Condensed heterocyclic compounds, compositions, mixtures, pest control methods, their use as pest control agents, and seeds

Abstract

The present invention provides fused heterocyclic compounds of formula (I): [Formula 1] JPEG2022536757000073.jpg3336 formula (I) [In the formula, R 1 , Y, Q, A, G, m, and E are as defined in the detailed description. The present invention further discloses the preparation process and use of the compound of formula (I) as a pest control agent.

Description

Technical Field

[0001] The present invention relates to a condensed heterocyclic compound. More specifically, the present invention relates to a condensed heterocyclic compound of formula (I) and a method for preparing the same. The present invention further relates to the use of the condensed heterocyclic compound of formula (I) as a pest control agent.

Background Art

[0002] Modern insecticides and acaricides currently available must meet many requirements, for example, levels of effectiveness, residual activity, and antibacterial spectra, as well as further beneficial effects, and their possible uses. Efforts have been made over the past few decades to develop selective insecticides that specifically act on biochemical mechanisms of action that exist only in insects or mites and that further exhibit advantageous properties different from known insecticides.

[0003] Heterocyclic compounds having control activity are known and are described, for example, in WO2016091731, WO2016162318, WO2017061497, WO2017125340, WO2017001311, WO2018095953, WO2019068572, and WO2019038195.

[0004] However, by using such control agents for a long period of time, many pests have acquired resistance, and it has become increasingly difficult to effectively control with existing insecticides and fungicides that have been conventionally used for many years, and this phenomenon has been increasing in recent years. Furthermore, some of those existing control agents are very toxic or remain in the environment for a long time due to their residual properties and can cause serious problems due to the destruction of the ecosystem.

[0005] Therefore, there is a continuing need for new compounds that are more effective, less toxic, environmentally safe, and / or have different modes of action.

[0006] In view of the above, the present invention contemplates such compounds that meet or overcome the drawbacks associated with the prior art.

[0007] Surprisingly, it has now been found that certain novel condensed heterocyclic compounds having a sulfur-containing substituent, which are the subject of the present invention, have desirable properties as pesticides.

SUMMARY OF THE INVENTION

[0008] Accordingly, the present invention provides a condensed heterocyclic compound of formula (I) or an agriculturally acceptable salt, isomer / structural isomer, stereoisomer, diastereomer, enantiomer, tautomer, metal complex, polymorph, or N-oxide thereof:

[0009]

CHEMICAL FORMULA

[0010] Formula (I)

[0011] [wherein, R 1 , Y, Q, A, G, m, and E are as defined in the detailed description].

[0012] In one embodiment, the present invention provides a process for preparing a compound of formula (I) or an agriculturally acceptable salt thereof.

[0013] In another embodiment, the present invention provides a composition for controlling or preventing invertebrate pest animals, comprising a biologically effective amount of a compound of formula (I), an agriculturally acceptable salt thereof, an isomer / structural isomer, a stereoisomer, a diastereomer, an enantiomer, a tautomer, a metal complex, a polymorph, or an N-oxide thereof, and at least one additional component selected from the group consisting of surfactants and adjuvants.

[0014] In yet another embodiment, the composition further comprises at least one additional biologically active and compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, or nutrients.

[0015] In yet another embodiment, the present invention provides the use of a compound of formula (I), an agriculturally acceptable salt thereof, an isomer / structural isomer, a stereoisomer, a diastereomer, an enantiomer, a tautomer, a metal complex, a polymorph, or an N-oxide, a composition, or a combination for controlling invertebrate pests or animal parasites in crops and / or horticultural crops.

[0016] In yet another embodiment, the present invention provides a method for controlling invertebrate pest animals, comprising contacting an invertebrate pest animal, its habitat, breeding ground, food supply, plant, seed, soil, area, material, or environment where it grows or can grow, or a material, plant, seed, soil, surface, or space protected from pest attack or infestation, with a biologically effective amount of a compound of formula (I) or an agriculturally acceptable salt thereof, an isomer / structural isomer, a stereoisomer, a diastereomer, an enantiomer, a tautomer, a metal complex, a polymorph, or an N-oxide, a composition, or a combination.

MODE FOR CARRYING OUT THE INVENTION

[0017] Definitions:

[0018] The definitions provided herein for the terms used in this disclosure are for illustrative purposes only and do not in any way limit the scope of the invention disclosed in this disclosure.

[0019] 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 that does not exclude any additional limitations. For example, a composition, mixture, process, or method that comprises the recited components is not necessarily limited to only those components, and may include other components not expressly listed or not peculiar to such composition, mixture, process, or method.

[0020] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. When in a claim, it closes the claim against the inclusion of materials other than those recited, except for impurities ordinarily associated therewith. When the phrase "consisting of" appears in the body of the claim, rather than immediately following the preamble, it limits only the components recited in that section, and other components are not excluded from the claim as a whole.

[0021] The transitional phrase "consisting essentially of" is used to define a composition or method that includes materials, steps, features, elements, or components in addition to those literally disclosed, provided that these additional materials, steps, features, elements, or components do not materially affect the basic and novel characteristics of the invention recited in the claim. The term "consisting essentially of" takes a middle ground between "comprising" and "consisting of."

[0022] Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or." For example, the condition A "or" B is satisfied by any of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0023] Also, the indefinite articles "a" and "an" preceding an element or component of the present invention are intended to be non - limiting with respect to the number of elements or components (i.e., occurrences). Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component includes the plural as well, unless the number is clearly meant to be singular.

[0024] As referred to in the present disclosure, the term "invertebrate pest" includes arthropods, gastropods, and nematodes that are economically important as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs, and sow bugs. The term "gastropod" includes snails, slugs, and other stylommatophorans. The term "nematode" refers to organisms in the phylum Nematoda. The term "helminth" includes roundworms, heartworms, phytophagous nematodes (Nematoda), flukes (Trematoda), hookworms, tapeworms (Cestoda).

[0025] The term "agronomic" refers to the production of field crops such as food and fiber, including the growth of corn, soybeans and other legumes, rice, grains (e.g., wheat, oats, barley, rye, rice, maize), leafy vegetables (e.g., lettuce, cabbage, and other vegetable crops), fruiting vegetables (e.g., tomatoes, peppers, eggplants, brassicas, and cucumbers), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome fruits, stone fruits, citrus), small fruit trees (e.g., berries, cherries) and other specialty crops (e.g., canola, sunflowers, olives).

[0026] The term "nonagronomic" refers to applications other than agricultural crops, such as horticultural crops (e.g., greenhouse plants not grown in the field, nursery plants, or ornamental plants), residential, agricultural, commercial, and industrial structures, turf (e.g., turf farms, pastures, golf courses, lawns, sports fields), wood products, stored products, agroforestry and vegetation management, public health (i.e., humans) and animal health (e.g., domesticated animals such as pets, livestock, and poultry, non - domesticated animals such as wildlife).

[0027] For non-agricultural uses, it typically involves administering to a protected animal a parasitically effective (i.e., biologically effective) amount of a compound of the present invention in the form of a composition formulated for veterinary use, thereby protecting the animal from invertebrate parasitic pests. As referred to in the present disclosure and claims, the terms "parasiticidal" and "parasitically" refer to the observable effects on invertebrate parasitic pests for protecting animals from pests. The parasiticidal effect typically relates to a decrease in the occurrence or activity of the target invertebrate parasitic pests. Such effects on pests include necrosis, death, growth retardation, reduced mobility, or reduced ability to remain on or within the host animal, reduced feeding, and inhibition of reproduction. These effects on invertebrate parasitic pests provide control (including prevention, reduction, or elimination) of parasite invasion or infection in animals.

[0028] The compounds of the present disclosure may exist in pure form or as a mixture of different possible isomeric forms such as stereoisomers or structural isomers. Various stereoisomers include enantiomers, diastereomers, chiral isomers, atropisomers, conformational isomers, rotational isomers, tautomers, optical isomers, polymorphs, and geometric isomers. Any desired mixture of these isomers is within the scope of the claims of the present disclosure. Those skilled in the art will understand that one stereoisomer may be more active and / or exhibit beneficial effects when concentrated or separated from other isomers. Furthermore, those skilled in the art know the processes or methods or techniques for separating, concentrating, and / or selectively preparing the above isomers.

[0029] Here, the meanings of various terms used in this description are explained.

[0030] The term "aliphatic compound" or "aliphatic group" as used herein is an organic compound in which carbon atoms are linked in a straight chain, branched chain, or non-aromatic ring.

[0031] The term "alkyl", used alone or in any of the compound words such as "alkylthio" or "haloalkyl" or -N(alkyl) or alkylcarbonylalkyl or alkylsulfonylamino, refers to a straight-chain or branched-chain C 1 ~C 24 alkyl, preferably C 1 ~C 15 alkyl, more preferably C 1 ~C 10 alkyl, most preferably C 1 ~C 6 It contains alkyl. Representative examples of alkyl include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, and 1-ethyl-2-methylpropyl, or different isomers are included. For example, when alkyl is at the end of a complex substituent, such as alkylcycloalkyl, the cycloalkyl part of the complex substituent at the start may be independently mono- or polysubstituted, either identically or differently, by alkyl. The same applies to complex substituents with other groups, such as alkenyl, alkynyl, hydroxyl, halogen, carbonyl, carbonyloxy, etc. at the end.

[0032] The term "alkenyl", used either alone or as part of a compound word, refers to a straight-chain or branched C 2 ~C 24 alkene, preferably a C 2 ~C 15alkene, more preferably a C 2 ~C 10 alkene, most preferably a C 2 ~C 6 It contains alkenes. Representative examples of alkenes include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 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, as well as different isomers, are included. "Alkyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. This definition also applies to alkenyl as part of a complex substituent, such as haloalkenyl, unless otherwise specifically defined.,

[0033] The term "alkynyl", used either alone or as part of a compound word, refers to a straight-chain or branched C 2 ~C 24 alkyne, preferably a C 2 ~C 15 alkyne, more preferably a C 2 ~C 10 alkyne, most preferably a C 2 ~C 6 It contains alkynes. 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 are included. This definition also applies to compound substituents, such as alkynyl as part of haloalkynyl, etc., unless otherwise specifically defined. The term "alkynyl" can also include moieties consisting of multiple triple bonds, such as 2,5-hexadiynyl.

[0034] The term "cycloalkyl" means alkyl that is closed to form a ring. Non-limiting examples include, but are not limited to, cyclopropyl, cyclopentyl, and cyclohexyl. This definition also applies to compound substituents, such as cycloalkyl as part of cycloalkylalkyl, etc., unless otherwise specifically defined.

[0035] The term "cycloalkenyl" means alkenyl that is closed to form a ring containing a monocyclic partially unsaturated hydrocarbyl group. Non-limiting examples include, but are not limited to, cyclopropenyl, cyclopentenyl, and cyclohexenyl. This definition also applies to compound substituents, such as cycloalkenyl as part of cycloalkenylalkyl, etc., unless otherwise specifically defined.

[0036] The term "cycloalkynyl" means an alkynyl that is closed to form a ring containing a monocyclic partially unsaturated group. Non-limiting examples include, but are not limited to, cyclopropynyl, cyclopentynyl, and cyclohexynyl. This definition also applies to cycloalkynyl as part of a complex substituent, such as cycloalkynylalkyl, unless otherwise specifically defined.

[0037] Terms such as "cycloalkoxy", "cycloalkenyloxy" are defined similarly. Non-limiting examples of cycloalkoxy include cyclopropyloxy, cyclopentyloxy, and cyclohexyloxy. This definition also applies to cycloalkoxy as part of a complex substituent, such as cycloalkoxyalkyl, unless otherwise specifically defined.

[0038] The term "halogen", alone or in any compound word such as "haloalkyl", includes fluorine, chlorine, bromine, or iodine. Further, when used in a compound word such as "haloalkyl", the alkyl 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 complex substituent, such as haloalkylaminoalkyl, unless otherwise specifically defined.

[0039] The terms "haloalkenyl", "haloalkynyl" are defined similarly, except that an alkenyl and an alkynyl group are present as part of the substituent instead of an alkyl group.

[0040] The term "haloalkoxy" means a linear or branched alkoxy group in which some or all of the hydrogen atoms of the group may be replaced by the halogen atoms specified above. Non-limiting examples of haloalkoxy include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, and 1,1,1-trifluoropropan-2-oxy. This definition also applies to haloalkoxy as part of a complex substituent, such as haloalkoxyalkyl, unless otherwise specifically defined.

[0041] The term "haloalkylthio" means a linear or branched alkylthio group in which some or all of the hydrogen atoms of the group may be replaced by the halogen atoms specified above. Non-limiting examples of haloalkylthio include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio, and 1,1,1-trifluoropropan-2-ylthio. This definition also applies to haloalkylthio as part of a complex substituent, such as haloalkylthioalkyl, unless otherwise specifically defined.

[0042] Non-limiting examples of "haloalkylsulfinyl" include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O), and CF 3 CF 2 It contains S(O). Examples of "haloalkylsulfonyl" include CF3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 , and CF 3 CF 2 S(O) 2 .

[0043] The term "hydroxy" means -OH, amino means -NRR, where R can be any possible substituent such as H or alkyl. Carbonyl means -C(O)-, carbonyloxy means -OC(O)-, sulfinyl means SO, and sulfonyl means S(O) 2 .

[0044] The term "alkoxy", used either alone or as part of a compound word, includes C 1 ~C 24 alkoxy, preferably C 1 ~C 15 alkoxy, more preferably C 1 ~C 10 alkoxy, and most preferably C 1 ~C 6 alkoxy. Examples of alkoxy include methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy, and 1-ethyl-2-methylpropoxy, as well as different isomers. This definition also applies to alkoxy as part of composite substituents, such as haloalkoxy, alkynylalkoxy, etc., unless otherwise specifically defined.

[0045] The term "alkoxyalkyl" indicates an alkoxy substitution on an alkyl. Non-limiting examples of "alkoxyalkyl" include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 , and CH 3CH 2 OCH 2 CH 2 .

[0046] The term "alkoxyalkoxy" indicates an alkoxy substitution on an alkoxy.

[0047] The term "alkylthio" refers to a branched or straight-chain alkylthio moiety, for example, methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio, and 1-ethyl-2-methylpropylthio, and different isomers are included.

[0048] Halogencycloalkyl, halogencycloalkenyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkoxyalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, haloalkylcarbonyl, cycloalkylcarbonyl, haloalkoxylalkyl, etc. are defined in the same manner as the above examples.

[0049] The term "alkylthioalkyl" means an alkylthio substitution on alkyl. Representative examples of "alkylthioalkyl" include -CH 2 SCH 2 , -CH 2 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 , and CH 3 CH 2 SCH 2 CH 2 . "Alkylthioalkoxy" indicates an alkylthio substitution on alkoxy. The term "cycloalkylalkylamino" indicates a cycloalkyl substitution on alkylamino.

[0050] Terms such as alkoxyalkoxyalkyl, alkylaminoalkyl, dialkylaminoalkyl, cycloalkylaminoalkyl, cycloalkylaminocarbonyl, etc. are defined in the same manner as "alkylthioalkyl" or cycloalkylalkylamino.

[0051] The term "alkoxycarbonyl" is an alkoxy group bonded to a skeleton via a carbonyl group (-CO-). This definition also applies to alkoxycarbonyl as part of a complex substituent, such as cycloalkylalkoxycarbonyl, unless otherwise specifically defined.

[0052] The term "alkoxycarbonylalkylamino" indicates an alkoxycarbonyl substitution on an alkylamino. "Alkylcarbonylalkylamino" indicates an alkylcarbonyl substitution on an alkylamino. Terms such as alkylthioalkoxycarbonyl and cycloalkylalkylaminoalkyl are defined similarly.

[0053] Non-limiting examples of "alkylsulfinyl" include methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl, pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, hexylsulfinyl, 1,1-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1,1,2-trimethylpropylsulfinyl, 1,2,2-trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl, and 1-ethyl-2-methylpropylsulfinyl, and different isomers are included, but not limited thereto. The term "arylsulfinyl" includes Ar-S(O), where Ar can be any carboxyl or heterocyclic ring. This definition also applies to alkylsulfinyl as part of a complex substituent, such as haloalkylsulfinyl, unless otherwise specifically defined.

[0054] Non-limiting examples of "alkylsulfonyl" include methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl, and 1-ethyl-2-methylpropylsulfonyl, and include, but are not limited to, different isomers. The term "arylsulfonyl" includes Ar-S(O)2 wherein Ar can be any carboxyl or heterocyclic ring. This definition also applies to alkylsulfonyl as part of a complex substituent, such as alkylsulfonylalkyl, etc., unless otherwise defined.

[0055] "Alkylamino", "dialkylamino", etc. are defined in the same manner as the above examples.

[0056] The term "carbocyclic ring" includes "aromatic carbocyclic ring systems" and "non-aromatic carbocyclic ring systems", or polycyclic or bicyclic (spiro, fused, bridged, non-fused) ring compounds where the ring may be aromatic or non-aromatic (aromatic indicates satisfying the Hückel's rule, and non-aromatic indicates not satisfying the Hückel's rule).

[0057] The term "hetero" related to a ring refers to a ring that can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, where at least one ring atom is not carbon (provided that each ring contains 4 or fewer nitrogens, 2 or fewer oxygens, and 2 or fewer sulfurs).

[0058] The term "aromatic" indicates that the Hückel's rule is satisfied, and the term "non-aromatic" indicates that the Hückel's rule is not satisfied.

[0059] The terms "heterocyclic" or "heterocyclic ring" or "heterocyclic ring system" include "aromatic heterocyclic" or "heteroaryl bicyclic ring system" and "non-aromatic heterocyclic ring system", or polycyclic or bicyclic (spiro, fused, bridged, non-fused) ring compounds where the ring may be aromatic or non-aromatic, where the heterocyclic ring contains at least one heteroatom selected from 0~2 N, O, S(O) * R * and / or the ring members of the heterocyclic ring may be replaced by C(=O), C(=S), C(=CR * ) and C=NR * , wherein is an integer.

[0060] The term "non-aromatic heterocyclic" or "non-aromatic heterocyclic ring" means the following: a saturated or partially unsaturated heterocyclic ring containing 1 to 4 heteroatoms from the group consisting of oxygen, nitrogen, and sulfur, having 3 to 15 members, preferably 3 to 12 members; a monocyclic, bicyclic, or tricyclic heterocyclic ring containing, in addition to carbon ring members, 1 to 3 nitrogen atoms and / or 1 oxygen or sulfur atom or 1 or 2 oxygen and / or sulfur atoms (when two or more oxygen atoms are contained in the ring, they are not directly adjacent); for example (but not limited to), oxetanyl, oxiranyl, aziridinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 1-pyrazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 1-imidazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-1-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-1-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, pyrrolinyl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, pyrazinyl, morpholinyl, thiomorpholinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl,3-Hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1,3,5-hexahydrotriazin-2-yl, 1,2,4-hexahydrotriazin-3-yl, cycloserine, 2,3,4,5-tetrahydro[1H]azepin-1- or -2- or -3- or -4- or -5- or -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin-2- or -3- or -4- or -5- or -6- or -7-yl, 2,3,4,7-tetrahydro[1H]azepin-1- or -2- or -3- or -4- or -5- or -6- or -7-yl, 2,3,6,7-tetrahydro[1H]azepin-1- or -2- or -3- or -4- or -5- or -6- or -7-yl, hexahydroazepin-1- or -2- or -3- or -4-yl, tetra-, and hexahydrooxepinyl, e.g., 2,3,4,5-tetrahydro[1H]oxepin-2- or -3- or -4- or -5- or -6- or -7-yl, 2,3,4,7-tetrahydro[1H]oxepin-2- or -3- or -4- or -5- or -6- or -7-yl, 2,3,6,7-tetrahydro[1H]oxepin-2- or -3- or -4- or -5- or -6- or -7-yl, hexahydroazepin-1- or -2- or -3- or -4-yl, tetra- and hexahydro-1,3-diazepinyl, tetra- and hexahydro-1,4-diazepinyl, tetra- and hexahydro-1,3-oxazepinyl, tetra- and hexahydro-1,4-oxazepinyl, tetra- and hexahydro-1,3-dioxepinyl, tetra- as well as hexahydro-1,4-dioxepinyl. This definition also applies to heterocyclyl as part of a complex substituent, e.g., heterocyclylalkyl, etc., unless otherwise specifically defined.,

[0061] The term "heteroaryl" or "aromatic heterocyclic" means the following: a 5- or 6-membered fully unsaturated monocyclic ring system containing 1 to 4 heteroatoms from the group of oxygen, nitrogen, and sulfur (wherein, when the ring contains multiple oxygen atoms, they are not directly adjacent): 5-membered heteroaryl containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom: a 5-membered heteroaryl group which may contain, in addition to carbon atoms, 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; nitrogen-bonded 5-membered heteroaryl containing 1 to 4 nitrogen atoms, or benzo-fused nitrogen-bonded 5-membered heteroaryl containing 1 to 3 nitrogen atoms: a 5-membered heteroaryl group which may contain, in addition to carbon atoms, 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms as ring members, and 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 group in which 1 or 2 carbon atoms may be replaced by nitrogen atoms, and these rings are bonded to the skeleton through 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.

[0062] 6-membered heteroaryl containing 1 to 4 nitrogen atoms: In addition to carbon atoms, for example, a 6-membered heteroaryl group that may contain 1 to 3 and 1 to 4 nitrogen atoms respectively as ring members, such as (but not limited to) 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, and 1,2,4,5-tetrazin-3-yl; benzo-fused 5-membered heteroaryl containing 1 to 3 nitrogen atoms or 1 nitrogen atom and 1 oxygen or sulfur atom: for example (but not limited to), indol-1-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl, benzimidazol-1-yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, indazol-1-yl, indazol-3-yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl, 1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl, 1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl, 1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl, 1-benzothiophen-5-yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl, 1,3-benzothiazol-2-yl, 1,3-benzothiazol-4-yl, 1,3-benzothiazol-5-yl, 1,3-benzothiazol-6-yl, 1,3-benzothiazol-7-yl, 1,3-benzoxazol-2-yl, 1,3-benzoxazol-4-yl, 1,3-benzoxazol-5-yl, 1,3-benzoxazol-6-yl, and 1,3-benzoxazol-7-yl;Benzofused 6-membered heteroaryl containing 1 to 3 nitrogen atoms: for example (but not limited to) quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl, and isoquinolin-8-yl.;

[0063] This definition also applies to heteroaryl as part of composite substituents, such as heteroarylalkyl, etc., unless otherwise specifically defined.

[0064] The term "trialkylsilyl" includes three branched and / or straight-chain alkyl groups bonded to and linked through a silicon atom, such as trimethylsilyl, triethylsilyl, and t-butyl-dimethylsilyl. "Halotrialkylsilyl" indicates that at least one of the three alkyl groups is partially or completely substituted with a halogen atom, which may be the same or different. "Alkoxytrialkyl The term "killsilyl" indicates that at least one of the three alkyl groups is substituted with one or more alkoxy groups, which may be the same or different. The term "trialkylsilyloxy" indicates a trialkylsilyl moiety bonded via oxygen.

[0065] Non-limiting examples of "alkylcarbonyl" include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 , and C(O)CH(CH 3 ) 2 is included. Non-limiting examples of "alkoxycarbonyl" include CH3 OC(=O), CH 3 CH 2 OC(=O), CH 3 CH 2 CH 2 OC(=O), (CH 3 ) 2 CHOC(=O), and different butoxy- or pentyloxycarbonyl isomers are included. Non-limiting examples of "alkylaminocarbonyl" include CH 3 NHC(=O), CH 3 CH 2 NHC(=O), CH 3 CH 2 CH 2 NHC(=O), (CH 3 ) 2 CHNHC(=O), and different butylamino- or pentylaminocarbonyl isomers are included. Non-limiting examples of "dialkylaminocarbonyl" include (CH 3 ) 2 NC(=O), (CH 3 CH 2 ) 2 NC(=O), CH 3 CH 2 (CH 3 )NC(=O), CH 3 CH 2 CH 2 (CH 3 )NC(=O), and (CH 3 ) 2 CHN(CH 3 )C(=O) is included. Non-limiting examples of "alkoxyalkylcarbonyl" include CH 3 OCH 2 C(=O), CH 3 OCH 2 CH 2 C(=O), CH 3 CH 2 OCH 2 C(=O), CH 3 CH 2 CH 2 CH 2 OCH 2 C(=O), and CH 3 CH 2 OCH 2 CH 2It contains C(=O). Non-limiting examples of "alkylthioalkylcarbonyl" include CH 3 SCH 2 C(=O), CH 3 SCH 2 CH 2 C(=O), CH 3 CH 2 SCH 2 C(=O), CH 3 CH 2 CH 2 CH 2 SCH 2 C(=O), and CH 3 CH 2 SCH 2 CH 2 It contains C(=O). Terms such as haloalkylsulfonylaminocarbonyl, alkylsulfonylaminocarbonyl, alkylthioalkoxycarbonyl, alkoxycarbonylalkylamino are defined similarly.

[0066] Non-limiting examples of "alkylaminoalkylcarbonyl" include CH 3 NHCH 2 C(=O), CH 3 NHCH 2 CH 2 C(=O), CH 3 CH 2 NHCH 2 C(=O), CH 3 CH 2 CH 2 CH 2 NHCH 2 C(=O), and CH 3 CH 2 NHCH 2 CH 2 It contains C(=O).

[0067] The term "amide" means A-R’C=ONR’’-B, where R’ and R’’ represent substituents, and A and B represent any groups.

[0068] The term "thioamide" means A-R’C=SNR’’-B, where R’ and R’’ represent substituents, and A and B represent any groups.

[0069] The total number of carbon atoms in the substituent is indicated by the prefix "C i ~C j ", and i and j are numbers from 1 to 21. For example, C 1 ~C 3 Alkylsulfonyl represents from methylsulfonyl to propylsulfonyl, and C 2 Alkoxyalkyl represents CH 3 OCH 2 , and C 3 Alkoxyalkyl represents, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 , or CH 3 CH 2 OCH 2 , and C 4 Alkoxyalkyl represents various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, and examples include CH 3 CH 2 CH 2 OCH 2 , and CH 3 CH 2 OCH 2 CH 2 is included. In the above description, when the compound of formula (I) consists of one or more heterocycles, all substituents are attached to these rings via any available carbon or nitrogen by replacing the hydrogen on the above carbon or nitrogen.

[0070] When the compound is substituted with a substituent having a subscript indicating that the number of the above substituents can exceed 1, the substituents (if there are more than one of them) are independently selected from the group of defined substituents. Further, when the subscript m of (R) m indicates an integer in the range of, for example, 0 to 4, the number of substituents can be selected from integers of 0 to 4.

[0071] When a substituent contains a substituent that can be hydrogen, it is recognized that when this substituent is hydrogen, the group is unsubstituted.

[0072] The embodiments of this specification, along with their various features and advantageous details, are described with reference to the non-limiting embodiments in this description. To avoid unnecessarily obscuring the embodiments of this specification, the description of well-known components and processing techniques is omitted. The examples used in this specification are merely intended to facilitate the understanding of how the embodiments of this specification can be implemented and to further enable those skilled in the art to implement the embodiments of this specification. Therefore, the examples should not be construed as limiting the scope of the embodiments of this specification.

[0073] The description of specific embodiments clearly reveals the general nature of the embodiments in this specification, so that others can, by applying current knowledge, easily modify and / or adapt such specific embodiments to various applications without departing from the general concept. Therefore, such adaptations and modifications should be intended to be within the meaning and scope of the equivalents of the disclosed embodiments and are intended to be so. It should be understood that the terms or technical terms used in this specification are for the purpose of explanation and not for the purpose of limitation. Therefore, although the embodiments of this specification are described with respect to the preferred embodiments, those skilled in the art will recognize that the embodiments of this specification can be implemented with modifications within the spirit and scope of the embodiments described in this specification.

[0074] Any discussion of any document, act, material, device, paper, etc. included in this specification is only for the purpose of providing relevance for the disclosure. None of these matters, either individually or in combination, should be considered as admitting that they formed part of the prior art base or were common general knowledge in the field related to this disclosure because they existed prior to the priority date of this application.

[0075] The numerical values described in this description and in the description / claims may form an important part of the present invention, but deviations from such numerical values shall still be within the scope of the present invention if such deviations follow the same scientific principles as the scientific principles of the present invention disclosed in the present invention. The inventive compounds of the present invention may, where appropriate, exist as mixtures of different possible isomeric forms, in particular as mixtures of stereoisomers, such as, for example, mixtures of E and Z, threo and erythro, and as mixtures of optical isomers, but may also exist as mixtures of tautomers where appropriate. Both the E and Z isomers, as well as the threo and erythro isomers, and the optical isomers, any desired mixtures of these isomers, and possible tautomers are disclosed and claimed.

[0076] For the purposes of the present disclosure, the term "pest" includes, but is not limited to, fungi, stramenopiles (oomycetes), bacteria, nematodes, mites, ticks, insects, and rodents. Pests are also animals and plants that are harmful to human concerns, including humans or crops, livestock, and forestry.

[0077] For the purposes of this specification, the term "plant" is understood to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants obtained by conventional breeding and optimization methods, or by biotechnological and genetic engineering methods, or combinations of these methods, and include transgenic plants as well as plant cultivars that can and cannot be protected by plant breeders' rights.

[0078] For the purposes of the present disclosure, the term "plant" typically includes organisms of the type exemplified by trees, shrubs, herbs, lawns, ferns, and mosses, which grow in a place, absorb water and necessary substances from their roots, and synthesize nutrients in their leaves by photosynthesis.

[0079] Examples of "plants" for the purposes of the present invention include agricultural crops such as wheat, rye, barley, triticale, oats, or rice; beets such as sugar beets or fodder beets; fruits and fruit trees such as pome fruits, stone fruits, or berries such as apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries, or gooseberries; leguminous plants such as lentils, peas, alfalfa, or soybeans; oil plants such as rapeseed, mustard, olive, sunflower, coconut, cocoa beans, sesame, oil palm, 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 mandarins; any horticultural plants, vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, gourds, or paprika; laurel family plants such as avocados, cinnamon, or camphor; cucurbitaceae; oleaginous plants; energy and raw material plants such as cereals, corn, soybeans, other leguminous plants, rapeseed, sugarcane, or oil palm; tobacco; nuts; coffee; tea; cocoa; bananas; pepper; grapevines (edible grapes and grape juice, wine); hops; turf; sweet leaves (also known as stevia); natural rubber plants or ornamental plants and forest plants such as flowers, shrubs, broad-leaved trees, or evergreen trees such as conifers; plant propagation materials such as seeds, and crop materials of these plants, but are not limited thereto.

