seedworms, and fruit worms of the family Tortricidae (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruit moth (Grapholita molesta Busck); and many other economically important Lepidoptera (e.g.,diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus); nymphs and adults of the order Blattodea, including cockroaches from the families Blattellidae and Blattidae (e.g., oriental cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella germanica Linnaeus), brownbanded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta Americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaeamaderae Fabricius); leaf-feeding larvae and adults of the order Coleoptera, including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g.,boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granaries Linnaeus), rice weevil (Sitophilus oryzae Linnaeus); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles and leaf miners of the family Chrysomelidae (e.g., Colorado potato beetle (Leptinotarsa ​​decemlineata Say), western corn rootworm (Diabrotica virgifera LeConte); chafers and other beetles from the Scarabeidae family (e.g., Japanese beetle, Popillia japonica Newman, and European chafer, Rhizotrogus majalis Razoumowsky); carpet beetles from the Dermestidae family; wireworms from the Elateridae family; bark beetles from the Scolytidae family, and flour beetles from the Tenebrionidae family. In addition, it also includes: adults and larvae of the order Dermaptera, including earwigs from the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius)); adults and nymphs of the orders Hemiptera and Homoptera,Such as plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers from the family Cicadellidae (e.g. Empoasca spp.), planthoppers from the families Fulgoroidae and Delphacidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae, and Margarodidae, lace bugs from the family Tingidae, chinch bugs from the family Lygaeidae (e.g., Blissus spp.) and other seed bugs, spittlebugs from the family Cercopidae, red bugs from the family Pyrrhocoridae, and cotton stainers. Also included are adults and larvae of the order Acari (Acarina), such as spider mites and red mites of the family Tetranychidae (e.g., European red mite, Panonychus ulmi Koch, two spotted spider mite, Tetranychus urticae Koch, McDaniel mite, Tetranychusmcdanieli McGregor), flat mites of the family Tenuipalpidae (e.g., citrus flat mite, Brevipalpus lewisi McGregor), rust mites and bud mites of the family Eriophyidae, and other spider-feeding mites and mites important to human and animal health,That is, dust mites of the family Epidermoptidae, ticks of the family Ixodidae (e.g., deer 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, itchmites of the families Psoroptidae, Pyemotidae, and Sarcoptidae; adults and larvae of the order Orthoptera, which includes grasshoppers, locusts, and crickets (e.g., migratory grasshoppers grasshopper (e.g., Melanoplussanguinipes Fabricius, M. differentialis Thomas), American grasshopper (e.g., Schistocerca Americana Drury), desert locust (Schistocerca gregaria Forskal), migratory locust (Locustamigratoria Linnaeus), house cricket (Acheta domesticus Linnaeus), mole cricket (Gryllotalpa spp.); adults and larvae of the order Diptera, which includes leafminers, midges, fruit flies (Tephritidae), fruit flies (e.g., Oscinella frit Linnaeus), soil maggots (e.g., Oscinella frit Linnaeus), maggot), house fly (e.g., Musca domestica Linnaeus), lesser house fly (e.g.,summer toilet fly (Fanniacanicularis Linnaeus), yellow toilet fly (F. femoralis Stein), stable fly (e.g., Stomoxys calcitrans Linnaeus), face fly, horn fly, blow fly (e.g., Chiysomya spp., Phormia spp.), and other fly pests, horse fly (e.g., Tabanus spp.), bot fly (e.g., Gastrophilus spp., Oestrus spp.), cattle grub (e.g., Hypoderma spp.), deer fly (e.g., Chrysops spp.), spp.), ked flies (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids and other Nematocera; adults and larvae of the order Thysanoptera, which includes onion thrips, Thrips tabaci Lindeman and other leaf-feeding thrips; pests of the order Hymenoptera, including ants of the family Formicidae,The ants include, for example, red carpenter ants (Camponotus ferrugineus Fabricius), black carpenter ants (Camponotus pennsylvanicus De Geer), Pharaoh ants (Monomorium pharaonis Linnaeus), little fire ants (Wasmannia auropunctata Roger), fire ants (Solenopsis geminata Fabricius), red imported fire ants (Solenopsis invicta Buren), Argentine ants (Iridomyrmex humilis Mayr), crazy ants (Paratrechina longicornis Latreille), pavement ants (Tetramorium caespitum Linnaeus), cornfield ants (Lasius alienus Fδrster) and odorous house ants (Tapinoma sessile Say). Other Hymenoptera include bees (including carpenter bees), hornets, yellow jackets, and wasps; Isoptera, which include eastern subterraneantermite (Reticulitermes flavipes Kollar), western subterraneantermite (Reticulitermes hesperus Banks), Formosan subterraneantermite (Coptotermes formosanus Shiraki), West Indian drywoodtermite (Incisitermes immigrans Snyder), and other termites of economic importance; Thysanura,Such as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard); pests of the order Mallophaga and including head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitszch), dog biting louse (Trichodectes canis De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurysternus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack humans and animals; pests of the order Siphonoptera, which includes the oriental rat flea (Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felis Bouche), dog flea (Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea (Pulex irritans Linnaeus), and other fleas that afflict mammals and birds. Other arthropod pests covered 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 common house centipede (Scutigeracoleoptrata Linnaeus). The compounds of the present disclosure are also active against members of the classes Nematoda, Cestoda, Trematoda, and Acanthocephala, including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida, such as, but not limited to, economically important agricultural pests (i.e., root knot nematodes of the genus Meloidogyne, lesion nematodes of the genus Pratylenchus, stubby root nematodes of the genus Trichodorus, etc.) and animal and human health pests (i.e., all economically important trematodes, tapeworms, and roundworms, such as Strongylus vulgaris of horses, Toxocara canis of dogs, etc.). canis, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.

[0309] The compounds of the present invention show particularly high activity against pests of the order Homoptera, including: pea aphid (Acyrthosiphon pisum Harris), cowpea aphid (Aphis craccivora Koch), black bean aphid (Aphis fabae Scopoli), cotton aphid (Aphis gossypiiGlover), melon aphid (Aphis melo), apple aphid (Aphis pomi De Geer), spirea aphid (Aphis spiraecola Patch), foxglove aphid (Aulacorthum solani Kaltenbach), strawberry aphid (Chaetosiphon fragaefolii Cockerell), Russian wheat aphid (Diuraphis noxia Kurdjumov / Mordvilko), rose apple aphid (Dysaphis raphis), and safflower aphid (Aphis serrata). plantaginea Paaserini, rosy apple aphid, Eriosoma lanigerum Hausmann, woolly apple aphid, Hyalopteruspruni Geoffroy, mealy plum aphid, Lipaphis erysimi Kaltenbach, turnip aphid, Metopolophium dirrhodum Walker, cereal aphid, Macrosiphum euphorbiae Thomas, peach-potato aphid, green peach aphid, Myzus persicae Sulzer, lettuce aphid, Pemphigus spp.) (root aphid and gall aphid), corn leaf aphid (Rhopalosiphum maidis Fitch), bird cherry-oat aphid (Rhopalosiphumpadi Linnaeus), greenbug (Schizaphis graminum Rondani), English grain aphid (Sitobion avenae Fabricius), spotted alfalfa aphid (Therioaphis maculate Buckton), black citrus aphid (Toxopteraaurantii Boyer de Fonscolombe), and brown citrus aphid (Toxopteracitricida Kirkaldy); Adelges spp.) (adelgid); pecan phylloxera (Phylloxera devastatrix Pergande); sweetpotato whitefly (Bemisia tabaci Gennadius), silverleaf whitefly (Bemisia argentifolii Bellows and Perring), citrus whitefly (Dialeurodes citri Ashmead), and greenhouse whitefly (Trialeurodesvaporariorum Westwood); potato leafhopper (Empoasca fabae Harris), smaller brown planthopper (Laodelphax striatellus Fallen), aster leafhopper (Macrolestes quadrilineatus Forbes), green leafhopper (Nephotettix cinticeps Uhler), and green leafhopper (Nephotettix cinticeps Uhler). leafhopper), rice leafhopper (Nephotettixnigropictus Stal), brown planthopper (Nilaparvata lugens Stal), corn planthopper (Peregrinus maidis Ashmead), white-backed planthopper (Sogatella furcifera Horvath), rice delphacid (Sogatodesorizicola Muir), white apple leafhopper (Typhlocyba pomaria McAfee), grape leafhopper (Erythroneoura spp.)(grape leafhopper); Magicidada septendecim Linnaeus, periodical cicada; cottony cushion scale (Icerya purchasi Maskell), pear round shield scale (Quadraspidiotus perniciosus Comstock, San Jose scale); citrus mealybug (Planococcus citri Risso, citrusmealybug); Pseudococcus spp. (other mealybug complexes); pear psylla (Cacopsyllapyricola Foerster), persimmonpsylla (Trioza diospyri Ashmead). The compounds of the invention also have significant commercial activity against members of the order Lepidoptera, such as Alabama argillacea Hubner (cotton leaf worm), Archipsargyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilosuppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice leaf roller), Crambus caliginosellus Clemens (cornroot webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Eariasinsulana Boisduval (spiny moth), bollworm), spotted bollworm (Earias vittella Fabricius, spotted bollworm), American stem borer (Helicoveipa armigera. American bollworm, corn earworm (Helicoverpa zea Boddie), tobacco budworm (Heliothis virescens Fabricius), sod webworm (Herpetogramma licarsisalis Walker), grape berry moth (Lobesia botrana Denis and grape berry moth), pink bollworm (Pectinophora gossypiella Saunders), citrus leafminer (Phyllocnistiscitrella Stainton), largewhite butterfly (Pieris brassicae Linnaeus), small white butterfly (Pieris rapae Linnaeus), diamondback moth (Plutella xylostella Linnaeus), beet armyworm (Spodoptera exiguaHubner), tobacco cutworm (Spodoptera litura Fabricius), fall armyworm (Spodoptera frugiperda JESmith), and powdery mildew (Trichoplusia ni cabbage looper) and tomato leafminer (Tuta absoluta Meyrick, tomato leafminer).

[0310] The compound is active against members of the order Hemiptera, including: green stink bug (Acrosternum hilare Say), squash bug (Anasa tristis De Geer), chinch bug (Blissus leucopterus leucopterus Say), cotton lace bug (Corythuca gossypii Fabricius), tomato bug (Cyrtopeltis modesta Distant), cotton stainer (Dysdercus suturellus Herrich-S chaffer), brown stink bug (Euchistus servus Say), one-spotted stink bug (Euchistus variolarius Palisot de Beauvois), and the complex of stink bugs (Graptósthetus spp.) (complex of broad shield bugs), leaf-footed pine seed bug (Leptoglossus corculus Say), tarnished plant bug (Lygus lineolaris Palisot de Beauvois), southern green stink bug (Nezaraviridula Linnaeus), rice stink bug (Oebalus pugnax Fabricius), large milkweed bug (Oncopeltus fasciatus DaEas), cotton fleahopper (Pseudatomoscelis seriatus Reuter).

[0311] Other insect orders controlled by the compounds of the invention include: Thysanoptera (e.g., Frankliniella occidentalis Pergande, western flower thrips), Citrus thrips ( citri Moulton, citrus thrips, soybean thrips, Sericothrips variabilis Beach, and onion thrips, Thrips tabaci Lindeman); and from the order of the Coleoptera (for example, Colorado potato beetle, Leptinotarsa ​​decemLineata Say, Mexican beetle, and nematodes of the genera Agriotes, Athous or Limonius).

[0312] In particular, the compounds of formula (I), their N-oxides, stereoisomers, polymorphs and salts thereof are particularly suitable for being used effectively against the following pests: insects from the order Lepidoptera, for example: Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographagamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia sphaeroides, pomonella), European pine caterpillar (Dendrolimus pini), melon borer (Diaphania nitidalis), giant corn borer (Diatraea grandiosella), cotton moth (Eariasinsulana), square bollworm (Earias vittella), small corn borer (Elasmopalpus lignosellus), grape borer (Eupoecilia ambiguella), European pine moth (Evetria bouliana), grain cutworm (Feltiasubterranea), greater wax moth (Galleria mellonella), plum borer (Grapholita funebrana), pear borer (Grapholita molesta), tomato armyworm (Helicoverpa armigera), American tobacco armyworm (Helicoverpa virescens), cotton bollworm (Helicoverpa zea), cabbage borer (Hellula undalis), gray skirt looper moth (Hibernia defoliaria), Hyphantria cunea, Hyponomeutamalinellus, Keiferia lycopersicella, Lambdinafiscellaria, Laphygma exiguaexigua), Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Leucinodesorbonalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestrabrassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridromasaucia, Phalera bucephala), Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusiaincludens, Rhyacionia frustrana, Scirpophaga incertulas, Scropipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera litura, Spodoptera exigua, Thaumatopoea serrata, Spodoptera litura, Spodoptera exigua, pityocampa), Oak Green Leaf-roller (Tortrix viridana), Cabbage Lobelia (Trichoplusia ni) and Spruce Leaf-roller (Zeiraphera canadensis); and

[0313] Beetles (Coleoptera), for example, Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athoushaemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida spp. nebulosa), bean leaf beetle (Cerotoma trifurcata), golden flower beetle (Cetonia aurata), cabbage pod weevil (Ceuthorrhynchus assimilis), stem weevil (Ceuthorrhynchus napi), beet shank flea beetle (Chaetocnema tibialis), tobacco wireworm (Conoderus vespertinus), asparagus beetle (Crioceris asparagi), click beetle subspecies (Ctenicera ssp.), long-horned leaf beetle (Diabroticalongicornis), cucumber semi-star leaf beetle (Diabrotica semipunctata), twelve-star melon leaf beetle (Diabrotica undecimpunctata), Brazilian leaf beetle (Diabrotica speciosa), corn root leaf beetle (Diabrotica virgifera), Mexican bean ladybug (Epilachna varivestis), tobacco flea beetle (Epitrix hirtipennis), cotton borer (Eutinobothrus brasiliensis), pine weevil (Hylobius abietis), Egyptian clover weevil (Hypera brunneipennis), clover leaf weevil (Hypera postica), spruce eight-toothed beetle (Ipstypographus), and striated mudworm (Lemabilineata), Lema melanopus, Leptinotarsa ​​decemLineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethesaeneus, Melolontha hippocastani, Melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola), Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitonalineatus and Sitophilus granaria; flies and mosquitoes (Diptera), for example, Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles vexans, leucosphyrus), Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomyabezziana), 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, Haplodiplosisequestris, Hippelates spp., Hylemyia platura, Hypodermalineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericatasericata), Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyzaflorum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psilarosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophagahaemorrhoidalis, Sarcophaga spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, Tabanus similis, Tipula oleracea and Tipula paludosa; termites (Isoptera), for example, Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus), Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes grassei, Termesnatalensis and house termites (Coptotermes formosanus); cockroaches (BlattariaBlattodea), for example, Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasianasiae and Blatta orientalis; ants, bees, wasps, sawflies (Hymenoptera), for example, Athalia rosae, Atta cephalotes, Atta capiguara, Atta orientalis. cephalotes), Attalaevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Lasius niger, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Bombus spp., Vespula squamosa), Common wasp (Paravespula vulgaris), Tree wasp (Paravespula pennsylvanica), German wasp (Paravespula germanica), White-faced wasp (Dolichovespulamaculata), Vespacrabro, Polistes rubiginosa, Camponotus floridanus and Linepithema humile; crickets, grasshoppers and locusts (Orthoptera), for example, Acheta domestica, Gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetesterminifera and Locustana pardalina; of the order Araneida, for example, Latrodectus mactans and Loxosceles reclusa; of the order Siphonaptera, for example, Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans), Tunga penetrans, and Nosopsyllus fasciatus; silverfish (Lepisma saccharina) and firebrat (Thermobiadomestica; centipedes (Chilopoda), for example Scutigera oleoptrata; millipedes (Diplopoda), for example Narceus spp.; earwigs (Dermaptera), for example forficula auricularia; lice (Phthiraptera), for example Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus usurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon allinae, Menacanthus spp. stramineus and Solenopotes capillatus; Collembola (springtails), for example, Onychiurus ssp.