[0080] Preferably, plants for the purposes of the present invention include cereals, corn, rice, soybeans, and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus fruits and citrus trees, any horticultural plants, cucurbits, oil plants, tobacco, coffee, tea, cocoa, sugarcane, sugar beets, cotton, potatoes, tomatoes, onions, pepper, and vegetables, ornamental plants, any flowering plant cultivation, and other plants for use by humans and animals, but are not limited thereto.

[0081] The term "plant part" is understood to mean all parts and organs of plants above and below the ground. For the purposes of the present disclosure, the term "plant part" includes, but is not limited to, cuttings, leaves, twigs, tubers, flowers, seeds, branches, taproots, lateral roots, root hairs, root tips, root caps, roots including rhizomes, slips, new shoots, fruits, fruit bodies, barks, stems, buds, axillary buds, meristems, nodes and internodes.

[0082] The term "in situ" includes the soil, the surroundings of the plant or plant part, and the equipment or apparatus used before, during or after sowing / planting the plant or plant part.

[0083] The application of the compounds of the present disclosure or compositions comprising the compounds of the present disclosure optionally together with other compatible compounds to plants or plant materials or in situ includes applications by techniques known to those skilled in the art including, but not limited to, spraying, coating, dipping, fumigating, impregnating, injecting, and dusting.

[0084] The term "applied" means physically or chemically adhering to a plant or plant part, including impregnating.

[0085] In one embodiment, the present invention provides a compound of formula (I):

[0086]

Chemical formula

[0087] Formula (I)

[0088] [wherein, R 1 is C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6- Haloalkenyl, C 3 ~C 8 - Cycloalkyl, and C 3 ~C 8 - Cycloalkyl - C 1 ~C 6 - Selected from the group consisting of alkyl, Y is independently O or NR Y Selected from R Y Is hydrogen, cyano, C 1 ~C 4 - Alkyl, C 2 ~C 4 - Alkenyl, C 2 ~C 4 - Alkynyl, C 1 ~C 4 - Haloalkyl, C 2 ~C 4 - Haloalkenyl, C 3 ~C 5 - Cycloalkyl, and C 3 ~C 5 - Cycloalkyl - C 1 ~C 3 - Selected from the group consisting of alkyl, A represents N or CR 2 And G represents N or C, provided that both Gs are not nitrogen simultaneously, R 2 Is hydrogen, halogen, cyano, C 1 ~C 6 - Alkyl, C 2 ~C 6 - Alkenyl, C 2 ~C 6 - Alkynyl, C 1 ~C 6 - Haloalkyl, C 2 ~C 6 - Haloalkenyl, C 3 ~C 8 - Cycloalkyl, OR 4 、CR 4 =NR 5 、NR 5 R 6 、S(O) 0~2 R 7 、C(=O)R 8 、S(O)0~1 R 9 =NR 10 、N=S(O) 0~1 (R 9 ) 2 、P(=O)(OR’) 2 、Si(R’) 3 、C 6 ~C 10 - aryl, C 7 ~C 14 - aralkyl, and C 3 ~C 10 - heterocyclyl selected from the group consisting of, each aliphatic group is optionally substituted with one or more R 2a groups, and the cyclic group of R 2 is optionally substituted with one or more R 2b groups, R 2a is halogen, cyano, C 1 ~C 6 - alkyl, C 2 ~C 6 - alkenyl, C 2 ~C 6 - alkynyl, C 1 ~C 6 - haloalkyl, C 3 ~C 8 - cycloalkyl, OR 4 、CR 4 =NR 5 、NR 5 R 6 、S(O) 0~2 R 7 、C(=O)R 8 、S(O) 0~1 R 9 =NR 10 、N=S(O) 0~1 (R 9 ) 2 、Si(R’) 3 、C 6 ~C 10 - aryl, C 7 ~C 14 - aralkyl, and C 3 ~C 10 - heterocyclyl selected from the group consisting of, R 2b is halogen, cyano, C1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, OR 4 , CR 4 =NR 5 , NR 5 R 6 , S(O) 0~2 R 7 , C(=O)R 8 , Si(R’) 3 , S(O) 0~1 R 9 =NR 10 , and N=S(O) 0~1 (R 9 ) 2 selected from the group consisting of, or two R 2a or two R 2b substituents, together with the atom to which they are attached, or together with a further atom selected from the group consisting of C, N, O, S, optionally contain 1 to 3 ring members selected from the group consisting of C(=O), C(=S), S(O) 0~2 , and Si(R’) 2 to form a 3- to 7-membered ring, which 3- to 7-membered ring may be substituted at one or more positions thereof with one or more R 2ab groups, R 2ab is halogen, cyano, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, OR 4, NR 5 R 6 , S(O) 0~2 R 7 , S(O) 0~1 R 9 =NR 10 , N=S(O) 0~1 (R 9 ) 2 , Si(R’) 3 , C 6 ~C 10 -aryl, C 7 ~C 14 -aralkyl, and C 3 ~C 10 -heterocyclyl selected from the group consisting of, Q represents a partially saturated or unsaturated 5- to 12-membered heterocyclic ring system which may be optionally substituted with one or more R 3 groups, and said heterocyclic ring system does not represent unsubstituted benzothiazolyl and unsubstituted N-methylbenzimidazolyl, R 3 is halogen, cyano, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, OR 4 , CR 4 =NR 5 , NR 5 R 6 , S(O) 0~2 R 7 , C(=O)R 8 , S(O) 0~1 R 9 =NR 10 , N=S(O) 0~1 (R 9 ) 2 , P(=O)(OR’) 2 , Si(R’) 3 , C 6 ~C 10 -aryl, C 7~C 14 - aralkyl, and C 3 ~C 10 - selected from the group consisting of heterocyclyl, each aliphatic group is optionally substituted with one or more R 3a groups, and the cyclic group of R 3 is optionally substituted with one or more R 3b groups, R 3a is halogen, cyano, C 1 ~C 6 - alkyl, C 2 ~C 6 - alkenyl, C 2 ~C 6 - alkynyl, C 1 ~C 6 - haloalkyl, C 3 ~C 8 - cycloalkyl, OR 4 、CR 4 =NR 5 、NR 5 R 6 、S(O) 0~2 R 7 、C(=O)R 8 、S(O) 0~1 R 9 =NR 10 、N=S(O) 0~1 (R 9 ) 2 、Si(R’) 3 、C 6 ~C 10 - aryl, C 7 ~C 14 - aralkyl, and C 3 ~C 10 - heterocyclyl selected from the group consisting of, R 3b is halogen, cyano, C 1 ~C 6 - alkyl, C 2 ~C 6 - alkenyl, C 2 ~C 6 - alkynyl, C 1 ~C 6 - haloalkyl, C 2 ~C 6 - haloalkenyl, C 3~C 8 -cycloalkyl, OR 4 , C(R’) 2 -NR 5 R 6 , C(R’) 2 -OR 4 , CR 4 =NR 5 , NR 5 R 6 , S(O) 0~2 R 7 , C(=O)R 8 , S(O) 0~1 R 9 =NR 10 , N=S(O) 0~1 (R 9 ) 2 , Si(R’) 3 , C 6 ~C 10 -aryl, C 7 ~C 14 -aralkyl, and C 3 ~C 10 -heterocyclyl selected from the group consisting of, Two R 3a or two R 3b substituents, together with the atoms to which they are attached, or together with additional atoms selected from the group consisting of C, N, O, S, C(=O), C(=S), S(O) m , and Si(R’) 2 optionally contain 1 to 3 ring members selected from the group consisting of to form a 3- to 7-membered ring, and the 3- to 7-membered ring may be substituted at one or more positions thereof with one or more R 3ab groups, and R 3ab is hydrogen, halogen, cyano, C 1 ~C 6 -alkyl, C 1 ~C 6 -haloalkyl, C 3 ~C 8 -cycloalkyl, OR 4 , NR 5 R 6 , S(O) 0~2 R 7 selected from the group consisting of, Two R 3together with the atoms to which they are attached, or together with a further atom selected from the group consisting of C, N, O, S, C(=O), C(=S), S(O) m , and Si(R’) 2 optionally contains 1 to 3 ring members selected from the group consisting of and forms a 3- to 7-membered ring, and the 3- to 7-membered ring is halogen, cyano, R 3c , OR 3c , SR 3c , NR 3c 2 , Si(R 3c ) 3 , COOR 3c , and CONR 3c 2 optionally substituted with one or more groups selected from the group consisting of, R 3c is selected from the group consisting of hydrogen, halogen, linear or branched C 1 ~C 6 -alkyl, and cyclic C 3~8 -alkyl, and each group of R 3c is optionally substituted with one or more halogens, Ring E represents a 5- or 6-membered heterocyclic ring fused to Ring D, and Ring E is optionally substituted with one or more R 11 groups, R 11 is halogen, cyano, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, OR 4 , CR 4 =NR 5 , NR 5 R 6 , S(O) 0~2 R 7 , C(=O)R 8 , S(O)0~1 R 9 =NR 10 、N=S(O) 0~1 (R 9 ) 2 、P(=O)(OR’) 2 、Si(R’) 3 、C 6 ~C 10 -aryl, C 7 ~C 14 -aralkyl, and C 3 ~C 10 -heterocyclyl selected from the group consisting of, each aliphatic group is optionally substituted with one or more R 11a groups, and the cyclic group of R 11 is optionally substituted with one or more R 11b groups, R 11a is halogen, cyano, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 3 ~C 8 -cycloalkyl, OR 4 、CR 4 =NR 5 、NR 5 R 6 、S(O) 0~2 R 7 、C(=O)R 8 、S(O) 0~1 R 9 =NR 10 、N=S(O) 0~1 (R 9 ) 2 、Si(R’) 3 、C 6 ~C 10 -aryl, C 7 ~C 14 -aralkyl, and C 3 ~C 10 -heterocyclyl selected from the group consisting of, R 11b is halogen, cyano, C1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, OR 4 , C(R’) 2 -NR 5 R 6 , C(R’) 2 -OR 4 , CR 4 =NR 5 , NR 5 R 6 , S(O) 0~2 R 7 , C(=O)R 8 , S(O) 0~1 R 9 =NR 10 , N=S(O) 0~1 (R 9 ) 2 , Si(R’) 3 , C 6 ~C 10 -aryl, C 7 ~C 14 -aralkyl, and C 3 ~C 10 selected from the group consisting of -heterocyclyl, R 4 is hydrogen, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, S(O) 2 R 7 , Si(R’) 3 , C 6 ~C 10-Aryl, C 7 ~C 14 -Aralkyl and C 3 ~C 10 -Heterocyclyl, and each aliphatic group is optionally substituted with R 4a and the cyclic group of R 4 may be optionally substituted with one or more R 4b groups, R 4a is halogen, cyano, C 1 ~C 6 -Alkyl, C 2 ~C 6 -Alkenyl, C 2 ~C 6 -Alkynyl, C 1 ~C 6 -Haloalkyl, C 3 ~C 8 -Cycloalkyl, OR’, NR’R’’, S(O) 0~2 R’, C(=O)R’, Si(R’) 3 , C 6 ~C 10 -Aryl, C 7 ~C 14 -Aralkyl, and C 3 ~C 10 -Heterocyclyl, and is selected from the group consisting of R 4b is halogen, cyano, C 1 ~C 6 -Alkyl, C 2 ~C 6 -Alkenyl, C 2 ~C 6 -Alkynyl, C 1 ~C 6 -Haloalkyl, C 2 ~C 6 -Haloalkenyl, C 3 ~C 8 -Cycloalkyl, OR, NR’R’’, S(O) 0~2 R’, C(=O)R’, Si(R’) 3 , C 6 ~C 10 -Aryl, C 7 ~C 14 -Aralkyl, and C 3 ~C10 selected from the group consisting of '-heterocyclyl'; R 5 is hydrogen, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, OR 4 、NR’R’’, S(O) 0~2 R 7 、C(=O)R 8 、Si(R’) 3 、C 6 ~C 10 -aryl, C 7 ~C 14 -aralkyl, and C 3 ~C 10 -heterocyclyl, and each aliphatic group is optionally substituted with R 5a ; the cyclic group of R 5 may be optionally substituted with one or more R 5b groups; R 5a is halogen, cyano, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 3 ~C 8 -cycloalkyl, OR’, NR’R’’, S(O) 0~2 R’, C(=O)R’, Si(R’) 3 、C 6 ~C 10 -aryl, C 7 ~C 14 -aralkyl, and C 3 ~C 10 -heterocyclyl selected from the group consisting of; R 5b is selected from the group consisting of halogen, cyano, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, OR’, NR’R’’, S(O) 0~2 R’, Si(R’) 3 、C(=O)R’, C 6 ~C 10 -aryl, C 7 ~C 14 -aralkyl and C 3 ~C 10 -heterocyclyl, R 6 is selected from the group consisting of hydrogen, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 1 ~C 6 -cycloalkyl, and C(=O)R 8 R 7 is C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, NR 5 R 6 、C​6 ~C 10 -aryl, C 7 ~C 14 -aralkyl and C 3 ~C 10 -heterocyclyl, and each aliphatic group may optionally be substituted with one or more R 7a groups, and the cyclic group of R 7 may optionally be substituted with one or more R 7b groups R 7a is halogen, cyano, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 3 ~C 8 -cycloalkyl, OR’, NR’R’’, S(O) 0~2 R’, C(=O)R’, C 6 ~C 10 -aryl, C 7 ~C 14 -aralkyl, and C 3 ~C 10 -heterocyclyl, and is selected from the group consisting of R 7b is halogen, cyano, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, OR’, NR’R’’, S(O) 0~2 R’, C(=O)R’, C 6 ~C 10 -aryl, C 7 ~C 14 -aralkyl, and C 3 ~C10 - selected from the group consisting of heterocyclyl, R 8 is hydrogen, C 1 ~C 6 - alkyl, C 2 ~C 6 - alkenyl, C 2 ~C 6 - alkynyl, C 1 ~C 6 - haloalkyl, C 2 ~C 6 - haloalkenyl, C 3 ~C 8 - cycloalkyl, OR 4 , NR 5 R 6 , N=S(O) 0~1 (R 9 ) 2 , C 6 ~C 10 - aryl, C 7 ~C 14 - aralkyl and C 3 ~C 10 - heterocyclyl selected from the group consisting of, each aliphatic group may be optionally substituted with one or more R 8a groups, and the cyclic group of R 8 may be optionally substituted with one or more R 8b groups, R 8a is halogen, cyano, C 1 ~C 6 - alkyl, C 2 ~C 6 - alkenyl, C 2 ~C 6 - alkynyl, C 1 ~C 6 - haloalkyl, C 3 ~C 8 - cycloalkyl, OR’, NR’R’’, S(O) 0~2 R’, C(=O)R’, C 6 ~C 10 - aryl, C 7 ~C 14 - aralkyl, and C 3 ~C 10 - heterocyclyl selected from the group consisting of, R8b is selected from the group consisting of halogen, cyano, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, OR’, NR’R’’, S(O) 0~2 R’, C(=O)R’, C 6 ~C 10 -aryl, C 7 ~C 14 -aralkyl, and C 3 ~C 10 -heterocyclyl, and is selected from the group consisting of R 9 is selected from the group consisting of C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, and C(=O)R 8 and is selected from the group consisting of R 10 is hydrogen, cyano, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, C 2 ~C 6 -haloalkenyl, C 3 ~C 8 -cycloalkyl, Si(R’) 3 , S(O) 0~2 R 7 , and C(=O)R8 selected from the group consisting of R’ is halogen, cyano, R’’, OR’’, N(R’’) 2 , S(O) 0~2 R’’, C(=O)R’’, C(=O)OR’’, and C(=O)N(R’’) 2 R 8 selected from the group consisting of R’’ is hydrogen, C 1 ~C 6 -alkyl, C 2 ~C 6 -alkenyl, C 2 ~C 6 -alkynyl, C 1 ~C 6 -haloalkyl, and C 3 ~C 8 -cycloalkyl, each of which may be optionally substituted with halogen, R 1 ~R 11 、R 2a 、R 2b 、R 2ab 、R 3a 、R 3b 、R 3ab 、R 3c 、R 4a 、R 4b 、R 5a 、R 5b 、R 7a 、R 7b 、R 8a 、and R 8b each group of R 2 、COOR’, and CON(R’) 2 may be optionally substituted with one or more groups selected from the group consisting of “m” is an integer in the range of 0 to 2 or an agriculturally acceptable salt, isomer / structural isomer, stereoisomer, diastereoisomer, enantiomer, tautomer, polymorph, metal complex or N-oxide thereof is provided.

[0089] In another embodiment, the compound of formula (I) is a compound of formula (IA):

[0090]

Chem.

[0091] Formula (IA)

[0092] is represented by

[0093] In yet another embodiment, the compound of formula (I) is a compound of formula (IB):

[0094]

Chem.

[0095] Formula (IB)

[0096] is represented by

[0097] In one embodiment, Q is selected from the group consisting of formulas Q1 to Q10:

[0098]

Chem.

[0099] wherein G 1 , G 2 , G 4 , and G 5 each independently represents N or CR 3 , G 3 is NR 6 , is O or S, Z is O or S, and "n" is an integer in the range of 0 to 4.

[0100] In a preferred embodiment, Q is Q1a to Q10b:

[0101]

Chem.

[0102] [Chemical]

[0103] selected from the group consisting of, wherein # represents a bonding point to ring D, and R 6 is hydrogen, C 1 ~C 6 -alkyl, and cyclic C 3~10 -alkyl, and each R 6 group is optionally substituted with one or more halogens, and "n" is an integer in the range of 0 to 4.

[0104] In one embodiment, the present invention provides a compound of formula (I) in which at least one nitrogen is present in the condensed ring system DE.

[0105] In another embodiment, the condensed ring system DE is DE-1 to DE-15:

[0106] [Chemical]

[0107] selected from the group consisting of, wherein # represents a bonding point to ring Q, and ● represents a bonding point to the group -S(Y) m R 1 to.

[0108] In a preferred embodiment, the present invention provides a compound of formula (I) wherein Q is Q1a, Q1b, Q1c, Q1h, Q2b, Q3a, Q5b, Q5d, Q6aQ6b, Q9a, Q9b, Q7a, or Q8a;

[0109] [Chemical]

[0110] selected from, and

[0111] wherein # represents a bonding point to ring D, R 3 is halogen, cyano, C 1 -C6 - alkyl, C 1 - C 6 - haloalkyl, C 3 ~ C 8 - cycloalkyl, and S(Y) 0~2 R 7 is selected from the group consisting of, R 6 is hydrogen, C 1 - C 6 - alkyl and C 3 ~ C 10 - cycloalkyl selected from the group consisting of, R 7 is C 1 ~ C 6 - alkyl, C 2 ~ C 6 - alkenyl, C 2 ~ C 6 - alkynyl, C 1 ~ C 6 - haloalkyl, C 2 ~ C 6 - haloalkenyl, C 3 ~ C 8 - cycloalkyl selected from the group consisting of, The fused ring DE is,

[0112]

Chemical formula

[0113] selected from the group consisting of,

[0114] In the formula, # indicates the bonding point to ring Q, and ● indicates the bonding point to the group - S(Y) m R 1 indicates the bonding point to, R 2 is halogen, cyano, C 1 ~ C 6 - alkyl, C 1 ~ C 6 - haloalkyl, C 3 ~ C 8 - cycloalkyl, C 6 ~ C 8 - aryl, C 7 ~ C 9 - aralkyl and C3 ~C 6 selected from the group consisting of -heterocyclyl, and each aliphatic group is optionally substituted with one or more R 2a groups, and the cyclic group of R 2 is optionally substituted with one or more R 2b groups, "m" is an integer in the range of 0 to 2, "n" is an integer in the range of 0 to 4, R 11 is halogen, cyano, C 1 ~C 6 -alkyl, C 1 ~C 6 -haloalkyl, C 3 ~C 8 -cycloalkyl, OR 4 , NR 5 R 6 , C 6 ~C 10 -aryl, C 7 ~C 14 -aralkyl, and C 3 ~C 10 -heterocyclyl selected from the group consisting of, and each aliphatic group is optionally substituted with one or more R 11a groups, and the cyclic group of R 11 is optionally substituted with one or more R 11b groups.

[0115] In another preferred embodiment, the compound of formula (I) is 2-(1-(3,5-dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(ethylsulfonyl)imidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 6-(1-bromo-2-(ethylsulfonyl)indolizin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine; 2-(2-(Ethylsulfonyl)imidazo[1,2-a]pyridin-3-yl)-5-(trifluoromethyl)benzo[d]oxazole; 2-(2-(Ethylsulfonyl)-7-(trifluoromethyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(8-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(1-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)-7-(trifluoromethyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole; 2-(2-(Ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole; 2-(2-(Ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole; 2-(2-(Ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole; 2-(2-(Ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-7-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-7-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole; 2-(2-(Ethylsulfonyl)-7-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole; 2-(2-(Ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole; 2-(2-(Ethylsulfonyl)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole; 2-(7-(4-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(4-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(4-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(4-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole; 2-(7-(4-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(4-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole; 2-(7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole; 2-(7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole; 2-(2-(Ethylthio)-5-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-5-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-5-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-Chloro-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-6-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-Chloro-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-Chloro-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-Chloro-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-6-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-5-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-(4-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-5-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-5-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-(4-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-6-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(5-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-6-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(5-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(5-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(5-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-Bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-Bromo-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-(4-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-(4-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-5-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-5-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-(3,5-dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(ethylthio)-6-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(ethylsulfonyl)-6-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(5-(4-chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(5-(4-chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(ethylthio)-6-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(ethylthio)-7-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(5-(4-chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(5-(4-chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-7-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 3-(7-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine; 2-(2-(Ethylthio)-7-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 3-(7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine; 2-(2-(Ethylthio)-6-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-6-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3,5-Difluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-6-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3,5-Difluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3-Chloro-5-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3-Chloro-5-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3,4-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 7-(3,5-Dichlorophenyl)-2-(ethylthio)-3-(1-methyl-5-(trifluoromethyl)-1H-benzo[d]imidazol-2-yl)pyrazolo[1,5-a]pyrimidine; 2-(Ethylthio)-3-(1-methyl-5-(trifluoromethyl)-1H-benzo[d]imidazol-2-yl)pyrazolo[1,5-a]pyrimidine; 7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)-3-(1-methyl-5-(trifluoromethyl)-1H-benzo[d]imidazol-2-yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylsulfonyl)-3-(1-methyl-5-(trifluoromethyl)-1H-benzo[d]imidazol-2-yl)pyrazolo[1,5-a]pyrimidine; 2-(2-(ethylsulfonyl)-6-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 3-(7-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine; 3-(7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine; 2-(7-(2,3-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(ethylthio)-7-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(2,3-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(ethylsulfonyl)-7-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(4-Chloro-3-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(4-Chloro-3-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(4-Chloro-3-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(2,4-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(2,4-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(2,4-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3-Chloro-5-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3-Chloro-5-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3,5-Bis(trifluoromethyl)phenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(3-(trifluoromethyl)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(3-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3,5-Bis(trifluoromethyl)phenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(3-(trifluoromethyl)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(3-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-methylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(3-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-7-methylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(3-(trifluoromethyl)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; (7-(3,5-Dichlorophenyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-6-sulfanone; 2-(2-(Ethylsulfonyl)-7-(3-(trifluoromethyl)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-7-(3-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-7-methylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3-Chloro-4-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5,7-bis(trifluoromethyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5,7-bis(trifluoromethyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one; 2-(7-Bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(Ethylsulfonyl)-N-methyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 6-(8-(4-Chloro-3-fluorophenyl)-2-(ethylsulfonyl)indolizine-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine; 2-(2-(Ethylsulfonyl)-7-(5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(Ethylthio)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2-(2-(Ethylsulfonyl)-7-(3-fluorophenoxy)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 6-(8-(4-Chloro-3-fluorophenyl)-2-(ethylsulfonyl)imidazo[1,2-a]pyridin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine; 2-(6-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)imidazo[1,2-a]pyrazine; 4-(2-(Ethylsulfonyl)-3-(7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazin-6-yl)indolizine-8-yl)-2-fluorobenzonitrile; 2-(8-(Cyclopropylmethyl)-2-(ethylsulfonyl)imidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(4-Chloro-1H-pyrazol-1-yl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(5-methyl-1H-1,2,4-triazol-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(1-methyl-1H-pyrazol-5-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-Cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyrazine; 2-(2-(Ethylsulfonyl)-7-(1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine; 4-(2-(Ethylsulfonyl)-3-(7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)morpholine; 2-(7-(4-Chloro-3-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidine; 2-(2-(Ethylsulfonyl)-7-(1H-1,2,4-triazol-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidine; 2-(2-(Ethylsulfonyl)-5,7-bis(trifluoromethyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 6-(1-Bromo-2-(ethylsulfonyl)-8-methylindolizin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine; 6-(8-Bromo-2-(ethylsulfonyl)indolizin-3-yl)-3-(difluoromethyl)-7-methyl-7H-imidazo[4,5-c]pyridazine; 2-(2-(Ethylsulfonyl)-7-methoxypyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(methylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(Ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidine-7(4H)-thione; 2-(2-(Ethylsulfonyl)-7-(1,1,2,2-tetrafluoroethoxy)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-Ethoxy-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)imidazo[1,2-a]pyrazine; Diethyl ((2-(ethylsulfonyl)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)-16-sulfanone; 2-(ethylsulfonyl)-N,N-dimethyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)imidazo[1,2-a]pyridin-8-amine; 6-(2-(ethylsulfonyl)-7-(5-(trifluoromethyl)pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine; 2-(7-(4-chloro-3-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3,5-dimethyl-6-(trifluoromethyl)-3,5-dihydro-4H-imidazo[4,5-c]pyridin-4-one; 2-(2-(ethylsulfonyl)-7-(3-(trifluoromethyl)-1H-1,2,4-triazol-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3,5-dimethyl-6-(trifluoromethyl)-3,5-dihydro-4H-imidazo[4,5-c]pyridin-4-one; 2-(7-(3-chloro-5-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyrazine; 2-(7-(3,5-dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine; 2-(7-(4-chloro-3-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-methyl-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidin-5(6H)-one; 2-(7-(5-Chloropyridin-2-yl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine; 2-(2-(Ethylsulfonyl)-7-(5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-methyl-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidin-5(6H)-one; 2-(2-(Ethylsulfonyl)-7-(3-(trifluoromethyl)-1H-1,2,4-triazol-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidine; Selected from ethyl (3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(methylimino)-16-sulfanon.

[0116] The compounds of the present invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers, and geometric isomers. Those skilled in the art will understand that one stereoisomer may be more active and / or exhibit beneficial effects when enriched or separated from other stereoisomers. Further, those skilled in the art know methods for separating, enriching, and / or selectively preparing the above stereoisomers. The compounds of the present invention can exist as a mixture of stereoisomers, as individual stereoisomers, or in optically active forms.

[0117] When the compound of formula (I) is cationic or can form a cation, the anionic part of the salt can be inorganic or organic. Alternatively, when the compound of formula (I) is anionic or can form an anion, the cationic part of the salt can be inorganic or organic. Examples of the inorganic anionic part of the salt include, but are not limited to, chloride, bromide, iodide, fluoride, sulfate, phosphate, nitrate, nitrite, bicarbonate, and bisulfate. Examples of the organic anionic part of the salt include, but are not limited to, formate, alkanoate, carbonate, acetate, trifluoroacetate, trichloroacetate, propionate, glycolate, thiocyanate, lactate, succinate, malate, citrate, benzoate, cinnamate, oxalate, alkyl sulfate, alkyl sulfonate, aryl disulfonate, alkyl phosphate, aryl phosphate, aryl diphosphate, p-toluenesulfonate, and salicylate. Examples of the inorganic cationic part of the salt include, but are not limited to, alkali metals and alkaline earth metals. Examples of the organic cationic part of the salt include, but are not limited to, pyridine, methylamine, imidazole, benzimidazole, histidine, phosphazene, tetramethylammonium, tetrabutylammonium, choline, and trimethylamine.

[0118] The metal ions in the metal complex of the compound of formula (I) are, in particular, ions of elements of Group 2, especially calcium and magnesium ions, ions of elements of Groups 3 and 4, especially aluminum, tin, and lead ions, and also ions of elements of Transition Groups 1 to 8, especially chromium, manganese, iron, cobalt, nickel, copper, zinc, etc. Metal ions of elements of the fourth period and Transition Groups 1 to 8 are particularly preferred. Here, the metal can exist in various valences that the metal can assume.

[0119] In one embodiment, the present invention provides a compound of formula (I), its agriculturally acceptable salts, metal complexes, structural isomers, stereoisomers, diastereoisomers, enantiomers, chiral isomers, atropisomers, conformational isomers, rotational isomers, tautomers, optical isomers, polymorphs, geometric isomers, or N-oxides, and compositions thereof comprising excipients, inert carriers, or surfactants, additives, solid diluents, liquid diluents, and other essential components.

[0120] The compounds of formula (I) (including all stereoisomers, N-oxides, and salts thereof) typically exist in two or more forms, and thus formula (I) includes all crystalline and amorphous forms of the compounds represented by formula (I). Amorphous forms include embodiments that are solids such as waxes and gums, as well as embodiments that are liquids such as solutions and melts. Crystalline forms include embodiments that essentially represent a single crystal form, and embodiments that represent a mixture of polymorphs (i.e., different crystal forms). The term "polymorph" refers to specific crystal forms of a compound that can crystallize in different crystal forms, and these forms have different arrangements and / or conformations of molecules in the crystal lattice. Polymorphs can have the same chemical composition, but can also differ in composition due to the presence or absence of co-crystallized water or other molecules that can bind weakly or strongly in the lattice. Polymorphs can differ in chemical, physical, and biological properties such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate, and bioavailability. Those skilled in the art will understand that the polymorphs of the compounds represented by formula (I) can exhibit beneficial effects (e.g., suitability for the preparation of useful formulations, improved biological performance) compared to another polymorph or a mixture of polymorphs of the same compound represented by formula (I). The preparation and isolation of specific polymorphs of the compounds represented by formula (I) can be achieved by methods known to those skilled in the art, including crystallization using a selected solvent and temperature.

[0121] In one embodiment, the present invention provides a process for preparing a compound of formula (I) or an agriculturally acceptable salt thereof.

[0122] The compound of formula (I) can be prepared according to Schemes 1-23 / Examples described herein.

[0123] The process for preparing the compound of formula (I), more specifically, the compound of formula (Ia) or the compound of formula (Ib) wherein Q is Q1 or Q2, comprises reacting the compound of formula (2) with the compound of formula (3) or (4) wherein M is O, S, NR', to obtain the compounds of formula (Ia) and (Ib).

[0124] This process is summarized in Scheme 1.

[0125] Scheme: 1

[0126]

Chemical formula

[0127] wherein R 1 , R 3 , A, G, G 1 , G 2 , G 3 , G 4 , G 5 , E, m and n have the meanings as defined above.

[0128] The compounds of formula (3) and formula (4) are commercially available or can be prepared using the methods known in US200369257, WO200665703, WO2009131237, WO2010125985, WO2011043404, WO2011040629, WO2012086848, WO2013018928, and WO2015000715 or methods described analogously therein.

[0129] In Scheme 1, the carboxylic acid group present in the compound of formula (2) is converted into a more reactive functional group such as acyl halide, mixed anhydride, acyl azide, N - acylbenzotriazole, active ester, etc., or activated in situ by a peptide coupling reagent such as bis(2 - oxo - 3 - oxazolidinyl)phosphinic acid chloride (BOP - Cl), dicyclohexylcarbodiimide (DCC), or 1 - ethyl - 3-(3 - dimethylaminopropyl)carbodiimide (EDC). Subsequently, an amide bond is formed with the compound of formula (3) in a solvent such as dichloromethane, dichloroethane, N,N - dimethylacetamide, tetrahydrofuran, acetonitrile, or a mixture thereof to obtain the compound of formula (5). An organic non - nucleophilic base such as triethylamine, ethyldiisopropylamine, pyridine, N - methylpyrrolidine, 1,8 - diazabicyclo[5.4.0]undec - 7 - ene may be used. The reaction can be carried out at a temperature in the range of about 0 °C to about 150 °C.

[0130] The compound of formula (5) can be converted into the compound of formula (Ia) by dehydrating it in an inert solvent such as N - methylpyrrolidine in the presence of an acid catalyst such as methanesulfonic acid or p - toluenesulfonic acid at a temperature in the range of about 25 °C to about 185 °C according to conventional conditions or under microwave conditions. Such processes have been previously described in WO2009131237, WO2010125985, WO2011043404, WO2011040629, WO2012086848, WO2013018928, WO2015000715, and WO2015121136.

[0131] Alternatively, the compound of formula (5) can be converted into the compound of formula (Ia) where M is oxygen in an inert solvent such as diethyl ether, tetrahydrofuran using diisopropyl azodicarboxylate, triphenylphosphine under Mitsunobu conditions known to those skilled in the art at a temperature in the range of about 25 °C to about 50 °C. This process has been previously described in WO2009131237.

[0132] By applying the method of Scheme 1 in the reaction of the compound of formula (2) and the compound of formula (4), the compound of formula (Ib) can be obtained.

[0133] The process for the synthesis of the compound of formula (I) represented by the compounds of formula (Ic and Id) is shown in Scheme 2. The compound of formula (Ic) or (Id) can be prepared by reacting the compound of formula (6) with the compound of formula (3) or (4) to obtain the compound of formula (7) or (8). Further, the compounds of formula (7) and (8) (wherein X is halogen, for example, fluorine, chlorine, or bromine) are optionally reacted with a suitable base, for example, an alkali metal carbonate such as sodium carbonate or potassium carbonate, or an alkali metal hydride such as sodium hydride, or an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, in an inert solvent at a temperature in the range of about 25 °C to about 110 °C, with the compound of formula (9) or M 1 where M is, for example, sodium or potassium, to obtain the compound of formula (Ic) or (Id).

[0134] Scheme: 2

[0135]

Chemical formula

[0136] wherein R 1 , R 3 , A, G, G 1 , G 2 , G 3 , G 4 , G 5 , E, m and n have the above meanings.

[0137] Alternatively, the above reaction can also be carried out in the presence of a palladium catalyst such as tris(dibenzylideneacetone)dipalladium(0) in the presence of a ligand such as xanthphos in an inert solvent, for example, in toluene or xylene, at a temperature in the range of about 100 °C to about 150 °C, as described in Tetrahedron, 2005, 61, 5253. Compounds of formula (I) where Y = O, m = 1 (sulfoxide), and / or m = 2 (sulfone) can be obtained by oxidizing the corresponding sulfide compounds of formula (Ic) and (Id) while applying suitable oxidizing agents and conditions well-known to those skilled in the art. Oxidizing agents such as m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide / acetic acid, hydrogen peroxide / trifluoroacetic acid, hydrogen peroxide / potassium permanganate, hydrogen peroxide / p-toluenesulfonylimidazole, urea hydrogen peroxide / trifluoroacetic acid, Oxone, sodium periodate, sodium hypochlorite, and other organic peracids can be used for this purpose. Examples of solvents used in this reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, and mixtures thereof.

[0138] where m = 1 or 2 and Y = NR Y Compounds of formula (I) where Y = NR and / or Y = O can be obtained by sulfoximination / sulfilimination of the corresponding sulfide compounds of formula (Ic) and (Id) using similar procedures described in Chem. Commun., 2017, 53, 2064 - 2067; Tetrahedron Lett. 2005, 46, 8007 - 8008 and WO2015071180A1.

[0139] The compound of formula (2) is selected from the group consisting of formula (2a), (2b), and (2c).

[0140]

Chemical Structure

[0141] In the formula, R 1 and R 11 have the same meaning as described above.

[0142] The synthesis of the compounds of formulas (2a), (2b), and (2c) is described in Schemes 3 to 9.

[0143] Scheme: 3

[0144]

Chemical formula

[0145] In the formula, R 1 , R 11 , and n have the above meanings.

[0146] The reaction of the compound of formula (11) and the compound of formula (12) is carried out in a suitable solvent at a temperature in the range of 50 to 200 °C to obtain the di-electrophilic compound of formula (13). Examples of the solvent include, but are not limited to, N,N-dimethylformamide, dimethylacetamide, 1,4-dioxane, 1,2-dichloromethane, toluene, xylene, etc.

[0147] In Step 2, which is the pyrimidine formation step, the pyrazole derivative compound of formula (14) can undergo a cyclocondensation reaction by treatment with a dielectrophilic compound of formula (13) or a 1,3-diketone compound of formula (15) (e.g., 1,3-dialdehyde or 3-(dialkylamino)-prop-2-enal) in the presence or absence of a base to obtain a bicyclic compound of formula (16). The preparation of the compound of formula (14) is described in the literature (Acta Chimica Sinica 2003, 63, 855; Organic & Biomolecular Chemistry 2010, 8, 3394). Examples of bases include, but are not limited to, piperidine, morpholine, N-methylpiperazine, diethylamine, triethylamine, etc. Examples of solvents include, but are not limited to, methanol, ethanol, isopropanol, ethylene glycol, etc. The reaction can be carried out at a temperature in the range of about 50 °C to about 150 °C.

[0148] If one or both of the electrophilic centers present in the compounds of formulas (13) and (15) are protected / masked (e.g., the aldehyde is masked as a ketal), the condensation can be carried out in a solvent in the presence of an acid. Examples of acids include acetic acid, sulfonic acid (e.g., PTSA), sulfuric acid, hydrochloric acid, which release reactive functional groups. Examples of solvents include, but are not limited to, methanol, ethanol, isopropanol, ethylene glycol, etc. The reaction can be carried out at a temperature in the range of about 0 °C to about 150 °C. The hydrolysis of the compound of formula (16) can be achieved by using a base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, bis(tributyltin)oxide, etc. in a solvent such as tetrahydrofuran, water, methanol, ethanol, or a mixture thereof to obtain the compound of formula (2a). The reaction can be carried out at a temperature in the range of about 50 °C to about 150 °C.

[0149] Alternatively, the compound of formula (2a) can also be prepared according to Scheme 4 below.

[0150] Scheme: 4

[0151]

Chem.

[0152] In the formula, X is a halogen, and R 1 and R 11 have the above meanings.

[0153] The compound of formula (19) can be obtained from the compound of formula (18) in the same manner as described in Step 1 of Scheme 3. The reaction of the compound of formula (18) can be carried out in the same manner as described in Step 2 of Scheme 3. Further, when Step 2 is carried out in the presence of acetic acid without carrying out Step 3, the compound of formula (20) can be obtained.

[0154] The conversion of the compound of formula (20) to the compound of formula (21) can be carried out in a solvent in the presence or absence of a halogenating agent and a base. Examples of the solvent include, but are not limited to, acetonitrile, chloroform, tetrahydrofuran, 1,4-dioxane, toluene, N,N-dimethylformamide, etc. Examples of the halogenating agent include, but are not limited to, phosphorus oxychloride, thionyl chloride, phosphorus pentachloride, oxalyl chloride, etc. Examples of the base include, but are not limited to, N,N-dimethylaniline, diisopropylethylamine, N-methylmorpholine, etc. The reaction can be carried out at a temperature in the range of 50 to 200 °C.

[0155] The compound of formula (21) can be conveniently coupled with a boronic acid or a boronic ester compound of formula (22) under standard Suzuki cross-coupling conditions to obtain the compound of formula (23). The Suzuki cross-coupling reaction can be catalyzed by a palladium-based catalyst including but not limited to dichlorobis(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) or tetrakis(triphenylphosphine)palladium(0) in a suitable solvent such as tetrahydrofuran (THF), N,N'-dimethylformamide (DMF), 1,2-dimethoxyethane, 1,4-dioxane, or a solvent system of a mixture such as THF / water, 1,2-dimethoxyethane / water, 1,4-dioxane / water. The reaction is usually carried out in the presence of a base such as potassium carbonate, cesium carbonate, or potassium phosphate. The reaction temperature can preferably range from ambient temperature (20 °C) to the boiling point of the reaction mixture as precedent exists in the literature (for example, see Chem. Soc. Rev. 2014, 43, 412-443 or WO2014070978). The hydrolysis of the compound of formula (23) can be achieved by using a base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, bis(tributyltin)oxide in a solvent such as tetrahydrofuran, water, methanol, ethanol, toluene, or a mixture thereof to obtain the compound of formula (2a). The reaction can be carried out at a temperature in the range of about 50 °C to 150 °C.

[0156] The compound of formula (2aa) can be prepared according to Scheme 5 below.

[0157] Scheme: 5

[0158]

Chemical formula

[0159] Wherein, R 1 and R 11 have the above meanings.

[0160] The pyrazole derivative compound of formula (14) can be cyclocondensed with the 1,3-dimethyluracil compound of formula (24) or the alkoxyacrylate derivative of formula (25) in the presence of a base to obtain the pyrimidin-5-one derivative of formula (26). Examples of the base include sodium ethoxide, sodium methoxide, potassium tert-butoxide, potassium carbonate, sodium carbonate, cesium carbonate, potassium phosphate, and the like. Examples of the solvent include methanol, ethanol, isopropanol, ethylene glycol, N,N-dimethylacetamide, N,N-dimethylformamide, and the like. The reaction can be carried out at a temperature in the range of about 50 °C to about 150 °C. Such reactions are well-known in the literature, and alternative reactions are also fully described in the literature (for example, J. Org. Chem 2007, 72, 1046; WO2018081417). By halogenating the compound of formula (26) with phosphorus oxychloride or phosphorus oxybromide, the compound of formula (28) described in, for example, WO201108689 can be obtained. The compound of formula (27) can be conveniently coupled under standard Suzuki cross-coupling conditions to obtain the compound of formula (28) described in Step 5 of Scheme 4. By subsequently subjecting the compound of formula (28) to alkaline hydrolysis as described in Step 6 of Scheme 4, the compound of formula (2aa) can be obtained.

[0161] The process for synthesizing the compound of formula (2ab) is shown in Scheme 6:

[0162] Scheme: 6

[0163]

Chemical formula

[0164] wherein R 1 and R 11 have the above meanings.

[0165] The bisacetal-protected malonaldehyde compound of formula (29) is halogenated under acidic conditions that can be generated by using an acid independently selected from hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoroacetic acid, tetrafluoroboric acid, or p-toluenesulfonic acid, in the presence of a suitable solvent, such as water, using a halogenating agent such as bromine, iodine, or chlorine, or N-bromosuccinimide, N-iodosuccinimide, or N-chlorosuccinimide, to activate it and obtain a halogenated aldehyde such as chloromalonaldehyde, iodomalonaldehyde, or bromomalonaldehyde of formula (30). After step 2, the compound of formula (30) can be reacted with the pyrazole derivative of formula (14) under suitable condensation conditions to obtain the compound of formula (31). Examples of solvents include, but are not limited to, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, and mixtures thereof. The reaction can be carried out at a temperature in the range of about 50 °C to about 150 °C. The compound of formula (31) can be more conveniently coupled under standard Suzuki cross-coupling conditions to obtain the compound of formula (32) described in step 5 of Scheme 4. By subsequently subjecting the compound of formula (32) to alkaline hydrolysis as described in step 6 of Scheme 4, the compound of formula (2ab) can be obtained.

[0166] Alternatively, the compound of formula (31) can also be prepared by cyclizing the pyrazole derivative of formula (14) with a commercially available 2-halomalonaldehyde of formula (33) under acid catalyst conditions. Examples of acids include, but are not limited to, acetic acid, sulfonic acids (e.g., PTSA), sulfuric acid, hydrochloric acid. Examples of solvents include, but are not limited to, methanol, ethanol, isopropanol, ethylene glycol, etc. The reaction can be carried out at a temperature in the range of about 0 °C to about 150 °C. The pyrazolo[1,5-a]pyrimidine derivative of formula (32) can also be prepared after cyclocondensation of the pyrazole derivative of formula (14) using either commercially available malonaldehyde (34) or its equivalent (35). The derivative (35) may be prepared by the method described in J.Het.Chem.1974,44,51.

[0167] The process for synthesizing the compound of formula (2b) is shown in Scheme 7:

[0168] Scheme:7

[0169]

Chemical Structure

[0170] Wherein R 11 and n have the meanings as described above.

[0171] The compound of formula (38) can be prepared from the 2-aminopyridine derivative of formula (36) in a two-step procedure. The first step involves a condensation reaction of the 2-aminopyridine derivative of formula (36) with a haloacetic acid (37) under basic conditions in a suitable solvent. Examples of suitable bases include, but are not limited to, tertiary amines such as trimethylamine and diisopropylethylamine. Examples of suitable solvents include, but are not limited to, water, methanol, ethanol, isopropanol, and mixtures thereof. The reaction can be carried out at a temperature in the range of about 50 °C to about 150 °C.

[0172] In the presence of phosphorus oxychloride or phosphorus oxybromide, in a suitable solvent (e.g., toluene), by intramolecular cyclization of the compound of formula (38) at a high temperature, a 2-haloimidazo[1,2-a]pyridine analog of formula (39) can be obtained. The alkoxycarbonylation of the compound of formula (38) using the chloroalkyl carbonate of formula (40) as one carbon source is carried out in an ether solvent such as tetrahydrofuran, diethyl ether, methyl tert-butyl ether, etc. using an organometallic reagent such as n-butyllithium to obtain the compound of formula (41). The reaction can be carried out at a temperature in the range of about -78°C to about 25°C (WO2011163355). By subsequently subjecting the compound of formula (41) to alkaline hydrolysis as described in step 6 of Scheme 4, the compound of formula (2b) can be obtained.

[0173] The process for synthesizing the compound of formula (2c) is shown in Scheme 8:

[0174] Scheme: 8

[0175]

Chemical formula

[0176] Wherein, R 2 、R 11 、and n have the above meanings.

[0177] The compound of formula (44) can be prepared by reacting the substituted pyridine compound of formula (42) with the alkyl 2-haloacetate of formula (43) in an inert solvent including but not limited to ethyl acetate, acetone, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, dichloromethane, chloroform, N,N-dimethylformamide, toluene, xylene, methanol, ethanol, and mixtures thereof. Bases such as trimethylamine, pyridine, N,N-diisopropylethylamine, 2,6-lutidine can be used in the reaction. The reaction can be carried out at a temperature ranging from 0 °C to the reflux temperature, and the reaction time usually ranges from 30 minutes to 48 hours, varying depending on starting materials, solvents used, reaction temperature, etc.

[0178] The indolizine derivative of formula (46) can be prepared by reacting the compound of formula (44) with the haloalkenyl tosylate of formula (45). The preparation of the compound of formula (45) is described in the literature (Tetrahedron 2018, 74, 5295; Organic Letters 2010, 12, 5518). As the inert solvent, ethyl acetate, acetone, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, dichloromethane, chloroform, N,N-dimethylformamide, toluene, xylene, methanol, ethanol, and mixtures thereof can be used in the reaction. As the base, potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium fluoride, lithium hydroxide, trimethylamine, pyridine, N,N-diisopropylethylamine, 2,6-lutidine can be used in the reaction. The reaction can be carried out at a temperature ranging from 0 °C to the reflux temperature. The reaction time is usually from 1 hour to 48 hours, varying depending on starting materials, solvents used, reaction temperature, etc. Such reactions are known in the literature and are well described, for example, in Tetrahedron 2004, 60, 5487, etc.

[0179] As described in step 6 of Scheme 4, the compound of formula (46) is then subjected to alkaline hydrolysis to obtain the compound of formula (2c).

[0180] The process for synthesizing the compound of formula (2ca) is shown in Scheme 9:

[0181] Scheme: 9

[0182]

Chemical formula

[0183] In the formula, R 1 , R 2 , R 11 , and n have the above meanings.

[0184] The indolizine derivative of formula (47) can be prepared by reacting the compound of (44) with the haloalkenyl tosylate of formula (45a) after step 2 described in Scheme 8. The compound of formula (47) can be reacted with the compound of formula (9) or the compound of formula (10), followed by oxidation to obtain the compound of formula (48). The compound of formula (49) can be prepared by halogenation of the compound of formula (48) using a halogenating agent such as N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide. The reaction can be carried out in an inert solvent selected from dichloromethane, 2-dichloromethane, chloroform, carbon tetrachloride, acetic acid, acetonitrile, methanol, N,N-dimethylformamide, etc., or a mixture thereof. The reaction can be carried out at a temperature in the range from 0 °C to the reflux temperature. The reaction time is usually 30 minutes to 48 hours and varies depending on the starting materials, the solvent used, and the reaction temperature.

[0185] The compound of formula (49) can be conveniently coupled under standard Suzuki cross-coupling conditions to obtain the compound of formula (50) described in step 5 of Scheme 4. By subsequently subjecting the compound of formula (50) to alkaline hydrolysis as described in step 6 of Scheme 4, the compound of formula (2ca) can be obtained.

[0186] Q is Q 3 and G 5 is CR 3 A subgroup of the compounds of formula (I) in which R = H can be represented by the compounds of formula (52), by reacting the compounds of formula (6b) with the compounds of formula (51) such that G 5 is CR 3 and R 3 = H, to obtain the compound of formula (52).

[0187] Scheme: 10

[0188]

Chemical formula

[0189] wherein R 3 , R 7 , A, G, G 1 , G 2 , G 4 , G 5 , E, and n have the meanings as defined above.

[0190] The cyclization to obtain the compound of formula (52) can be carried out in the presence of a Lewis acid such as indium(III) triflate or zinc(II) iodide, in a solvent such as 1,2-dichlorobenzene or chlorobenzene, in the presence of a catalytic copper(II) salt such as copper(II) acetate, under an oxygen or air atmosphere. The reaction can be carried out at a temperature in the range of about 100 °C to about 180 °C. Such reactions have precedents in the literature (see, for example, Adv. Synth. Catalysis, 2013, 355, 1741; J. Org. Chem, 2013, 78, 12494). The synthesis of the compound of formula (51) is described in WO2015000715.

[0191] The compound of formula (52) can be reacted with the compound of formula (9) or the compound of formula (10) to obtain the compound of formula (53).

[0192] The compound of formula (53A) can be prepared according to the synthetic processes described in Chem. Commun., 2017, 53, 2064 - 2067; Tetrahedron Lett. 2005, 46, 8007 - 8008 and WO2015071180A1.

[0193] Scheme: 11

[0194]

Chemical Structure

[0195] wherein R 1 , R 3 , A, G, G 1 , G 2 , G 4 , G 5 , E, m and n have the above meanings.

[0196] The compound represented by formula (54) where m = 1 (sulfoxide) and / or m = 2 (sulfone) can be obtained by oxidizing the corresponding sulfide compound of formula (53) while applying appropriate oxidizing agents and conditions well-known to those skilled in the art. Oxidizing agents such as m-chloroperbenzoic acid (mCPBA), hydrogen peroxide / glacial acetic acid, hydrogen peroxide / trifluoroacetic acid, hydrogen peroxide / potassium permanganate, hydrogen peroxide / p-toluenesulfonylimidazole, urea hydrogen peroxide / trifluoroacetic acid, Oxone, sodium periodate, sodium hypochlorite, and other organic peracids can be used for the oxidation. Examples of solvents used in this reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, and mixtures thereof.

[0197] In a polar aprotic solvent such as acetonitrile or N,N-dimethylformamide, at ambient temperature, by a halogenating agent such as N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, G 5 =CR 3 wherein, R 3 = H, the compound of formula (54) is halogenated to obtain the compound of formula (Ic 1 ).

[0198] Scheme: 12

[0199]

Chemical formula

[0200] In the formula, R 1 , R 3 , A, G, G 1 , G 2 , G 4 , G 5 , E, m and n have the above meanings.

[0201] The compound of formula (Ic 1 ) is reacted with a compound R 3 -B(OR’’’) 2React with (R’’’’ = H or R’’’’ = pinacolato) to obtain G 5 =CR 3 wherein a compound of formula (Ic) can be obtained, where R 3 = alkyl, cycloalkyl, aryl, heteroaryl. Such Suzuki reactions have sufficient precedents in the literature (see, for example, WO2012133607).

[0202] The process for synthesizing the compound of formula (6b) is shown in Scheme 12a:

[0203] Scheme: 12a

[0204]

Chemical formula

[0205] wherein G, E, and A have the above meanings.

[0206] The carboxylic acid of formula (6) can be converted to the Weinreb amide of formula (55) by reacting it with N,O-dimethylhydroxylamine by a method known to those skilled in the art in the same manner as the procedures described in WO201175643 and EP2671582. Then, according to the method described in Tetrahedron Letters 1981, 22, 3815, the Weinreb amide of formula (55) is treated with a Grignard reagent of formula (R 7 CH 2 MgHal) to obtain the compound of formula (6b).

[0207] When Q is Q 4 and G 5 is nitrogen and G 4 is CR 3 The process for synthesizing the compound of formula (1d) is shown in Scheme 13. Then, the compound of formula (1d) can be prepared by reacting the compound of formula (56) and the compound of formula (57) optionally in the presence of a suitable base in an inert solvent. Alternatively, G 4When X is nitrogen, the compound of formula (Id) is - prepared by reacting a compound of formula (58) wherein X is a halide ion or mesitylsulfonate with a compound of formula (59) optionally in the presence of a suitable base in an inert solvent.

[0208] Scheme: 13

[0209]

Chemical formula

[0210] In the formula, R 1 , R 3 , A, G, G 1 , G 2 , G 4 , G 5 , E, m and n have the above meanings.

[0211] The synthesis of the compound of formula (56) is described in the literature WO2015000715. The synthesis of the compound of formula (57) can be achieved in the same manner as, for example, EP1371638. The compound of formula (58) can be prepared by N - amination by reacting the compound of formula (56) with O - mesitylenesulfonylhydroxylamine (MSH) or one of its equivalents as an amination reagent as described in, for example, J. Heterocyclic Chem. 1975, 12, 107 and Synthesis 1977, 1, 17.

[0212] A subgroup of the compounds of formula (I) wherein Q is Q 5 and G 5 is CR 3 can be represented by the compound of formula (Ie). The compound of formula (Ie) can be synthesized by reacting the compound of formula (60) with the compound of formula (6b) in the same manner as the preparation of the compound of formula (Ic).

[0213] Scheme: 14

[0214] [Chemical]

[0215] In the formula, R 1 , R 3 , A, G, G 1 , G 2 , G 5 , E, m and n have the above meanings.

[0216] Those skilled in the art will recognize that a compound of formula (If) in which Q is Q 6 and G 5 is CR 3 can be similarly prepared by reacting a compound of formula (61) with a compound of formula (57a) or (6a).

[0217] Scheme: 15

[0218] [Chemical]

[0219] In the formula, R 1 , R 3 , A, G, G 1 , G 2 , G 5 , E, m and n have the above meanings.

[0220] A subgroup of compounds of formula (I) in which Q is Q 3 and G 5 is nitrogen can be represented by a compound of formula (Ig) and can be prepared by reacting a compound of formula (62) with a compound of formula (59) in an inert solvent in the presence of an optionally suitable base.

[0221] Scheme: 16

[0222] [Chemical]

[0223] In the formula, R1 , R 3 , A, G, G 1 , G 2 , G 5 , E, m and n have the above meanings.

[0224] The compound of formula (62) can be prepared by N - amination by reacting the compound of formula (51) with O - mesitylenesulfonylhydroxylamine (MSH) or one of its equivalents as an amination reagent, as described, for example, in J. Heterocyclic Chem. 1975, 12, 107 and Synthesis 1977, 1, 17. When Q is Q 5 and G 5 is nitrogen, the subgroup of the compounds of formula (I) can be represented by the compounds of formula (Ih) and can be prepared by reacting the compound of formula (63) with the compound of formula (59) in an inert solvent in the presence of an optionally suitable base.

[0225] The compound of formula (63) can be prepared by N - amination by reacting the compound of formula (60) with O - mesitylenesulfonylhydroxylamine (MSH) as an amination reagent. This process is described in J. Heterocyclic Chem. 1975, 12, 107 and Synthesis 1977, 1, 17. The synthesis of the compound of formula (60) is described in the literature WO2007113558.

[0226]

Chemical formula

[0227] In the formula, R 3 , G 1 , and G 2 have the above meanings.

[0228] In a further embodiment, when Q is Q 7 react the compound of formula (64) with the compound of formula (65) such that G 5 is CR 3It involves obtaining a compound of formula (Ii) which is either N. The process for the compound of formula (Ii) is summarized in Scheme 17.

[0229] Scheme: 17

[0230] [Chemical formula]

[0231] wherein R 1 , R 3 , G, A, G 1 , G 2 , G 5 , G 6 , E, m and n have the meanings as described above.

[0232] The compound of formula (65) is commercially available or can be prepared by methods known per se in WO2017113558 and WO2011090122 or in a similar manner as described therein.

[0233] In Scheme 17, the N-substituted amidine of formula (66) can be prepared by reacting the compound of formula (64) with the compound of formula (65) in the presence of a suitable base. Examples of suitable bases are alkali metal hydrides such as sodium hydride, alkali metal salts of hexamethyldisilazane such as sodium hexamethyldisilazane, alcoholates such as potassium or sodium tert-butoxide, or lithium diisopropylamide. The reaction can be carried out in a solvent, preferably in a solvent that is inert under general reaction conditions, for example, ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, diisopropyl ether, 1,2-dimethoxyethane, tert-butyl methyl ether; nitriles such as acetonitrile or propionitrile; aromatic hydrocarbons such as toluene, xylene; aprotic polar solvents such as N,N-dimethylformamide, N-methylpyrrolidine, or dimethyl sulfoxide. The reaction can be carried out at a temperature in the range of about 0 °C to about 150 °C. Such reactions are precedent in the literature (see, for example, J. Am. Chem. Soc. 2009, 131, 15080).

[0234] The intramolecular oxidative cyclization of the N-substituted amidine of formula (66) in the presence or absence of a suitable base can be carried out in the same manner as described in J. Org. Chem 2015, 80, 7219; J. Org. Chem 2014, 79, 4687. Examples of oxidizing agents include hypervalent iodine(III) reagents such as sodium hypochlorite, lead(IV) acetate, manganese dioxide, iodine, phenyl iodine(III) diacetate (PIDA), and phenyl iodine(III) bis(trifluoroacetate) (PIFA). The reaction can be carried out in a solvent, preferably in a solvent that is inert under common reaction conditions, such as nitriles like acetonitrile or propionitrile; aromatic hydrocarbons like toluene or xylene; aprotic polar solvents such as N,N-dimethylformamide, N-methylpyrrolidone, or dimethyl sulfoxide, or ethyl acetate; halogenated hydrocarbons like dichloromethane or dichloroethane; alcohol solvents such as hexafluoroisopropanol, methanol, ethanol, trifluoroethanol, isopropanol. Suitable bases include potassium carbonate, sodium carbonate, and cesium carbonate. The reaction can be carried out at a temperature in the range of about 25 °C to about 180 °C.

[0235] Alternatively, the compound of formula (1i) can be synthesized in a single step, which includes the oxidative coupling of the compound of formula (65) and the compound of formula (64) with a transition metal catalyst after step 3, in the same manner as described in WO201341472 and J. Am. Chem. Soc. 2009, 131, 15080. Transition metal catalysts include salts of zinc or copper such as copper(I) bromide, copper(I) chloride, copper(I) iodide, copper(II) acetate, zinc chloride, zinc(II) bromide, zinc iodide. Suitable bases include, for example, 1,10-phenanthroline, cesium carbonate, sodium carbonate, potassium carbonate. The reaction can be carried out in a solvent, preferably in a solvent that is inert under common reaction conditions, such as aromatic hydrocarbons like 1,2-dichlorobenzene, toluene, or xylene. The reaction can be carried out at a temperature in the range of 50 °C to 150 °C.

[0236] The compound of formula (64) is selected from the group consisting of formulas (64a), (64b), and (64c).

[0237]

Chemical Structure

[0238] In the formula, R 11 and n have the above-mentioned meanings.

[0239] The synthesis of the compounds of formulas (64a), (64b), and (64c) is described in Scheme 18 and Scheme 19.