[0314] The compounds are also suitable for controlling nematodes: plant parasitic nematodes, for example, root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogynespecies; cyst-forming nematodes, Globodera rostochiensis, and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seedgall nematodes, Anguina nematodes, including species of the genus Aphelenchoides; stinging nematodes, including Belonolaimus longicaudatus and other Belonolaimus species; pine nematodes, including Bursaphelenchus xylophilus and other Bursaphelenchus species; ring nematodes, including Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; stem and bulb nematodes, including Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species. species); Awl nematodes, Dolichodorus species;Spiral nematodes, Helicotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora and Hemicriconemoides; Hirshmanniella species; Lance nematodes, Hoploaimus species; False rootknot nematodes, Nacobbus species; 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; Reniform nematodes, Rotylenchus robustus, and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus, and other Trichodorus species, Paratrichodorus species; Stunt nematodes, nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species;Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species. ;

[0315] The compounds of formula (I) and their salts are also effective for controlling arachnids (Arachnoidea), such as the order Acarina, for example the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius spp. megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei; and Eriophyidae spp., such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp., such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp., such as Brevipalpus phoenicis); Tetranychidae spp.), such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri and Oligonychus pratensis.

[0316] In yet another embodiment, the present invention provides compounds of formula (I) as active and useful compounds for controlling insects selected from sucking or piercing insects, such as insects from the orders Thysanoptera, Diptera and Hemiptera, in particular the following species:

[0317] Thysanoptera: Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci;

[0318] Order of Diptera, for example, Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax), Chrysomya cellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contariniasorghicola, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae), onion field fly (Delia antique), wheat field fly (Delia coarctata), gray field fly (Delia platura), cabbage field fly (Delia radicum), human skin fly (Dermatobia hominis), yellow-bellied stable fly (Fanniacanicularis), Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossinata chinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus), Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis), Sarcophaga spp., Simulium vittatum, Stomoxyscalcitrans), gadfly (Tabanus bovinus), black fly (Tabanus atratus), banded horse fly (Tabanus lineola), pseudo-horse fly (Tabanus similis), common crane fly (Tipula oleracea) and European crane fly (Tipula paludosa);

[0319] From the order Hemiptera, especially the aphids: Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Brachycaudus cardui, Brachycaudus ushelichrysi, Brachycaudus persicae, Brachycaudus plum blossom aphid. prunicola), Brevicoryne brassicae, Capitophorus horni, Cerosiphagossypii, Chaetosiphon fragaefolii, Cryptomyzusribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum sibiricum, euphorbiae), Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzusascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla iri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa), wheat aphid (Sitobion avenae), greenhouse whitefly (Trialeurodes vaporariorum), citrus aphid (Toxoptera aurantiiand) and grape phylloxera (Viteus).

[0320] In a preferred embodiment, the compounds of formula (I) of the present invention can be used to control, for example, western flower thrips (Frankliniella occidentalis), potato leafhopper (Empoasca fabae), rice brown planthopper (Nilaparvata lugens), rice green leafhopper (Nephotettix virescens), cotton / melon aphid (Aphis gossypii), green peach aphid (Myzus persicae), tobacco / sweetpotato whitefly (Bemisia tabaci) and silverleaf whitefly (Bemisia argentifolii).

[0321] In one embodiment, the present invention further provides a composition comprising a biologically effective amount of a compound of formula (I) and at least one additional biologically active compatible compound selected from the group consisting of a fungicide, an insecticide, a nematicide, a miticide, a biopesticide, a herbicide, a plant growth regulator, an antibiotic, a fertilizer, or a nutrient. The compounds used in the composition and in combination with the compound of formula (I) are also referred to as active compatible compounds.

[0322] Known reported fungicides, insecticides, nematicides, miticides, biopesticides, herbicides, plant growth regulators, biostimulants, antibiotics and nutrients can be combined with at least one compound of formula (I) of the present invention. For example, fungicides, insecticides, nematicides, miticides, biopesticides, herbicides, plant growth regulators, biostimulants, antibiotics, fertilizers and nutrients disclosed and reported in PCT Patent Publication No. WO2016156129 and / or PCT Patent Publication No. WO2017153200 can be combined with at least one compound of formula (I) of the present invention.

[0323] In some cases, combinations with other invertebrate pest control compounds or agents (which have similar control spectra but different modes of action) will be particularly beneficial for resistance management. Thus, the compositions of the present invention may further comprise a biologically effective amount of at least one additional invertebrate pest control compound or agent having a similar control spectrum but a different mode of action. Contacting plants or plant loci genetically modified to express plant protection compounds (e.g., proteins) with a biologically effective amount of a compound of the present invention may also provide broader plant protection and facilitate resistance management.

[0324] In one embodiment of the present invention, the biologically effective amount of the compound of formula (I) in the composition is 0.1% to 99% relative to the total weight of the composition, preferably 5% to 50% relative to the total weight of the composition.

[0325] The present invention also provides a method for controlling insect and acarid pests, which comprises contacting the insect and acarid pests, their habitats, breeding grounds, food supplies, plants, seeds, soils, areas, materials or environments where the insect and acarid pests are growing or may grow, or materials, plants, seeds, soils, surfaces or spaces protected from pest infestation or infection with a biologically effective amount of the compound of the present invention or its composition.

[0326] Control of invertebrate pests and protection of agronomic, horticultural and specialty crops, animals and human health by applying an effective amount of one or more compounds of the invention to the pest's environment (including agronomic and / or non-agronomic crop infestations), to the area to be protected, or directly to the pest to be controlled. Thus, the invention further includes methods for controlling foliar and soil invertebrates and protecting agronomic and / or non-agronomic crops, which methods comprise contacting the invertebrate or its environment with a biologically effective amount of one or more compounds of the invention, or with a composition comprising at least one such compound, or comprising at least one such compound and an effective amount of at least one additional biologically active compound or agent. A preferred method of contact is by spraying. Alternatively, a granular composition comprising the compounds of the invention may be applied to plant foliage or soil. The compounds of the invention may also be effectively delivered by plant absorption by contacting the plant with a composition comprising the compounds of the invention applied as a soil drench in a liquid formulation, a granular formulation applied to the soil, a seedling box treatment, or a transplant dip. Other methods of contact include application of the compounds or compositions of the invention by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic absorption, baits, ear tags, boluses, sprays, fumigants, aerosols, dusts and many others.

[0327] The compounds of the invention may be incorporated into baits consumed by invertebrate pests or used in devices such as traps, bait stations and the like. Granules or baits containing 0.01%-5% active ingredient, 0.05%-10% humectant and 40%-99% vegetable powder are effective in controlling soil insects at very low application rates, especially at doses of active ingredient that are lethal by ingestion rather than by direct contact. The compounds of the invention may be applied as pure substances, but are most commonly applied as formulations containing one or more compounds with suitable carriers, diluents and surfactants, and may be combined with food depending on the intended end use. Preferred methods of application include spraying aqueous dispersions or refined oil solutions of the compounds. Combination with spray oils, spray oil concentrates, spreaders, adhesives, adjuvants, other solvents and synergists such as piperonyl butoxide generally enhances the efficacy of the compounds.

[0328] The application rate required for effective control (i.e., the "biologically effective amount") will depend on such factors as the type of invertebrate to be controlled, the pest's life cycle, life stage, its size, location, season, host crop or animal, feeding behavior, mating behavior, ambient humidity, temperature, and the like. Under normal circumstances, an application rate of about 0.01 kg to 2 kg of active ingredient per hectare is sufficient to control pests in agronomic ecosystems, but as little as 0.0001 kg per hectare may be sufficient or as much as 8 kg per hectare may be desirable. For non-agricultural applications, effective application rates should be in the range of about 1.0 mg / m2 to 50 mg / m2, but as little as 0.1 mg / m2 may be sufficient or as much as 150 mg / m2 may be desirable. The biologically effective amount required for the desired degree of invertebrate pest control can be readily determined by one of ordinary skill in the art.

[0329] Animal pests (i.e., arthropods, gastropods, and nematodes), plants, soil or water in which the plants grow can be contacted with the compound of formula (I), its N-oxide and salt, or a composition comprising the compound of formula (I), its N-oxide and salt by any application method known in the art to which the present invention belongs. As used herein, the term "contacting" includes 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).

[0330] The compounds of the present invention or the insecticidal compositions comprising the compounds can be used to protect growing plants / crops from being attacked or infected by animal pests (especially Insecta, Acaridae or Arachnida) by contacting the plants / crops with at least one insecticidally effective amount of the compounds of the present invention. The term "crops" refers to both growing and harvested crops.

[0331] Therefore, the present invention relates to a method for protecting crops from attack or infestation by invertebrate pests, which method comprises contacting the crops with a biologically effective amount of a compound of the present invention or a composition, isomer, polymorph, N-oxide or salt thereof.

[0332] The compound of the present invention itself or in the form of a composition, by applying an insecticidal effective amount of the active compound to insects or plants, plant propagation materials (such as seeds, soil, surfaces, materials or spaces protected from insecticidal attacks). The above application can be carried out before and after plants, plant propagation materials (such as seeds, soil, surfaces, materials or spaces) are infested by insects.

[0333] Therefore, the present invention also relates to a method for protecting seeds from soil insects and protecting seedling roots and shoots from soil and foliar insects, which comprises: contacting the seeds with the compound or composition of the present invention, its N-oxide or salt before sowing and / or germination.

[0334] Furthermore, the present invention relates to a method for treating or protecting an animal from parasitic infestation or infection, the method comprising: administering or applying a biologically effective amount of a compound of the present invention or its composition, isomer, polymorph, N-oxide or veterinarily acceptable salt to the animal orally, topically or parenterally.

[0335] For use in the treatment of crops, the application rate (effective dosage) of the compounds of the present invention may be in the range of 1 gram of active ingredient (gai) to 5000 grams of active ingredient (gai) per hectare in agricultural or horticultural crops, preferably 25 grams to 600 grams per hectare, more preferably 35 grams to 300 grams per hectare.

[0336] The compounds and compositions of the invention are particularly suitable for controlling a wide variety of insects on a variety of cultivated plants, such as cereals, root crops, oilseed crops, vegetables, spices, ornamentals, for example, durum wheat seed and other wheat, barley, oats, rye, corn (fodder corn and sugar corn / sweet corn and regular corn), soybeans, oilseed crops, crucifers, cotton, sunflowers, bananas, rice, rapeseed, turnip rape, sugar beet, fodder beet, eggplant, potato, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin / squash, cabbage, iceberg lettuce, peppers, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geraniums / pelargoniums, pansies and impatiens.

[0337] In particular, the compounds or compositions of the present invention can be used to protect agricultural crops, such as cereals, corn, rice, soybeans and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbits, oil plants, tobacco, coffee, tea, cocoa, sugar beets, sugar cane, cotton, potatoes, tomatoes, onions, peppers and other vegetables and ornamental plants.

[0338] The present invention also relates to a process for preparing a compound selected from formula (I).

[0339] The compounds of the invention are effective both by contact (via soil, glass, walls, mosquito nets, carpets, plant parts or animal parts) and by ingestion (baits or plant parts).

[0340] The compounds of the present invention can also be used to combat non-crop insect or acarid pests, such as ants, termites, wasps, flies, mosquitoes, crickets or cockroaches. In order to combat the non-crop pests, the compounds of the present invention are preferably used in bait compositions.

[0341] Bait can be a liquid, solid or semi-solid formulation (e.g. gel). Solid baits can be formed into various shapes and forms suitable for individual application, such as granules, blocks, sticks, discs. Liquid baits can be filled in various devices such as open containers, spray devices, droplet sources or evaporation sources to ensure proper application. Gels can be based on aqueous or oily bases and can be formulated for specific needs in terms of viscosity, water retention or aging characteristics.

[0342] The bait used in the composition is a product that is sufficiently attractive to lure insects such as ants, termites, wasps, flies, mosquitoes, crickets, etc. or cockroaches to eat the bait. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are selected from, for example, but not limited to, animal and / or plant proteins (meat meal, fish meal or blood meal, insect parts, egg yolks), from fats and oils of animal and / or plant origin, or mono-, oligo- or poly-organic sugars, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or rotten parts of fruits, crops, plants, animals, insects or specific parts thereof can also be used as feeding stimulants. It is known that sex pheromones are more insect-specific. Specific pheromones are described in the literature and are known to those skilled in the art.

[0343] In the case of bait compositions, typical amounts of active ingredients are from 0.001% to 15%, desirably from 0.001% to 5%, by weight of active compound.

[0344] Formulations of the compounds of the invention in the form of aerosols (eg in spray cans), oil sprays or pump sprays are highly suitable for use by the non-professional user to control pests such as flies, fleas, ticks, mosquitoes or cockroaches. Aerosol preparations are preferably composed of the following: active compounds; solvents, such as lower alcohols (e.g., methanol, ethanol, propanol, butanol), ketones (e.g., acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g., kerosene) having a boiling point range of about 50°C to 250°C, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons (e.g., toluene, xylene), water; in addition, adjuvants, such as emulsifiers, such as sorbitan monooleate, oleyl ethoxylates with 3 to 7 mols of ethylene oxide, fatty alcohol ethoxylates, perfume oils (e.g., essential oils), esters of medium-carbon fatty acids and lower alcohols, aromatic carbonyl compounds; where appropriate, stabilizers (e.g., sodium benzoate), amphoteric surfactants, lower carbon epoxides, triethyl orthoformate; and where necessary, propellants, such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or a mixture of these gases.

[0345] Oil spray formulations differ from aerosol formulations in that no propellant is used. When used in spray compositions, the active ingredient content is 0.001 to 80 wt%, preferably 0.01 to 50 wt%, and most preferably 0.01 to 15 wt% of the active compound.

[0346] The compounds of the present invention and their respective compositions can also be used in mosquito coils and fumigating coils, chimneys, evaporator panels or long-term evaporators, as well as moth repellent papers, moth repellent mats or other evaporator systems not related to heat.

[0347] The method of controlling infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis and leishmaniasis) with the compounds of formula (I) and their respective compositions also comprises treating the surfaces of sheds and houses, aerial spraying and impregnating curtains, tents, clothing articles, mosquito nets, tsetse fly traps or the like. The insecticidal composition applied to fibers, fabrics, knitwear, nonwovens, netting materials or foils and tarpaulins preferably comprises a mixture comprising an insecticide, optionally a repellent and at least one binder. Suitable repellents are, for example, N,N-diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3-cyclohexan-1-yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl)acetic acid lactone ... lactone), 2-ethyl-1,3-hexandiol, indalone, methylneodecanamide (MNDA), pyrethroids not used for insect control (such as {(+ / -)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysanthemate ({(+ / -)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysanthemate yl4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysantemate (Esbiothrin), repellents derived from plant extracts or the same (such as limonene, eugenol, (+)-eucalol (1)), (-)-1-epi-eucamalol (-)-l-epi-eucamalol), or repellents derived from crude plant extracts of plants (such as limonamine (Eucalyptus maculata), Vitex rotundifolia, Cymbopogan martinii, lemongrass (Cymbopogan citratus), lemongrass (Cymopogan nartdus)).Suitable binders are selected, for example, from polymers and copolymers of vinyl esters of aliphatic acids such as vinyl acetate and vinyl versatate, acrylates and methacrylates of alcohols such as butyl acrylate, 2-ethylhexyl acrylate and methyl acrylate, monoolefinically and diolefinically unsaturated hydrocarbons such as styrene and aliphatic dienes such as butadiene.