[0240] Scheme: 18

[0241]

Chemical Structure

[0242] In the formula, R 1 , R 11 , and m have the above-mentioned meanings.

[0243] In the pyrimidine formation step, following the same procedure as described in Scheme 3, the pyrazole derivative of formula (67) is treated with a di-electrophilic compound of formula (13) or a 1,3-diketone of formula (15) (e.g., 1,3-dialdehyde or 3-(dialkylamino)-prop-2-enal) to undergo a cyclocondensation reaction to obtain the compound of formula (64a). The preparation of the compound of formula (67) is described in the literature (Journal of Heterocyclic Chemistry 2016, 53, 1231).

[0244] Scheme: 19

[0245]

Chemical Structure

[0246] In the formula, R11 and n has the meaning as defined above.

[0247] The compound of formula (68) can be prepared from the compound of formula (41) using an ammonia source, in a similar manner to the methods described in WO201065760 and WO2016133838. Usually, ammonium hydroxide or an ammonia solution in methanol is used as the ammonia source. The synthesis of the compound of formula (41) is described in Scheme 7. The reaction can be carried out at a temperature in the range of about 25 °C to about 100 °C under general reaction conditions using an ether solvent such as 1,4-dioxane or tetrahydrofuran or an alcohol solvent such as methanol or ethanol. The compound of formula (64b) can be prepared by reacting the compound of formula (68) with a dehydrating reagent such as, but not limited to, phosphoryl chloride or trifluoroacetic anhydride, in a similar manner to the methods described in WO201065760 and EP2740730. The reaction can be carried out at a temperature in the range of about 25 °C to about 120 °C under general reaction conditions using an ether solvent such as 1,4-dioxane or tetrahydrofuran.

[0248] The compound of formula (64c) can be prepared starting from the compound of formula (46) according to the same reaction sequence and conditions as described for the preparation of the compound of formula (64b) in Scheme 19. The general synthesis of the compound of formula (46) is described in Scheme 8.

[0249] In one embodiment, Q is Q 8 and reacting the compound of formula (2) or formula (59) or formula (69) with the compound of formula (70) to obtain a compound of formula (1j) wherein G 4 and G 5 is N. Scheme 20 describes a method for preparing the compound of formula (Ij).

[0250] Scheme: 20

[0251]

Chemical formula

[0252] In the formula, R 1 , R 3 , A, Z, G, G 1 , G 2 , E, m, and n have the above-mentioned meanings.

[0253] The halo derivatives of the compound of formula (71) are commercially available or can be prepared by methods known in the literature or by other methods known to those skilled in the art. The reaction of the compound of formula (71) with hydrazine can be carried out using reaction conditions known to those skilled in the art (for example, Larock, R.C. "Comprehensive Organic Transformations: A Guide to functional Group Preparations, 2nd Ed.", 1999, Wiley-VCH). The intermediate compound of formula (70) in step 2 can be reacted with the acid of the compound of formula (2) using a suitable amide coupling reagent set such as N-methylmorpholine / isobutyl chloroformate, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide / hydroxybenzotriazole or other reagents described in "The Practice of Peptide Synthesis, 2nd Ed., Spring-Verlag, Bodanszy, Miklos (1993)" to provide the intermediate hydrazide of formula (71). Further, the acylhydrazide of formula (71) can be prepared after reacting the compound of formula (70) with the acid chloride of formula (59) in the presence of a suitable base such as N,N-diisopropylethylamine or triethylamine. The formation of the triazolo compound of formula (Ij) can be achieved by cyclodehydrating the compound of formula (71) at high temperature using phosphorus oxychloride / phosgene, Lawesson's reagent, acetic acid, or polyphosphoric acid under conventional procedures or under microwave irradiation. Alternatively, the conversion is carried out with the compound of formula (71) and triphenylphosphine dichloride or P(alkyl) 3It can also be achieved by reacting with carbon tetrachloride in the presence of a base such as triethylamine or N,N - diisopropylethylamine, or according to other methods known to those skilled in the art. As another approach, the hydrazone of formula (72) can be prepared by reacting the compound of formula (70) with the aldehyde compound of formula (69) after step 4, or by other methods known to those skilled in the art or methods known in the literature (for example, Larock, R.C. "Comprehensive Organic Transformations: A Guide to functional Group Preparations, 2nd Ed.", 1999, Wiley - VCH). Further, after step 5, the compound of formula (Ij) can also be prepared by the oxidative cyclization of the hydrazone of formula (72) using an oxidizing agent such as diacetoxyiodobenzene, N - bromosuccinimide, chloramine T, cerium ammonium nitrate, trichloroisocyanuric acid, and copper(II) chloride.

[0254] The compound of formula (69) is selected from the group consisting of formula (69a), (69b), and (69c).

[0255]

Chemical formula

[0256] In the formula, R 1 , R 11 , and n have the above - mentioned meanings.

[0257] The compounds of formula (69a - c) can be prepared by partial reduction of the compounds of formula (23), (41), and (46) by methods known in the literature (for example, Larock, R.C. "Comprehensive Organic Transformations: A Guide to functional Group Preparations, 2nd edition", 1999, Wiley - VCH).

[0258] When Q is Q 9The process for preparing the compound of formula (I) which is, reacts the compound of formula (6b) with the compound of formula (73) to give G 3 =CR 3 and gives the compound of formula (74) where R 3 =H. Thereafter, the compound of formula (1k) can be obtained from the compound of formula (74) according to the series of general reactions described for the synthesis of compound (1c) in Scheme 1. The synthesis of the compound of formula (73) is described in WO2018206479.

[0259] Scheme: 21

[0260]

Chemical formula

[0261] wherein R 1 , R 3 , R 6 , A, G, G 1 , G 2 , G 3 , Z, E, m, and n have the above meanings.

[0262] The process for preparing the compound of formula (I) where Q is Q 10 reacts the compound of formula (2) with the compound of formula (75) to give G 3 =NR 6 and gives the compound of formula (76). Thereafter, the compound of formula (IL) can be obtained from the compound of formula (76) according to the series of general reactions described in Scheme 1. The synthesis of the compound of formula (75) is described in WO2017084879.

[0263] Scheme: 22

[0264]

Chemical formula

[0265] wherein X is halogen, R 1 , R 3, R 6 , R’, A, Z, G 1 , G 3 , E, m, and n have the above meanings.

[0266] The process for preparing the compound of formula (I) represented by the compound of formula (IB) is by sulfinylation / sulfoximation of the compound of chemical formula (IA) where n = 0, as described in Chem.Commun., 2017, 53, 2064 - 2067; Tetrahedron Lett. 2005, 46, 8007 - 8008 and WO2015071180A1.

[0267] Scheme: 23

[0268]

Chemical formula

[0269] In the formula, Q, R 1 , R Y , A, G, E, and n have the above meanings.

[0270] In one embodiment, the present invention provides a composition for controlling or preventing invertebrate pests. The composition comprises a biologically effective amount of a compound of formula (I) and at least one additional component selected from the group consisting of surfactants and adjuvants.

[0271] In yet another embodiment, the present invention provides a compound of formula (I) or its N-oxide and salts in conventional types of pesticidal compositions, such as solutions, emulsions, suspensions, powders, dusts, pastes, granules, pressings, capsules, and mixtures thereof. Examples of types of compositions include suspensions (SC, OD, FS, etc.), emulsifiable concentrates (EC, etc.), emulsions (EW, EO, ES, ME, etc.), capsules (CS, ZC, etc.), pastes, troches, wettable powders, powders (e.g., WP, SP, WS, DP, DS), pressings (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticides (e.g., LN), and gel formulations (e.g., GF) for the treatment of plant propagation materials such as seeds. These and other types of compositions are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No.2, 6 th Ed. May 2008, CropLife International.

[0272] The compositions are prepared by known methods as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, TandF Informa, London, 2005.

[0273] Examples of suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration promoters, protective colloids, adhesives, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreezing agents, antifoaming agents, colorants, tackifiers, or binders.

[0274] Suitable solvents and liquid carriers are water and organic solvents, such as medium to high boiling mineral oil fractions, such as kerosene, diesel oil; oils derived from plants or animals; aliphatic hydrocarbons, cyclic hydrocarbons, and aromatic hydrocarbons, such as toluene, paraffin, tetrahydronaphthalene, alkylated naphthalene; alcohols, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, such as cyclohexanone; esters, such as lactate esters, carbonate esters, fatty acid esters, γ-butyrolactone; fatty acids; phosphonates; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof.

[0275] Suitable solid carriers or fillers are mineral earths, such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; vegetable-derived products, such as cereal flour, bark flour, wood flour, nut shell flour, and mixtures thereof.

[0276] Suitable surfactants are surfactant 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 promoters, protective colloids, or adjuvants. Examples of surfactants are listed in McCutcheon’s, Vol.1:Emulsifiers and Detergents, McCutcheon’s Directories, Glen Rock,USA,2008 (International Edition or North American Edition).

[0277] Suitable anionic surfactants are alkali salts, alkaline earth salts, or ammonium salts of sulfonic acids, sulfuric acids, phosphoric acids, and carboxylic acids, and mixtures thereof. Examples of sulfonates include alkylaryl sulfonates, diphenyl sulfonates, alpha olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecyl benzenes, sulfonates of naphthalene and alkylnaphthalenes, sulfosuccinates, or sulfosuccinamates. Examples of sulfates include 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 alkyl carboxylates and carboxylated alcohol or alkylphenol ethoxylates.

[0278] Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids, or fatty acid esters, which are alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide may be used for alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters, or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters, or alkyl polyglucosides. Examples of polymeric surfactants are homopolymers or copolymers of vinyl pyrrolidone, vinyl alcohol, or vinyl acetate.

[0279] Suitable cationic surfactants are quaternary surfactants, for example, quaternary ammonium compounds having one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are A-B type or A-B-A type block polymers containing blocks of polyethylene oxide and polypropylene oxide, or A-B-C type block polymers containing alkanol, polyethylene oxide, and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamine or polyethyleneamine.

[0280] Suitable adjuvants are compounds that have negligible pesticidal activity by themselves or even no pesticidal activity and improve the biological performance of Compound I against the target. Examples include surfactants, mineral oils or vegetable oils, and other auxiliaries. Further examples are listed in Knowles, Adjuvants and additives, Agrow Reports DS256, TandF Informa UK, 2006, chapter 5.

[0281] Suitable thickeners are polysaccharides (e.g., xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkyl isothiazolinone and benzisothiazolinone. Suitable antifreezing agents are ethylene glycol, propylene glycol, urea, and glycerin. Suitable defoaming agents are silicones, long-chain alcohols, and salts of fatty acids. Suitable colorants (e.g., red, blue, or green) are pigments with low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g., iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (e.g., alizarin, azo, and phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylate, biological or synthetic waxes, and cellulose ethers.

[0282] Examples of the types of compositions and their preparations are as follows:

[0283] i) Water-soluble concentrates (SL, LS) 10 - 60% by weight of compound I or its N-oxide or salt and 5 - 15% by weight of a wetting agent (e.g., alcohol alkoxylate) are dissolved in water and / or a water-soluble solvent (e.g., alcohol) up to 100% by weight. The active substance dissolves when diluted with water.

[0284] ii) Dispersible concentrates (DC)

[0285] 5 - 25% by weight of compound I or its N-oxide or salt and 1 - 10% by weight of a dispersant (e.g., polyvinylpyrrolidone) are dissolved in an organic solvent (e.g., cyclohexanone) up to 100% by weight. A dispersion is obtained by dilution with water.

[0286] iii) Emulsifiable concentrates (EC)

[0287] 15 to 70% by weight of Compound I or its N-oxide or salt and 5 to 10% by weight of an emulsifier (e.g., calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in a water-insoluble organic solvent (e.g., aromatic hydrocarbon) at up to 100% by weight. By diluting with water, an emulsion is obtained.

[0288] iv) Emulsion (EW, EO, ES)

[0289] 5 to 40% by weight of Compound I or its N-oxide or salt and 1 to 10% by weight of an emulsifier (e.g., calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20 to 40% by weight of a water-insoluble organic solvent (e.g., aromatic hydrocarbon). This mixture is introduced into water by an emulsifying device at up to 100% by weight to form a uniform emulsion. By diluting with water, an emulsion is obtained.

[0290] v) Suspension (SC, OD, FS)

[0291] In a stirred ball mill, 20 to 60% by weight of Compound I or its N-oxide or salt is ground by the addition of 2 to 10% by weight of a dispersant and wetting agent (e.g., sodium lignosulfonate and alcohol ethoxylate), 0.1 to 2% by weight of a thickener (such as xanthan gum), and up to 100% by weight of water to produce a fine active substance suspension. By diluting with water, a stable suspension of the active substance is obtained. For FS-type compositions, up to 40% by weight of a binder (e.g., polyvinyl alcohol) is added.

[0292] vi) Water-dispersible granules and water-soluble granules (WG, SG)

[0293] 50 to 80% by weight of Compound I or its N-oxide or salt is finely ground by the addition of up to 100% by weight of a dispersant and wetting agent (e.g., sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by technical equipment (e.g., extrusion, spray tower, fluidized bed). By diluting with water, a stable dispersion or solution of the active substance is obtained.

[0294] vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)

[0295] 50 to 80% by weight of Compound I or its N-oxide or salt, 1 to 5% by weight of a dispersant (e.g., sodium lignosulfonate), 1 to 3% by weight of a wetting agent (e.g., alcohol ethoxylate), and up to 100% by weight of a solid carrier, such as silica gel, are added and ground in a rotor-stator mill. By diluting with water, a stable dispersion or solution of the active substance is obtained.

[0296] viii) Gels (GW, GF)

[0297] In a stirred ball mill, 5 to 25% by weight of Compound I or its N-oxide or salt, 3 to 10% by weight of a dispersant (e.g., sodium lignosulfonate), 1 to 5% by weight of a thickening agent (e.g., carboxymethyl cellulose), and up to 100% by weight of water are added and ground to obtain a fine suspension of the active substance. By diluting with water, a stable suspension of the active substance is obtained.

[0298] iv) Microemulsions (ME)

[0299] 5 to 20% by weight of Compound I or its N-oxide or salt are added to 5 to 30% by weight of an organic solvent blend (e.g., fatty acid dimethylamide and cyclohexanone), 10 to 25% by weight of a surfactant blend (e.g., alcohol ethoxylate and arylphenol ethoxylate), and up to 100% of water. The mixture is stirred for 1 hour to spontaneously form a thermodynamically stable microemulsion.

[0300] iv) Microcapsules (CS)

[0301] Disperse an oil phase containing 5 to 50% by weight of Compound I or its N-oxide or salt, 0 to 40% by weight of a water-insoluble organic solvent (e.g., aromatic hydrocarbon), and 2 to 15% by weight of an acrylic monomer (e.g., methyl methacrylate, methacrylic acid, and diol triacrylate) in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). Poly(methyl acrylate) microcapsules are formed by radical polymerization initiated by a radical initiator. Alternatively, disperse an oil phase containing 5 to 50% by weight of Compound I according to the present invention, 0 to 40% by weight of a water-insoluble organic solvent (e.g., aromatic hydrocarbon), and an isocyanate monomer (e.g., diphenylmethane-4,4'-diisocyanate) in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). Polyurea microcapsules are formed by the addition of a polyamine (e.g., hexamethylenediamine). The amount of the monomer is 1 to 10% by weight. % by weight is based on the total of the CS composition.

[0302] ix) Dustable powders (DP, DS)

[0303] Finely grind 1 to 10% by weight of Compound I or its N-oxide or salt and mix intimately with up to 100% by weight of a solid carrier, e.g., micronized kaolin.

[0304] x) Granules (GR, FG)

[0305] Finely grind 0.5 to 30% by weight of Compound I or its N-oxide or salt and associate with up to 100% by weight of a solid carrier (e.g., silicate). Granule formation is carried out by extrusion, spray drying, or fluid bed.

[0306] xi) Ultra-low volume liquids (UL)

[0307] Dissolve 1 to 50% by weight of Compound I or its N-oxide or salt in up to 100% by weight of an organic solvent, e.g., aromatic hydrocarbon.

[0308] The types of the compositions of (i) to (xi) may optionally further contain auxiliary agents such as 0.1 to 1% by weight of a bactericide, 5 to 15% by weight of an antifreezing agent, 0.1 to 1% by weight of an antifoaming agent, and 0.1 to 1% by weight of a colorant, etc.

[0309] In another embodiment, the present invention provides an agrochemical composition compound of formula (I), which contains 0.01 to 95% by weight, preferably 0.1 to 90%, more preferably 1 to 70%, particularly 10 to 60% by weight of an active substance. The active substance is used at a purity of 90% to 100%, preferably 95% to 100% (by NMR spectrum).

[0310] Water-soluble concentrates (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are usually used for the purpose of treating plant propagation materials, especially seeds. The composition in question provides an active substance concentration of 0.01 to 60% by weight, preferably 0.1 to 40% by weight, in a preparation that can be used immediately after being diluted 2 to 10 times. Application can be carried out before sowing or during sowing.

[0311] Methods for applying or treating Compound I and its compositions to plant propagation materials, especially seeds, respectively, include methods of dressing, coating, pelletizing, dusting, dipping, and in-furrow application of the propagation materials. Preferably, Compound I or its composition is applied to plant propagation materials by methods such as seed dressing, pelletizing, coating, and dusting that do not induce germination.

[0312] When used for plant protection, the amount of the active substance applied is 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, particularly 0.1 to 0.75 kg per hectare, depending on the type of desired effect.

[0313] For example, in the treatment of plant propagation materials such as seeds by dusting, coating, or water soaking seeds, an amount of the active substance of 0.1 to 1000 g, preferably 1 to 500 g, more preferably 1 to 100 g, and most preferably 5 to 100 g per 100 kilograms of the plant propagation material (preferably seeds) is generally required.

[0314] When used for the protection of materials or storage products, the amount of the active substance applied varies depending on the type of the application area and the desired effect. The amount usually applied for the protection of materials is 0.001 g to 2 kg, preferably 0.005 g to 1 kg of the active substance per 1 cubic meter of the treated material.

[0315] Various types of oils, wetting agents, adjuvants, fertilizers, or micronutrients, and other control agents (e.g., herbicides, insecticides, fungicides, growth regulators, safeners) can be added as a premix to the active substance or the composition containing the active substance, or added just before use if appropriate (tank mix). These agents can be mixed with the composition according to the present invention at a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0316] The user can usually apply the composition according to the present invention from a pre-application device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the pesticide composition is composed of water, a buffer solution, and / or further auxiliaries to the desired application concentration, and thus, a spray liquid or a pesticide composition according to the present invention in a ready-to-use state is obtained. Usually, 20 to 6000 liters, preferably 35 to 1000 liters, and more preferably 50 to 500 liters of the ready-to-use spray liquid per 1 hectare of the agricultural useful area are applied.

[0317] According to one embodiment, the individual components of the composition according to the present invention, such as a part of a kit or a part of a binary or ternary mixture, may be mixed by the user himself in a spray tank, and further auxiliaries may be added if necessary.

[0318] Accordingly, the compounds and compositions of the present invention are agriculturally useful for protecting field crops from phytophagous invertebrate pests and are also non-agriculturally useful for protecting other horticultural crops and plants from phytophagous invertebrate pests. This usefulness includes the protection of crops and other plants (i.e., both agricultural and non-agricultural) that contain genetically engineered (i.e., transgenic) or mutagenized genetic material to provide advantageous traits.

[0319] The compounds of the present invention are characterized by favorable metabolic and / or soil residue patterns and exhibit activity against a range of agricultural and non-agricultural invertebrate pests. The compounds of the present invention are active ingredients that are prophylactically and / or therapeutically valuable in the field of pest control even at low application rates, and the active ingredients can be used against pest control-resistant pests such as insects and mites and are well tolerated by warm-blooded species, fish, and plants.

[0320] In the context of the present invention, "control of invertebrate pests" means inhibition of the occurrence (including mortality) of invertebrate pests that causes a significant reduction in food or other injury or damage caused by the pests. (Related expressions are defined similarly.) As referred to in the present invention, the term "invertebrate pest" includes arthropods, gastropods, and nematodes that are economically important as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs, and woodlice.

[0321] The term "gastropod" includes slugs, snails, and other stylommatophorans. The term "helminth" includes all helminths such as roundworms, dog heartworms, phytophagous nematodes (class Nematoda), flukes (class Trematoda), hookworms, tapeworms (class Cestoda), etc. Those skilled in the art will recognize that not all compounds are equally effective against all pests.

[0322] The compounds of the present invention are active against economically important agricultural pests in forests, greenhouses, seedlings, ornamental plants, turf, food and fiber, public and animal health, household and commercial structures, and household and stored products pests. These include larvae of Lepidoptera such as armyworm larvae, cutworms, wireworms, and heliothines

[0323] (e.g., fall armyworm (Spodoptera fugiperda J. E. Smith), beet armyworm (Spodoptera exigua Hubner), black cutworm (Agrotis ipsilon Hufnagel), cabbage looper (Trichoplusia ni Hubner), tobacco budworm (Heliothis virescens Fabricius));

[0324] Pyralid borers, casebearers, webworms, and coneworms, leaf beetles, and skeletonizers (e.g., European corn borer (Ostrinia nubilalis Hubner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), and sod webworm (Herpetogramma licarsisalis Walker));

[0325] Leafrollers, green worms, and seed worms, and fruit worms (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruit moth (Grapholita molesta Busck)) of the Tortricidae family;

[0326] And many other economically important Lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus));

[0327] Nymphs and adults of the order Blattodea, including cockroaches of the families Blattellidae and Blattidae (e.g., oriental cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella gemnanica Linnaeus), brown-banded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius));

[0328] Coleopteran leaf-feeding larvae and adults, including weevils of the families Curculionidae, Bruchidae, and Chrysomelidae (e.g., boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus));

[0329] Fleas of the family Pulicidae, cucumber beetles, rootworms, fleas, potato beetles, and leaf miners (e.g., Colorado potato beetle (Leptinotarsa decemlineata Say), western corn rootworm (Diabrotica virgifera virgifera LeConte));

[0330] Japanese beetles and other beetles of the family Scarabaeidae (e.g., Japanese beetle (Popillia japonica Newman) and European chafer (Rhizotrogus majalis Razoumowsky));

[0331] Carpet beetles of the family Dermestidae;

[0332] Wireworm larvae of the family Elateridae;

[0333] Bark beetles of the family Scolytidae, and flour beetles of the family Tenebrionidae. Further, this includes adults and larvae of the order Dermaptera, including earwigs of the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches mono Fabricius));

[0334] Adult and nymph stages of Hemiptera, such as the plant bug of the family Miridae (e.g., Lygus spp.), the cicada of the family Cicadidae, the leafhopper of the family Cicadellidae (e.g., Empoasca spp.), the planthopper of the families Fulgoroidae and Delphacidae, the treehopper of the family Membracidae, the psyllid of the family Psyllidae, the whitefly of the family Aleyrodidae, the aphid of the family Aphididae, the phylloxera of the family Phylloxeridae, the mealybug of the family Pseudococcidae, the scale of the families Coccidae, Diaspididae, and Margarodidae, and the lace bug of the family Tingidae, the stink bug of the family Pentatomidae, the cinch bug of the family Lygaeidae (e.g., Blissus spp.), and other seed bugs, the spittlebug of the family Cercopidae, the squash bug of the family Coreidae, and the red bug of the family Pyrrhocoridae, and the cotton stainer are included.Adult and larval arachnids, 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 (Tetranychus mcdanieli McGregor)), flat mites of the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor)), and rust mites and bud mites of the family Eriophyidae, as well as other leaf-feeding mites and mites important to human and animal health, namely, dust mites of the family Epidermoptidae, follicle mites of the family Demodicidae, grain mites of the family Glycyphagidae, mites 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 and itch mites of the families Psoroptidae, Pyemotidae, and Sarcoptidae;。

[0335] Adult and larval Orthoptera including grasshoppers, locusts, and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American grasshopper (e.g., Schistocerca americana Drury), desert locust (Schistocerca gregaria Forskal), migratory locust (Locusta migratoria Linnaeus), house cricket (Acheta domesticus Linnaeus), mole cricket (Gryllotalpa spp.));

[0336] Leafminers, midges, fruit flies (Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chiysomya spp., Phonnia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), botflies (e.g., Gastrophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (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, including adult and larval Diptera;

[0337] Onion thrips (Thrips tabaci Lindeman), and other leaf-feeding thrips, including adult and larval Thysanoptera;

[0338] Ants (e.g., red carpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant (Camponotus pennsylvanicus De Geer), Pharaoh ant (Monomorium pharaonis Linnaeus), little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsis geminata Fabricius), red imported fire ant (Solenopsis invicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechina longicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus), cornfield ant (Lasius alienus Förster), odorous house ant (Tapinoma sessile Say)), bees (including carpenter bee), hornets, yellow jackets, and wasps, including hymenopteran insect pests;

[0339] Termites, including eastern subterranean termite (Reticulitermes flavipes Kollar), western subterranean termite (Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans Snyder), and other economically important termites, including isopteran insect pests;

[0340] Insect pests of the order Thysanura, including, for example, silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard);

[0341] Insect pests of the order Phthiraptera, including head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitszch), dog biting louse (Trichodectes cams De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurystemus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus), and other sucking and piercing parasitic lice that attack humans and animals;

[0342] Insect pests of the order Siphonoptera, including the oriental rat flea (Xenopsylla cheopis Rothschild), the cat flea (Ctenocephalides felis Bouche), the dog flea (Ctenocephatides canis Curtis), the hen flea (Ceratophyllus gallinae Schrank), the sticktight flea (Echidnophaga gallinacea Westwood), the human flea (Pulex irritans Linnaeus), and other fleas that attack mammals and birds. Additional arthropod pests included are spiders of the order Araneae, such as the brown recluse spider (Loxosceles reclusa Gertsch and Mulaik), and the black widow spider (Latrodectus mactans Fabricius), and centipedes of the order Scutigeromorpha, such as the house centipede (Scutigera coleoptrata Linnaeus).The activity includes members of the classes Nematoda, Cestoda, Trematoda, and Acanthocephala, including economically important members of the orders Rhabditida, Strongylida, Oxyurida, Spirurida, and Enoplida, for example, 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.), as well as animal and human health pests (i.e., all economically important flukes, tapeworms, and roundworms, for example, Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofllaria immitis Leidy in dogs, Anoplocephala peifoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.).

[0343] The compounds of the present invention are useful against Lepidopteran pests (e.g., Alabama argillacea Hubner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller), and other Archips spp., Chilo suppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoveipa armigera Hubner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod webworm), Lobesia botrana Denis and Schiffeπnuller (grape berry moth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafminerIt shows particularly high activity against Liriomyza huidobrensis (leafminer), Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Hubner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm), Trichoplusia ni Hubner (cabbage looper), and Tuta absoluta Meyrick (tomato leafminer).

[0344] The compounds of the present invention also have commercially significant activity against members of the Homoptera including: Acyrthisiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov / Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (mealy plum aphid), Lipaphis erysimi Kaltenbach (tarnip aphid), Metopolophium dirrhodum Walker (cereal aphid), Macrosipum euphorbiae Thomas (pqtato aphid), Myzus persicae Sulzer (peach-potato aphid, green peach aphid), Nasonovia ribisnigriMosley (lettuce aphid), Pemphigus spp. (root aphid and gall aphid), Rhopalosiphum maidis Fitch (corn leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry - oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English grain aphid), Theriaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii, Boyer de Fonscolombe (black citrus aphid), and Toxoptera citricida Kirkaldy (brown citrus aphid); Adelges spp. (adelgid); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisia tabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisia argentifolii Bellows and Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citrus whitefly) and Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris, (potato leafhopper), Laodelphax striatellusFallen (smaller brown planthopper), Macrolestes quadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler (green leafhopper), Nephotettix nigropictus Stal (rice leafhopper), Nilaparvata lugens Stal (brown planthopper), Peregrinus maidis Ashmead (corn planthopper), Sogatellafurcifera Horvath (white-backed planthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocyba pomaria McAfee white apple leafhopper, Erythroneoura spp. (grape leafhopper); Magicidada septendecim Linnaeus (periodical cicada); Iceryapurchasi Maskell (cottony cushion scale), Quadraspidiotus perniciosus Comstock (San Jose scale); Planococcus citri Risso (citrus mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmon psylla).

[0345] These compounds are also active against members of the Hemiptera including: Acrostemum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolrius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp. (complex of seed bug), Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois (tarnished plant bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatus DaEas (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper).

[0346] Other insects controlled by the compounds of formula (I) of the present invention include the following: Thysanoptera (e.g., Frankliniella occidentalis Pergande (western flower thrip), Scirthothnps citri Moulton (citrus thrip), Sericothrips variabilis Beach (soybean thrip), and Thrips tabaci Lindeman (onion thrip)); and other Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle)) and larvae of wireworms of the genus Agriotes, Athous, or Limonius).

[0347] In particular, the compounds of formula (I), their N-oxides, their isomers, their polymorphs, and their salts are particularly suitable for effectively controlling the following pests:

[0348] Lepidopteran insects (Lepidoptera), for example, Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Chilo infuscatellus, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Earias vittella, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita funebrana, Grapholita molesta, Helicoverpa armigera, Helicoverpa virescens, Helicoverpa zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Leucinodes orbonalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, OstriniaOstrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scirpophaga incertulas, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Spodoptera exigua, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis; and

[0349] Beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica undecimpunctata Diabrotica speciosa, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria;.

[0350] Flies, mosquitoes (Diptera), e.g., 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 macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, 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, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa;.

[0351] Termites (Isoptera), for example, Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus;

[0352] Cockroaches (Dictyoptera), e.g., Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis;

[0353] Ants, bees, wasps (Hymenoptera), e.g., Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, 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, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile;

[0354] Crickets, grasshoppers, locusts (Orthoptera), for example, Acheta domestica, Gryllotalpa 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, Chortoicetes terminifera, and Locustana pardalina; Spider families, for example, Latrodectus mactans, and Loxosceles reclusa;

[0355] Fleas (Siphonaptera), e.g., Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, silverfish, firebrats (Thysanura), e.g., Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g., Scutigera oleoptrata, millipedes (Diplopoda), e.g., Narceus spp., earwigs (Dermaptera), e.g., forficula auricularia, lice (Phthiraptera), e.g., Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon allinae, Menacanthus stramineus, and Solenopotes capillatus, springtails (Collembola), e.g., Onychiurus ssp.