[0348] Impregnation of curtains and mosquito nets is generally carried out by dipping the textile material into the emulsion or dispersion or by spraying the emulsion or dispersion onto the net.

[0349] The compounds and mixtures of the present invention and their compositions can be used to protect wooden materials, such as trees, wooden fences, sleepers, frames, artworks, etc. and buildings, and also to protect building materials, furniture, leather, fibers, vinyl products, wires and cables, etc. from ants and / or termites, and to control ants and termites from causing damage to crops or humans (e.g., when pests invade houses and public facilities). The compounds of the present invention are not only applied to the surrounding soil surface or the soil under the floor to protect wooden materials, but also can be applied to wood products (e.g., the surface of concrete under the floor, niche columns, beams, plywood, furniture, etc.), wood products (e.g., particleboard, half board, etc.) and vinyl products (e.g., coated wires, vinyl sheets, insulation materials (e.g., foamed styrene), etc.).

[0350] Seed treatment

[0351] The present invention further relates to a seed comprising a compound of the present invention, in particular in an amount of about 0.0001% to about 1% by weight of the seed before treatment.

[0352] The compounds of the present invention are particularly useful for protecting seeds from soil pests and protecting the roots and shoots of the resulting plants from soil pests and foliar insects. Preferably, the roots and shoots of the resulting plants are protected. More preferably, the shoots of the resulting plants are protected from piercing-sucking insects, with the most preferred being protection from aphids.

[0353] Therefore, the present invention includes a method for protecting seeds from insects (especially soil insects) and protecting the seedling roots and shoots of the seeds from insects (especially soil and foliar insects), which method comprises: before sowing the seeds and / or after the seeds are pre-germinated, the seeds are contacted with the compounds of the present invention. Particularly preferred is a method for protecting the roots and shoots of plants; more preferred is a method for protecting the shoots of plants from piercing and sucking insects; and most preferred is a method for protecting the shoots of plants from aphids.

[0354] The term seed encompasses all kinds of seeds and plant propagules, including but not limited to seed pieces, suckers, corms, bulbs, fruits, tubers, grains, cuttings, cuttings and the like, and in a preferred embodiment means true seeds.

[0355] The term seed treatment encompasses all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.

[0356] The present invention also includes seeds coated with or containing active compounds. Such seeds can be coated with a seed coating composition containing a compound of the present invention. For example, seed coating compositions are reported in European Patent No. EP3165092, European Patent No. EP3158864, PCT Patent Publication No. WO2016198644, PCT Patent Publication No. WO2016039623, PCT Patent Publication No. WO2015192923, Canadian Patent No. CA2940002, U.S. Patent Publication No. US2006150489, U.S. Patent Publication No. US200423 7395, PCT Patent Publication No. WO2011028115, European Patent No. EP2229808, PCT Patent Publication No. WO2007067042, European Patent No. EP1795071, European Patent No. EP1273219, PCT Patent Publication No. WO200178507, European Patent No. EP1247436, Netherlands Patent No. NL1012918 and Canadian Patent No. CA2083415.

[0357] The term "coated with and / or containing" generally means that the active ingredient is mostly on the surface of the propagation product at the time of application, although a greater or lesser portion of the ingredient may penetrate into the propagation product, depending on the method of application. When the propagation product is (re)planted, it may absorb the active ingredient.

[0358] Suitable seeds are, for example, cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seeds of durum wheat and other wheat, barley, oats, rye, corn (fodder corn and sugar corn / sweet corn and regular corn), soybeans, oil crops, crucifers, cotton, sunflower, bananas, rice, rapeseed, turnip rape, sugar beet, fodder beet, eggplant, potato, grass, lawn, turf, fodder grass, tomato, leek, pumpkin / squash, cabbage, iceberg lettuce, pepper, cucumber, melon, Brassica, melon, beans, peas, garlic, onion, carrot, seeds of tuberous plants such as potato, sugar cane, tobacco, grapes, petunia, geranium / geranium, pansies and impatiens.

[0359] In addition, the compounds according to the invention can also be used to treat seeds from plants which have been bred (including genetically engineered) to tolerate the action of herbicides or fungicides or insecticides.

[0360] For example, the compounds of the present invention can be used to treat seeds from plants that are resistant to herbicides selected from the group consisting of sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium and similar active substances (see, for example, European Patent No. EP242236, European Patent No. EP242246) (PCT Patent Publication No. WO92 / 00377) (U.S. Patent No. EP257993, U.S. Patent No. US5013659), or in genetically modified crop plants (such as cotton) that have the ability to produce Bacillus thuringiensis toxins (Bt toxins) and make the plants resistant to certain pests (European Patent No. EP142924, European Patent No. EP193259).

[0361] In addition, the compounds of the invention can be used to treat seeds from plants having modified properties compared to existing plants, which can be produced, for example, by conventional breeding methods and / or the generation of mutants, or by recombinant procedures. For example, many cases have described the recombinant modification of crop plants for the purpose of modifying the starch synthesized in plants (e.g., PCT Patent Publication No. WO92 / 11376, PCT Patent Publication No. WO92 / 14827, PCT Patent Publication No. WO91 / 19806) or for the purpose of genetically transfecting crop plants with modified fats (PCT Patent Publication No. WO91 / 13972).

[0362] The seed treatment application of the compound of the present invention is carried out by spraying or broadcasting before the plants are sown and before the plants emerge.

[0363] Compositions particularly suitable for seed treatment are, for example:

[0364] A. Water-soluble concentrate (SL, LS)

[0365] B. Emulsion (EW, EO, ES)

[0366] C. Suspension (SC, OD, FS)

[0367] D. Water dispersible granules and water soluble granules (WG, SG)

[0368] E. Water dispersible powders and water soluble powders (WP, SP, WS)

[0369] F. Gel formulation (GF)

[0370] G. Powderable powder (DP, DS)

[0371] Conventional seed treatment formulations include, for example, flowable concentrates (FS), solutions (LS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS) and emulsions (ES and EC) and gel formulations (GF). The formulation can be applied to diluted or undiluted seeds. It can be applied directly to the seeds before sowing, or applied to the seeds after the seeds have germinated.

[0372] In one embodiment, FS preparation is used for seed treatment. Generally, FS preparation may contain 1-800 g / l active ingredient, 1-200 g / l surfactant, 0 to 200 g / l antifreeze agent, 0 to 400 g / l binder, 0 to 200 g / l pigment and up to 1 liter solvent, preferably water.

[0373] Other preferred FS formulations of the compounds of the invention for seed treatment comprise 0.1 to 80% by weight (1 to 800 g / l) of active ingredient, 0.1 to 20% by weight (1 to 200 g / l) of at least one surfactant (e.g. 0.05 to 5% by weight of a wetting agent) and 0.5 to 15% by weight of a dispersant, up to 20% by weight (e.g. 5 to 20% by weight) of an antifreeze agent, 0 to 15% by weight (e.g. 1 to 15% by weight) of a pigment and / or dye, 0 to 40% by weight (e.g. 1 to 40% by weight) of a binder (adhesive / sticker), optionally up to 5% by weight (e.g. 0.1 to 5% by weight) of a thickener, optionally 0.1 to 2% by weight of an antifoam and optionally a preservative (e.g. a biocide, an antioxidant, etc., e.g. in an amount of 0.01 to 1% by weight) and up to 100% by weight of a filler / carrier.

[0374] The seed treatment formulation may additionally contain a binder and optionally a colorant.

[0375] Binders may be added to improve the adhesion of the active material to the seeds after treatment. Suitable binders are homopolymers and copolymers from alkylene oxides (e.g. ethylene oxide or propylene oxide), polyvinyl acetate, polyvinyl alcohol, polyvinyl pyrrolidone and its copolymers, ethylene-vinyl acetate copolymers, homopolymers and copolymers of acrylic acid, polyvinylamine, polyvinylamide and polyvinylpyrimidine, polysaccharides (e.g. cellulose, cellulose and starch), homopolymers and copolymers of polyolefins (e.g. olefin / maleic anhydride copolymers, polyurethanes, polyesters, homopolymers and copolymers of polystyrene).

[0376] Optionally, a colorant may also be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, CI Pigment Red 112, CI 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.

[0377] An example of a gelling agent is carrageenan

[0378] In seed treatment, the application rate of the compounds of the present invention is generally 0.1 gram to 10 kilograms per 100 kilograms of seeds, preferably 1 gram to 5 kilograms per 100 kilograms of seeds, more preferably 1 gram to 1 kilogram per 100 kilograms of seeds, especially 1 gram to 200 grams per 100 kilograms of seeds. Therefore, the present invention also provides seeds comprising a compound of formula (I) as defined herein or an agriculturally useful salt of a compound of formula (I). The amount of a compound of formula (I) or its agriculturally useful salt is generally 0.1 gram to 10 kilograms per 100 kilograms of seeds, preferably 1 gram to 5 kilograms per 100 kilograms of seeds, especially 1 gram to 1 kilogram per 100 kilograms of seeds. For specific crops, such as lettuce, the application rate can be higher.

[0379] Animal Health

[0380] The present invention also provides an agricultural and / or veterinary composition comprising at least one compound of the present invention.

[0381] The present invention also relates to the use of the compound, N-oxide or veterinarily acceptable salt, or a composition thereof, for preparing a medicament for treating or protecting animals from infestation or infection by insects, mites or parasites.

[0382] The compounds of formula (I), their N-oxides and / or their veterinarily acceptable salts are also particularly suitable for controlling parasites in and on animals.

[0383] It is therefore an object of the present invention to provide a novel method for controlling parasites in and on animals. It is another object of the present invention to provide safer pesticides for use in animals. It is another object of the present invention to provide pesticides for use in animals that can be used at lower doses than existing pesticides. It is another object of the present invention to provide pesticides for use in animals that provide long-lasting control of parasites.

[0384] The present invention also relates to a composition comprising a parasiticidal effective amount of at least one compound of formula (I), N-oxide or a veterinarily acceptable salt thereof and an acceptable carrier, which is used for preventing and controlling parasites in and on animals.

[0385] The present invention also provides a method for treating, controlling, preventing and protecting animals from parasitic infestation and infection, which comprises orally, topically or parenterally administering or applying a parasiticidal effective amount of the compound of the present invention or a composition containing the compound to the animal.

[0386] The present invention also provides a method for preparing a composition for treating, controlling, preventing or protecting animals from parasitic infestation or infection, wherein the composition comprises a parasiticidal effective amount of the compound of the present invention or a composition comprising the compound.

[0387] The activity of a compound against agricultural pests does not indicate its suitability for controlling endoparasites and ectoparasites in and on animals, which requires, for example, low non-emetic doses (under oral administration), metabolic compatibility with animals, low toxicity and safe handling.

[0388] It has surprisingly been found that the compounds of the present invention are suitable for combating endoparasites and ectoparasites in and on animals.

[0389] The compounds of the present invention and compositions comprising the compounds are preferably used to control and prevent infestations and infections of animals including warm-blooded animals (including humans) and fish. They are suitable, for example, for controlling and preventing infestations and infections of mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, buffaloes, donkeys, yellow deer and reindeer; and fur animals such as minks, chinchillas and raccoons; birds such as chickens, geese, turkeys and ducks; and fish such as freshwater fish and saltwater fish such as trout, carp and eels.

[0390] The compounds of the present invention and compositions comprising the compounds are preferably used to control and prevent infestations and infections in domestic animals such as dogs or cats.

[0391] Infestations of warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, snout bugs, ticks, biting flies, moss flies, flies, myiasis fly larvae, chiggers, gnats, mosquitoes and fleas.

[0392] The compounds of the invention and compositions comprising the compounds are suitable for systemic and / or non-systemic control of ectoparasites and / or endoparasites. They are active against all or some stages of development.

[0393] The compounds of the present invention and compositions containing the compounds are particularly suitable for preventing and controlling external parasites.

[0394] The compounds of the invention are particularly useful against parasites of the following orders and species, respectively: fleas (Siphonaptera), for example Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tungapenetrans and Nosopsyllus fasciatus, cockroaches (Blattaria-Blattodea), for example Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasianasiae and Blatta orientalis. orientalis, flies and mosquitoes (Diptera), for example, Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya cellaria, Chrysops discalis), Chrysops silacea, Chrysops atlanticus, Cochliomyiahominivorax), Cordylobia anthropophaga, Culicoides furens, Culex pipens, 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, Oestrus ovis, Phlebotomus argentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus), black horse fly (Tabanusatratus), slender horse fly (Tabanus lineola), and zebra horse fly (Tabanussimilis, lice (order Phthiraptera), for example Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotescapillatus, ticks and parasitic mites (order Parasitiformes): ticks (suborder Ixodida), for example Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus philippinarum, sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryommama culatum, Ornithodorus hermsi, Ornithodorus turicata, and parasitic mites (Mesostigmata), for example, Ornithonyssus bacoti and Dermanyssus gallinae, Actinedida (Prostigmata), and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp. spp.), Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphusspp.), Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp., Stink bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp.), Panstrongylus ssp. and Arilus critatus, from the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp., from the order of the Mallophagida (suborder Arnblycerina and Ischnocerina), for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp. spp.) and Felicola spp.

[0395] Roundworms Nematoda:

[0396] Wipeworms and Trichinosis (Trichosyringida), e.g., Trichinellidae (Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp., Rhabditida, e.g., Rhabditis spp., Strongyloides spp., Helicephalobus spp., Strongylida, e.g., Strongylus spp., Ancylostomas spp., Necator americanus, Bunostomum spp. (Hookworm), Trichostrongylus spp. spp.), Haemonchus contortus., Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus, Syngamustrachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp.), Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp.), Aleurostrongylus abstrusus and Dioctophyma renale, gastrointestinal roundworms (Ascaridida), for example Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp. and Oxyuris equi, Camallanida, for example Dracunculus medinensis (Guinea worm), worm), from the order of the Spiruridae, for example, Thelazia spp., Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilaria spp., Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi and Habronema spp., hookworms (order of the Acanthocephala), for example, Acanthocephalus spp., Macracanthorhynchus hirudinaceus and Oncicola spp. spp.), turbellarians (Plathelminthes): trematodes (Trematoda), for example, Faciola spp., Fascioloides magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp.), Alariaalata, Paragonimus spp. and Nanocyetes spp., Cercomeromorpha, in particular Cestoda (Tapeworms), for example Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp.), Anoplocephala spp., and Hymenolepis spp.

[0397] The compound of formula (I) and compositions containing the compound are particularly suitable for controlling pests of the orders Diptera, Siphonaptera and Ixodida.

[0398] In addition, the use of the compound of formula (I) and the composition comprising the same for controlling mosquitoes is an embodiment of the present invention.

[0399] The use of the compound of the present invention and the composition comprising the same for controlling flies is another embodiment of the present invention.

[0400] In addition, use of the compound of the present invention and the composition comprising the same for controlling fleas is another embodiment of the present invention.

[0401] Use of the compound of the present invention and the composition comprising the same for controlling ticks is another embodiment of the present invention.

[0402] The compounds according to the invention are also particularly suitable for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).

[0403] Administration can be performed prophylactically or therapeutically.

[0404] Administration of the compounds of the invention is carried out directly or in the form of a suitable formulation, orally, topically / dermally or parenterally.

[0405] For oral administration to warm-blooded animals, the compounds of the present invention can be formulated into animal feed, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, pills and capsules. In addition, the compounds of the present invention can be administered to animals in their drinking water. For oral administration, the selected dosage form should provide the animal with 0.01 mg to 100 mg of the compound of the present invention per kilogram of animal body weight per day, preferably 0.5 mg to 100 mg of the compound of the present invention per kilogram of animal body weight per day.