[0356] The compounds of formula (I) of the present invention are effective against nematodes: plant parasitic nematodes, such as root knot nematodes, e.g., Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, e.g., Globodera rostochiensis, and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematode, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematode, and Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; Awl nematode, Dolichodorus species; Spiral nematode, Heliocotylenchus multicinctus, and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species, and Hemicriconemoides species; Hirshmanniella species; Lance nematode, Hoploaimus species; false rootknot nematode, Nacobbus species;It is also suitable for controlling 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, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, and other Tylenchorhynchus species; citrus nematodes, Tylenchulus species; dagger nematodes, Xiphinema species; and other plant-parasitic nematode species.

[0357] The compounds of formula (I) and their salts are useful for controlling arachnids (Arachnida), such as spiders (Araneae), for example, ticks (Ixodidae, Argasidae, etc.), 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 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.

[0358] In one embodiment of the present invention, the present invention provides a compound of formula (I) that is useful for controlling insects selected from sucking or piercing insects, such as insects from the genus Thrips, Diptera, and Hemiptera, particularly the following species:

[0359] Thrips genus: Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, and Thrips tabaci,

[0360] Diptera: 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 macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, 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, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa;.

[0361] Hemiptera, in particular, 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 helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mail, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphuminsertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii.

[0362] In one embodiment, the present invention provides a composition comprising a biologically effective amount of a compound of formula (I) and at least one additional biologically active and compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, and nutrients. The compounds used in the composition and used in combination with the compound of formula (I) are also referred to as active and compatible compounds.

[0363] Known and reported fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, and nutrients can be combined with at least one compound of formula (I) of the present disclosure. For example, the fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, and nutrients disclosed and reported in WO2016156129 and / or WO2017153200 can be combined with at least one compound of formula (I) of the present disclosure.

[0364] The fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, and nutrients reported in WO2016156129 and / or WO2017153200 are incorporated herein by reference as non-limiting examples for combination with at least one compound of formula (I) of the present disclosure.

[0365] In particular, the compounds of the present invention can form multi-component control agents and, in order to provide a broader agricultural utility, can be mixed with at least one additional biologically active and compatible compound (mixing partner) such as an insecticide, fungicide, nematicide, bactericide, acaricide, a growth regulator such as a rooting stimulant, a chemical sterilant, a semiochemical, a repellent, an attractant, a pheromone, a feeding stimulant, other biologically active compounds, or an entomopathogenic bacterium, virus, or fungus, but not limited thereto.

[0366] Examples of such biologically active compounds or agents / mixing partners that can be combined / formulated with the compounds of formula (I) of the present invention are disclosed in WO2019072906A1 (pages 27 - 37).

[0367] In one embodiment, the biological agents for mixing with the compounds of the present invention include Bacilllus thuringiensis, Bacilllus thuringiensis delta endotoxin, and naturally occurring genetically modified virus insecticides including members of the Baculoviridae family and entomophagous fungi.

[0368] In certain examples, combinations with other invertebrate pest control compounds or agents that have a similar control spectrum but different modes of action are particularly beneficial for resistance management. Thus, the compositions of the present invention can further comprise at least one additional invertebrate pest control compound or agent that has a similar control spectrum but different modes of action in a biologically effective amount. Contacting a plant protection compound (e.g., a protein) or a plant that has been genetically modified to express a locus of the plant with a biologically effective amount of the compound of the present invention also provides a broader spectrum of plant protection and is beneficial for resistance management.

[0369] In one embodiment of the present invention, the biologically effective amount of the compound of formula (I) in the composition ranges from 0.1 wt% to 99 wt%, preferably from 5 wt% to 50 wt% based on the total weight of the composition.

[0370] The present invention further provides a method for controlling invertebrate pests, which comprises contacting an invertebrate pest, its habitat, breeding ground, food supply, plant, seed, soil, area, material, or environment in which the invertebrate pest grows or can grow, or the material, plant, seed, soil, surface, or space protected from pest attack or infestation, with a biologically effective amount of a compound or composition of the present invention.

[0371] The invertebrate pests are controlled, and the protection of agriculture, horticulture, and / or special crops, animals, and human health is achieved by directly applying one or more of the compounds of the present invention in an effective amount to the environment of the pests, the area to be protected, or the pests to be controlled, including agricultural and / or non-agricultural infestation sites. Accordingly, the present invention further includes a method for controlling invertebrate pests inhabiting leaves and soil and protecting agricultural and / or non-agricultural crops, which comprises contacting the invertebrate or its environment with one or more of the compounds of the present invention in a biologically effective amount, or a composition containing at least one such compound, or a composition containing 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 containing a compound of the present invention can be applied to the leaves or soil of plants. The compounds of the present invention are effective in delivery through plant uptake by contacting the plants with a composition containing the compounds of the present invention applied as a soil drench of a liquid formulation, a granular formulation to the soil, treatment of a seedling tray, or dipping of transplants. Other methods of contact include application of the compounds or compositions of the present invention by direct and residual spraying, aerial spraying, seed coating, microencapsulation, systemic uptake, bait, ear tags, boluses, atomizers, fumigants, aerosols, dusts, and many others.

[0372] The compounds of the present invention can be incorporated into the food consumed by invertebrates or into devices such as traps. Granules or baits containing 0.01 - 5% active ingredient, 0.05 - 10% humectant, and 40 - 99% vegetable wheat flour are effective in controlling soil insects at very low application rates, especially at lethal doses of the active ingredient by ingestion without direct contact. The compounds of the present invention can be applied in their pure state, but in most cases, the application involves one or more compounds together with suitable carriers, diluents, and surfactants, and in some cases, the application of formulations in combination with food depending on the intended end use. Preferred methods of application include spraying an aqueous dispersion or purified oil solution of the compound. Combinations with spray oils, spray oil concentrations, spreaders, stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance the efficacy of the compound.

[0373] The application rate required for effective control (i.e., the "biologically effective amount") varies depending on factors such as the species of invertebrate to be controlled, the pest life cycle, life stage, its size, location, time, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, etc. Under normal circumstances, an application rate of about 0.01 - 2 kg of active ingredient per hectare is sufficient to control pests in an agricultural ecosystem, but in some cases 0.0001 kg / hectare may be sufficient, or 8 kg / hectare may be required. For non - agricultural uses, the effective usage amount is in the range of about 1.0 - 50 mg per square meter, but in some cases 0.1 mg per square meter may be sufficient, or 150 mg per square meter may be required. A person skilled in the art can easily determine the biologically effective amount required to achieve the desired level of control of invertebrate pests.

[0374] Animal pests, namely insects, spiders, and nematodes, plants, the soil or water in which the plants are growing can be brought into contact with a compound of formula (I), its N-oxide and salts, or a composition containing them by application methods known in the art. Thus, "contact" includes both direct contact (applying the compound / composition directly to the animal pest or plant, typically 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).

[0375] The compounds of the present invention or the control compositions containing them can be used to protect growing plants and crops from attack or infestation by animal pests, particularly insects, spider mites, or spiders, by bringing the plants / crops into contact with an insecticidally effective amount of at least one compound of the present invention. The term "crop" refers to both growing crops and harvested crops.

[0376] In one embodiment, the present invention provides a method for protecting crops from attack or infestation by invertebrate pests, comprising bringing the crops into contact with a biologically effective amount of a compound or composition of the present invention, its isomers, polymorphs, N-oxides, or salts.

[0377] The compounds of the present invention are used in the form of themselves or compositions by treating plant propagation materials such as insects or plants, seeds protected from insecticidal attack, soil, surfaces, materials, or rooms with an insecticidally effective amount of the active compound. Application can be carried out both before and after infection of the plant propagation materials such as plants, seeds, soil, surfaces, materials, or rooms by insects.

[0378] In one embodiment, the present invention provides a method for protecting seeds from soil insects and the roots and shoots of seedlings from soil and foliar insects, comprising bringing the seeds into contact with a compound or composition of the present invention, its N-oxide, or salt before sowing and / or after pre-germination.

[0379] Furthermore, the present invention provides a method for treating or protecting an animal against infestation or infection by a parasite, which method comprises administering or applying to the animal a biologically effective amount of a compound or composition of the present invention, an isomer, polymorph, N-oxide, or veterinarily acceptable salt thereof, orally, topically, or parenterally.

[0380] When used for treating crop plants, the application rate (effective dosage) of the compounds of the present invention can range from 1 gai to 5000 gai per hectare of agricultural or horticultural crop, preferably from 25 g to 600 g per hectare, more preferably from 50 g to 500 g per hectare.

[0381] The compounds and compositions of the present invention are particularly useful for controlling a number of insects on various cultivated plants such as cereals, root crops, oil crops, vegetables, spices, ornamental plants such as durum wheat and other wheats, barley, oats, rye, maize (fodder maize and sugar maize / sweet corn and field corn), soybeans, oil crops, rape, cotton, sunflowers, bananas, rice, rapeseed, turnips, sugar beets, fodder beets, eggplants, potatoes, grasses, lawns, turf, fodder grasses, tomatoes, leeks, pumpkins / squashes, cabbages, iceberg lettuces, peppers, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuber plants such as potatoes, sugarcane, tobacco, grapes, petunias, geraniums / pelargoniums, pansies, and impatiens.

[0382] In particular, the compounds or compositions of the present invention are useful for protecting agricultural crops such as cereals, maize, rice, soybeans and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus fruits and citrus trees, any horticultural plants, cucurbitaceous plants, oil-containing plants, tobacco, coffee, tea, cocoa, sugar beets, sugarcane, cotton, potatoes, tomatoes, onions, peppers, and other vegetables, and ornamental plants.

[0383] The compounds of the present invention are effective via both contact (through soil, glass, walls, bed nets, carpets, plant parts, or animal parts) and ingestion (through food or plant parts).

[0384] The compounds of the present invention can also be applied to non-crop invertebrate pests such as ants, termites, bees, flies, mosquitoes, crickets, or cockroaches. When used against the above non-crop pests, the compounds of the present invention are preferably used in a food composition.

[0385] The food can be a liquid, solid, or semi-solid preparation (e.g., gel). The solid food can be formed into various shapes and forms suitable for each application, such as granules, blocks, sticks, or disks. The liquid food can be filled into various devices, such as a lidless container, a spray device, a droplet source, or an evaporation source, to ensure proper application. Open. The gel can be based on an aqueous or oily matrix and can be formulated according to specific requirements from the viewpoints of adhesiveness, moisture retention, or aging characteristics.

[0386] The food used in the composition is a product that is attractive enough to stimulate insects such as ants, termites, bees, flies, mosquitoes, crickets, or cockroaches to eat it. The attractiveness can be manipulated using feeding stimulants or sex pheromones. Feeding stimulants are selected, for example, but not limited to, animal and / or plant proteins (meat blood meal, fish blood meal, insect parts, egg yolk), animal and / or plant-derived oils and fats, or especially monosaccharides, oligosaccharides, or polyorganic sugars derived from sucrose, lactose, fructose, dextrose, glucose, starch, pectin, or even molasses or honey. Fresh or spoiled parts of fruits, crops, plants, animals, insects, or specific parts thereof can also function as feeding stimulants. Sex pheromones are known to be more insect-specific. Specific pheromones are described in the literature and are known to those skilled in the art.

[0387] When used in bait compositions, typical contents of the active ingredient are from 0.001% to 15% by weight, preferably from 0.001% to 5% by weight of the active compound.

[0388] Formulations of the compounds of the invention as aerosols (e.g., in spray cans), oil sprays, or pump sprays are very suitable for non-expert users for controlling pests such as flies, fleas, mites, mosquitoes, or cockroaches. The recipe for an aerosol preferably consists of the active compound, a solvent such as a lower alcohol (e.g., methanol, ethanol, propanol, butanol), a ketone (e.g., acetone, methyl ethyl ketone), a paraffinic hydrocarbon having a boiling range of about 50 to 250 °C (e.g., kerosene), dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, an aromatic hydrocarbon such as toluene, xylene, water, further auxiliaries such as an emulsifier such as sorbitol monooleate, oleyl ethoxylate having 3 to 7 mol of ethylene oxide, a fatty alcohol ethoxylate, an essential oil such as an ether oil, an ester of a medium-chain fatty acid and a lower alcohol, an aromatic carbonyl compound, and, if appropriate, a stabilizer such as sodium benzoate, an amphoteric surfactant, a lower epoxide, triethyl orthoformate, and, if desired, a propellant such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or a mixture of these gases.

[0389] Oil spray formulations differ from aerosol recipes in that no propellant is used. When used in spray compositions, the content of the active ingredient is from 0.001 to 80% by weight, preferably from 0.01 to 50% by weight, most preferably from 0.01 to 15% by weight.

[0390] The compounds of the invention and their respective compositions can also be used in mosquito coils and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers, and can also be used in moth papers, moth pads, or other heat-independent vaporizer systems.

[0391] Methods for controlling insect-transmitted infections (e.g., malaria, dengue fever and yellow fever, lymphatic filariasis, and leishmaniasis) using the compounds of formula (I) and their respective compositions also include the treatment of the surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing, mosquito nets, tsetse fly traps, etc. The pesticidal compositions for application to fibers, fabrics, knitted products, non-woven fabrics, net materials, or foils, and tarpaulins preferably include a mixture containing a pesticide, optionally a repellent, and at least one binder. Suitable repellents are, for example, Ν,Ν-diethyl-meta-toluamide (DEET), Ν,Ν-diethylphenylacetamide (DEPA), 1-(3-cyclohexan-1-yl-carbonyl)-2-methylpiperidine, (2-hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1,3-hexanediol, indalone, methyl neodecanamide (MNDA), pyrethroids not used for insect control, such as {(+ / -)-3-allyl-2-methyl 4-oxocyclopenta-2-(+)-enyl-(+)-trans-chrysantemate (Esbiothrin), limonene, eugenol, (+)-eucamalol (1), (-)-l-epi-eucamalol, etc. plant extracts or crude plant extracts derived from plants such as Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemongrass), Cymopogan nartdus (citronella), or repellents identical thereto. Suitable binders are selected, for example, from vinyl esters of fatty acids (such as vinyl acetate and vinyl versatate), acrylic and methacrylic acid esters of alcohols, such as butyl acrylate, 2-ethylhexyl acrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic dienes, such as polymers and copolymers of butadiene.

[0392] The impregnation of curtains and mosquito nets is generally carried out by immersing the fiber material in an emulsion or dispersion of the pesticide or spraying them onto the net.

[0393] The compounds and compositions of the present invention can be used to protect wooden materials such as trees, fences, and sleepers, and buildings such as houses, sheds, and factories, as well as building materials, furniture, leather, fibers, vinyl products, electric wires, and cables from ants and / or termites, and to control ants and termites from causing harm to crops or humans (for example, 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 to the surface of the concrete under the floor, wooden products such as floor posts, beams, plywood, and furniture, wooden products such as particle boards and half boards, and vinyl products such as coated electric wires and vinyl sheets, and heat insulating materials such as styrofoam.

[0394] In the case of application against ants that cause harm to crops or humans, the compounds of the present invention are applied to the crops or the surrounding soil, or directly to ant nests, etc.

[0395] Seed treatment The present invention further provides treated seeds containing an amount of the compound of the present invention in the range of about 0.0001% to about 1% by weight of the seeds before treatment.

[0396] The compounds of the present invention are also suitable for seed treatment to protect seeds from insect pests, particularly insect pests inhabiting the soil and mite pests, and to protect the roots and buds of the resulting plants from soil pests and foliar insects.

[0397] The compounds of the present invention are particularly useful for protecting seeds from soil pests, and the roots (larvae of the Chrysomelidae family, termites, rice weevil larvae) and buds of the resulting plants from soil pests and foliar insects. Protection of the roots and buds of the resulting plants is preferred. More preferred is to protect the buds of the resulting plants from sucking insects, and most preferred is protection from aphids, leafhoppers, thrips, and whiteflies.

[0398] Accordingly, the present invention provides a method for protecting seeds from insects, particularly soil insects, and for protecting the roots and shoots of seedlings from insects, particularly soil and foliar insects, which comprises contacting the seeds with a compound of the invention before sowing and / or after pre-germination. Particularly preferred is a method in which the roots and shoots of plants are protected, more preferably a method in which the shoots of plants are protected from sucking insects, and most preferably a method in which the shoots of plants are protected from aphids.

[0399] The term "seed" encompasses all kinds of seeds and plant propagules including but not limited to true seeds, seed parts, suckers, bulbs, corms, fruits, tubers, grains, cuttings, cut shoots, etc., and in a preferred embodiment means true seeds.

[0400] The term "seed treatment" includes all suitable seed treatment techniques known in the art such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, etc.

[0401] The present invention also includes seeds coated with an active compound or seeds containing an active compound. The seeds can be coated with a seed coating composition containing a compound of the invention. For example, the seed coating compositions reported in EP3165092, EP3158864, WO2016198644, WO2016039623, WO2015192923, CA2940002, US2006150489, US2004237395, WO2011028115, EP2229808, WO2007067042, EP1795071, EP1273219, WO200178507, EP1247436, NL1012918, and CA2083415.

[0402] The term "coated and / or containing" generally means that the active ingredient is mostly on the surface of the propagation product at the time of application, but depending on the application method, more or less of the component may penetrate into the propagation product. When the propagation product is (re)planted, it can absorb the active ingredient together with moisture.

[0403] Suitable seeds are seeds of cereals, root crops, oil crops, vegetables, spices, ornamental plants, for example, durum wheat and other wheats, barley, oats, rye, maize (feed maize and sugar maize / sweet corn and feed maize), soybeans, oil crops, rape, cotton, sunflower, banana, rice, rapeseed, turnip, sugar beet, fodder beet, aubergine, potato, grass, lawn, turf, forage grass, tomato, leek, pumpkin / squash, cabbage, iceberg lettuce, pepper, cucumber, melon, brassica seeds, melon, bean, pea, garlic, onion, carrot, tuber plants, for example, potato, sugar cane, tobacco, grape, petunia, geranium / perargonium, pansy, and impatiens.

[0404] Furthermore, the compounds of the invention can be used for treating seeds derived from plants that are resistant to the action of herbicides or fungicides or insecticides for breeding, including genetic engineering methods.

[0405] For example, the compounds of the invention can be used for treating seeds derived from plants that are resistant to herbicides from the group consisting of sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium, and similar active substances (see, for example, EP242236, EP242246) (WO92 / 00377) (EP257993, US5013659), or can be used in transgenic crop plants, for example, cotton, which have the ability to produce Bacillus thuringiensis toxins (Bt toxins) that make the plant resistant to certain pests (EP142924, EP193259).

[0406] Furthermore, the compounds of the present invention can be used for the treatment of seeds from plants having modified characteristics compared to existing plants, which can be produced, for example, by conventional breeding methods and / or generation of mutants, or by recombinant procedures. For example, recombinant modification of crop plants for the purpose of modifying starch synthesized in plants (e.g., WO92 / 11376, WO92 / 14827, WO91 / 19806) or some cases of transgenic crop plants having a modified fatty acid composition (WO91 / 13972) are described.

[0407] The application of the compounds of the present invention for seed treatment is carried out by spraying or dusting the seeds before sowing of the plants and before emergence of the plants.

[0408] Compositions particularly useful for seed treatment are, for example: A. Soluble concentrates (SL, LS) B. Emulsions (EW, EO, ES) C. Suspensions (SC, OD, FS) D. Water-dispersible granules and water-soluble granules (WG, SG) E. Water-dispersible powders and water-soluble powders (WP, SP, WS) F. Gel formulations (GF) G. Dustable powders (DP, DS)

[0409] Conventional seed treatment formulations include, for example, flowable concentrates FS, solutions LS, powders for dry treatment DS, water-dispersible powders WS for slurry treatment, water-soluble powders SS, emulsions ES and EC, and gel formulations GF. These formulations can be applied to diluted or undiluted seeds. Application to seeds is carried out directly on the seeds before sowing or after pre-germination of the seeds.

[0410] In one embodiment, an FS formulation is used for seed treatment. Typically, an FS formulation can contain 1 - 800 g / l of active ingredient, 1 - 200 g / l of surfactant, 0 - 200 g / l of antifreeze, 0 - 400 g / l of binder, 0 - 200 g / l of pigment, and up to 1 liter of solvent, preferably water.

[0411] In particular, the FS formulations of the compounds of the present invention for seed treatment usually contain 0.1 to 80% by weight (1 to 800 g / l) of the active ingredient, 0.1 to 20% by weight (1 to 200 g / l) of at least one surfactant, for example 0.05 to 5% by weight of a wetting agent, and 0.5 to 15% by weight of a dispersing agent, up to 20% by weight, for example 5 to 20% of an antifreezing agent, 0 to 15% by weight, for example 1 to 15% by weight of a pigment and / or dye, 0 to 40% by weight, for example 1 to 40% by weight of a binder (sticker / adhesive), optionally up to 5% by weight, for example 0.1 to 5% by weight of a thickening agent, optionally 0.1 to 2% of an antifoaming agent, and optionally, for example, a biocide, a preservative such as an antioxidant in an amount of 0.01 to 1% by weight, and up to 100% by weight of a filler / vehicle.

[0412] The seed treatment formulation may further contain a binder and optionally a colorant.

[0413] The binder can be added to improve the adhesion of the active material to the treated seeds. Suitable binders are homopolymers and copolymers derived from alkylene oxides such as ethylene oxide or propylene oxide, polyvinyl acetate, polyvinyl alcohol, polyvinyl pyrrolidone, and their copolymers, ethylene-vinyl acetate copolymers, acrylic homopolymers and copolymers, polyethylene amines, polyethylene amides, and polyethylene pyrimidines, polysaccharides such as cellulose, tylose, and starch, polyolefin homopolymers and copolymers such as olefin / maleic anhydride copolymers, polyurethanes, polyesters, polystyrene homopolymers and copolymers.

[0414] Optionally, a colorant can also be included in the formulation. Suitable colorants or dyes for the seed treatment formulation are Rhodamine B, C.I. Pigment Red 112, C.I. Solvent Red 1, Pigment Blue 15:4, Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 80, Pigment Yellow 1, Pigment Yellow 13, Pigment Red 112, Pigment Red 48:2, Pigment Red 48:1, Pigment Red 57:1, Pigment Red 53:1, Pigment Orange 43, Pigment Orange 34, Pigment Orange 5, Pigment Green 36, Pigment Green 7, Pigment White 6, Pigment Brown 25, Basic Violet Red 10, Basic Violet Red 49, Acid Red 51, Acid Red 52, Acid Red 14, Acid Blue 9, Acid Yellow 23, Basic Red 10, Basic Red 108.

[0415] An example of a gelling agent is carrageenan (Satiagel®).

[0416] In the treatment of seeds, the application rate of the compounds of the present invention is generally from 0.1 g to 10 kg per 100 kg of seeds, preferably from 1 g to 5 kg per 100 kg of seeds, more preferably from 1 g to 1000 g, particularly from 1 g to 200 g per 100 kg of seeds. Accordingly, the present invention also provides seeds comprising a compound of formula (I) as defined herein or an agriculturally useful salt of I. The amount of compound I or its agriculturally useful salt generally varies from 0.1 g to 10 kg per 100 kg of seeds, preferably from 1 g to 5 kg per 100 kg of seeds, particularly from 1 g to 1000 g. In the case of certain crops such as lettuce, the amount can be higher.

[0417] Animal health The present invention also provides an agricultural and / or veterinary composition comprising at least one compound of the present invention.

[0418] The present invention further relates to the use of a compound, an N-oxide, or a veterinarily acceptable salt thereof, or a composition of the present invention, in the preparation of a medicament for treating or protecting an animal from infestation or infection by invertebrate pests or parasites.

[0419] The compounds of formula (I), their N-oxides, and / or veterinarily acceptable salts are also particularly suitable for use in controlling parasites in and on animals.

[0420] Accordingly, one object of the present invention is to provide a novel method for controlling parasites in and on animals. Another object of the present invention is to provide a control agent that is safer for animals. Another object of the present invention is to provide a control agent for animals that can be used at a lower dose than existing control agents. Another object of the present invention is to provide a control agent for animals that provides long-term residual control of parasites.

[0421] The present invention also relates to a composition comprising a parasitically effective amount of at least one compound of formula (I), its N-oxide, or a veterinarily acceptable salt thereof, and an acceptable carrier for controlling parasites in and on animals.

[0422] The present invention also provides a method for treating, controlling, preventing, and protecting an animal against infestation and infection by parasites, comprising administering or applying orally, topically, or parenterally to the animal a parasitically effective amount of a compound of the present invention or a composition comprising the same.

[0423] The present invention also provides a process for preparing a composition for treating, controlling, preventing, or protecting an animal against infestation or infection by parasites, comprising a parasitically effective amount of a compound of the present invention or a composition comprising the same.

[0424] The activity of the compounds against agricultural pests does not suggest suitability for the control of internal and external parasites in and on animals, which requires, for example, low non-emetic dosages in the case of oral administration, compatibility of metabolism with animals, low toxicity, and safe handling.

[0425] Surprisingly, it has now been found that the compounds of the present invention are suitable for controlling internal and external parasites in and on animals.

[0426] The compounds of the present invention and compositions containing them are preferably used for controlling and preventing infestation and infection in animals including warm-blooded animals (including humans) and fish. They are suitable for controlling and preventing infestation and infection, for example, in mammals such as cattle, sheep, pigs, camels, deer, horses, pigs, poultry, rabbits, goats, dogs, and cats, water buffalo, donkeys, fallow deer, and reindeer, and fur-bearing animals such as mink, chinchilla, and raccoon, birds such as hens, geese, turkeys, and ducks, and fish such as freshwater fish and saltwater fish such as trout, carp, and eels.

[0427] The compounds of the present invention and compositions containing them are preferably used for controlling and preventing infestation and infection in domestic animals such as dogs or cats.

[0428] Infestation of warm-blooded animals and fish includes, but is not limited to, lice, fleas, mites, fly larvae, sheep keds, stable flies, muscoid flies, biting flies, flies, myiasis fly larvae, ticks, bedbugs, mosquitoes, and fleas.

[0429] The compounds of the present invention and compositions containing them are suitable for systemic and / or non-systemic control of external and / or internal parasites. They can be active against all or some stages of the disease.

[0430] The compounds of the present invention are particularly useful for controlling external parasites.

[0431] The compounds of the present invention are particularly useful for controlling the following orders and species of parasites: fleas (order Siphonaptera), such as Ctenocephalides felis, Ctenocephalides cams, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus; cockroaches (Blattaria Blattodea), such as Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis; flies, mosquitoes (order Diptera), such as 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 macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigrip quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilusintestinalis, 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 spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, lice (Phthiraptera), for example, Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus, and Solenopotes capillatus, mites and parasitic mites (Parasitiformes): mites (Ixodida), for example, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryommamaculatum, Ornithodorus hermsi, Ornithodorus turicata, and parasitic mites (Mesostigmata), for example, Orinithonyssus bacoti, and Dermanyssus gallinae, Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapisa spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp., bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius spp., Panstrongylus spp., and Arilus critatus, Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp., Mallophagida (suborders Arnblycerina, and Ischnocerina), for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp.

[0432] Roundworms:

[0433] Wipeworm larvae, and Trichinosis (Trichosyringida), for example, Trichinellidae (Trichinella spp.), (Trichuridae), Trichuris spp., Capillaria spp., Rhabditida, for example, Rhabditis spp., Strongyloides spp., Helicephalobus spp., Strongylida, for example, Strongylus spp., Ancylostoma spp., Necator americanus, Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus, Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus, Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioctophyma renale, Intestinal 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), Spirurida, for example, Thelazia spp., Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp., DiDipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habronema spp., Thorny headed worm (Acanthocephala), for example, Acanthocephalus spp., Macracanthorhynchus hirudinaceus, and Oncicola spp., Planarian (Plathelminthe): Fluke (Trematoda), for example, Faciola spp., Fascioloides magtna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria a lata, Paragonimus spp., and Nanocyetes spp., Cercomeromorpha, particularly 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.

[0434] The compounds of formula (I) and compositions containing them are particularly useful for the control of pests from Diptera, Siphonaptera, and Ixodida.

[0435] In one embodiment, the present invention provides the use of the compounds of formula (I) and compositions containing them for repelling mosquitoes.

[0436] In one embodiment, the present invention provides the use of the compounds of formula (I) and compositions containing them for repelling flies.

[0437] In one embodiment, the present invention provides the use of the compounds of formula (I) and compositions containing them for repelling fleas.

[0438] The use of the compounds of the present invention and compositions containing them for repelling mites is yet another embodiment of the present invention.

[0439] The compounds of the present invention are also particularly useful for controlling internal parasites (roundworms, hookworms, and planarians).

[0440] In one embodiment, the administration of the compounds of the present invention can be carried out both prophylactically and therapeutically.

[0441] In another embodiment, the administration of the compounds of the present invention is carried out orally, topically / dermally, or parenterally, either directly or in the form of a suitable preparation.

[0442] For oral administration to warm-blooded animals, the compounds of the present invention can be formulated as animal feed, animal feed premixes, animal feed concentrates, boluses, solutions, pastes, suspensions, drenches, gels, tablets, boluses, and capsules. Further, the compounds of the present invention can be administered to animals in their drinking water. For oral administration, the dosage form selected should provide the animal with from 0.01 mg / kg to 100 mg / kg of the compound of the present invention per day, preferably from 0.5 mg / kg to 100 mg / kg of the compound of the present invention per day based on the animal's body weight.

[0443] Alternatively, the compounds of the present invention can be administered to animals parenterally, for example, into the rumen, intramuscularly, intravenously, or subcutaneously. The compounds of the present invention can be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of the present invention can be formulated into implants for subcutaneous administration. Further, the compounds of the present invention can be administered to animals transdermally. In the case of parenteral administration, the dosage form selected should be capable of delivering to the animal from 0.01 mg / kg to 100 mg / kg of the compound of the present invention per day based on the animal's body weight.