[0406] Alternatively, the compounds of the present invention may be administered parenterally to animals, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds of the present invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of the present invention may be formulated into implants for subcutaneous administration. In addition, the compounds of the present invention may be administered transdermally to animals. For parenteral administration, the selected dosage form should provide the animal with 0.01 mg to 100 mg of the compound of the present invention per kg of animal body weight per day.

[0407] The compounds of the present invention can also be applied to animals in the form of dips, powders, powders, rings, discs, sprays, shampoos, drops and pour-on preparations and in the form of ointments or oil-in-water emulsions or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5000 ppm and preferably 1 ppm to 3000 ppm of the compounds of the present invention. In addition, the compounds of the present invention can be formulated into ear tags for animals, especially quadrupeds such as cattle and sheep.

[0408] Suitable formulations are: solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pour-on preparations, gels; emulsions and suspensions for oral or transdermal administration; semisolid formulations; formulations in which the active compound is processed in an ointment base or in an oil-in-water emulsion or a water-in-oil emulsion base; solid formulations such as powders, premixes or concentrates, granules, pellets, lozenges, boluses, capsules; aerosols and inhalants, and shaped articles containing the active compound.

[0409] Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding other ingredients such as acids, bases, buffer salts, preservatives and solubilizers.

[0410] The solution was filtered and filled aseptically.

[0411] Suitable solvents are physiologically tolerable solvents, such as water; alkanols, such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycol; N-methyl-pyrrolidone; 2-pyrrolidone and mixtures thereof.

[0412] The active compound can optionally be dissolved in physiologically tolerated vegetable or synthetic oils suitable for injection.

[0413] Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinyl pyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil and polyoxyethylated sorbitan esters.

[0414] Suitable preservatives are benzyl alcohol, chlorobutanol, parabens and n-butyl alcohol.

[0415] Oral solutions are administered directly. Concentrates are administered orally after being diluted to the use concentration in advance. Oral solutions and concentrates are prepared according to the prior art and as described above for injection solutions, and sterile procedures are not required.

[0416] Solutions for application to the skin are dripped, spread, wiped, sprinkled or sprayed thereon.

[0417] Solutions for application to the skin are prepared according to the prior art and as described above for injection solutions, sterile procedures not being necessary.

[0418] Other suitable solvents are polypropylene glycol; phenylethyl alcohol; phenoxyethanol; esters, such as ethyl acetate or butyl acetate, benzyl benzoate; ethers, such as alkanediol alkyl ethers (e.g. dipropylene glycol monomethyl ether); ketones, such as acetone, methyl ethyl ketone; aromatic hydrocarbons; vegetable and synthetic oils; dimethylformamide; dimethylacetamide; diethylene glycol monoethyl ether (transcutol); glycerol acetone acetone (solketal); propylene carbonate and mixtures thereof.

[0419] It may be advantageous to add a thickener during the preparation process. Suitable thickeners are inorganic thickeners (eg bentonites, colloidal silicic acid, aluminum monostearate), organic thickeners (eg cellulose derivatives, polyvinyl alcohol and copolymers thereof), acrylates and methacrylates.

[0420] The gel is applied or spread on the skin or introduced into a body cavity. The gel is prepared by treating a solution prepared as described in the case of an injection solution with sufficient thickening agent formed of a transparent substance having an ointment-like consistency. The thickening agent used is the thickening agent listed above.

[0421] Pour-on preparations are poured or sprayed on a limited area of ​​the skin. The active compound penetrates the skin and acts systemically. Pour-on preparations are prepared by dissolving, suspending or emulsifying the active compound in a suitable skin-compatible solvent or solvent mixture. Other adjuvants (such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives) are added as appropriate.

[0422] Suitable solvents are: water; alkanols; glycols; polyethylene glycols; polypropylene glycols; glycerol; aromatic alcohols such as benzyl alcohol, phenylethyl alcohol, phenoxyethanol; esters such as ethyl acetate, butyl acetate, benzyl benzoate; ethers such as alkanediol 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; N-alkylpyrrolidone such as methylpyrrolidone, N-butylpyrrolidone or N-octylpyrrolidone; N-methylpyrrolidone; 2-pyrrolidone; 2,2-dimethyl-4-oxy-methylene-1,3-dioxolane or glycerol formal.

[0423] Suitable colorants are all colorants which are permitted for use on animals and which are soluble or suspendable.

[0424] Suitable absorption-promoting substances are: dimethyl sulfoxide; spreading oils, such as isopropyl myristate, dipropylene glycol nonanoate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.

[0425] Suitable antioxidants are sulfites or metabisulfites (such as potassium metabisulfite), ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.

[0426] Suitable light stabilizers are, for example, 2-phenylbenzimidazole-5-sulfonic acid (novantisolic acid). Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacrylates, natural polymers such as alginates, gelatin. The emulsion can be administered orally, percutaneously or by injection. The emulsion is of the water-in-oil type or of the oil-in-water type.

[0427] They are prepared by dissolving the active compound in a hydrophobic phase or in a hydrophilic phase and homogenizing it with other phase solvents with the aid of suitable emulsifiers and, where appropriate, other auxiliary agents (such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances).

[0428] Suitable hydrophobic phases (oils) are:

[0429] Liquid paraffin; silicone oil; natural vegetable oils such as sesame oil, almond oil, castor oil; synthetic triglycerides such as caprylic / capric diglyceride, triglyceride mixtures formed with vegetable fatty acids of chain length Cs-Ci2 or other specially selected natural fatty acids; partial glyceride mixtures of saturated or unsaturated fatty acids that may also contain hydroxyl groups; monoglycerides and diglycerides of Cs-do fatty acids; fatty acid esters such as ethyl stearate, di-n-butyl adipate, hexyl laurate, dipropylene glycol nonanoate; branched chain fatty acids with medium chain length and chain length C 16 -C 18 Esters of saturated fatty alcohols; Isopropyl myristate; Isopropyl palmitate; Chain length C 12 -C 18 Caprylic / capric esters of saturated fatty alcohols; isopropyl stearate; oleyl oleate; decyl oleate; ethyl oleate; ethyl lactate; waxy fatty acid esters such as synthetic duck tail 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.

[0430] Suitable emulsifiers are: nonionic surfactants, for example polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; amphoteric surfactants, such as di-sodium N-lauryl-p-iminodipropionate or lecithin.

[0431] Suitable anionic surfactants are: sodium lauryl sulfate, fatty alcohol ether sulfate, mono / dialkyl polyglycol ether orthophosphoric acidester monoethanolamine salt; suitable cationic surfactants are: hexadecyltrimethylammonium chloride.

[0432] Suitable further auxiliaries are: substances which increase viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycol, waxes, colloidal silicic acid or mixtures of the substances mentioned.

[0433] The suspension can be administered orally or topically / dermally. It is prepared by suspending the active compound in a suspending agent, if appropriate, by adding other auxiliary agents such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.

[0434] Liquid suspensions are all homogeneous solvents and solvent mixtures.

[0435] Suitable wetting agents (dispersants) are the emulsifiers listed above.

[0436] Further auxiliaries which may be mentioned are the auxiliaries listed above.

[0437] Semisolid formulations can be administered orally or topically / dermally. They differ from the above-mentioned suspensions and emulsions only in their higher viscosity.

[0438] For the production of solid formulations, the active compound is mixed with suitable excipients, if appropriate with the addition of auxiliaries, and brought into the desired form.

[0439] Suitable excipients are all solid inert substances that are physiologically tolerable. The excipients used are inorganic or organic substances. Inorganic substances are, for example, sodium chloride, carbonates (such as calcium carbonate), bicarbonates, aluminum oxide, titanium oxide, silicic acid, clay, precipitated silica or colloidal silica or phosphates. Organic substances are, for example, sugars, cellulose, food and feed (such as milk powder, animal meal, grain meal and grain crumbs), starch.

[0440] Suitable auxiliaries are the preservatives, antioxidants and / or colorants already mentioned above.

[0441] Other suitable adjuvants are lubricants and glidants, such as magnesium stearate, stearic acid, talc, bentonite; disintegration-promoting substances, such as starch or cross-linked polyvinyl pyrrolidone; binders, such as starch, gelatin or linear polyvinyl pyrrolidone; and anhydrous binders, such as microcrystalline cellulose.

[0442] In general, "parasiticidally effective amount" means the amount of active ingredient required to achieve an observable effect on growth, including death, delay, prevention, removal, and destruction or otherwise reducing the appearance and activity of the target organism. The parasiticidal effective amount of the various compounds / compositions used in the present invention may vary. The parasiticidal effective amount of the composition will also vary depending on the prevailing conditions (such as the desired parasiticidal effect and duration, target species, mode of application, and the like). Compositions useful in the present invention generally contain about 0.001% to 95% of the compounds of the present invention.

[0443] In general, it is advisable to apply the compound of the present invention with a total amount of 0.5mg / kg to 100mg / kg, preferably 1mg / kg to 50mg / kg every day. It is 10ppm to 80% by weight that the preparation contains a concentration, preferably 0.1% by weight to 65% by weight, more preferably 1% by weight to 50% by weight, and most preferably 5% by weight to 40% by weight, which acts on parasites, preferably on ectoparasites. It is 0.5% by weight to 90% by weight that the preparation diluted before use contains a concentration, preferably 1% by weight to 50% by weight, which acts on ectoparasites. In addition, it is 10ppm to 2% by weight that the preparation comprises a concentration, preferably 0.05% by weight to 0.9% by weight, and especially preferably 0.005% by weight to 0.25% by weight of the compound of the present invention against endoparasites.

[0444] In one embodiment, the compositions comprising the compounds of the invention are administered transdermally / topically.

[0445] In another embodiment, topical application is carried out in the form of shaped articles containing the compound, such as rings, discs, ear tags, strips and adhesive strips and foils that are fixed to a body part.

[0446] Generally, it is preferred to apply a solid formulation which releases a total amount of 10 to 300 mg, preferably 20 to 200 mg, and most preferably 25 to 160 mg of the compound of the invention per kg body weight of the treated animal over a three week period.

[0447] When preparing shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyethylene resins, polyurethanes, polyacrylates, epoxy resins, cellulose, cellulose derivatives, polyamides and polyesters that are fully compatible with the compounds of the present invention. A detailed list of plastics and elastomers and the preparation procedures of shaped articles are listed, for example, in PCT Patent Publication No. WO 2003 / 086075.

[0448] Digital Technology

[0449] The compounds of the invention can be used in combination with models, for example, embedded in computer programs, for site-specific crop management, satellite farming, precision farming or precision agriculture. Such models support data from various sources (e.g., soil, weather, crops (e.g., varieties, growth stages, plant health), weeds (e.g., varieties, growth stages), diseases, pests, nutrients, water, humidity, biomass, satellite data, yields, etc.) to achieve the purpose of optimizing profitability, sustainability and environmental protection. In particular, such models help optimize agronomic decisions, control the accuracy of pesticide application and record the work performed.

[0450] For example, if a model simulates the development of pests and calculates that a threshold has been reached that would recommend application of a compound of the invention to a crop, the compound of the invention can be applied to the crop according to an appropriate dosage regimen.

[0451] Commercially available systems including agronomic models are, for example, FieldScripts™ from The Climate Corporation, Xarvio™ from BASF, AGLogic™ from John Deere, and the like.

[0452] The compounds of the present invention may also be used in combination with intelligent spraying equipment, such as spot spraying or precision spraying equipment attached to or mounted on agricultural vehicles (e.g., tractors, robots, helicopters, airplanes, unmanned aerial vehicles (UAVs) (e.g., drones, etc.). Such equipment typically includes an input sensor (e.g., a camera) and a processing unit, which is configured to analyze input data and is configured to provide a decision based on the analysis of the input data to apply the compounds of the present invention to crops (respectively, weeds) in a specific and precise manner. The use of such intelligent spraying equipment typically also requires a positioning system (e.g., a GPS receiver) to locate recorded data and guide or control agricultural vehicles; a geographic information system (GIS) is also required to represent information on an understandable map, and appropriate agricultural vehicles are also required to perform the desired agricultural actions (e.g., spraying).

[0453] In one example, pests can be detected from an image 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 utilize artificial intelligence algorithms. In this way, the compounds described herein can be applied only when needed.

[0454] Positive crop response:

[0455] The compounds of the present invention not only effectively control insect and mite pests, but also show positive crop responses, such as plant growth promotion effects (such as enhancing root growth and enhancing tolerance to drought, high salt, high temperature, cold, frost or light radiation), improving flowering, improving nutrient utilization (such as improving nitrogen assimilation), improving the quality of plant products, increasing the number of productive tillers, enhancing resistance to insect pests, etc., thereby increasing yield.

[0456] General synthesis process:

[0457] The present invention will now be described in further detail by the following examples, but no limitation is imposed thereon.

[0458] Process-1:

[0459]

[0460] In one preferred embodiment, the compound of formula (I) (wherein D represents D1 and Z is 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 a compound of formula D1-1, following the process described in US 20190297887 and the literature further cited therein. The compound of formula D1-1 can be purchased on the market or prepared by the method described in Chem.Eur.J.2021,27,17293-17321, European Journal of Medicinal Chemistry2017,126,225-245, Chem.Commun.,2017,53,348-351, J.Am.Chem.Soc.2020,142(36),15445-15453 and the literature further cited therein. Unless otherwise stated, the definitions of the variables are as described in the compound of formula (I) above.

[0461] The CN coupling reaction is usually carried out in the presence of a solvent. The solvent that can be used for the 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 can be used for 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); among which N,N-dimethylformamide and toluene are the best. The reaction is carried out in the presence of a base selected from but 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 dihydrogen phosphate and potassium hydride), organic bases (such as triethylamine, N,N-diisopropylethylamine and pyridine). Preferred bases include metal alkoxides (such as potassium tert-butoxide and sodium tert-butoxide). The palladium catalyst that can be used for the reaction includes, but is not limited to, palladium-carbon, inorganic palladium salts (such as 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(dibenzylidene acetone)dipalladium(0)), and polymer-immobilized organic palladium complexes (such as polymer-supported bis(acetyl)triphenylphosphinepalladium(II) and polymer-carried di(acetyl)dicyclohexylphosphinepalladium(II)). Palladium catalysts, such as palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, 1,1'-Bis(diphenylphosphino)phenylpalladium(II) dichloride and tris(dimethylbenzylacetone)dipalladium(0) are more preferred. 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, biphenyl), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropylbiphenyl cyclohexylphosphino-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, ethyl-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, (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'-biphenyl4,5,6-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. Preferred ligands include 2-(di-tert-butylphosphino)biphenyl, 2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl, (2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2',4',6'-triisopropyl-1,1'-biphenyl, )bis[dicyclohexyl]phosphine, 1,1'-ferrocenediyl-bis(diphenylphosphine) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene.

[0462] The reaction can be carried out at a temperature ranging from 0 to 200°C, preferably at a temperature ranging from 50 to 150°C, and lasting from 30 minutes to 24 hours.

[0463] Process-2:

[0464]

[0465] In another preferred embodiment, the compound of formula (I) (wherein D represents D1 and Z is -C=O) can be prepared by a metal-catalyzed aminocarbonylation reaction or an amide coupling reaction between a compound of formula A-1C (A-2 is an amide coupling reaction) (wherein LG represents a leaving group) and a compound of formula D1-1, following the processes described in WO2016144351, Chem.Eur.J.2021, 27, 17293-17321 and the literature further cited therein. The compound of formula D1-1 can be purchased on the market or prepared by the method described in Chem.Eur.J.2021,27,17293-17321, European Journal of Medicinal Chemistry2017,126,225-245, Chem.Commun.,2017,53,348-351, J.Am.Chem.Soc.2020,142(36),15445-15453 and the literature further cited therein. Unless otherwise stated, the definition of each variable is as described in the compound of formula (I) above.

[0466] The metal-catalyzed amine carbonylation reaction, as depicted in Scheme 2, is carried out in the presence of a solvent such as, but not limited to, N-amides, for example, N,N-dimethylformamide, N-dimethylacetamide and 1-methyl-2-pyrrolidone; N,N-dimethylformamide is a preferred solvent. The metal hexacarbonyl used 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, which is 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, cesium carbonate), organic amine salts (such as triethylamine, N,N-diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene; preferably in the presence of organic amines (such as N,N-diisopropylethylamine and 1,8-diazabicyclo[5.4.0]undec-7-ene) The catalyst that can be used in this reaction includes, for example, but not limited to, organic palladium complexes (e.g., polymer-supported bis(acetyl)triphenylphosphine palladium (II), trans-di-μ-acetatobis[2-[bis(2-methylphenyl)phosphino]benzyl]dipalladium and polymer-supported di(acetyl)dicyclohexylphosphine palladium (II)). An example of a ligand for the reaction is tri-tert-butylphosphonium tetrafluoroborate. The reaction is usually carried out at a temperature range of 0-200°C, preferably 50-180°C, and lasts for 30 minutes to 24 hours. The reaction can also be carried out under microwave irradiation.

[0467] The amide coupling reaction, as depicted in Scheme 2, is typically carried out in the presence of a solvent such as, but not limited to, an N-amide, for example, N,N-dimethylformamide, N-dimethylacetamide and 1-methyl-2-pyrrolidone; N,N-dimethylformamide is a preferred solvent. In addition, these reactions are carried out in the presence of a base, which is selected from but not limited to organic amine salts (e.g., triethylamine, N,N-diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene); triethylamine and N,N-diisopropylethylamine are preferred bases. The coupling agents that can be used in this reaction are, but not limited to, N,N′-dicyclohexylcarbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methiodide, 1-hydroxybenzotriazole hydrate, hydrate), 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxid hexafluorophosphate and N-[(dimethylamino)-1H-1,2,3-triazolo[4,5-b]pyridin-1-ylmethylene]-N-methylmethanaminium hexafluorophosphate N-oxide. The reaction can be carried out at a temperature ranging from 0 to 200°C, preferably from 0 to 50°C, and for a duration ranging from 30 minutes to 24 hours.

[0468] Process-3:

[0469]

[0470] In another preferred embodiment, the compound of formula (I) (wherein D represents D1 and Z is -C=S) can be prepared from the compound of formula (I) (wherein D represents D1 and Z represents -C=O) under suitable sulfonylation reaction conditions in the presence of Lawesson's reagent, as described in the document Chem. Sci., 2021, 12, 6393-6405 and the documents otherwise cited therein. Unless otherwise stated, the definition of each variable is as described above for the compound of formula (I). The sulfonylation reaction, as depicted in Scheme 3, is carried out in the presence of a solvent, such as, but not limited to, aromatic hydrocarbons (e.g., benzene, toluene and xylene), preferably in the presence of toluene. The reaction can be carried out at a temperature range of 0-200°C, preferably 50-150°C, and the duration is between 30 minutes and 24 hours.

[0471] Process-4:

[0472]

[0473] In another preferred embodiment, the compound of formula (I) (wherein D represents D3 and Z is a direct bond) can be prepared by a metal-catalyzed coupling reaction between a compound of formula A-1 (wherein LG represents a leaving group) and an alkoxytrizolones of formula D3-1, following the process described in document US20190297887 and the documents further cited therein. Alkoxytrizolones of formula D3-1 are commercially available or prepared by the methods described in U.S. Patent Publication No. US005606070A and the documents further cited therein. Unless otherwise stated, the definitions of the variables are as described above for the compound of formula (I).

[0474] The reaction is carried out in the presence of a solvent such as, but not limited to, ethers (e.g., dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether), aromatic hydrocarbons (e.g., benzene, toluene and xylene), N,N-dimethylformamide, N-amides (e.g., N-dimethylacetamide and 1-methyl-2-pyrrolidone), alcohols (e.g., methanol, ethanol, propanol, butanol, 2-propanol, 2-methyl-2-propanol and 2-methyl-2-butanol), nitriles (e.g., acetonitrile) and water or a mixture thereof. Preferred solvents include amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide and 1-methyl-2-pyrrolidone) and alcohols (e.g., methanol, ethanol, propanol, butanol, 2-propanol, 2-methyl-2-propanol and 2-methyl-2-butanol); N,N-dimethylformamide and 2-methyl-2-butanol.

[0475] Bases that can be used in the 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 dihydrogen phosphate, and potassium hydride), and organic bases (such as triethylamine, N,N-diisopropylethylamine, and pyridine). Preferred bases include phosphates (such as sodium phosphate, potassium phosphate, potassium hydrogen phosphate) and carbonates (such as sodium carbonate, potassium carbonate, and cesium carbonate); wherein carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate are more preferred bases. The palladium catalyst that can be used for the reaction includes, but is not limited to, palladium-carbon, inorganic palladium salts (such as 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(dibenzylidene acetone)dipalladium(0)), and polymer-immobilized organic palladium complexes (such as polymer-supported bis(acetyl)triphenylphosphinepalladium(II) and polymer-carried di(acetyl)dicyclohexylphosphinepalladium(II)). Palladium catalysts such as palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, 1,1'-bis(diphenylphosphine)phenylpalladium(II) dichloride and tris(diylidenebenzylacetone)dipalladium(0) are more preferred. Examples of ligands that can be used in this reaction include, but are not limited to, tris(o-tolyl)phosphine, tricyclohexylphosphine, tri-tert-butylphosphoniumtetrafluoroborate, (oxydi-2,1-phenylene)bis[dicyclohexyl]phosphine, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl, and 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl.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 riphenyl-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, 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-sulfonicacid, 2'-(dicyclohexylphosphino)-2,6-dimethoxy-sodium salt. 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, and 5-(dicyclohexylphosphino)-1',3',5'-triphenyl-1'H-[1,4']bipyrazole. ipyrazole), 5-[di(1-adamantyl)phosphino]-1',3',5'-triphenyl-1'H-[1,4']bipyrazole, 1,1'-ferrocenediyl-bis(diphenylphosphine) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene. The reaction can be carried out at a temperature range of 0-200°C, preferably 50-150°C, and the duration is between 30 minutes and 24 hours.

[0476] Process-5:

[0477]

[0478] In another preferred embodiment, the compound of formula (I) (wherein D represents D2, Z is a direct bond and R 7represents hydrogen), can be derivatized on its imino (-NH) functional group by reactions such as N-(halo)alkylation, N-(hetero)arylation, N-acylation, N-amidation, N-halogenation and N-nitrilation to form a compound of formula (I) (wherein D represents D2, Z is a direct bond and R 7 Represents its general meaning but excludes hydrogen), the following suitable methods are described in the literature, such as 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 PCT Patent Publication No. WO2019150219 and the literature further cited therein. Unless otherwise stated, the definitions of the variables are as described above.

[0479] Process-6:

[0480]

[0481] In another preferred embodiment, various sulfur-containing representatives represented by formula (I) (wherein D represents D2, Z is a direct bond and R is a 2-hydroxy- ... 7As defined above), for example, but not limited to: sulfoximines, sulfilimines and sulfondiimides. Unless otherwise specified, the definitions of the variables are as described above for compounds of formula (I). The sulfonimide of formula (I) can be prepared from the sulfide of formula A-3 in the presence of ammonium carbamate and diacetoxyiodobenzene (for example, see Angew. Chem. Int. Ed. 2016, 55, 7203-7207). Alternatively, the sulfonimide (I) can also be prepared by oxidation of the sulfoximide (I) (for example, see Chem. Rev. 1977, 77, 409-435). On the other hand, the sulfonyl imide of formula (I) can be obtained from the sulfide of formula (A-3) by using an electrophilic aminating agent, such as O-(mesitylsulfonyl)hydroxylamine (MSH) or O-(2,4-dinitrophenyl)hydroxylamine (DPH), according to the procedures described in the literature, for example Angew. Chem. Int. Ed. 2012, 51, 4440-4443 and the literature further cited therein. Sulfinyl imines of formula (I) can also be prepared from sulfides of formula (A-4) by imidization by: a) using Burgess-type reagents, as described in the literature, such as Adv. Catal. 2013, 355, 3363-3368 and further references therein, or b) rhodium-catalyzed conditions in the presence of an electrophilic aminating agent, such as but not limited to O-(mesitylenesulfonyl)hydroxylamine (MSH) or O-(2,4-dinitrophenyl)hydroxylamine (DPH), as described in the literature, such as described in Chem. Commun., 2014, 50, 9687-9689 and further references therein. The sulfonyl diimide of formula (I) can be synthesized by the following methods: a) direct imidization of the sulfide of formula A-3, as described in the literature, for example, in Chem. Ber. 1984, 117, 2779-2784 and the literature further cited therein, or b) imidization of the sulfonyl imide of formula (I) as described in the literature, for example, in Angew. Chem. Int. Ed. 2012, 51, 4440-4443 and the literature further cited therein, or c) imidization of the sulfonyl imide salt represented by formula A-5 using N-chlorosuccinimide and an amine, as described in the literature, for example, in Angew. Chem. Int. Ed. 2012, 51, 4440-4443 and the literature further cited therein.

[0482] According to the features of the present invention, the compound of formula A-3 (wherein all substituents are as defined above) can be prepared by the methods disclosed in Scheme 7, Scheme 8, Scheme 9 or the experimental examples. The representative scheme is shown below; however, the present disclosure should not be interpreted as limiting the scope of the synthesis of the compound of formula A-3.

[0483] Process-7:

[0484]

[0485] According to Scheme 7, the compound represented by formula A-3 can be prepared by the compound of formula A-1 and formula R described in PCT Patent Publication No. WO2020257145 and the literature further cited therein. 6 The CS coupling reaction between thiols of SH and SH was mediated by a base and catalyzed by a metal. 6 SH mercaptans are commercially available. Unless otherwise indicated, the variables A1, A2, A3, A4, A5, R 3 , R 6 , R 8 and R 8a The definition of is as described above. LG represents a leaving group such as a halogen or tosylate.

[0486] General Procedure for CS Coupling: The reaction is usually carried out in the presence of a solvent, for example, ethers (e.g., dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, methylene glycol dimethyl ether and diethylene glycol dimethyl ether), aromatic hydrocarbons (e.g., benzene, toluene and xylene), N-amides (e.g., N,N-dimethylformamide, N-dimethylacetamide and 1-methyl-2-pyrrolidone), alcohols (e.g., methanol, ethanol, propanol, butanol, 2-propanol, 2-methyl-2-propanol and 2-methyl-2-butanol), nitriles (e.g., acetonitrile) or water or a mixture thereof. Preferred solvents include amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide and 1-methyl-2-pyrrolidone) and aromatic hydrocarbons (e.g., benzene, toluene and xylene); among which N,N-dimethylformamide and toluene are the most preferred. The reaction is carried out in the presence of a base, which is selected from but not limited to the following: 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 dihydrogen phosphate and potassium hydride), 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); among which carbonates (such as cesium carbonate) and metal alkoxides (such as potassium tert-butoxide and sodium tert-butoxide) are more preferred bases. The palladium catalyst that can be used for the reaction includes, but is not limited to, palladium-carbon, inorganic palladium salts (such as 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(dibenzylidene acetone)dipalladium(0)), and polymer-immobilized organic palladium complexes (such as polymer-supported bis(acetyl)triphenylphosphinepalladium(II) and polymer-carried di(acetyl)dicyclohexylphosphinepalladium(II)). Palladium catalysts, such as palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) chloride, 1,1'-Bis(diphenylphosphino)phenylpalladium(II) chloride and tris(dimethylbenzylacetone)dipalladium(0) are more preferred. 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, 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-(di-tert-butylphosphino)-1',3',5'-triphenyl-1'H-[1,4']bipyrazole), 5-(dicyclohexylphosphino)-1',3',5'-triphenyl-1'H-[1,4']bipyrazole, 5-[bis(1-adamantane)phosphine]-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'-triisopropylbiphenyl4',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, (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 l-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-sulfonicacid, 2'-(dicyclohexylphosphino)-2,6-dimethoxy-sodium salt. 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-[bis(1-adamantane)phosphine]-1',3',5'-triphenyl-1'H-[1,4']bipyrazole, and 1',3',5'-triphenyl-1'H-[1,4']bipyrazole.4'] bipyrazole (5-[di(1-adamantyl)phosphino]-1',3',5'-triphenyl-1'H-[1,4']bipyrazole), 1,1'-ferrocenediyl-bis(diphenylphosphine) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene). The reaction can be carried out at a temperature range of 0-200°C, preferably 50-150°C, and the duration is between 30 minutes and 24 hours. ,

[0487] Process-8:

[0488]

[0489] Alternatively, the compound of formula A-3 can also be prepared as described in Scheme 8 according to the above-mentioned "General Procedure for CS Coupling". 6 Appropriate metal thiolates of SM can provide compounds of formula A-3, as described in PCT Patent Publication No. WO2020257145 and the literature further cited therein. 6 Metal thiolates of SM (wherein M may be, but is not limited to, sodium or potassium) can be obtained from the market or can be generated in situ by treating the corresponding thiolates with organic or inorganic bases. 3 , R 6 , R 8 and R 8a LG represents a leaving group such as a halogen or tosylate.

[0490] Process-9:

[0491]

[0492] In another embodiment of the present invention, the compound of formula A-3 (wherein all substituents are as defined above) can be prepared by the method given in Reaction Scheme 9. The compound of formula A-1 can be subjected to a metal-catalyzed CS coupling reaction in the presence of a trialkylsilanethiol (such as triisopropylsilanethiol) under the general procedure of CS coupling as described above to obtain a sulfur silane compound of formula A-6 (Path-A). Then, as described in the literature in PCT Patent Publication No. WO2020257145 and the literature further cited therein, by using a suitable base (such as but not limited to sodium carbonate, potassium carbonate, cesium carbonate) or a metal hydride base (such as but not limited to sodium hydride, potassium hydride) and a fluorine source (such as a metal fluoride (such as but not limited to cesium fluoride, sodium fluoride) or a reagent in which the metal ion is exchanged with a tetraalkylammonium (such as but not limited to tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride)), the sulfur silane compound of formula A-6 can be deprotected to obtain a compound of formula A-7. The thiol of formula A-7 can also be deprotected using a catalytic amount of 1,2-ethanedithiol (path-B; for example, see Synlett 2017; 28 (17) 2272-2276 and further references therein), obtained by metal-catalyzed coupling reaction between a compound of formula A-1 and commercial sodium sulfide (Na2S.9H2O). The thiol of formula A-7 can be prepared in the presence of a suitable inorganic or organic base and a suitable formula R 6 Further alkylation in the presence of an alkyl halide of X gives a compound of formula A-3. 6 The alkyl halide of X can be obtained from the market. Alternatively, as described in PCT Patent Publication No. WO2011087712, PCT Patent Publication No. WO2004087156 and the literature further cited therein, the sulfur silane compound of formula A-6 can be in the form of a suitable (hetero)aryl halide, or trifluoride, or a sulfhydryl halide of formula R 6 In the presence of toluenesulfonate of X, using appropriate metal-catalyzed CC cross-coupling reaction conditions, a compound of formula A-3 is obtained. In addition, the compound of formula A-1 can be subjected to a metal-catalyzed CS coupling reaction in the presence of methyl thioglycolate as described in the general procedure above to obtain a sulfide of formula A-7a (path-C) (wherein R represents an alkyl group). A base-mediated retro-Michel reaction can be further designed to produce an in-situ metal sulfide, as described in J.Med.Chem.2020,63,2308-2324 and the literature cited herein, and these metal sulfides can be subjected to various S-alkylation reactions with appropriate alkyl halides to obtain various A-3 sulfides. Unless otherwise specified, the definition of each variable is the same as that defined above. X- represents a leaving group, such as a halogen, a trifluorate, a mesylate or a tosylate.