[0444] The compounds of the present invention can also be applied topically to animals in the form of dips, powders, dusts, collars, medals, sprays, shampoos, spot-ons, and pour-ons, as well as in the form of ointments or water-in-oil or oil-in-water emulsions. In the case of topical application, dip and spray formulations typically contain from 0.5 ppm to 5,000 ppm, preferably from 1 ppm to 3,000 ppm, of the compound of the present invention. Further, the compounds of the present invention can be formulated as ear tags for animals, particularly for four-legged animals such as cattle and sheep.

[0445] Suitable preparations are solutions, for example, oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pour-on formulations, gels; emulsions and suspensions for oral or dermal administration; semi-solid preparations; preparations in which the active compound is processed in an ointment base or a water-in-oil or oil-in-water emulsion base: solid preparations, for example, powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and shaped articles containing the active compound.

[0446] Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizing agents.

[0447] The solution is filtered and filled under aseptic conditions.

[0448] Suitable solvents are physiologically acceptable solvents such as water, alkanols, for example, ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycol, N-methylpyrrolidone, 2-pyrrolidone, and mixtures thereof.

[0449] The active compound can optionally be dissolved in a physiologically acceptable vegetable oil or synthetic oil suitable for injection.

[0450] Suitable solubilizers are solvents that promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan esters.

[0451] Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.

[0452] Oral solutions are administered directly. Concentrates are administered orally after being pre-diluted to the concentration used. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, and no sterilization procedure is required.

[0453] Solutions for use on the skin are dripped, spread, rubbed, sprinkled, or sprayed.

[0454] Solutions for use on the skin are prepared according to the state of the art and as described above for injection solutions, and no sterilization procedure is required.

[0455] Even more suitable solvents are polypropylene glycol, phenylethanol, phenoxyethanol, esters such as ethyl acetate or butyl acetate, benzyl benzoate, alkylene glycol alkyl ethers, for example, ethers such as dipropylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons, vegetable oils and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylene carbonate, and mixtures thereof.

[0456] It may be advantageous to add a thickening agent during preparation. Suitable thickening agents are inorganic thickening agents, for example, bentonite, colloidal silica, aluminum monostearate, organic thickening agents, for example, cellulose derivatives, polyvinyl alcohol and its copolymers, acrylates and methacrylates.

[0457] 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 for injection solutions with a thickening agent sufficient to obtain a transparent material having a consistency like that of an ointment. The thickening agent used is the above-mentioned thickening agent.

[0458] The poultice preparation is poured or sprayed onto a limited area of the skin, and the active compound penetrates the skin and acts systemically. The poultice preparation is prepared by dissolving, suspending, or emulsifying the active compound in a suitable skin-compatible solvent or solvent mixture. Optionally, other auxiliaries such as colorants, bioavailability enhancers, antioxidants, light stabilizers, adhesives, etc. are added.

[0459] Suitable solvents include, for example, water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers, 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 oils or synthetic oils, DMF, dimethylacetamide, methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, n-alkylpyrrolidones such as N-methylpyrrolidone, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1,3-dioxolane, or glycerol formal.

[0460] Suitable colorants are, for example, all colorants that are approved for use in animals and can be dissolved or suspended.

[0461] Suitable absorption promoters are, for example, dimethyl sulfoxide, diffusion oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils, and copolymers thereof with polyethers, fatty acid esters, triglycerides, or fatty alcohols.

[0462] Suitable antioxidants are, for example, sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, or tocopherol.

[0463] Suitable light stabilizers are, for example, novantisolic acid. Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacrylates, or natural polymers such as alginates, gelatin. The emulsion can be administered orally, topically to the skin, or by injection. The emulsion can be either oil-in-water or water-in-oil type.

[0464] They are prepared by dissolving the active compound in either a hydrophobic or a hydrophilic phase, with the aid of a suitable emulsifier and, if appropriate, other auxiliaries such as colorants, absorption promoters, preservatives, antioxidants, light stabilizers, viscosity enhancers, and homogenizing this in a solvent of the other phase.

[0465] Suitable hydrophobic phases (oils) are liquid paraffin, silicone oil, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as di(caprylic / capric acid) glyceride, triglyceride mixtures with vegetable fatty acids having a chain length of C 1 ~C 12 and other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids which may also contain hydroxyl groups, mono- and diglycerides of Cs-do fatty acids, fatty acid esters such as ethyl stearate, di-n-butyl adipate, hexyl laurate, dipropylene glycol pelargonate, esters of medium-chain branched fatty acids with saturated fatty alcohols having a chain length of C 16 ~C 18 isopropyl myristate, isopropyl palmitate, esters of saturated fatty acids having a chain length of C 12 ~C 18 caprylic / capric acid esters of saturated fatty acid esters, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck uropygial gland fat, dibutyl phthalate, diisopropyl adipate, and related ester mixtures thereof, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid, and mixtures thereof. Suitable hydrophilic phases are water, alcohols such as propylene glycol, glycerol, sorbitol, and mixtures thereof.

[0466] Suitable emulsifiers are, for example, nonionic surfactants such as polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; amphoteric surfactants such as disodium N-lauryl-p-iminodipropionate or lecithin.

[0467] Suitable anionic surfactants are, for example, sodium lauryl sulfate, fatty alcohol ether sulfates, mono / dialkyl polyglycol ether orthophosphate monoethanolamine salts. Suitable cationic surfactants are cetyltrimethylammonium chloride.

[0468] Suitable further auxiliaries are, for example, substances that enhance viscosity and stabilize the emulsion, such as carboxymethyl cellulose, methyl cellulose, and other celluloses, and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycol, waxes, colloidal silica, or mixtures of the above substances.

[0469] The suspensions can be administered orally or topically / dermally. They are prepared, if necessary, by adding other auxiliaries such as wetting agents, colorants, bioabsorption promoters, preservatives, antioxidants, light stabilizers, and suspending the active compound in a suspending agent.

[0470] Liquid suspensions are all homogeneous solvents and solvent mixtures.

[0471] Suitable wetting agents (dispersants) are the above-mentioned emulsifiers.

[0472] Other auxiliaries that may be mentioned are the above-mentioned ones.

[0473] The semi-solid preparations can be administered orally or topically / dermally. They differ from the above suspensions and emulsions only in that they have a high viscosity.

[0474] For the manufacture of solid preparations, the active compounds are, where appropriate, mixed with suitable excipients, with the addition of auxiliaries if appropriate, and brought into the desired form.

[0475] All suitable excipients are physiologically acceptable solid inert substances. Those used are inorganic and organic substances. The inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogen carbonates, aluminum oxide, titanium oxide, silicic acid, argillaceous earth, precipitated or colloidal silica, or phosphates. The organic substances are, for example, sugars, cellulose, foods and feeds such as milk powder, animal meal, cereal meal and flakes, starch, etc.

[0476] Suitable auxiliaries are the above-mentioned preservatives, antioxidants, and / or colorants.

[0477] Other suitable auxiliaries are lubricants and flow promoters such as magnesium stearate, stearic acid, talc, bentonite, disintegration promoters such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin, or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.

[0478] Generally, an "effective amount for anthelmintic use" means the amount of the active ingredient necessary to achieve an observable effect on growth, including effects such as necrosis, death, retardation, prevention, removal, destruction, or otherwise a reduction in the occurrence and activity of the target organisms. The effective amount for anthelmintic use can vary for the various compounds / compositions used in the present invention. The effective amount for anthelmintic use of the composition also varies depending on general conditions such as the desired anthelmintic effect and duration, the target species, the mode of application, etc. The compositions that can be used in the present invention generally contain from about 0.001 to 95% of the compounds of the present invention.

[0479] Generally, it is preferred to apply the compounds of the present invention at a total amount of 0.5 mg / kg to 100 mg / kg per day, preferably 1 mg / kg to 50 mg / kg per day. Preparations in ready-to-use form contain the compounds acting against parasites, preferably ectoparasites, at a concentration of 10 ppm to 80 weight percent, preferably 0.1 to 65 weight percent, more preferably 1 to 50 weight percent, most preferably 5 to 40 weight percent. The preparations are diluted before use and contain the compounds acting against ectoparasites at a concentration of 0.5 to 90 weight percent, preferably 1 to 50 weight percent. Furthermore, the preparations contain the compounds of the present invention against endoparasites at a concentration of 10 ppm to 2 weight percent, preferably 0.05 to 0.9 weight percent, very particularly preferably 0.005 to 0.25 weight percent.

[0480] In one embodiment, the composition containing the compound of the present invention is applied dermally / topically.

[0481] In another embodiment, the topical application is carried out in the form of collars, medals, ear tags, bands for fixing to body parts, and shaped articles containing the compound such as adhesive strips and foils.

[0482] Generally, it is preferred to apply a solid preparation that releases the compounds of the present invention at a weight of 10 mg / kg to 300 mg / kg, preferably 20 mg / kg to 200 mg / kg, most preferably 25 mg / kg to 160 mg / kg of the treated animal over a period of 3 weeks.

[0483] For the preparation of shaped articles, thermoplastics and soft plastics, as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethanes, polyacrylates, epoxy resins, celluloses, cellulose derivatives, polyamides, and polyesters that are sufficiently compatible with the compounds of the present invention. A detailed listing of plastics and elastomers, as well as the procedure for preparing shaped articles, is shown in WO2003 / 086075.

[0484] Positive crop reaction: The compounds of the present invention not only effectively control insect pests and mite pests, but also bring about an increase in yield, plant growth enhancement effects, such as enhancement of root growth, drought tolerance, high salinity tolerance, high temperature tolerance, cold tolerance, frost tolerance or light radiation tolerance, improvement of flowering, enhancement of nutrient utilization (such as improvement of nitrogen assimilation), improvement of quality of plant products, more number of effective tillers, and positive crop responses such as enhancement of resistance to fungi, insects, pests, etc.

[0485] Chemical Examples:

[0486] The following examples illustrate methods and processes for preparing the compounds of the present invention without limiting the same, and include the best mode contemplated by the inventors for practicing the present invention.

[0487] Example 1: Synthesis of 2-(1-(3,5-dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No. 1):

[0488] a) Step 1: 1-(2-Ethoxy-2-oxoethyl)pyridin-1-ium: To a stirred solution of pyridine (10.2 mL, 126 mmol) in acetonitrile (10 mL) was added ethyl 2-bromoacetate (15.4 mL, 139 mmol), and the reaction mixture was heated to reflux for 18 hours. After completion of the reaction, the reaction mixture was cooled to 25 °C. The resulting precipitate was filtered to obtain 1-(2-ethoxy-2-oxoethyl)pyridin-1-ium (20 g, 120 mmol, 95% yield). 1 H-NMR (400 MHz, DMSO-d6) δ 9.09 - 9.11 (m, 2H), 8.70 - 8.74 (m, 1H), 8.25 (dd, J = 7.9, 6.7 Hz, 2H), 5.73 (s, 2H), 4.22 (q, J = 7.1 Hz, 2H), 1.21 (t, J = 7.1 Hz, 3H); ESI MS (m / z) 166.20 (MH) + .

[0489] b) Step 2: Ethyl 2-fluorindolizine-3-carboxylate:

[0490] To a stirred solution of 1-(2-ethoxy-2-oxoethyl)pyridin-1-ium (8 g, 48.1 mmol) in N,N-dimethylformamide (80 mL) was added 2,2-difluorovinyl 4-methylbenzenesulfonate (7.9 g, 33.7 mmol), potassium carbonate (6.7 g, 48.1 mmol), and triethylamine (6.7 mL, 48.1 mmol). The reaction mixture was heated at 70 °C for 12 h. After completion of the reaction, the reaction mixture was cooled to 25 °C. Water (150 mL) was added to the above reaction mixture, and the mixture was extracted twice with ethyl acetate (300 mL). The combined ethyl acetate layers were washed with brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude product. The crude product was purified by flash column chromatography on silica gel using ethyl acetate in hexane as the eluent to give ethyl 2-fluoroisoindoline-3-carboxylate (4.2 g, 20.3 mmol, 42% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 9.29 (dq, J = 7.2, 1.0 Hz, 1H), 7.51 - 7.65 (m, 1H), 7.23 - 7.27 (m, 1H), 6.72 - 7.08 (m, 1H), 6.27 - 6.50 (m, 1H), 4.33 (q, J = 7.1 Hz, 2H), 1.34 (t, J = 7.1 Hz, 3H); ESI MS (m / z) 208.20 (MH) + .

[0491] c) Step 3: 2-Fluoro-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)isoindoline-3-carboxamide:

[0492] A solution of potassium tert-butoxide (1.2 g, 10.9 mmol) in N,N-dimethylformamide (5 mL) was stirred, and a solution of ethyl 2-fluoroisoindoline-3-carboxylate (0.9 g, 4.4 mmol) and N-2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (1 g, 5.2 mmol) in N,N-dimethylformamide (5 mL) was added thereto at 0 °C. The reaction mixture was stirred at 25 °C for 2 h. After completion of the reaction, tetrahydrofuran was removed under reduced pressure to obtain a crude product, which was dissolved in water (25 mL) and extracted with ethyl acetate (75 mL). The ethyl acetate layer was washed with brine (50 mL) and water (50 mL), dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was purified by column chromatography on silica gel using 40% ethyl acetate in hexane to obtain 2-fluoro-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)isoindoline-3-carboxamide (550 mg, 1.6 mmol, yield 36%). 1 1H-NMR (400 MHz, DMSO-d6) δ 9.38 (dd, J = 7.1, 0.7 Hz, 1H), 8.75 (d, J = 4.6 Hz, 1H), 8.30 (t, J = 1.1 Hz, 1H), 7.51 - 7.72 (m, 2H), 7.17 - 7.21 (m, 1H), 6.94 - 7.05 (m, 2H), 6.55 (s, 1H), 2.84 - 2.89 (d, J = 4.6 Hz, 3H); ESI MS (m / z) 352.95 (MH) + .

[0493] d) Step 4: 2-(2-Fluoroisoindolin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0494] A mixture of 2-fluoro-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)indolizine-3-carboxamide (1.4 g, 4 mmol) and p-toluenesulfonic acid monohydrate (2.3 g, 11.9 mmol) in N-methyl-2-pyrrolidone (15 mL) was irradiated in a microwave oven at 150 °C for 1 hour under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was cooled to 25 °C. Water (100 mL) was added to the above reaction mixture, followed by extraction with ethyl acetate (200 mL). The ethyl acetate layer was washed with water (50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by flash column chromatography on silica gel using 20% ethyl acetate in hexane as the eluent to obtain 2-(2-fluoroindolizine-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (830 mg, 2.5 mmol, 62% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 9.12 (dd, J = 7.1, 0.7 Hz, 1H), 8.78 - 8.82 (m, 1H), 8.55 (d, J = 1.5 Hz, 1H), 7.65 - 7.75 (m, 1H), 7.16 - 7.19 (m, 1H), 6.96 (td, J = 7.0, 1.3 Hz, 1H), 6.68 (s, 1H), 3.92 (s, 3H); ESI MS (m / z) 335 (MH) + .

[0495] e) Step 5: 2-(2-(ethylsulfonyl)indolizine-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0496] To a stirred solution of 2-(2-fluoroindolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (830 mg, 2.5 mmol) in dry N,N-dimethylformamide (10 mL) was added sodium hydride (149 mg, 3.7 mmol) at 0 °C and the reaction mixture was stirred for 30 minutes. Ethanethiol (0.4 mL, 5 mmol) was added dropwise to the above reaction mixture at 0 °C and the reaction mixture was heated at 60 °C for 1 hour. After completion of the reaction, the reaction mixture was cooled to 25 °C. Water (50 mL) was added to the reaction mixture and then extracted with ethyl acetate (150 mL). The ethyl acetate layer was washed with water (50 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the crude product. The crude product was purified by flash column chromatography on silica gel using ethyl acetate in hexane as the eluent to give 2-(2-(ethylthio)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (730 mg, 1.94 mmol, 78% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 8.83 (q, J = 0.9 Hz, 1H), 8.59 - 8.60 (m, 1H), 8.43 (dd, J = 7.1, 0.7 Hz, 1H), 7.57 (dd, J = 7.8, 1.2 Hz, 1H), 7.00 (ddd, J = 9.0, 6.6, 1.0 Hz, 1H), 6.81 (s, 1H), 6.72 (td, J = 6.9, 1.2 Hz, 1H), 3.89 (s, 3H), 2.90 - 2.96 (q, J = 7.1 Hz, 2H), 1.19 (t, J = 7.3 Hz, 3H); ESI MS (m / z) 377.05 (MH+) + .

[0497] f) Step 6: 2-(2-(Ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0498] To a solution of 2-(2-(ethylthio)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (200 mg, 0.5 mmol) in dichloromethane (3 mL) was added m-chloroperbenzoic acid (306 mg, 1.1 mmol) portionwise at 0 - 5 °C. The reaction mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was diluted with an aqueous sodium thiosulfate solution and extracted with dichloromethane (150 mL). The dichloromethane layer was washed with a saturated aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by flash column chromatography on silica gel using 40% ethyl acetate in hexane as the eluent to give 2-(2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (150 mg, 0.4 mmol, 69% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 8.91 (t, J = 1.0 Hz, 1H), 8.70 (d, J = 1.5 Hz, 1H), 8.14 (dd, J = 7.1, 1.0 Hz, 1H), 7.71 - 7.91 (m, 1H), 7.11 - 7.16 (m, 2H), 6.88 - 6.91 (m, 1H), 3.7 (s, 3H), 3.39 (q, J = 7.1 hz, 2H), 1.15 (t, J = 7.1 Hz, 3H); ESI MS (m / z) 409 (MH) + .

[0499] g) Step 7: 2-(1-Bromo-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0500] To a stirred solution of 2-(2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (185 mg, 0.45 mmol) in dichloromethane (2 mL) was added N-bromosuccinimide (89 mg, 0.5 mmol) at 0 °C, and the reaction mixture was stirred at 25 °C for 30 minutes. After completion of the reaction, the reaction mixture was diluted with water (20 mL) and extracted three times with dichloromethane (50 mL). The combined dichloromethane layers were washed with brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give the crude product. The crude product was purified by flash column chromatography on silica gel using 30% ethyl acetate in hexane to give 2-(1-bromo-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (160 mg, 0.3 mmol, 72% yield). 1 H-NMR (400 MHz, DMSO-d6) δ 8.90 (d, J = 1.8 Hz, 1H), 8.69 (d, J = 1.8 Hz, 1H), 8.11 (d, J = 7.3 Hz, 1H), 7.68 (d, J = 9.2 Hz, 1H), 7.24 (dd, J = 9.2, 6.7 Hz, 1H), 6.90 - 6.94 (m, 1H), 3.70 (s, 3H), 3.36 - 3.46 (m, 2H), 1.12 (t, J = 7.3 Hz, 3H); ESI MS (m / z) 486.85, 489.05 [(MH) + Br 79,81 .

[0501] h) Step 8: 2-(1-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0502] A solution of 2-(1-bromo-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (110 mg, 0.2 mmol) and (3,5-dichlorophenyl)boronic acid (43.1 mg, 0.2 mmol) in a mixture of 1,4-dioxane (2 mL) and water (0.2 mL) was added with sodium carbonate (71.8 mg, 0.7 mmol) and tetrakis(triphenylphosphine)palladium(0) (13 mg, 0.01 mmol). The reaction mixture was thoroughly deoxygenated by subjecting it to three cycles of vacuum / nitrogen and heated at 110 °C for 1.5 h in a microwave oven. After completion of the reaction, the reaction mixture was cooled to 25 °C and filtered through a pad of celite. The filtrate was concentrated under reduced pressure, and the crude product was purified by flash column chromatography on silica gel using ethyl acetate in hexane as the eluent to give 2-(1-(3,5-dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (73 mg, 0.1 mmol, yield 58%). 1 1H-NMR (400 MHz, DMSO-d6) δ 8.92 (t, J = 2.2 Hz, 1H), 8.71 (t, J = 2.2 Hz, 1H), 8.15 - 8.17 (m, 1H), 7.68 - 7.74 (m, 3H), 7.52 - 7.55 (m, 1H), 7.16 - 7.20 (m, 1H), 6.93 - 6.99 (m, 1H), 3.79 (s, 3H), 3.05 (dtd, J = 63.8, 14.5, 7.3 Hz, 2H), 0.89 - 1.1 (m, 3H); ESI-MS (m / z) 553.90, 554.90 [(MH)+ + Cl 35,37 .

[0503] Example 2: Synthesis of 2-(2-(ethylsulfonyl)imidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No. 2):

[0504] a) Step 1: 2-(2-iminopyridin-1(2H)-yl)acetic acid:

[0505] To a stirred solution of 2-chloroacetic acid (4.0 g, 42.3 mmol) in water (10 mL), triethylamine (6.8 mL, 48.7 mmol) was added dropwise at 25 °C. After stirring for 10 minutes, pyridin-2-amine (4.8 g, 50.8 mmol) was added and the resulting brown solution was heated at 90 °C for 5 hours. After cooling to 25 °C, ethanol (20 mL) was added and the resulting suspension was stirred at 5 °C for 2 hours. The precipitate was collected by filtration and washed with cold ethanol (30 mL) to obtain 2-(2-iminopyridin-1(2H)-yl)acetic acid (4.2 g, 28 mmol, 65% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 8.11 (s, 1H), 7.79 - 7.91 (m, 2H), 6.98 (d, J = 7.8 Hz, 1H), 6.82 (s, 1H), 4.44 (s, 2H); ESI MS (m / z) 152.95 (MH) + .

[0506] b) Step 2: 2-chloroimidazo[1,2-a]pyridine:

[0507] To a stirred solution of 2-(2-iminopyridin-1(2H)-yl)acetic acid (4.2 g, 27.6 mmol) in toluene (50 mL), phosphorus oxychloride (7.7 mL, 83 mmol) was added dropwise and the resulting reaction mixture was heated at 100 °C for 16 hours. After completion of the reaction, the reaction mixture was cooled to 25 °C. Cold water (500 mL) was added and the solution was stirred for 15 minutes. The aqueous layer was neutralized with 10% aqueous sodium hydroxide solution and extracted twice with dichloromethane (250 mL). The combined dichloromethane layers were washed with water (100 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was purified by flash column chromatography on silica gel using ethyl acetate in hexane as the eluent to obtain 2-chloroimidazo[1,2-a]pyridine (3.2 g, 21 mmol, 76% yield). 1H-NMR (400 MHz, DMSO-d6) δ 8.50 (dt, J = 6.8, 1.2 Hz, 1H), 8.05 - 8.08 (m, 1H), 7.54 (dq, J = 9.1, 0.9 Hz, 1H), 7.33 (ddd, J = 9.2, 6.8, 1.3 Hz, 1H), 6.99 (td, J = 6.8, 1.2 Hz, 1H); ESI MS (m / z) 152.90 (MH) + .

[0508] c) Step 3: Ethyl 2-chloroimidazo[1,2-a]pyridine-3-carboxylate:

[0509] To a stirred solution of 2-chloroimidazo[1,2-a]pyridine (0.5 g, 3.3 mmol) in tetrahydrofuran (10 mL) was added dropwise n-butyllithium (1.8 mL, 3.6 mmol) at -78 °C. After stirring for 30 minutes, ethyl chloroformate (0.36 g, 3.3 mmol) in tetrahydrofuran (10 mL) was added to the reaction mixture at the same temperature. The reaction mixture was stirred at -78 °C for 1 hour and then at 25 °C for an additional 1 hour. After completion of the reaction, the reaction was quenched by adding saturated ammonium chloride solution (20 mL) and extracted twice with ethyl acetate (100 mL). The combined ethyl acetate layers were washed with water (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the crude product. The crude product was purified by flash chromatography on silica gel using 30% ethyl acetate in hexane as the eluent to give ethyl 2-chloroimidazo[1,2-a]pyridine-3-carboxylate (0.5 g, 2.2 mmol, 68% yield). 1 H-NMR (400 MHz, DMSO-d6) δ 9.24 (dt, J = 6.9, 1.2 Hz, 1H), 7.77 (dt, J = 9.0, 1.2 Hz, 1H), 7.66 (ddd, J = 9.0, 6.9, 1.3 Hz, 1H), 7.31 (td, J = 6.9, 1.3 Hz, 1H), 4.35 (q, J = 7.1 Hz, 2H), 1.45 (t, J = 6.8 Hz, 3H); ESI MS (m / z) 224.90 (MH) + .

[0510] d) Step 4: 2-Chloro-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)imidazo[1,2-a]pyridine-3-carboxamide:

[0511] A solution of potassium tert-butoxide (0.5 g, 4.5 mmol) in tetrahydrofuran (10 mL) was stirred, and a solution of ethyl 2-chloroimidazo[1,2-a]pyridine-3-carboxylate (0.5 g, 2.2 mmol) and N-2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (0.4 g, 2.2 mmol) in tetrahydrofuran (10 mL) was added thereto at 0 °C. The reaction mixture was stirred at 25 °C for 1 hour. After completion of the reaction, tetrahydrofuran was removed under reduced pressure to obtain a crude product, which was dissolved in water (20 mL) and extracted with dichloromethane (75 mL). The dichloromethane layer was washed with brine (50 mL) and water (50 mL), dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was purified by column chromatography on silica gel using 40% ethyl acetate in hexane to obtain 2-chloro-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)imidazo[1,2-a]pyridine-3-carboxamide (0.45 g, 1.2 mmol, yield 55%). 1 1H-NMR (400 MHz, DMSO-d6) δ 9.16 - 9.22 (m, 2H), 8.34 (q, J = 1.1 Hz, 1H), 7.59 - 7.76 (m, 3H), 7.24 (td, J = 7.0, 1.4 Hz, 1H), 7.03 (q, J = 4.6 Hz, 1H), 2.90 (d, J = 4.6 Hz, 3H); ESI MS (m / z) 369.85 (MH) + .

[0512] e) Step 5: 2-(2-Chloroimidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0513] A mixture of 2-chloro-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)imidazo[1,2-a]pyridine-3-carboxamide (0.25 g, 0.68 mmol) and p-toluenesulfonic acid monohydrate (0.39 g, 2.03 mmol) in N-methyl-2-pyrrolidone (10 mL) was irradiated in a microwave oven at 150 °C for 2 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was cooled to 25 °C. Water (50 mL) was added to the above reaction mixture, followed by extraction with ethyl acetate (150 mL). The ethyl acetate layer was washed with water (50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by flash column chromatography on silica gel using 40% ethyl acetate in hexane as the eluent to obtain 2-(2-chloroimidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (0.2 g, 0.5 mmol, 76% yield). 1 H-NMR (400 MHz, DMSO-d6) δ 8.89 (q, J = 0.9 Hz, 1H), 8.68 - 8.73 (m, 2H), 7.79 (dt, J = 9.0, 1.1 Hz, 1H), 7.60 (ddd, J = 9.0, 7.0, 1.3 Hz, 1H), 7.20 (td, J = 7.0, 1.2 Hz, 1H), 3.92 (s, 3H); ESI MS (m / z) 352.05 (MH) + .

[0514] f) Step 6: 2-(2-(Ethylthio)imidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0515] A stirred solution of 2-(2-chloroimidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (0.3 g, 0.9 mmol) in dry N,N-dimethylformamide (5 mL) was added with sodium hydride (0.1 g, 1.7 mmol) at 0 °C, and the reaction mixture was stirred for 30 minutes. Ethanethiol (0.1 mL, 1.3 mmol) was added to the above reaction mixture at 0 °C, and the reaction mixture was heated at 60 °C for 2 hours. After completion of the reaction, the reaction mixture was cooled to 25 °C. Cold water (150 mL) was added to the reaction mixture, and the resulting precipitate was filtered off, washed with water (10 mL), and dried under vacuum to obtain a crude product. The crude product was purified by flash column chromatography on silica gel using 40% ethyl acetate in hexane as the eluent to give 2-(2-(ethylthio)imidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (0.25 g, 0.7 mmol, 78% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 8.85 (t, J = 1.0 Hz, 1H), 8.63 - 8.65 (m, 2H), 7.74 (dt, J = 9.0, 1.1 Hz, 1H), 7.50 (ddd, J = 9.0, 6.8, 1.2 Hz, 1H), 7.08 (td, J = 6.8, 1.2 Hz, 1H), 3.90 (s, 3H), 3.25 (q, J = 7.3 Hz, 2H), 1.23 (t, J = 6.8 Hz, 3H); ESI MS (m / z) 378.10 (MH) + .

[0516] g) Step 7: 2-(2-(Ethylsulfonyl)imidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0517] A solution of 2-(2-(ethylthio)imidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (0.2 g, 0.5 mmol) in dichloromethane (5 mL) was added portionwise with m-chloroperbenzoic acid (0.3 g, 1 mmol) at 0 - 5 °C. The reaction mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was diluted with an aqueous sodium thiosulfate solution and extracted with dichloromethane (15 mL). The dichloromethane extract was washed with a saturated aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude product. The crude product was purified by flash column chromatography on silica gel using 35% ethyl acetate in hexane as the eluent to give 2-(2-(ethylsulfonyl)imidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (0.1 g, 0.3 mmol, 67% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 8.93 - 8.93 (m, 1H), 8.73 (dd, J = 2.1, 0.6 Hz, 1H), 8.47 (dt, J = 7.0, 1.1 Hz, 1H), 7.94 (dt, J = 9.2, 1.1 Hz, 1H), 7.68 (ddd, J = 9.0, 6.8, 1.2 Hz, 1H), 7.22 (td, J = 6.9, 1.1 Hz, 1H), 3.86 (s, 3H), 3.49 - 3.52 (q, J = 6.8 Hz, 2H), 1.15 - 1.24 (t, J = 7.6 Hz, 3H); ESI MS (m / z) 409.95 (MH) + .

[0518] Example 3: Synthesis of 2-(8-(3,5-dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No. 6):

[0519] a) Step 1: 3-bromo-1-(2-ethoxy-2-oxoethyl)pyridin-1-ium

[0520] To a stirred solution of 3-bromopyridine (12.4 mL, 127 mmol) in acetonitrile (200 mL) was added ethyl 2-bromoacetate (15.5 mL, 139 mmol), and the reaction mixture was heated to reflux for 16 h. After completion of the reaction, the reaction mixture was cooled to 25 °C, and the resulting precipitate was filtered to give 3-bromo-1-(2-ethoxy-2-oxoethyl)pyridin-1-ium (30 g, 122 mmol, 97% yield). 1 1H-NMR (400 MHz, chloroform-D) δ 9.56 (m, 1H), 9.35 (s, 1H), 8.62 (d, J = 8.3 Hz, 1H), 6.28 (s, 2H), 4.36 (q, J = 7.1 Hz, 3H), 1.33 - 1.4 (t, J = 7.2 Hz, 3H); ESI MS (m / z) 243.85, 245.85 [(MH)+ + Br 79,81 .

[0521] b) Step 2: Ethyl 6-bromo-2-fluoroisoindoline-3-carboxylate and ethyl 8-bromo-2-fluoroisoindoline-3-carboxylate:

[0522] To a stirred solution of 3-bromo-1-(2-ethoxy-2-oxoethyl)pyridin-1-ium (3 g, 12.2 mmol) in N,N-dimethylformamide (80 mL) were added 2,2-difluorovinyl 4-methylbenzenesulfonate (1 g, 4.3 mmol), potassium carbonate (0.85 g, 6.1 mmol), and triethylamine (0.85 mL, 6.1 mmol). The reaction mixture was heated at 70 °C for 16 h. After completion of the reaction, the reaction mixture was cooled to 25 °C. Water (50 mL) was added to the above reaction mixture, and the mixture was extracted twice with ethyl acetate (200 mL). The combined ethyl acetate layers were washed with brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude product. The crude product was purified by reverse-phase preparative HPLC to give ethyl 6-bromo-2-fluoroisoindoline-3-carboxylate (240 mg, 0.8 mmol, 14% yield) and ethyl 8-bromo-2-fluoroisoindoline-3-carboxylate (160 mg, 0.56 mmol, 9% yield).

[0523] i. Ethyl 6-bromo-2-fluoroindolizine-3-carboxylate: 1 H-NMR (400 MHz, DMSO-d6) δ 9.37 - 9.47 (m, 1H), 7.63 - 7.71 (m, 1H), 7.35 - 7.41 (m, 1H), 6.58 - 6.69 (m, 1H), 4.35 (q, J = 7.1 Hz, 2H), 1.35 (t, J = 7.2 Hz, 3H); ESI MS (m / z) 286.05, 288.05 [(MH) + Br 79,81 .

[0524] ii. Ethyl 8-bromo-2-fluoroindolizine-3-carboxylate: 1 H-NMR (400 MHz, DMSO-d6) δ 9.28 - 9.40 (m, 1H), 7.58 - 7.64 (m, 1H), 6.97 (t, J = 7.2 Hz, 1H), 6.57 (d, J = 11.5 Hz, 1H), 4.33 (q, J = 7.2 Hz, 2H), 1.3 (t, J = 7.2 Hz, 3H); ESI MS (m / z) 286, 288 [(MH) + Br 79,81 .

[0525] c) Step 3: 8-Bromo-2-fluoro-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)indolizine-3-carboxamide:

[0526] By reacting ethyl 6-bromo-2-fluoroindolizine-3-carboxylate (2.1 g, 7.3 mmol) and N-2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (1 g, 5.23 mmol) as appropriate reactants according to the same synthetic procedure described in Step 3 of Example 34, 8-bromo-2-fluoro-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)indolizine-3-carboxamide (1.3 g, 3 mmol, yield 41%) was obtained. 1H-NMR (400 MHz, chloroform-D) δ 9.62 (d, J = 7.0 Hz, 1H), 8.37 (d, J = 0.9 Hz, 1H), 7.72 (dd, J = 6.7, 2.1 Hz, 1H), 7.46 - 7.52 (m, 1H), 7.33 - 7.38 (m, 1H), 6.75 (t, J = 7.3 Hz, 1H), 6.49 (s, 1H), 5.13 (d, J = 4.3 Hz, 1H), 3.05 - 3.08 (d, J = 5.2 Hz, 3H); ESI MS (m / z) 430.75, 432.75 [(MH) + Br 79,81 .

[0527] d) Step 4: 2-(8-Bromo-2-fluoroindolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0528] Cyclization was carried out using 8-bromo-2-fluoro-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)indolizine-3-carboxamide (2.2 g, 5.10 mmol), and 2-(8-bromo-2-fluoroindolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (1.8 g, 4.4 mmol, 85% yield) was obtained according to the same synthetic procedure described in Step 4 of Example 34. ESI MS (m / z) 412.70, 414.70 [(MH) + Br 79,81 .

[0529] e) Step 5: 2-(8-Bromo-2-(ethylthio)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0530] Using 2-(8-bromo-2-fluoroindolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (100 mg, 0.2 mmol) as an appropriate starting material, following the same synthetic procedure as described in Step 5 of Example 34, 2-(8-bromo-2-(ethylthio)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5]-b]pyridine (50 mg, 0.1 mmol, yield 45%) was obtained. 1 H-NMR (400 MHz, DMSO-d6) δ 8.83 (d, J = 1.2 Hz, 1H), 8.61 (d, J = 1.5 Hz, 1H), 8.41 (d, J = 7.0 Hz, 1H), 7.33 (dd, J = 7.3, 0.6 Hz, 1H), 6.83 (d, J = 0.6 Hz, 1H), 6.66 (t, J = 7.2 Hz, 1H), 3.82 (s, 3H), 2.98 (q, J = 7.3 Hz, 2H), 1.18 (q, J = 7.1 Hz, 3H); ESI MS (m / z) 454.95, 456.95 [(MH) + Br 79,81 .

[0531] f) Step 6: 2-(8-Bromo-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0532] By oxidizing 2-(8-bromo-2-(ethylthio)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (840 mg, 1.84 mmol) following the same synthetic procedure as described in Step 6 of Example 34, 2-(8-bromo-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine pyridine (800 mg, 1.6 mmol, yield 89%) was obtained. 1H-NMR (400 MHz, DMSO-d6) δ 8.89 - 8.93 (m, 1H), 8.55 - 8.72 (m, 1H), 8.12 - 8.23 (m, 1H), 7.50 - 7.57 (m, 1H), 7.11 - 7.26 (m, 1H), 6.75 - 6.85 (m, 1H), 3.72 (s, 3H), 3.39 - 3.51 (q, J = 6.8 Hz, 2H), 1.15 (t, J = 7.1 Hz, 3H); ESI MS (m / z) 487.05, 489.05 [(MH) + Br 79,81 .

[0533] g) Step 7: 2-(8-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)indolizine-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0534] Following the same synthetic procedure described in Step 7 of Example 34, 2-(8-(3,5-dichlorophenyl)-2-(ethylsulfonyl)indolizine-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (65 mg, 0.1 mmol, 38% yield) was obtained by Suzuki coupling using 2-(8-bromo-2-(ethylsulfonyl)indolizine-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (150 mg, 0.31 mmol) and (3,5-dichlorophenyl)boronic acid (58.7 mg, 0.31 mmol). 1 H-NMR (400 MHz, DMSO-d6) δ 8.93 (s, 1H), 8.73 (s, 1H), 8.22 (d, J = 7.1 Hz, 1H), 7.81 (s, 3H), 7.27 (d, J = 6.8 Hz, 1H), 6.99 - 7.13 (m, 2H), 3.73 (s, 3H), 3.40 (q, J = 7.2 Hz, 2H), 1.11 (t, J = 7.3 Hz, 3H); ESI-MS (m / z) 553.15, 555.15 [(MH) + Cl 35,37 .

[0535] Example 4: Synthesis of 2-(6-(3,5-dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No. 8):

[0536] Starting from ethyl 8-bromo-2-fluoroindolizine-3-carboxylate obtained in Step 2 of Example 42, the title compound was prepared according to the same sequence of Steps 3 to 7 described for the synthesis of 2-(8-(3,5-dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine, and 2-(6-(3,5-)dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine was obtained. 1 H-NMR (400 MHz, DMSO-d6) δ 8.92 - 8.93 (m, 1H), 8.71 - 8.71 (m, 1H), 8.55 (d, J = 0.7 Hz, 1H), 7.90 - 7.94 (m, 1H), 7.73 - 7.77 (m, 2H), 7.62 (m, 1H), 7.53 (dd, J = 9.4, 1.6 Hz, 1H), 7.01 - 7.28 (m, 1H), 3.75 (s, 3H), 3.33 - 3.42 (m, 2H), 1.15 (t, J = 6.2 Hz, 3H); ESI MS (m / z) 553.00, 555.00 [(MH) + Cl 35,37 .

[0537] Example 5: Synthesis of 2-(2-(ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No. 9):

[0538] a) Step 1: Ethyl 2-(ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidine-3-carboxylate:

[0539] Ethyl 5-amino-3-(ethylthio)-1H-pyrazole-4-carboxylate (2 g, 9.3 mmol) [prepared according to the procedures described in Acta Chimica Sinica 2003, 63, 855; Organic & Biomolecular Chemistry, 2010, 8, 3394] and 2,4-pentanedione (1.15 mL, 11.15 mmol) in acetic acid (20 mL) were added 2 drops of concentrated sulfuric acid to the stirred solution. The resulting mixture was heated at 50 °C for 15 minutes. After completion of the reaction, the reaction mixture was cooled to 25 °C. Water (5 mL) was added to the above reaction mixture, and the reaction mixture was extracted three times with ethyl acetate (10 mL). The combined ethyl acetate layers were dried over sodium sulfate and concentrated under reduced pressure to give a crude product. The crude product was purified by column chromatography on silica gel using 20% ethyl acetate in hexane as the eluent to give ethyl 2-(ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidine-3-carboxylate (2.0 g, 7.20 mmol, 77% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 7.04 (d, J = 0.7 Hz, 1H), 4.25 (q, J = 7.1 Hz, 2H), 3.17 (q, J = 7.3 Hz, 2H), 2.67 - 2.83 (m, 3H), 2.56 (d, J = 23.7 Hz, 3H), 1.36 - 1.53 (m, 3H), 1.30 (q, J = 6.9 Hz, 3H); ESI MS (m / z) 280.20 (MH) + .

[0540] b) Step 2: 2-(Ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidine-3-carboxylic acid:

[0541] To a stirred suspension of ethyl 2-(ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidine-3-carboxylate (2.3 g, 8.2 mmol) in a mixture of ethanol (37.5 mL) and water (37.5 mL) was added lithium hydroxide monohydrate (5.18 g, 123.0 mmol). The reaction mixture was stirred at 60 °C for 17 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove ethanol. The residue was treated with 1 N hydrochloric acid solution, and the precipitate of 2-(ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidine-3-carboxylic acid (88 mg, 0.35 mmol, 59% yield) was filtered off, washed with water (10 mL), and dried under vacuum. 1 1H-NMR (400 MHz, DMSO-d6) δ 12.16 (s, 1H), 7.02 (d, J = 0.7 Hz, 1H), 3.15 (q, J = 7.3 Hz, 2H), 2.67 (d, J = 0.9 Hz, 3H), 2.53 (s, 3H), 1.37 (t, J = 7.3 Hz, 3H); ESI MS (m / z) 252.15 (MH) + .

[0542] c) Step 3: 2-(Ethylthio)-5,7-dimethyl-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide:

[0543] A solution of 2-(ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidine-3-carboxylic acid (500 mg, 2 mmol) in anhydrous N,N-dimethylformamide (27 mL) was added with 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazol[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU) (908 mg, 2.4 mmol), and the reaction mixture was stirred at 0 - 5 °C for 15 minutes. Then, N-2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (761 mg, 4 mmol) and N,N-diisopropylethylamine (1 mL, 6 mmol) were added to the above reaction mixture, and the reaction was heated at 100 °C for 16 hours. After completion of the reaction, water (40 mL) was added to the reaction mixture, which was then extracted three times with ethyl acetate (30 mL). The combined ethyl acetate layers were dried over sodium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel using 40% ethyl acetate in hexane as the eluent to obtain 2-(ethylthio)-5,7-dimethyl-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide (510 mg, 1.20 mmol, yield 60%). 1 H-NMR(400MHz,DMSO-d6)δ9.74(s,1H),8.27(d,J=1.3Hz,1H),8.05 - 8.07(m,1H),7.14 - 7.28(m,1H),6.80(d,J=4.9Hz,1H),3.22(q,J=7.3Hz,2H),2.92(d,J=4.6Hz,3H),2.76(d,J=0.5Hz,3H),2.64(s,3H),1.41(t,J=7.3Hz,3H);ESI MS(m / z)425.20(MH) + .

[0544] d) Step 4: 2-(2-(ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0545] A mixture of 2-(ethylthio)-5,7-dimethyl-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide (380 mg, 0.90 mmol) and p-toluenesulfonic acid monohydrate (511 mg, 2.7 mmol) in N-methyl-2-pyrrolidone (8 mL) was irradiated in a microwave oven at 150 °C for 1.5 h under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was cooled to 25 °C. Water (50 mL) was added to the above reaction mixture, followed by extraction with ethyl acetate (50 mL). The ethyl acetate layer was washed with water (30 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by flash column chromatography on silica gel using 40% ethyl acetate in hexane as an eluent to obtain 2-(2-(ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (194 mg, 0.5 mmol, 53% yield). 1 H-NMR(400MHz,CDCl 3 )δ8.64(d,J=1.2Hz,1H),8.31(d,J=1.5Hz,1H),6.65(d,J=0.7Hz,1H),4.02(s,3H),3.29(q,J=7.4Hz,2H),2.79(d,J=0.7Hz,3H),2.57(s,3H),1.46(t,J=7.3Hz,3H);ESI MS(m / z)407.10(MH) + .

[0546] Example 6: Synthesis of 2-(2-(ethylsulfonyl)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No. 10):

[0547] A solution of 2-(2-(ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (165 mg, 0.4 mmol) in dichloromethane (8 mL) was added portionwise with m-chloroperbenzoic acid (255 mg, 0.8 mmol) at 0 - 5 °C. The reaction mixture was stirred at 25 °C for 5 h. After completion of the reaction, the reaction mixture was diluted with an aqueous sodium thiosulfate solution and extracted with dichloromethane (20 mL). The dichloromethane layer was washed with a saturated aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude product. The crude product was purified by flash column chromatography on silica gel using 60% ethyl acetate in hexane as an eluent to give 2-(2-(ethylsulfonyl)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (92 mg, 0.2 mmol, 52% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 8.84 (s, 1H), 8.61 (d, J = 2.0 Hz, 1H), 7.36 (d, J = 1.0 Hz, 1H), 3.78 (s, 3H), 3.73 (q, J = 7.3 Hz, 2H), 2.83 (s, 3H), 2.57 (s, 3H), 1.25 (t, J = 7.3 Hz, 3H); ESI MS (m / z) 439.25 (MH) + .

[0548] Example 7: Synthesis of 2-(2-(ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No. 19):

[0549] a) Step 1: Ethyl 2-(ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidine-3-carboxylate

[0550] To a stirred solution of ethyl 3-amino-5-(ethylthio)-1H-pyrazole-4-carboxylate (1.9 g, 9 mmol) in acetic acid (65.4 mL) was added (E)-3-(dimethylamino)-1-(4-fluorophenyl)prop-2-en-1-one (1.7 g, 9 mmol), and the resulting mixture was heated at 50 °C for 2 h. After completion of the reaction, acetic acid was removed under reduced pressure to give a crude product. The crude product was purified by column chromatography on silica gel using 30% ethyl acetate in hexane as the eluent to give ethyl 2-(ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidine-3-carboxylate (2.2 g, 6.37 mmol, 71% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 8.77 (d, J = 4.6 Hz, 1H), 8.20 - 8.25 (m, 2H), 7.44 - 7.49 (m, 2H), 7.42 (d, J = 4.6 Hz, 1H), 4.30 (q, J = 7.1 Hz, 2H), 3.09 (q, J = 7.3 Hz, 2H), 1.33 (dt, J = 15.6, 7.2 Hz, 6H); ESI MS (m / z) 346.30 (MH) + .

[0551] b) Step 2: 2-(Ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid:

[0552] To a stirred suspension of ethyl 2-(ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidine-3-carboxylate (2.2 g, 6.4 mmol) in a mixture of ethanol (30 mL) and water (30 mL) was added lithium hydroxide monohydrate (2.7 g, 63.7 mmol). The reaction mixture was stirred at 60 °C for 2 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove ethanol. The residue was treated with 1N hydrochloric acid solution, and the precipitate of 2-(ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (1.6 g, 5 mmol, 79% yield) was filtered off, washed with water (10 mL), and dried under vacuum. 1H-NMR (400 MHz, DMSO-d6) δ 8.44 (d, J = 4.6 Hz, 1H), 8.28 (ddd, J = 12.1, 5.3, 3.2 Hz, 2H), 7.43 - 7.49 (m, 2H), 7.19 (d, J = 4.6 Hz, 1H), 3.00 (q, J = 7.3 Hz, 2H), 1.32 (t, J = 7.3 Hz, 3H); ESI MS (m / z) 317.90 (M) + .

[0553] c) Step 3: 2-(Ethylthio)-7-(4-fluorophenyl)-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide:

[0554] To a suspension of 2-(ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (500 mg, 1.58 mmol) in anhydrous dichloromethane (15 mL) was added 2 drops of N,N-dimethylformamide, followed by oxalyl chloride (0.2 mL, 2.4 mmol). The resulting reaction mixture was stirred at 25 °C for 4 h. The reaction mixture was evaporated under reduced pressure at a bath temperature of 60 °C. The resulting residue was dissolved in anhydrous dichloromethane (15 mL) and added dropwise to a stirred solution of N-2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (304 mg, 1.6 mmol) and triethylamine (0.9 mL, 6.6 mmol) at 0 °C. The reaction mixture was stirred at 25 °C for 16 h. After completion of the reaction, water (40 mL) was added to the reaction mixture, which was then extracted three times with ethyl acetate (20 mL). The combined ethyl acetate layers were dried over sodium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel using 40% ethyl acetate in hexane as the eluent to give 2-(ethylthio)-7-(4-fluorophenyl)-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide (377 mg, 0.8 mmol, 49% yield). 1H-NMR (400 MHz, DMSO-d6) δ 9.51 (s, 1H), 8.85 (d, J = 4.6 Hz, 1H), 8.28 - 8.34 (m, 3H), 7.90 (d, J = 1.8 Hz, 1H), 7.49 - 7.53 (m, 3H), 6.92 (d, J = 4.6 Hz, 1H), 3.14 (q, J = 7.2 Hz, 2H), 2.89 (d, J = 4.6 Hz, 3H), 1.33 - 1.39 (m, 3H); ESI MS (m / z) 490.95 (M) + .

[0555] d) Step 4: 2-(2-(Ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine:

[0556] A mixture of 2-(ethylthio)-7-(4-fluorophenyl)-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide (377 mg, 0.8 mmol) and p-toluenesulfonic acid monohydrate (439 mg, 2.3 mmol) in N-methyl-2-pyrrolidone (8 mL) was irradiated in a microwave oven at 150 °C for 1.5 h under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was cooled to 25 °C. Water (50 mL) was added to the above reaction mixture, followed by extraction with ethyl acetate (150 mL). The ethyl acetate layer was washed with water (50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by flash column chromatography on silica gel using 40% ethyl acetate in hexane as the eluent to give 2-(2-(ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (185 mg, 0.4 mmol, 51% yield). 1H-NMR(400MHz, DMSO-d6) δ 8.77 (q, J = 0.9 Hz, 1H), 8.75 (d, J = 4.4 Hz, 1H), 8.54 - 8.54 (m, 1H), 8.29 - 8.33 (m, 2H), 7.49 - 7.53 (m, 2H), 7.43 (d, J = 4.6 Hz, 1H), 3.97 (s, 3H), 3.17 (q, J = 7.3 Hz, 2H), 1.36 (t, J = 7.3 Hz, 3H); ESI MS (m / z) 473.00 (MH) + .

[0557] Example 8: Synthesis of 2-(2-(Ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (Compound No. 22):

[0558] a) Step 1: Ethyl 2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate

[0559] To a stirred solution of ethyl 5-amino-3-(ethylthio)-1H-pyrazole-4-carboxylate (1.3 g, 6 mmol) in acetic acid (38 mL) was added 3-(dimethylamino)acrolein (0.9 mL, 9.1 mmol). The reaction mixture was stirred at 25 °C for 24 h. After completion of the reaction, the reaction mixture was neutralized with saturated aqueous sodium bicarbonate and extracted three times with ethyl acetate (20 mL). The combined ethyl acetate layers were dried over sodium sulfate and concentrated under reduced pressure to give a crude product. The crude product was purified by column chromatography on silica gel using 30% ethyl acetate in hexane as the eluent to give ethyl 2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate (0.9 g, 3.5 mmol, 57% yield). 1 H-NMR(400MHz,DMSO-d6)δ9.18(dd,J=6.9,1.7Hz,1H),8.74(q,J=1.9Hz,1H),7.20(dd,J=7.0,4.3Hz,1H),4.27(q,J=7.1Hz,2H),3.16(q,J=7.3Hz,2H),1.37(t,J=7.3Hz,3H),1.25 - 1.31(m,3H);ESI MS(m / z)252.10(MH)+ .

[0560] b) Step 2: 2-(Ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid:

[0561] To a stirred suspension of ethyl 2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate (0.9 g, 3.5 mmol) in a mixture of ethanol (50 mL) and water (50 mL) was added lithium hydroxide monohydrate (1.45 g, 34.6 mmol). The reaction mixture was stirred at 60 °C for 2 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove ethanol. The residue was treated with 1N hydrochloric acid solution, and the resulting precipitate of 2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (0.6 g, 2.8 mmol, 81% yield) was filtered off, washed with water (10 mL), and dried under vacuum. 1 H-NMR (400 MHz, DMSO-d6) δ 12.38 (s, 1H), 9.16 (dd, J = 7.0, 1.8 Hz, 1H), 8.69 (q, J = 2.0 Hz, 1H), 7.16 (dd, J = 6.7, 4.3 Hz, 1H), 3.14 (q, J = 7.3 Hz, 2H), 1.36 (t, J = 7.5 Hz, 3H); ESI MS (m / z) 223.85 (M) + .

[0562] c) Step 3: 2-(Ethylthio)-N-(5-(methylamino)-2-(trifluoromethyl)pyridin-4-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide:

[0563] A suspension of 2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (325 mg, 1.5 mmol) in anhydrous dichloromethane (14 mL) was added with 2 drops of N,N-dimethylformamide, followed by oxalyl chloride (0.2 mL, 2.2 mmol). The resulting mixture was stirred at 25 °C for 4 h. The reaction mixture was evaporated under reduced pressure at a bath temperature of 60 °C. The obtained residue was dissolved in anhydrous dichloromethane (14 mL) and added dropwise to a stirred solution of N-3-methyl-6-(trifluoromethyl)pyridine-3,4-diamine (278 mg, 1.5 mmol) and triethylamine (0.85 mL, 6.1 mmol) at 0 °C. The reaction mixture was stirred at 25 °C for 16 h. After completion of the reaction, water (40 mL) was added to the reaction mixture, and the mixture was extracted three times with ethyl acetate (20 mL). The combined ethyl acetate layers were dried over sodium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel using 40% ethyl acetate in hexane as the eluent to obtain 2-(ethylthio)-N-(5-(methylamino)-2-(trifluoromethyl)pyridin-4-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide (392 mg, 1 mmol, yield 68%). 1 H-NMR(400MHz,CDCl 3 )δ8.45(d,J=6.8Hz,1H),8.26(d,J=3.9Hz,1H),8.11(d,J=6.1Hz,1H),6.95(s,1H),6.72(dd,J=6.8,4.2Hz,1H),5.18-4.61(2H),3.35(s,3H),3.21(q,J=7.3Hz,2H),1.41-1.44(m,3H);ESI MS(m / z)397.05(MH) + .

[0564] d) Step 4: 2-(2-(Ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine:

[0565] A mixture of 2-(ethylthio)-N-(5-(methylamino)-2-(trifluoromethyl)pyridin-4-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide (392 mg, 1 mmol) and p-toluenesulfonic acid monohydrate (564 mg, 3 mmol) in N-methyl-2-pyrrolidone (9 mL) was irradiated in a microwave oven at 150 °C for 1.5 h under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was cooled to 25 °C. Water (50 mL) was added to the above reaction mixture, followed by extraction with ethyl acetate (150 mL). The ethyl acetate layer was washed with water (30 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by flash column chromatography on silica gel using 40% ethyl acetate in hexane as an eluent to obtain 2-(2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (256 mg, 0.7 mmol, yield 68%). 1 H-NMR (400 MHz, DMSO-d6) δ 9.27 (dd, J = 6.8, 1.7 Hz, 1H), 9.14 (s, 1H), 8.70 (dd, J = 4.3, 1.6 Hz, 1H), 8.19 (d, J = 0.7 Hz, 1H), 7.21 (dd, J = 6.8, 4.2 Hz, 1H), 4.01 (s, 3H), 3.22 (q, J = 7.3 Hz, 2H), 1.32 - 1.38 (m, 3H); ESI MS (m / z) 378.90 (MH) + .

[0566] Example 9: Synthesis of 2-(2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (Compound No. 23):

[0567] A solution of 2-(2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (187 mg, 0.5 mmol) in dichloromethane (9 mL) was added portionwise with m-chloroperbenzoic acid (262 mg, 1 mmol) at 0 - 5 °C. The reaction mixture was stirred at 25 °C for 5 h. After completion of the reaction, the reaction mixture was diluted with an aqueous sodium thiosulfate solution and extracted with dichloromethane (20 mL). The dichloromethane extract was washed with a saturated aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude product. The crude product was purified by flash column chromatography on silica gel using 60% ethyl acetate in hexane as the eluent to give 2-(2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (105 mg, 0.3 mmol, 52% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 9.50 (dd, J = 7.1, 1.7 Hz, 1H), 9.22 (s, 1H), 8.87 (q, J = 2.0 Hz, 1H), 8.25 (d, J = 0.7 Hz, 1H), 7.51 (dd, J = 7.2, 4.0 Hz, 1H), 3.90 (s, 3H), 3.74 (q, J = 7.4 Hz, 2H), 1.24 (t, J = 7.5 Hz, 3H) ESI MS (m / z) 411.05 (MH) + .

[0568] Example 10: Synthesis of 2-(2-(ethylsulfonyl)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No. 25):

[0569] A solution of 2-(2-(ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (185 mg, 0.4 mmol) in dichloromethane (6 mL) was added with m-chloroperbenzoic acid (208 mg, 0.8 mmol) portionwise at 0 - 5 °C. The reaction mixture was stirred at 25 °C for 5 h. After completion of the reaction, the reaction mixture was diluted with an aqueous sodium thiosulfate solution and extracted with dichloromethane (15 mL). The dichloromethane layer was washed with a saturated aqueous sodium bicarbonate solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by flash column chromatography on silica gel using 60% ethyl acetate in hexane as an eluent to obtain 2-(2-(ethylsulfonyl)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (120 mg, 0.2 mmol, yield 61%). 1 1H-NMR (400 MHz, DMSO-d6) δ 8.90 (d, J = 4.6 Hz, 1H), 8.85 (d, J = 1.5 Hz, 1H), 8.63 (d, J = 1.5 Hz, 1H), 8.25 - 8.28 (m, 2H), 7.69 (d, J = 4.6 Hz, 1H), 7.53 - 7.59 (m, 2H), 3.81 (s, 3H), 3.73 (q, J = 7.4 Hz, 2H), 1.26 (t, J = 7.3 Hz, 3H); ESI MS (m / z) 505.10 (MH) + .

[0570] Example 11: Synthesis of 2-(7-(3-chloro-5-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound No. 102):

[0571] a) Step 1: 2-cyano-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)acetamide:

[0572] To a stirred solution of 2-cyanoacetic acid (7 g, 82 mmol), N2-methyl-5-(trifluoromethyl)pyridine-2,3-diamine (12.58 g, 65.8 mmol), and hydroxybenzotriazole (HOBt) (15.12 g, 99 mmol) in dimethylformamide (350 mL) were added 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC-HCl) (18.93 g, 99.0 mmol) and N,N-diisopropylethylamine (35.9 mL, 206 mmol). The resulting mixture was stirred at 25 °C for 24 h under a nitrogen atmosphere. After completion of the reaction, water (100 mL) was added to the above reaction mixture, and the reaction mixture was extracted three times with ethyl acetate (100 mL). The combined ethyl acetate layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel using 30% ethyl acetate in hexane as the eluent to give 2-cyano-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)acetamide (11.8 g, 45.7 mmol, 55.5% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 9.61 (s, 1H), 8.26 (d, J = 1.0 Hz, 1H), 7.64 (d, J = 2.4 Hz, 1H), 6.94 (d, J = 4.4 Hz, 1H), 3.83 (d, J = 17.6 Hz, 2H), 2.87 (d, J = 4.6 Hz, 3H); ESI MS (m / z) 258 (M)+.

[0573] b) Step 2: 2-(3-Methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acetonitrile:

[0574] A solution of 2-cyano-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)acetamide (11.8 g, 45.7 mmol) in acetic acid (120 mL) was heated at 100 °C for 2 hours. After completion of the reaction, the reaction mixture was cooled to 25 °C. The reaction mixture was concentrated under reduced pressure to remove acetic acid. Water (100 mL) was added to the concentrated reaction mixture, and the reaction mixture was extracted three times with ethyl acetate (75 mL). The ethyl acetate layer was washed with water (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by flash column chromatography on silica gel using 15% ethyl acetate in hexane as the eluent to obtain 2-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acetonitrile (9.0 g, 37.5 mmol, yield 82%). 1 1H-NMR (400 MHz, DMSO-d6) δ 8.76 (t, J = 1.0 Hz, 1H), 8.55 - 8.56 (m, 1H), 4.69 (s, 2H), 3.82 (s, 3H); ESI MS (m / z) 240.95 (MH)+.