[0493] Process-10:

[0494]

[0495] According to Scheme 10, the present invention provides a central pyrazole ring of formula A-1 with R 8 A method for selective CH functionalization at the same R 8 represents hydrogen and all other variables have their usual meanings. In the presence of N-chlorosuccinimide (NCS), A-1 can be selectively R- 8 Chlorination reaction to form a compound of formula A-1 (wherein pyrazole-R 8 represents Cl). In addition, the same R 8 Hydrogen can also be alkylated in two consecutive steps. First, a similar R 8 Iodination, then in various alkyl boronic acids (formula R 8 In the presence of B(OH)2), a metal-catalyzed Suzuki coupling reaction is carried out to form a compound of formula A-1 (wherein pyrazole-R 8 represents different alkyl groups (about indazole R 8 For a comprehensive review of CH functionalization, see: Org. Biomol. Chem., 2022, 20, 7746)).

[0496] Process-11:

[0497]

[0498] In another embodiment according to Scheme 11, the present invention provides a method for preparing a compound of formula A-2 (wherein all substituents are as defined above). 3 , R 8 and R 8aThe above-defined general meaning and LG represents a leaving group (preferably a halogen) can be converted into a carboxylic acid of formula A-2 according to the process described in PCT Patent Publication No. WO 2016144351 and the literature further cited therein. The metal hexacarbonyl used 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 a base, which is 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, cesium carbonate), organic amine salts (such as triethylamine, N,N-diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene); organic amines (such as N,N-diisopropylethylamine and 1,8-diazabicyclo[5.4.0]undec-7-ene) are preferred bases. Catalysts that can be used in this reaction include, for example but not limited to Organic palladium complexes (e.g. polymer-supported bis(acetyl)triphenylphosphine palladium(II), trans-di-μ-acetatobis[2-[bis(2-methylphenyl)phosphino]benzyl]dipalladium and polymer-borne di(acetyl)dicyclohexylphosphine palladium(II)). Examples of ligands used in the reaction are selected from, but not limited to, tri-tert-butylphosphine tetrafluoroborate. The reaction is usually carried out at a temperature range of 0-200°C, preferably 50-180°C, and the duration is between 30 minutes and 24 hours. The reaction can also be carried out under microwave irradiation.

[0499] Process-12:

[0500]

[0501] According to Scheme 12, the present invention provides a substituted benzaldehyde (wherein A1, A2, A3, R 8 and R 8a As defined above) a method for preparing a compound of formula A-1. LG and LG 1 represents a leaving group, preferably a halogen substituent. The appropriately substituted benzaldehyde of formula E-1 can undergo a nucleophilic substitution reaction in the presence of a nucleophilic organic or inorganic azide at room temperature or elevated temperature to obtain an aryl azide of formula C-1. The aryl azide of formula C-1 can be further reacted with a heteroarylamine of formula B-1 (where A4, A5 and R 3As defined above) to form an imine intermediate, which is cyclized in situ at high temperature to obtain the desired bicyclic product of formula A-1 (for example, see PCT Patent Publication No. WO2016144351). However, depending on the nature of the substrate, this high temperature in situ cyclization method may bring additional challenges. To circumvent this problem, a lower temperature copper / ligand-mediated method can be implemented to cyclize C-2, such as the document Chem. Commun., 2011, 47, 10133-10135 and the documents cited therein (step 3).

[0502] Process-13:

[0503]

[0504] Alternatively, compounds of formula A-1 can be prepared according to the method described in Scheme 13. A substituted benzaldehyde of formula E-1 (wherein A1, A2, A3, R 8 and R 8a As defined above and LG and LG 1 represents a leaving group (preferably a halogen substituent)) and a heteroarylamine of formula B-1 (wherein A4, A5 and R 3 As defined above), react at room temperature or elevated temperature to form an imine of formula C-3. The imine of formula C-3 can first undergo an intermolecular substitution reaction in the presence of a nucleophilic organic or inorganic azide at room temperature or elevated temperature, followed by a subsequent intramolecular cyclization reaction to obtain a bicyclic product of formula A-1 (for example, see PCT Patent Publication No. WO2016144351).

[0505] Process-14:

[0506]

[0507] Alternatively, compounds of formula A-1 can be prepared as described in Scheme 14. An appropriately substituted 2-nitrobenzaldehyde of formula E-2 (wherein A1, A2, A3, R 8 and R 8a As defined above) can be combined with a heterocyclic amine of formula B-1 (where A4, A5 and R 3 As defined above) to form imine C-4. Therefore, in the second reaction step, in the presence of a suitable phosphorus (III) reagent (e.g., triethyl phosphite), a reductive cyclization is carried out at high temperature to obtain a bicyclic compound of formula A-1 (e.g., see U.S. Patent Publication No. US2019029788). There are several alternative reductive cyclization methods to choose from, and can be implemented as described in Org.Lett.2014,16,3114-3117 and the literature cited therein.

[0508] In one embodiment, the present invention provides a method for preparing a compound of formula (I) wherein D is D1, comprising the steps of:

[0509] i. reacting a compound of formula (D1-1) or (D3-1) with a compound of formula (A-1) to obtain a compound of formula (I) wherein Z is a direct bond;

[0510]

[0511] or

[0512] i. reacting a compound of formula (D1-1) or (D3-1) with a compound of formula (A-2) to obtain a compound of formula (I) wherein Z is a -C(=O)- bond;

[0513]

[0514] Among them, LG, A1, A2, A3, A4, A5, R 1 , R 2 , R 3 , R 4 , R 5 , R 8 and R 8a The definition is the same as in the specification.

[0515] In another embodiment, the present invention provides a method for preparing a compound of formula (I) wherein D is D2, comprising the steps of:

[0516] i. With formula R 6 The SH compound reacts with the compound of formula (A-1) to obtain a compound of formula (A-3) wherein Z is a direct bond;

[0517]

[0518] ii. converting the compound of formula (A-3) into a compound of formula (I) by O- and NH- transfer using a suitable oxidant and a nitrogen source,

[0519]

[0520] In one embodiment, the present invention provides a compound of formula (I) wherein D is D2, and step ii can be performed in a single step as described below:

[0521] ii. converting the compound of formula (A-3) into a compound of formula (I) by O- and NH- transfer using a suitable oxidant and a nitrogen source,

[0522]

[0523] In one embodiment, the present invention provides a compound of formula (I) wherein D is D2, and step ii can be performed in two steps as described below:

[0524] ii. oxidizing a compound of formula (A-3) using a suitable oxidizing agent to obtain a compound of formula (A-4), which is further converted to a compound of formula (I) by imidization using a suitable nitrogen source or imidizing agent;

[0525]

[0526] ii. using a suitable nitrogen source or imidizing agent to imide the compound of formula (A-3) to obtain formula (A-5a)

[0527] Compound, which is further oxidized with a suitable oxidizing agent to be converted into a compound of formula (I);

[0528]

[0529] Wherein LG represents a leaving group and A1, A2, A3, A4, A5, R 3 , R 6 , R 7 , R 8 and R 8a The definition is the same as in claim 1.

[0530] The suitable oxidizing agent for step (ii) is selected from: H2O2; H2O2, FeCl3 (catalyst); H2O2, cerium molybdenum oxide (Cerium molybdenum oxide) (catalyst); H2O2, trifluoromethanesulfonic acid, sodium tungsten oxide (Sodium tungsten oxide (Na2WO4)); m-chloroperbenzoic acid; sodium periodate; phenyliodine (III) diacetate (PIDA); hydrochloric acid or acetic acid, hydrogen peroxide; peracetic acid; triphenylmethyl hydroperoxide (Triphenylmethyl hydroperoxide); hydroperoxide), Catalyst: Bis(acetylacetonato)dioxomolybdenum; H2O2, Tetraphenylphosphonium bromide(PB-7-23-111'1'2)-Diaquaoxodiperoxymolybdenum1H-Imidazolium, 1,3-bis[(1S)-1-carboxy-2-methylpropyl]-, inner salt; 2-(1-Hydroperoxy-1-methylethyl)furan, Catalyst: Diethyltartrate, Titanium isopropoxide isopropoxide; H2O2, catalyst: Tantalum pentachloride; tert-Butyl hydroperoxide; oxygen, catalyst: nitrogen dioxide; oxygen, catalyst: nitrosonium tetrafluoroborate; tert-Butyl hypochlorite; chlorotrimethylsilane, H2O2;Tetrabutylammonium nitrate, catalyst: copper nitrate, tetracarbonylbis(triphenylphosphine)Molybdenum; or H2O2, zirconium chloride (ZrCl4). ;

[0531] Suitable nitrogen sources or imidizing agents for step ii are selected from:

[0532] Ammonium carbamate; Sodium azide, sodium bicarbonate; FeSO4, phenanthroline and MeCN (0.4 mL); Sodium azide, concentrated sulfuric acid; Trifluoroacetamide, MgO and Rh2(OAc)4, PhI(OAc)2; O-(mesitylsulfonyl)hydroxylamine; Ph-I = N-Ts (Ts = tolylsulfonyl); Ph-I = N-Ns (Ns = N-alkylnitrobenzenesulfenamide); Ph-I = N-Ses (2-(trimethylsilyl)ethanesulfonyl); or Rh2(esp)2 and O-(2,4-dinitrophenyl)hydroxylamine.

[0533] In one embodiment, the oxidizing agent and the nitrogen source or imidizing agent can be used in one pot or used separately in a stepwise reaction.

[0534] In one embodiment, the oxidizing agent and the nitrogen source or the imidizing agent can be used alone or in combination.

[0535] Without further elaboration, it is reasonably believed that any person skilled in the art using the preceding description can utilize the present invention to its fullest extent.

[0536] Chemical Examples:

[0537] The following examples illustrate the manner and process for preparing the compounds of the present invention, but are not limited thereto and include the best mode contemplated by the inventors for carrying out the invention.

[0538] Experimental process:

[0539] Example 1: Isopropyl((2-(pyrimidin-5-yl)-2H-indazol-5-yl)imino)(3,3,3-trifluoropropyl)-λ 6-Thionone (isopropyl((2-(pyrimidin-5-yl)-2H-indazol-5-yl)imino)(3,3,3-trifluoropropyl)-λ 6 Synthesis of -sulfanone)101

[0540]

[0541] 5-bromo-2-(pyrimidin-5-yl)-2H-indazole (0.25 g, 0.909 mmol), imino(isopropyl)(3,3,3-trifluoropropyl)-λ 6 -Sulfanone (imino(isopropyl)(3,3,3-trifluoropropyl)-λ 6 -sulfanone)(0.185 g, 0.909 mmol) in toluene (5 mL) was treated with tris(dibenzylideneacetone)dipalladium(0))(Pd2(dba)3)(0.042 g, 0.045 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane))(Xantphos)(0.053 g, 0.091 mmol), sodium tert-butoxide (NaOtBu) (0.087 g, 0.909 mmol) and irradiated at 120°C in a microwave apparatus (MW) for 1 hour. After completion of the reaction, the reaction mixture was quenched by the addition of 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. The residue was purified by reverse phase preparative HPLC (gradient method: 10 mM ammonium acetate buffer in water: acetonitrile, from 19:1 to 0:100) to give the desired isopropyl((2-(pyrimidin-5-yl)-2H-indazol-5-yl)imino)(3,3,3-trifluoropropyl)-λ 6 -Thionone (isopropyl((2-(pyrimidin-5-yl)-2H-indazol-5-yl)imino)(3,3,3-trifluoropropyl)-λ 6 -sulfanone) 101 (209 mg, 0.526 mmol, yield 58%).

[0542] Table 1: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 1.

[0543] Note: For certain substrates, better results have been found when cesium carbonate (Cs2CO3) or potassium phosphate (K3PO4) is substituted for sodium tert-butoxide.

[0544]

[0545]

[0546]

[0547]

[0548]

[0549]

[0550]

[0551]

[0552]

[0553]

[0554]

[0555]

[0556]

[0557]

[0558]

[0559]

[0560]

[0561]

[0562]

[0563]

[0564]

[0565]

[0566]

[0567]

[0568]

[0569]

[0570]

[0571]

[0572]

[0573]

[0574]

[0575]

[0576]

[0577]

[0578]

[0579]

[0580]

[0581]

[0582]

[0583]

[0584]

[0585]

[0586]

[0587]

[0588]

[0589] Example 2: N-(dimethyl(side oxy)-λ 6 -sulfane ylidene)-2-(pyridin-3-yl)-2H-indazole-4-carboxamide (N-(dimethyl(oxo)-λ 6Synthesis of -sulfaneylidene)-2-(pyridin-3-yl)-2H-indazole-4-carboxamide)92

[0590]

[0591] 4-bromo-2-(pyridin-3-yl)-2H-indazole (0.3 g, 1.094 mmol), iminodimethyl-λ 6 -Thiocanone (iminodimethyl-λ 6 A solution of -sulfanone (0.306 g, 3.28 mmol) in dimethyl formamide (DMF) (5 mL) was prepared with molybdenum hexacarbonyl (Mo(CO)6)) (0.144 g, 0.547 mmol), tri-tert-butylphosphine tetrafluoroborate (TTBP.HBF4) (0.016 g, 0.055 mmol), trans-Di(μ-acetato)bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II) (Herrman N's catalyst) catalyst)) (0.026 g, 0.027 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)) (0.330 ml, 2.189 mmol) were treated and irradiated in a microwave apparatus (MW) at 160°C for 1 hour. After the reaction was completed, 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. The residue was purified by reverse phase preparative high performance column chromatography to obtain the desired N-(dimethyl(side oxy)-λ 6 -sulfane ylidene)-2-(pyridin-3-yl)-2H-indazole-4-carboxamide (N-(dimethyl(oxo)-λ 6 -sulfaneylidene)-2-(pyridin-3-yl)-2H-indazole-4-carboxamide)92 (220 mg, 0.700 mmol, yield 63.9%).

[0592] Table 2: Representative compounds of the present disclosure were prepared according to the appropriate method described in Example 2.

[0593]

[0594]

[0595] Example 3: N-(ethyl(isopropyl)(oxy)-λ 6 -sulfane ylidene)-2-(pyridin-3-yl)-2H-indazole-5-carboxamide (N-(ethyl(isopropyl)(oxo)-λ 6 Synthesis of -sulfaneylidene)-2-(pyridin-3-yl)-2H-indazole-5-carboxamide)105

[0596]

[0597] 2-(pyridin-3-yl)-2H-indazole-5-carboxylic acid (0.1 g, 0.418 mmol), ethyl(imino)(isopropyl)-λ 6 -Thiocanone (ethyl(imino)(isopropyl)-λ 6 A solution of 1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium3-oxid 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) in dimethyl formamide (DMF) (2 mL) was treated with 1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium3-oxid 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 hours. After completion of the reaction, the reaction mixture was quenched by the addition of 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. The residue was purified by Purification by chromatography (normal phase; run isocratic with 100% ethyl acetate) gave the desired N-(ethyl(isopropyl)(oxo)-λ 6-sulfane ylidene)-2-(pyridin-3-yl)-2H-indazole-5-carboxamide (N-(ethyl(isopropyl)(oxo)-λ 6 -sulfaneylidene)-2-(pyridin-3-yl)-2H-indazole-5-carboxamide) 105 (80 mg, 0.224 mmol, yield 53.7%).

[0598] Table 3: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 3.

[0599]

[0600] Example 4: Synthesis of N,N4-trimethyl-N'-(2-(pyridin-3-yl)-2H-indazol-5-yl)benzenesulfonimidamide 93

[0601]

[0602] 5-bromo-2-(pyridin-3-yl)-2H-indazole (0.27 g, 0.985 mmol), N,N-trimethylbenzenesulfonyl imide amide (N,N A solution of 4-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), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (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 in a microwave (MW) at 120 °C for 1 hour. After completion of the reaction, the reaction mixture was quenched by the addition of 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 give an oily residue. The remainder is Purification by chromatography gave N,N 4-trimethyl-N'-(2-(pyridin-3-yl)-2H-indazol-5-yl)benzenesulfonimidamide 93 (133 mg, 0.340 mmol, 34.5% yield).

[0603] Table 4: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 4.

[0604]

[0605]

[0606] Example 5: 5-methoxy-4-methyl-2-(2-(pyridin-3-yl)-2H-indazol-5-yl)-2,4-dihydro-3H-1,2,4-triazol-3-one

[0607] Synthesis of 110

[0608]

[0609] 5-bromo-2-(pyridin-3-yl)-2H-indazole (0.6 g, 2.189 mmol) and 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (0.791 g, 6.13 mmol) in dimethylformamide (DMF) To a solution of 1,2-dimethylaminocyclohexane (6 mL), cuprous iodide (CuI) (0.083 g, 0.438 mmol), trans-1,2-bis(methylamino)cyclohexane (0.249 g, 0.876 mmol), potassium iodide (KI) (0.109 g, 0.657 mmol) and potassium carbonate (K2CO3) (0.908 g, 6.57 mmol) were added, and the mixture was irradiated in a microwave apparatus (MW) at 150°C for 1 hour. After completion of the reaction, the reaction mixture was quenched by the addition of water (20 mL) and extracted with ethyl acetate (3×25 mL). The combined organic layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a gummy residue. The residue was irradiated with 1% ethyl acetate (20 mL). Chromatographic purification gave 5-methoxy-4-methyl-2-(2-(pyridin-3-yl)-2H-indazol-5-yl)-2,4-dihydro-3H-1,2,4-triazol-3-one 110 (0.184 g, 0.571 mmol, 26.1% yield).

[0610] Table 5: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 5.

[0611]

[0612]

[0613]

[0614] 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

[0615]

[0616] 4-Bromo-2-(5-fluoropyridin-3-yl)-2H-indazole (300 mg, 1.027 mmol), 4-ethyl-5-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one (162 mg, 1.130 mmol), tris(dibenzylideneacetone)dipalladium )dipalladium(Pd2(dba)3))(103mg, 0.113mmol), 5-(di-tert-butylphosphino)-1',3',5'-triphenyl-1'H-[1,4']bipyrazole(BippyPhos))(97mg, 0.191mmol) and cesium carbonate (Cs2CO3) (970mg, 2.98mmol) were poured into a flask, and a condenser was installed. The reaction mixture was stirred under a nitrogen atmosphere. Tertiary-amyl alcohol was added and the reaction mixture was heated at 95°C for 16 hours under a nitrogen atmosphere. After the reaction was completed, the reaction mixture was concentrated under reduced pressure to obtain a dark residue, which was then Chromatographic purification gave 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 (132.5 mg, 0.374 mmol, 36.4% yield).

[0617] Table 6: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 6.

[0618]

[0619]

[0620]

[0621]

[0622]

[0623]

[0624]

[0625]

[0626]

[0627]

[0628] Example 7: (Cyclopropylmethyl)(Imino)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 -Sulfanone((cyclopropylmethyl)(imino)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 Synthesis of -sulfanone)450

[0629]

[0630] Step-1: Synthesis of 5-((cyclopropylmethyl)thio)-2-(pyrimidin-5-yl)-2H-indazole

[0631] To a stirred solution of 5-bromo-2-(pyrimidin-5-yl)-2H-indazole (15 g, 54.5 mmol) in toluene (200 mL) were added Xantphos (9.46 g, 16.36 mmol) and sodium tert-butoxide (10.48 g, 109 mmol) under nitrogen atmosphere, 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 reaction mixture was heated at 110°C for 18 hours. After completion of the reaction, the reaction 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 material. The crude product The product was purified by chromatography to give 5-((cyclopropylmethyl)thio)-2-(pyrimidin-5-yl)-2H-indazole (15 g, 53.1 mmol, 97% yield).

[0632] Step-2: (Cyclopropylmethyl)(Imino)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 -Sulfanone((cyclopropylmethyl)(imino)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 Synthesis of -sulfanone)450

[0633] 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 allowed to return to room temperature (25°C) and stirred at this temperature for 1 hour. The reaction mixture was cooled to 0°C again and (diacetoxyiodo)benzene (PIDA, 37.6 g, 117 mmol) was added. The resulting solution was stirred at 25°C for 16 hours. After the reaction was complete, the methanol was concentrated under reduced pressure and the crude residue was diluted with a minimum amount of water (1X50 mL). The solution was further acidified with concentrated hydrochloric acid (pH = 1-2) and the aqueous layer was extracted with ethyl acetate (3X200 mL) to remove the remaining non-polar organic impurities. The aqueous layer was basified with sodium bicarbonate solution (pH = 8) and extracted with chloroform (3X250 mL). The combined organic layers were washed with brine solution (1X250 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain a crude solid. The crude solid was triturated with methyl tert-butyl ether (50 mL) to obtain (cyclopropylmethyl)(imino)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 -Sulfanone((cyclopropylmethyl)(imino)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 -sulfanone) 450 (10 g, 31.9 mmol, yield 60%).

[0634] Table 7: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 7.

[0635]

[0636]

[0637] Example 8: (Cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 -Sulfanone((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 Synthesis of -sulfanone)468

[0638]

[0639] Step 1: Synthesis of methyl 3-((2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)thio)propanoate

[0640] 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) were added to a degassed toluene (150 mL) solution of 5-bromo-2-(5-fluoropyridin-3-yl)-2H-indazole (10 g, 34.2 mmol) under nitrogen atmosphere, and the resulting reaction mixture was heated at 110° C. for 16 hours. After the reaction was completed, it 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 then Chromatographic purification gave the desired methyl 3-((2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)thio)propanoate (10 g, 30.2 mmol, 88% yield) as a light yellow solid.

[0641] Step 2: Synthesis of 5-((cyclobutylmethyl)thio)-2-(5-fluoropyridin-3-yl)-2H-indazole

[0642] To a stirred solution of methyl 3-((2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)thio)propanoate (4 g, 12.07 mmol) in N,N-dimethylformamide (20 mL) was added sodium hydride (60% dispersion in mineral oil, 0.966 g, 24.14 mmol) at 0°C and stirred for 0.5 hours, followed by addition of (bromomethyl)cyclobutane (2.71 mL, 24.14 mmol) at the same temperature, and the resulting reaction mixture was stirred at 25°C for 16 hours. After completion of the reaction, it 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 give the crude product 5-((cyclobutylmethyl)thio)-2-(5-fluoropyridin-3-yl)-2H-indazole (3.5 g, 11.17 mmol, 93% yield), which was used directly in the next step.

[0643] Step 3: (Cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 -Sulfanone((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 Synthesis of -sulfanone)468

[0644] 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 stirred at 25°C for 0.5 hours. Iodobenzene diacetate (8.55 g, 26.5 mmol) was added portionwise at 0°C and the resulting mixture was stirred at 25°C for 16 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, neutralized with sodium bicarbonate and extracted with dichloromethane (3X50 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain a crude solid. The crude product was Chromatographic purification gave (cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 -Sulfanone((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 -sulfanone) 468 (2.3 g, 6.68 mmol, yield 55%).

[0645] Table 8: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 8.

[0646]

[0647]

[0648]

[0649]

[0650]

[0651] Example 9: (Cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)((6(trifluoromethyl)pyrazin-2-yl)imino)-λ 6 -Sulfanone ((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)((6(trifluoromethyl)pyrazin-2-yl)imino)-λ 6Synthesis of -sulfanone)473

[0652]

[0653] In the degassed (cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 -Sulfanone((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 To a solution of 2-(4-(4-(4-(4-(4-(4-thiazolyl)pyrrolidone)-1-yl)-1-nitropropene (1-nitropropene)-1-nitropropene)-2 ... The combined suspension was concentrated under reduced pressure to obtain a crude residue, which was then purified by preparative HPLC column chromatography to obtain the desired (cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)((6(trifluoromethyl)pyrazin-2-yl)imino)-λ 6 -Sulfanone ((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)((6(trifluoromethyl)pyrazin-2-yl)imino)-λ 6 -sulfanone) 473 (130 mg, 0.265 mmol, yield 30.4%).

[0654] Table 9: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 9.

[0655]

[0656]

[0657]

[0658] Example 10: N-((Cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(oxo)-λ 6 -sulfane ylidene)acetamide (N-((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(oxo)-λ 6 Synthesis of -sulfaneylidene)acetamide)472

[0659]

[0660] In stirred (cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 -Sulfanone((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 To a solution of (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 cooled to 0°C, and acetyl chloride (0.057 mL, 0.798 mmol) was added to the reaction mixture and stirred at 25°C for 16 hours. After the reaction was completed, the reaction mixture was poured into water (10 mL), and the aqueous layer was extracted with dichloromethane (3X20 mL). The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain a crude solid. The crude product was purified by preparative HPLC column chromatography to obtain the desired N-((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(oxo)-λ 6 -sulfane ylidene)acetamide (N-((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(oxo)-λ 6 -sulfaneylidene)acetamide) 472 (110 mg, 0.285 mmol, yield 39.2%).

[0661] Table 10: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 10.

[0662]

[0663]

[0664]

[0665]

[0666]

[0667]

[0668]

[0669]

[0670]

[0671]

[0672] For fluorinated acyl analogs, the corresponding anhydride was used.

[0673] Example 11: N-((Cyclopropylmethyl)(oxo)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 -sulfane ylidene)-3,3-difluorocyclobutane-1-carboxamide (N-((cyclopropylmethyl)(oxo)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 Synthesis of -sulfaneylidene)-3,3-difluorocyclobutane-1-carboxamide)429

[0674]

[0675] In stirred (cyclopropylmethyl)(imino)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 -Sulfanone((cyclopropylmethyl)(imino)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6To a solution of 1-(2-(4-(dimethylamino)-1-thiazolyl)-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxidehexafluorophosphate) (455 mg, 1.197 mmol) of 1-(2-(dimethylamino)-1-thiazolyl)-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxidehexafluorophosphate (250 mg, 0.798 mmol) in N,N-dimethylformamide (3 mL) was added at 25°C. Then, N,N-diisopropylethylamine (0.278 mL, 1.596 mmol) was added and the resulting mixture was stirred at 25°C for 16 hours. After the reaction was completed, the reaction mixture was quenched by adding water (10 mL), extracted with ethyl acetate (3×25 mL) and washed with brine solution (1×25 mL). The organic layer was then dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain a crude gum. The crude product was purified by preparative high performance liquid column chromatography to obtain the desired N-((cyclopropylmethyl)(oxo)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 -sulfane ylidene)-3,3-difluorocyclobutane-1-carboxamide (N-((cyclopropylmethyl)(oxo)(2-(pyrimidin-5-yl)-2H-indazol-5-yl)-λ 6 -sulfaneylidene)-3,3-difluorocyclobutane-1-carboxamide) 429 (88 mg, 0.204 mmol, yield 26%).

[0676] Table 11: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 11.

[0677]

[0678]

[0679]

[0680]

[0681]

[0682] Example 12: (2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(isopropyl)(methylimino)-λ 6 -Sulfanone((2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(isopropyl)(methylimino)-λ 6 Synthesis of -sulfanone)407

[0683]

[0684] In a degassed and stirred (2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)(isopropyl)-λ 6 -Sulfanone((2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)(isopropyl)-λ 6 To a solution of 2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(isopropyl)(methylimino)-λ was added copper(II) acetate(257mg, 1.413mmol), pyridine(0.183mL, 2.262mmol) and methylboronic acid(282mg, 4.71mmol). The resulting mixture was stirred at reflux (100°C) for 16 hours. After the reaction was completed, 1,4-dioxane was removed under reduced pressure, and the reaction mixture was diluted with ethyl acetate (60mL). The organic layer was extracted with water (3X20 mL), washed with brine solution (1X25 mL) and dried over anhydrous sodium sulfate. It was then concentrated under reduced pressure to obtain a crude solid. The crude material was further purified by preparative HPLC column chromatography to obtain the desired 2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(isopropyl)(methylimino)-λ 6 -Sulfanone (2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(isopropyl)(methylimino)-λ 6 -sulfanone) 407 (175 mg, 0.526 mmol, yield 56%).

[0685] Table 12: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 12.

[0686]

[0687]

[0688] Example 13: (Cyclobutylmethyl)(ethylimino)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)-λ 6 -Sulfanone((cyclobutylmethyl)(ethylimino)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)-λ 6 Synthesis of -sulfanone)471

[0689]

[0690] In stirred (cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 -Sulfanone((cyclobutylmethyl)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)(imino)-λ 6 To a solution of 2-(4-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-piperidin-1-yl)-2H-indazol-5-yl)-1 ...yl)-1-(2-(4-(2-piperidin-1-yl)-2H-indazol-5-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)-1-yl)- 6 -Sulfanone((cyclobutylmethyl)(ethylimino)(2-(5-fluoropyridin-3-yl)-2H-indazol-5-yl)-λ 6 -sulfanone) 471 (167 mg, 0.448 mmol, yield 62%).

[0691] Table 13: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 13.

[0692]

[0693]

[0694]

[0695]

[0696]

[0697]

[0698] Example 14: N-(isopropyl(oxo)(2-(pyridin-3-yl)-2H-indazol-5-yl)-λ 6 -sulfane ylidene) nitrile amide (N-(isopropyl(oxo)(2-(pyridin-3-yl)-2H-indazol-5-yl)-λ 6 Synthesis of -sulfaneylidene)cyanamide)392

[0699]

[0700] In the stirred imino(isopropyl)(2-(pyridin-3-yl)-2H-indazol-5-yl)-λ 6 -Thiocanone (imino(isopropyl)(2-(pyridin-3-yl)-2H-indazol-5-yl)-λ 6 To a solution of 2-(2-(2-(pyridin-3-yl)-2H-indazol-5-yl)-1-(2-(2-(pyridin-3-yl)-2H-indazol-5-yl)-1-(2-(2-(pyridin-3-yl)-2H-indazol-5-yl)-1-(2-(2-(pyridin-3-yl)-2H-indazol-5-yl)-1-(2-(2-(pyridin-3-yl)-2H-indazol-5-yl)-1-(2-(2-(pyridin-3-yl)-2H-indazol-5-yl)-1-(2-(2-(2-(pyridin-3-yl)-2H-indazol-5-yl)-1-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2- 6 -sulfane ylidene) nitrile amide (N-(isopropyl(oxo)(2-(pyridin-3-yl)-2H-indazol-5-yl)-λ 6-sulfaneylidene)cyanamide)392 (130 mg, 0.400 mmol, 40.0% yield).

[0701] Table 14: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 14.

[0702]

[0703] Example 15: ((2,2-difluoroethyl)imino)(isopropyl)(2-(pyridin-3-yl)-2H-indazol-4-yl)-λ 6 -Sulfanone(((2,2-difluoroethyl)imino)(isopropyl)(2-(pyridin-3-yl)-2H-indazol-4-yl)-λ 6 Synthesis of -sulfanone)424

[0704]

[0705] In the stirred imino(isopropyl)(2-(pyridin-3-yl)-2H-indazol-4-yl)-λ 6 -Thiocanone (imino(isopropyl)(2-(pyridin-3-yl)-2H-indazol-4-yl)-λ 6 To a solution of 2-(4-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2-(2- The crude material was purified by flash column chromatography to give the desired ((2,2-difluoroethyl)imino)(isopropyl)(2-(pyridin-3-yl)-2H-indazol-4-yl)-λ 6-Sulfanone(((2,2-difluoroethyl)imino)(isopropyl)(2-(pyridin-3-yl)-2H-indazol-4-yl)-λ 6 -sulfanone) 424 (70 mg, 0.192 mmol, yield 19.23%).

[0706] Table 15: Representative compounds of the present disclosure were prepared according to the appropriate starting materials and methods described in Example 15.

[0707]

[0708] *Compound names are generated using Chemdraw Professional 19.1

[0709] The compounds of formula A-1, A-2 or A-3 are synthesized according to the general schemes 6-14 described in the specification. In particular, the compounds of formula A-1 wherein A1, A2 and A3 represent C are synthesized according to the steps described in PCT patent publication number WO 201614435, and the compounds of formula A-1 wherein one of A1, A2 and A3 represents N are synthesized according to the following steps.

[0710] Reaction process:

[0711] Instance-16:

[0712]

[0713] 3-azido-6-bromopicolinaldehyde:

[0714]

[0715] Sodium azide (3.06 g, 47.1 mmol) was added to a stirred solution of 6-bromo-3-fluoropicolinaldehyde E-1 (8 g, 39.2 mmol) in N,N-dimethylformamide (80 ml), and the resulting mixture was stirred at 25°C for 16 hours. After the reaction was completed, the reaction mixture was diluted with water, and the aqueous layer was extracted with ethyl acetate (3×100 ml). The organic layer was washed with brine solution (1×100 ml). The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain 3-azido-6-bromopicolinaldehyde C-1 (6 g, 26.4 mmol, yield 67.4%). The thin layer chromatography sheet was compared with the authentic spot.

[0716] 5-bromo-2-(pyridin-3-yl)-2H-pyrazolo[4,3-b]pyridine:

[0717]

[0718] To a stirred solution of 3-azido-6-bromopicolinaldehyde C-1 (6 g, 26.4 mmol) in 1,4-dioxane (60 ml), pyridin-3-amine B-1 (2.74 g, 29.1 mmol) was added, and the resulting mixture was stirred at 120° C. for 48 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure and water was added to give a crude solid, which was filtered, collected and further purified by flash chromatography to give the desired 5-bromo-2-(pyridin-3-yl)-2H-pyrazolo[4,3-b]pyridine A-1 (4.1 g, 14.90 mmol, 56.4% yield).

[0719] As described herein, the compounds of formula (I) exhibit insecticidal activity against a variety of insects that attack important agricultural crops. The activity of the compounds of the invention was evaluated as described in the following test:

[0720] Biological examples:

[0721] Example A: Tobacco whitefly (Bemisia tabaci)

[0722] The test was conducted using the leaf dip method wherein the required amount of compound was weighed and dissolved in a test tube containing the solvent solution. The test tube was placed in a vortex at 2000 rpm for proper mixing and then diluted to the required test concentration with 0.01% Triton-X solution. Brinjal leaves were dipped in the compound solution for 10 seconds, shade dried for 20 minutes and then placed with the abaxial side of the leaves facing upwards on perforated container lids each containing 4 ml of solidified 1% agar-agar solution. A known number of newly hatched whitefly adults were collected by a modified aspirator and released into a perforated container, the lid of which contained the treated leaves. The containers were stored in a plant growth chamber at 25°C and 70% relative humidity. After 72 hours of adult release, the number of dead, moribund and surviving adults was recorded. The percentage mortality calculated was obtained by combining the percentage mortality of dead and moribund adults and comparing it with the untreated one. The following compounds reported had a mortality rate greater than or equal to 70% at 300 ppm: 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 7, 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.

[0723] Example B: Peach Aphid (Myzus persicae)

[0724] The test was conducted using the leaf dip method, wherein the required amount of compound was weighed and dissolved in a test tube containing the solvent solution. The test tube was placed in a vortex at 2000 rpm for proper mixing and then diluted to the required test concentration with 0.01% Triton-X solution. Pepper (capsicum) leaves were dipped in the compound solution for 10 seconds, shade dried for 20 minutes and then placed with the abaxial side of the leaves facing upwards on bioassay plates each containing 4 ml of solidified 1% agar-agar solution. A known number of third instar nymphs of green peach aphid were collected in a petri dish and released into the unit with the treated leaves, which was covered with a perforated lid for better ventilation. The assay plates were stored in a plant growth chamber at a temperature of 25°C and a relative humidity of 70%. After 72 hours of nymph release, the dead, moribund and surviving nymphs were recorded. The calculated percentage mortality was obtained by combining the percentage mortality of dead and moribund nymphs and comparing it with the untreated one. The following compounds reported had a mortality rate of greater than or equal to 70% at 300 ppm: 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 0, 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.

[0725] Example C: Brown Rice Patch (Nilaparvata lugens)

[0726] The test was conducted using the seedling dip method, wherein the required amount of compound was weighed and dissolved in a test tube containing the solvent solution. The test tube was placed in a vortex at 2000 rpm for proper mixing and then diluted to the required test concentration using 0.01% Triton-X solution. Rice (paddy) seedlings were dipped in the compound solution for 10 seconds, dried in the shade for 20 minutes, and then the seedlings were placed in glass test tubes and the roots were kept in water. 15 third instar nymphs of brown rice hopper were released into each test tube and the test tubes were stored in a plant growth chamber at a temperature of 25°C and a relative humidity of 75%. After 72 hours of the nymph release, the dead, moribund and surviving nymphs were recorded. The calculated percentage mortality was obtained by combining the percentage mortality of dead and moribund nymphs and comparing it with one of the untreated ones. The following compounds recorded had a mortality rate greater than or equal to 70% at 300 ppm: 1, 2, 3, 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, 15 2, 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.

[0727] Having described the invention with reference to certain preferred embodiments, other embodiments will become apparent to those skilled in the art from consideration of the specification.

Claims

1. A compound of formula (I), in, Z is selected from a direct bond or -C(=O)-; D is selected from the group consisting of D1, D2 and D3, 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 at the same time; R 1 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, phenethyl and C2-C6 heterocyclyl; R 2 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 Selected from the group consisting of hydrogen, halogen, nitrile, 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 Selected from the group consisting of hydrogen, C1-C6 alkyl, C1-C6 haloalkyl and C3-C8 cycloalkyl; R d 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, C3-C6 cycloalkyl-C1-C4 alkyl; or R c and R d The substituent and the atom to which it is attached or together with other atoms may form a 3-6 membered ring, wherein the other atom is selected from the group consisting of C, N, O, C(=O), C(=S) and S(O). 0-2 , the ring may be optionally substituted by one or more substituents selected from the group consisting of halogen, CN and C1-C6 alkyl; R 5 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 substituent and the atom to which it is attached or together with other atoms may form a 3-6 membered ring, wherein the other atom is selected from the group consisting of C, N, O, C(=O), C(=S) and S(O). 0-2 , the ring may be optionally 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, 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, nitrile, 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 ; R 8 and R 8a Independently selected from the group consisting of: hydrogen, halogen, nitrile, C1-C4 alkyl, C1-C4 haloalkyl; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Each aliphatic group can be optionally replaced by R a One or more groups of R are substituted; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 The ring group may be optionally replaced by R b One or more groups of R a Selected from the group consisting of halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl; R b Selected from the group consisting of halogen, nitrile, 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; or a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof.

2. The compound of formula (I) as claimed in claim 1, wherein D is D1.

3. The compound of formula (I) as claimed in claim 1, wherein D is D2.

4. The compound of formula (I) as claimed in claim 1, wherein D is D3.

5. The compound of formula (I) as claimed in claims 1 to 4, wherein Z is a direct bond.

6. The compound of formula (I) according to claim 1, wherein D is D1; Z is a direct bond or -C(=O)-; R 3 Selected from the group consisting of: hydrogen, halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl and C1-C6 alkoxy; R 4 Selected from the group consisting of C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl and -NR c R d ; Among them, R c Selected from the group consisting of: hydrogen or C1-C6 alkyl; R d Selected from the group consisting of: hydrogen or C1-C6 alkyl; R 5 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 5 The substituent and the atom to which it is attached or together with other atoms may form a 4-6 membered ring, wherein the other atom is selected from the group consisting of C, N, O, C(=O), C(=S) and S(O). 0-2 , the ring may be optionally substituted by one or more substituents selected from the group consisting of halogen, CN and C1-C6 alkyl; Among them, R 5 , R 6 and R 7 Each aliphatic group can be optionally replaced by R a and R 4 as well as R 5 The ring group may be optionally replaced by R b One or more groups of R a Selected from the group consisting of halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl; R b Selected from the group consisting of halogen, nitrile, 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 independently selected from the group consisting of hydrogen, halogen, nitrile, C1-C4 alkyl and C1-C4 haloalkyl; A1, A2, A3, A4 and A5 are as defined in claim 1; or a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof.

7. The compound of formula (I) as claimed in claim 1, wherein D is D2; Z is a direct bond; R 3 Selected from the group consisting of hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C1-C6 alkoxy; R 6 Selected from the group consisting of C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl and -NR c R d ; in, R c Selected from the group consisting of: hydrogen or C1-C6 alkyl; R d Selected from the group consisting of: hydrogen or C1-C6 alkyl; R 7 Selected from the group consisting of: C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, -COR 5 , phenyl, benzyl, C2-C6 heterocyclic group and nitrile group; Among them, R 5 Selected from the group consisting of: C1-C6 alkyl and C3-C8 cycloalkyl; Among them, R 5 , R 6 and R 7 Each aliphatic group can be optionally replaced by R a and R 5 , R 6 and R 7 The ring group may be optionally replaced by R b One or more groups of R a Selected from the group consisting of halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl; R b Selected from the group consisting of halogen, nitrile, 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 independently selected from the group consisting of hydrogen, halogen, nitrile, C1-C4 alkyl and C1-C4 haloalkyl; A1, A2, A3, A4 and A5 are as defined in claim 1; or a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof.

8. The compound of formula (I) as claimed in claim 1, wherein D is D3; Z is a direct bond; R 1 Selected from the group consisting of C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, phenyl, benzyl, phenethyl and C2-C6 heterocyclyl; in, R 1 Each aliphatic group can be optionally replaced by R a and R 1 The ring group may be optionally replaced by R b One or more groups of R a Selected from the group consisting of halogen, nitrile, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, phenyl and C2-C6 heterocyclyl; R b Selected from the group consisting of halogen, nitrile, 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 2 is a C1-C6 alkyl group; R 3 Selected from the group consisting of hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl and C1-C6 alkoxy; R 8 and R 8a independently selected from the group consisting of hydrogen, halogen, nitrile, C1-C4 alkyl and C1-C4 haloalkyl; A1, A2, A3, A4 and A5 are as defined in claim 1; or a salt, stereoisomer, tautomer, polymorph, metal complex or N-oxide thereof.

9. A compound of formula (I) as claimed in claim 6 or 7 or 8, 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; 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. A method for preparing the compound of formula (I) or its salt, metal complex, stereoisomer, polymorph or N-oxide as claimed in claim 1, wherein D is D1 or D3, comprising the steps of: i. reacting a compound of formula (D1-1) or (D3-1) with a compound of formula (A-1) to obtain a compound of formula (I) wherein Z is a direct bond; or i. reacting a compound of formula (D1-1) or (D3-1) with a compound of formula (A-1) to obtain a compound of formula (I) wherein Z is a -C(=O)- bond; in, LG represents a leaving group and A1, A2, A3, A4, A5, R 1 , R 2 , R 3 , R 4 , R 5 , R 8 and R 8a The definition is the same as that of claim 1.

11. A method for preparing the compound of formula (I) or its salt, metal complex, stereoisomer, polymorph or N-oxide as claimed in claim 1, wherein D is D2, comprising the steps of: i. With formula R 6 The SH compound reacts with the compound of formula (A-1) to obtain a compound of formula (A-3) wherein Z is a direct bond; ii. using a suitable oxidant and a nitrogen source to convert the compound of formula (A-3) into a compound of formula (I) by (O) and (N) transfer to obtain the compound of formula (I), in, A1, A2, A3, A4, A5, R 3 , R 6 , R 7 , R 8 and R 8a The definition is the same as that of claim 1.

12. A composition comprising the compound of formula (I) or its salt, metal complex, stereoisomer, polymorph or N-oxide as claimed in claim 1 and at least one additional component selected from the group consisting of: a surfactant and an adjuvant.

13. The composition of claim 12, wherein the composition additionally comprises at least one biologically active compatible compound selected from the group consisting of fungicides, insecticides, nematicides, miticides, 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 of 0.1% to 99% by weight of the total weight of the composition.

15. A composition comprising a biologically effective amount of a compound of formula (I) as claimed in claim 1 and at least one additional biologically active compatible compound selected from the group consisting of fungicides, insecticides, nematicides, miticides, biopesticides, herbicides, plant growth regulators, biostimulants, antibiotics, fertilizers and nutrients.

16. A method for controlling insect and mite pests, comprising: Contacting insects and acarid pests, their habitats, breeding grounds, food supplies, plants, seeds, soils, areas, materials or environments where insects and acarid pests are growing or may grow, or materials, plants, seeds, soils, surfaces or spaces to be protected from pest attack or infection with the compound of formula (I) as claimed in claim 1 or its salt, stereoisomer, polymorph, metal complex, N-oxide, the composition as claimed in claim 12 or the composition as claimed in claim 15.

17. A method for protecting crops from insect and acarid pests, comprising: The crop is contacted with the compound of formula (I) or its salt, stereoisomer, polymorph, metal complex, N-oxide as claimed in claim 1, or with the composition as claimed in claim 12, or with the composition as claimed in claim 15.

18. The method of claim 16 or 17, wherein the method comprises: The compound of formula (I) is applied to agricultural or horticultural crops at an effective dose of 1 gram of active ingredient (gai) to 5000 grams of active ingredient per hectare.

19. A method for protecting seeds, plants and plant parts from soil insects and protecting seedling roots and shoots from soil and foliar insects, comprising: Before sowing and / or after pre-germination, the seeds are contacted with the compound of formula (I) or its salt, stereoisomer, polymorph, metal complex, N-oxide as claimed in claim 1, or the composition as claimed in claim 12 or the composition as claimed in claim 15.

20. Use of a compound of formula (I) or its salt, stereoisomer, polymorph, metal complex, N-oxide as claimed in claim 1, or a composition as claimed in claim 12 or a composition as claimed in claim 15 for controlling insect and acarid pests in crops, horticultural crops, household and vector control and animal parasites.

21. The use of a compound of formula (I) as claimed in claim 20, wherein the crop is cereals, corn, sorghum, pearl millet (bajra), rice, soybean, oil seeds and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbits, oil plants, tobacco, coffee, tea, cocoa, sugar beet, sugar cane, cotton, potato, tomato, onion, pepper, other vegetables and ornamental plants.

22. A seed comprising the compound of formula (I) as claimed in claim 1 or its salt, stereoisomer, polymorph, metal complex, N-oxide, or the composition as claimed in claim 12 or the composition as claimed in claim 15, wherein the amount of the compound of formula (I) in the seed is 0.0001% to 1% by weight.

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