[0575] c) Step 3: 3,3-bis(ethylthio)-2-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acrylonitrile

[0576] To a stirred solution of 2-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acetonitrile (8.8 g, 36.6 mmol) in acetonitrile (80 mL) was added potassium hydroxide (4.84 g, 73.3 mmol) at 25 °C. The resulting reaction mixture was stirred at 25 °C for 1 h. The reaction mixture was further cooled to -5 °C, and carbon disulfide (2.2 mL, 36.6 mmol) was added dropwise over 10 min. The reaction mixture was stirred at -5 °C for 1 h. Further, ethyl iodide (5.92 mL, 73.3 mmol) was added dropwise to the reaction mixture at 0 °C over 15 min. The reaction mixture was stirred at 0 °C for 2 h and then left at 25 °C for 16 h. The reaction mixture was concentrated under reduced pressure. The crude product was purified by flash column chromatography on silica gel using 10% ethyl acetate in hexane as the eluent to give 3,3-bis(ethylthio)-2-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acrylonitrile (12.4 g, 33.3 mmol, 91% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 8.84 (q, J = 1.0 Hz, 1H), 8.62 (q, J = 0.9 Hz, 1H), 3.87 (s, 3H), 3.25 (q, J = 7.3 Hz, 2H), 2.84 (q, J = 7.4 Hz, 2H), 1.37 (t, J = 7.2 Hz, 3H), 1.14 (t, J = 7.3 Hz, 3H); ESI MS (m / z) 373.00 (MH)+.

[0577] d) Step 4: 3-(Ethylthio)-4-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-1H-pyrazol-5-amine

[0578] To a stirred solution of 3,3-bis(ethylthio)-2-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acrylonitrile (1 g, 2.69 mmol) in a mixture of acetonitrile (1 mL) and ethanol (2 mL) was added dropwise hydrazine monohydrate (0.17 mL, 2.69 mmol (79% w / v)) at 0 °C. The reaction mixture was stirred at 0 °C for 1 h. The reaction mixture was diluted with ice-cold water (20 mL) to precipitate the solid. The precipitated solid was filtered, washed with water and dried under vacuum to give the crude product. The crude product was purified by column chromatography on silica gel using 100% ethyl acetate as the eluent to give 3-(ethylthio)-4-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-1H-pyrazol-5-amine (720 mg, 2.1 mmol, 78% yield). 1H-NMR (400 MHz, DMSO-D6) δ 12.01 (s, 1H), 8.66 (s, 1H), 8.37 (s, 1H), 5.75 (s, 2H), 3.77 (s, 3H), 2.88 (q, J = 6.8 Hz, 2H), 1.15 (t, J = 6.8 Hz, 3H); ESI MS (m / z) 343.00 (MH) + .

[0579] e) Step 5: 2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one

[0580] To a stirred solution of 3-(ethylthio)-4-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-1H-pyrazole-5-amine (550 mg, 1.61 mmol) and its non-cyclized intermediate in acetic acid (5 mL) was added methyl 3,3-dimethoxypropionate (0.34 mL, 2.41 mmol). The reaction mixture was heated at 100 °C for 6 h. The reaction mixture was cooled to 25 °C and concentrated under reduced pressure to remove acetic acid. Water (20 mL) was added to the concentrated reaction mixture, and the reaction mixture was extracted three times with ethyl acetate (25 mL). The ethyl acetate layer was washed with water (50 mL), dried over anhydrous sodium sulfate, concentrated under reduced pressure to give a crude product. The crude product was purified by flash column chromatography on silica gel using 5% methanol in dichloromethane as the eluent to give 2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one (375 mg, 0.95 mmol, 59% yield). 1 1H-NMR (400 MHz, DMSO-d6) δ 12.40 (s, 1H), 8.80 (q, J = 0.9 Hz, 1H), 8.56 (dd, J = 2.1, 0.6 Hz, 1H), 7.84 (d, J = 7.3 Hz, 1H), 5.87 (d, J = 7.3 Hz, 1H), 3.77 (s, 3H), 3.16 (q, J = 7.3 Hz, 2H), 1.32 (t, J = 7.3 Hz, 3H); ESI MS (m / z) 395.00 (M-H)+.

[0581] f) Step 6: 2-(7-Bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine

[0582] To a stirred solution of 2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one (1.05 g, 2.66 mmol) in acetonitrile (28 mL) were added potassium carbonate (1.10 g, 7.99 mmol) and phosphorus oxychloride (2.29 g, 7.99 mmol) at 25 °C. The reaction mixture was further heated at 95 °C for 4 h. The reaction mixture was cooled to 0 °C. The reaction mixture was diluted with ice-water mixture (50 mL). The pH of the reaction mixture was adjusted to 7 - 8 by slowly adding saturated aqueous sodium bicarbonate solution. The reaction mixture was extracted three times with ethyl acetate (50 mL). The ethyl acetate layer was washed with water (50 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the crude product. The crude product was purified by flash column chromatography on silica gel using 50% ethyl acetate in hexane as the eluent to give 2-(7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (980 mg, 2.14 mmol, 80% yield). 1 H-NMR(400MHz,DMSO-d6)δ8.77(t,J=1.1Hz,1H),8.55(d,J=1.5Hz,1H),8.48(d,J=4.6Hz,1H),7.65(d,J=4.6Hz,1H),3.92(s,3H),3.25(q,J=7.3Hz,2H),1.40(t,J=7.3Hz,3H);ESI MS(m / z)456.95,458.95(MH;Br 79,81 )+

[0583] g) Step 7: 2-(7-(3-Chloro-5-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine

[0584] A solution of 2-(7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (170 mg, 0.37 mmol) and (3-chloro-5-fluorophenyl)boronic acid (78 mg, 0.446 mmol) in a mixture of tetrahydrofuran (4 mL) and water (2 mL) was added sodium carbonate (197 mg, 1.86 mmol). The reaction mixture was thoroughly deoxygenated by subjecting it to three cycles of vacuum / nitrogen. Tetrakis(triphenylphosphine)palladium(0) (12.9 mg, 0.01 mmol) was added to the reaction mixture and heated at 85 °C for 4 h. After completion of the reaction, the reaction mixture was cooled to 25 °C and filtered through a pad of celite. The filtrate was concentrated under reduced pressure and the crude product was purified by flash column chromatography on silica gel using 20% ethyl acetate in hexane as eluent to give 2-(7-(3-chloro-5-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (120 mg, 0.24 mmol, 64% yield). 1 H-NMR (400 MHz, DMSO-d6) δ 8.77 - 8.79 (m, 2H), 8.55 (d, J = 1.5 Hz, 1H), 8.23 (d, J = 1.5 Hz, 1H), 8.10 (dq, J = 9.7, 1.2 Hz, 1H), 7.79 (dt, J = 8.8, 2.1 Hz, 1H), 7.55 (d, J = 4.6 Hz, 1H), 3.96 (s, 3H), 3.16 (q, J = 7.3 Hz, 2H), 1.40 (t, J = 7.2 Hz, 3H); ESI MS (m / z) 506.95, 508.95 (MH; Cl 35,37 )+.

[0585] Example 12: Synthesis of 3-(7-(3,5-dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine (Compound No. 111)

[0586] a) Step 1: 2-Hydrazinyl-5-(trifluoromethyl)pyridine:

[0587] Hydrazine hydrate (5.18 g, 123 mmol) was added to a stirred solution of 2-chloro-5-(trifluoromethyl)pyridine (10.0 g, 55.1 mmol) in ethanol. The resulting reaction mixture was stirred at 90 °C for 16 h. The reaction mixture was cooled to 25 °C and concentrated under reduced pressure to remove ethanol. Water (50 mL) was added to the concentrated reaction mixture, and the reaction mixture was extracted three times with ethyl acetate (200 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 2-hydrazinyl-5-(trifluoromethyl)pyridine (8.50 g, 48.00 mmol, 87% yield). 1 H-NMR (400 MHz, DMSO-d6) δ 8.25 (d, J = 0.7 Hz, 2H), 7.68 (dd, J = 9.0, 2.4 Hz, 1H), 6.78 (d, J = 9.0 Hz, 1H), 4.32 (s, 2H); ESI MS (m / z) 178.10 (MH) + .

[0588] b) Step 2: 7-(3,5-Dichlorophenyl)-2-(ethylthio)-N'-(5-(trifluoromethyl)pyridin-2-yl)pyrazolo[1,5-a]pyrimidine-3-carbohydrazide:

[0589] To a stirred solution of 2-hydrazinyl-5-(trifluoromethyl)pyridine (0.80 g, 4.52 mmol) in N,N-dimethylformamide (8 mL) were added 7-(3,5-dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (1.66 g, 4.52 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (1.29 g, 6.77 mmol), 1-hydroxybenzotriazole (0.91 g, 6.77 mmol), and N,N-diisopropylethylamine (1.75 mL, 13.55 mmol) at 0 °C. The reaction mixture was stirred at 25 °C for 16 h under a nitrogen atmosphere. After completion of the reaction, water (20 mL) was added to the reaction mixture, and the resulting precipitate was filtered and dried under reduced pressure to give 7-(3,5-dichlorophenyl)-2-(ethylthio)-N'-(5-(trifluoromethyl)pyridin-2-yl)pyrazolo[1,5-a]pyrimidine-3-carbohydrazide (1.2 g, 2.27 mmol, 50% yield). 1 H-NMR (400 MHz, DMSO-d6) δ 9.78 (s, 1H), 9.39 (s, 1H), 8.83 (dd, J = 11.9, 4.6 Hz, 1H), 8.42 (d, J = 20.2 Hz, 1H), 8.24 - 8.29 (m, 2H), 7.91 - 7.99 (m, 1H), 7.84 (dd, J = 8.9, 2.1 Hz, 1H), 7.58 - 7.61 (m, 1H), 6.77 (d, J = 8.7 Hz, 1H), 3.09 (q, J = 7.2 Hz, 2H), 1.40 (t, J = 7.2 Hz, 3H); ESI MS (m / z) 527.25 (MH) + .

[0590] c) Step 3: 3-(7-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine:

[0591] To 7-(3,5-dichlorophenyl)-2-(ethylthio)-N'-(5-(trifluoromethyl)pyridin-2-yl)pyrazolo[1,5-a]pyrimidine-3-carbohydrazide (1 g, 1.90 mmol), phosphoryl chloride (3 mL) was added, and the resulting reaction mixture was heated at 90 °C for 6 h. The reaction mixture was cooled to 25 °C and concentrated under reduced pressure. The reaction mixture was further cooled to 0 °C, and the resulting mass was treated with saturated sodium bicarbonate solution to make the pH basic (pH 9). The resulting mixture was extracted three times with ethyl acetate (50 mL). The combined ethyl acetate layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel using 25% ethyl acetate in hexane as the eluent to give 3-(7-(3,5-dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine (500 mg, 0.98 mmol, yield 52%). 1 1H-NMR (400 MHz, DMSO-d6) δ 9.09 (d, J = 1.0 Hz, 1H), 8.72 (d, J = 4.4 Hz, 1H), 8.32 (d, J = 2.0 Hz, 2H), 8.09 (d, J = 9.8 Hz, 1H), 7.96 (t, J = 2.0 Hz, 1H), 7.68 (dd, J = 9.7, 1.6 Hz, 1H), 7.56 - 7.58 (m, 1H), 3.17 (q, J = 7.3 Hz, 2H), 1.42 (t, J = 7.3 Hz, 3H); ESI MS (m / z) 508.70 (MH)+.

[0592] d) Step 4: 3-(7-(3,5-dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidine-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine:

[0593] A solution of 3-(7-(3,5-dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine (0.35 g, 0.68 mmol) in dichloromethane (8 mL) was added with m-chloroperbenzoic acid (0.58 g, 2.06 mmol, 60%) at 0 °C. The resulting reaction mixture was stirred at 25 °C for 16 h. The reaction mixture was diluted with dichloromethane (20 mL), washed twice with saturated aqueous sodium bicarbonate solution (20 mL), and then washed with water (10 mL). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel using 30% ethyl acetate in hexane as the eluent to obtain 3-(7-(3,5-dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine (210 mg, 0.388 mmol, yield 56%). 1 1H-NMR (400 MHz, DMSO-d6) δ 8.90 (d, J = 4.4 Hz, 2H), 8.24 (d, J = 1.7 Hz, 2H), 8.15 (d, J = 9.5 Hz, 1H), 8.01 (t, J = 2.0 Hz, 1H), 7.82 (d, J = 4.6 Hz, 1H), 7.74 (dd, J = 9.7, 1.6 Hz, 1H), 3.62 (q, J = 7.3 Hz, 2H), 1.27 (t, J = 7.5 Hz, 3H); ESI MS (m / z) 540.90 (MH)+.

[0594] Example 13: Synthesis of (7-(3,5-dichlorophenyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ 6 -sulfanone (Compound No. 135):

[0595] To a stirred solution of 2-(7-(3,5-dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (312 mg, 0.60 mmol) and ammonium carbamate (140 mg, 1.79 mmol) in methanol (6 mL) was added iodosobenzene diacetate (384 mg, 1.19 mmol) at 0 °C. The resulting reaction mixture was stirred at 25 °C for 16 h. The reaction mixture was concentrated under reduced pressure. The crude residue was diluted with water (20 mL) and the mixture was extracted three times with ethyl acetate (50 mL). The ethyl acetate layer was washed with water (30 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the crude product. The crude product was purified by preparative HPLC to give (7-(3,5-dichlorophenyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-λ 6 -sulfanone (110 mg, 0.2 mmol, 44% yield). 1H-NMR (400 MHz, DMSO-d6) δ 8.90 (d, J = 4.4 Hz, 1H), 8.84 (d, J = 1.2 Hz, 1H), 8.62 (t, J = 1.1 Hz, 1H), 8.25 (d, J = 2.0 Hz, 2H), 7.98 (t, J = 2.0 Hz, 1H), 7.75 (d, J = 4.4 Hz, 1H), 4.80 (s, 1H), 3.81 (s, 3H), 3.49 - 3.56 (m, 2H), 1.28 (t, J = 7.5 Hz, 3H); ESI MS (m / z) 554.00 (MH)+.

[0596] The following compounds (Table-1) were obtained using similar procedures as described in Schemes 1 - 23 or the Examples.

[0597]

Table 1-1

[0598]

Table 1-2

[0599]

Table 1-3

[0600]

Table 1-4

[0601]

Table 1-5

[0602]

Table 1-6

[0603]

Table 1-7

[0604]

Table 1-8

[0605]

Table 1-9

[0606]

Table 1-10

[0607]

Table 1-11

[0608]

Table 1-12

[0609]

Table 1-13

[0610]

Table 1-14

[0611]

Table 1-15

[0612]

Table 1-16

[0613]

Table 1-17

[0614]

Table 1-18

[0615]

Table 1-19

[0616]

Table 1-20

[0617]

Table 1-21

[0618]

Table 1-22

[0619]

Table 1-23

[0620] The compound names were created using Chemdraw Professional 18.1

[0621] The following compounds (Table 2) can be obtained using similar procedures described in Schemes 1 - 23 or in the Examples

[0622]

Table 2 - 1

[0623]

Table 2 - 2

[0624]

Table 2 - 3

[0625] The compound names were created using Chemdraw Professional 18.1

[0626] As described herein, the compounds of formula (I) exhibit insecticidal activity against a number of insects that attack important crops. As described in the following tests, the compounds of the invention were evaluated for their activity:

[0627] Biological Examples

[0628] Example A: Helicoverpa armigera

[0629] The diet incorporation method was used where the required amount of the test compound was weighed, dissolved in a surfactant solution, vortexed for 90 minutes for proper mixing, and then diluted with water to the desired test concentration. When the temperature reached about 50 °C in the bioassay container, the solution was incorporated into the semi-synthetic diet. The diet and the solution were stirred well for proper mixing and then cooled for 30 minutes. The solidified diet was cut into equal portions and each piece was transferred to one cell of the bioassay tray. A single starved third-instar larva was released into each of these cells of the bioassay tray and each tray was covered with a lid. The bioassay tray was maintained under laboratory conditions of 25 °C temperature and 70% relative humidity. Observations of dead larvae, moribund larvae, and living larvae were recorded 96 hours after the larvae were released. Mortality was calculated by combining dead and moribund larvae and comparing the result with one of the untreated controls. Compounds 15, 21, 25, 26, 27, 28, 32, 39, 83, 87, 90, 91, 93, 97, 99, 101, 102, 103, 104, 109, 118, 120, 126, and 136 showed activity with a mortality rate exceeding 70% at 300 PPM.

[0630] Example B: Spodoptera litura

[0631] A diet uptake method was used in which the necessary amount of the test compound was weighed, dissolved in a surfactant solution, vortexed for 90 minutes for proper mixing, and then diluted with water to the desired test concentration. When the temperature in the bioassay container reached about 50 °C, the solution was incorporated into the semi-synthetic diet. The diet and the solution were stirred well for proper mixing and cooled for 30 minutes. The solidified diet was cut into equal portions and each piece was transferred to one cell of the bioassay tray. Single starved third instar larvae were released into each of these cells of the bioassay tray and the tray was covered with a lid. The bioassay tray was maintained under laboratory conditions of a temperature of 25 °C and a relative humidity of 70%. Observations of dead larvae, moribund larvae, and live larvae were recorded 96 hours after the larvae were released. Mortality was calculated by combining dead and moribund larvae and comparing the result with one of the untreated controls. Compounds 15, 21, 25, 26, 37, 63, 83, 87, 90, 93, 101, 103, 118, 126, 129, and 134 showed activity with a mortality rate exceeding 70% at 300 PPM.

[0632] Example C: Plutella xylostella

[0633] The leaf dip method was used in the test, where the required amount of the compound was weighed, dissolved in a surfactant solution, vortexed at 2000 rpm for 90 minutes using zirconia beads for proper mixing, and then diluted with 0.01% Triton-X solution to the desired test concentration. The cabbage leaves were dipped in the solution for 10 seconds, dried in the shade for 20 minutes, and then transferred to a bioassay tray. Newly hatched 1-day-old larvae were released into the cells of each bioassay tray, and the tray was covered with a lid. The bioassay tray was maintained under laboratory conditions of a temperature of 25 °C and a relative humidity of 70%. Observations of dead larvae, moribund larvae, and living larvae were recorded 72 hours after the larvae were released. Mortality was calculated by combining dead and moribund larvae and comparing the result with one of the untreated controls. Compounds 5, 6, 9, 12, 15, 18, 20, 21, 22, 25, 26, 27, 28, 29, 30, 32, 34, 35, 37, 39, 40, 43, 46, 48, 50, 62, 63, 66, 67, 69, 70, 71, 74, 80, 81, 83, 87, 88, 90, 91, 93, 95, 96, 99, 100, 101, 103, 104, 109, 114, 115, 118, 119, 129, 130, 131, 133, 135, 136, and 137 showed activities with mortality rates exceeding 70% at 300 PPM.

[0634] Example D: Bemisia tabaci The leaf dip method was used in the test, where the required amount of the test compound was weighed, dissolved in a surfactant solution, vortexed at 2000 rpm for 90 minutes using zirconia beads for proper mixing, and then diluted with 0.01% Triton-X solution to the desired test concentration. Cotton leaves were dipped in the solution for 10 seconds, dried in the shade for 20 minutes, and then maintained in a glass unit while being dipped in water. A known number of newly used adults were released and maintained in a plant growth chamber at a temperature of 25 °C and a relative humidity of 70%. Observations of dead adults, moribund adults, and living adults were recorded 72 hours after release. Mortality was calculated by combining dead and moribund adults and comparing the result with one of the untreated controls. Compounds 22 and 119 showed activities with mortality rates exceeding 70% at 300 PPM.

[0635] Example E: Myzus persicae

[0636] The leaf immersion method was used in the test. The required amount of the test compound was weighed, dissolved in a surfactant solution, vo...

Claims

1. A compound of formula (I), 【Chemical 1】 Formula (I) wherein R １ is C １ to C ６ -alkyl and Y is independently O or NR Ｙ selected from R Ｙ is selected from the group consisting of hydrogen, cyano, C １ to C ４ -alkyl, C ２ to C ４ -alkenyl, C ２ to C ４ -alkynyl, C １ to C ４ -haloalkyl, C ２ to C ４ -haloalkenyl, C ３ to C ５ -cycloalkyl, and C ３ to C ５ -cycloalkyl-C １ to C ３ -alkyl, and is selected from the group consisting of the condensed rings D and E are selected from the following DE-1 to DE-15, 【Chemical Formula 2】 Here, # indicates the bonding point to the ring Q, and ● indicates the group -S(Y) ｍ R １ indicates the bonding point to, and n is an integer from 0 to 4 R ２ is selected from the group consisting of hydrogen, halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ８ -cycloalkyl, C ６ to C １０ -aryl, C ７ to C １４ -aralkyl, and C ３ to C １０ -heterocyclyl, and each aliphatic group may be optionally substituted with one or more R ２ａ groups, and the cyclic group of R ２ may be optionally substituted with one or more R ２ｂ groups. R ２ａ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ３ to C ８ -cycloalkyl, OR ４ , CR ４ =NR ５ , NR ５ R ６ , S(O) ０～２ R ７ , C(=O)R ８ , S(O) ０～１ R ９ =NR １０ , N=S(O) ０～１ (R ９ ) ２ , Si(R') ３ , C ６ to C １０ -aryl, C ７ to C １４ -aralkyl, and C ３ to C １０ -heterocyclyl, and is selected from the group consisting of: R ２ｂ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ８ -cycloalkyl, OR ４ , CR ４ =NR ５ , NR ５ R ６ , S(O) ０～２ R ７ , C(=O)R ８ , Si(R') ３ , S(O) ０～１ R ９ =NR １０ , and N=S(O) ０～１ (R ９ ) ２ and is selected from the group consisting of Q is selected from the following Q1a to Q10b, 【Chemical 3】 Here, # indicates the bonding point to the condensed ring D, and ● indicates the group - S(Y) ｍ R １ indicates the bonding point to, and n is an integer from 0 to 4 R ３ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ８ -cycloalkyl, S(O) ０～２ R ７ and S(O) ０～１ R ９ =NR １０ ; each aliphatic group may be optionally substituted with one or more R ３ａ groups, and the cyclic group of R ３ may be optionally substituted with one or more R ３ｂ groups. R ３ａ is selected from the group consisting of halogen and cyano, R ３ｂ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, and C １ to C ６ -haloalkyl, Two Rs ３ together with the atoms to which they are attached, or together with further atoms selected from the group consisting of C, N, O, S, optionally contain 1 to 3 ring members selected from the group consisting of C(=O), C(=S), S(O) ｍ , and Si(R')[[]]END]] ２ to form a 3- to 7-membered ring, which 3- to 7-membered ring may optionally be substituted at a part thereof with one or more groups selected from the group consisting of halogen, cyano, R ３ｃ , OR ３ｃ , SR ３ｃ , NR ３ｃ ２ , Si(R ３ｃ ), ３ , COOR ３ｃ , and CONR ３ｃ ２ . R ３ｃ is selected from the group consisting of hydrogen, halogen, linear or branched C １ to C ６ -alkyl, and cyclic C ３ to C ８ -alkyl, and the group of R ３ｃ is optionally substituted with one or more halogens, R １１ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ８ -cycloalkyl, OR ４ , CR ４ =NR ５ , NR ５ R ６ , S(O) ０～２ R ７ , C(=O)R ８ , S(O) ０～１ R ９ =NR １０ , N=S(O) ０～１ (R ９ ) ２ , P(=O)(OR')[[]END]] ２ , Si(R')[[]END]] ３ , C ６ to C １０ -aryl, C ７ to C １４ -aralkyl, and C ３ to C １０ -heterocyclyl, and each aliphatic group may be optionally substituted with one or more R １１ａ groups, and the cyclic group of R １１ may be optionally substituted with one or more R １１ｂ groups. R １１ａ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ３ to C ８ -cycloalkyl, OR ４ , CR ４ =NR ５ , NR ５ R ６ , S(O) ０～２ R ７ , C(=O)R ８ , S(O) ０～１ R ９ =NR １０ , N=S(O) ０～１ (R ９ ) ２ , Si(R') ３ , C ６ to C １０ -aryl, C ７ to C １４ -aralkyl, and C ３ to C １０ -heterocyclyl, and is selected from the group consisting of: R １１ｂ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ８ -cycloalkyl, OR ４ , C(R') ２ -NR ５ R ６ , C(R') ２ -OR ４ , CR ４ =NR ５ , NR ５ R ６ , S(O) ０～２ R ７ , C(=O)R ８ , S(O) ０～１ R ９ =NR １０ , N=S(O) ０～１ (R ９ ) ２ , Si(R') ３ , C ６ to C １０ -aryl, C ７ to C １４ -aralkyl, and C ３ to C １０ -heterocyclyl, and is selected from the group consisting of R ４ is selected from the group consisting of hydrogen, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ８ -cycloalkyl, and C ６ to C １０ -aryl, and each aliphatic group may optionally be substituted with R ４ａ , and the cyclic group of R ４ may optionally be substituted with one or more R ４ｂ groups, R ４ａ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ３ to C ８ -cycloalkyl, OR', NR'R'', and S(O) ０～２ R', and is selected from the group consisting of R ４ｂ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, and C １ to C ６ -haloalkyl, R ５ is selected from the group consisting of hydrogen, C １ ~C ６ -alkyl, C ２ ~C ６ -alkenyl, C ２ ~C ６ -alkynyl, C １ ~C ６ -haloalkyl, C ２ ~C ６ -haloalkenyl, C ３ ~C ８ -cycloalkyl, OR ４ , NR'R'', S(O) ０～２ R ７ , C(=O)R ８ , Si(R') ３ , C ６ ~C １０ -aryl, C ７ ~C １４ -aralkyl, and C ３ ~C １０ -heterocyclyl, and each aliphatic group may be optionally substituted with R ５ａ , and the cyclic group of R ５ may be optionally substituted with one or more R ５ｂ groups, R ５ａ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ３ to C ８ -cycloalkyl, OR', NR'R'', S(O) ０～２ R', C(=O)R', Si(R') ３ , C ６ to C １０ -aryl, C ７ to C １４ -aralkyl, and C ３ to C １０ -heterocyclyl, R ５ｂ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ８ -cycloalkyl, OR', NR'R'', S(O) ０～２ R', Si(R') ３ , C(=O)R', C ６ to C １０ -aryl, C ７ to C １４ -aralkyl and C ３ to C １０ -heterocyclyl, and is selected from the group consisting of R ６ is selected from the group consisting of hydrogen, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ６ -cycloalkyl, and C(=O)R ８ and is selected from the group consisting of R ７ is selected from the group consisting of C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ８ -cycloalkyl, NR ５ R ６ , C ６ to C １０ -aryl, C ７ to C １４ -aralkyl and C ３ to C １０ -heterocyclyl, and each aliphatic group may be optionally substituted with one or more R ７ａ groups, and the cyclic group of R ７ may be optionally substituted with one or more R ７ｂ groups. R ７ａ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ３ to C ８ -cycloalkyl, OR', NR'R'', S(O) ０～２ R', C(=O)R', C ６ to C １０ -aryl, C ７ to C １４ -aralkyl, and C ３ to C １０ -heterocyclyl; R ７ｂ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ８ -cycloalkyl, OR', NR'R'', S(O) ０～２ R', C(=O)R', C ６ to C １０ -aryl, C ７ to C １４ -aralkyl, and C ３ to C １０ -heterocyclyl, and is selected from the group consisting of R ８ is hydrogen, C １ ~C ６ -alkyl, C ２ ~C ６ -alkenyl, C ２ ~C ６ -alkynyl, C １ ~C ６ -haloalkyl, C ２ ~C ６ -haloalkenyl, C ３ ~C ８ -cycloalkyl, OR ４ , NR ５ R ６ , N = S(O) ０～１ (R ９ ) ２ , C ６ ~C １０ -aryl, C ７ ~C １４ -aralkyl and C ３ ~C １０ -heterocyclyl selected from the group consisting of, each aliphatic group may be optionally substituted with one or more R ８ａ groups, and the cyclic group of R ８ may be optionally substituted with one or more R ８ｂ groups. R ８ａ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ３ to C ８ -cycloalkyl, OR', NR'R'', S(O) ０～２ R', C(=O)R', C ６ to C １０ -aryl, C ７ to C １４ -aralkyl, and C ３ to C １０ -heterocyclyl, R ８ｂ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ８ -cycloalkyl, OR', NR'R'', S(O) ０～２ R', C(=O)R', C ６ to C １０ -aryl, C ７ to C １４ -aralkyl, and C ３ to C １０ -heterocyclyl, R ９ is selected from the group consisting of C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ８ -cycloalkyl, and C(=O)R ８ and is selected from the group consisting of: R １０ is selected from the group consisting of hydrogen, cyano, C １ to C ６ -alkyl, C ２ to C ６ -alkenyl, C ２ to C ６ -alkynyl, C １ to C ６ -haloalkyl, C ２ to C ６ -haloalkenyl, C ３ to C ８ -cycloalkyl, Si(R') ３ , S(O) ０～２ R ７ , and C(=O)R ８ and is selected from the group consisting of R' is halogen, cyano, R'', OR'', N(R''), ２ , S(O) ０～２ R'', C(=O)R'', C(=O)OR'', and C(=O)N(R'')[[]] ２ R ８ selected from the group consisting of R’’ is hydrogen, C １ ~C ６ -alkyl, C ２ ~C ６ -alkenyl, C ２ ~C ６ -alkynyl, C １ ~C ６ -haloalkyl, and C ３ ~C ８ -cycloalkyl, and is each optionally substituted with halogen, R １ ~R １１ 、R ２ａ 、R ２ｂ 、R ２ａｂ 、R ３ａ 、R ３ｂ 、R ３ａｂ 、R ３ｃ 、R ４ａ 、R ４ｂ 、R ５ａ 、R ５ｂ 、R ７ａ 、R ７ｂ 、R ８ａ 、and R ８ｂ Each group of R, R', OR', SR', N(R') ２ 、COOR', and CON(R') ２ may be optionally substituted with one or more groups selected from the group consisting of, m is an integer in the range of 0 to 2, a compound, or an agriculturally acceptable salt, stereoisomer, diastereoisomer, enantiomer, tautomer, polymorph, metal complex, or N-oxide thereof.

2. Q is selected from the following, 【Chemical Formula 4】 wherein # indicates the point of attachment to the condensed ring D, R ３ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C １ to C ６ -haloalkyl, C ３ to C ８ -cycloalkyl, and S(Y) ０～２ R ７ and is selected from the group consisting of R ６ is selected from the group consisting of hydrogen, C １ to C ６ -alkyl, and C ３ to C １０ -cycloalkyl, the condensed rings D and E are selected from the following, [Chemical Formula 5] Here, # indicates the bonding point to the ring Q, and ● indicates the group -S(Y) ｍ R １ and indicates the bonding point to R ２ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C １ to C ６ -haloalkyl, C ３ to C ８ -cycloalkyl, C ６ to C ８ -aryl, C ７ to C ９ -aralkyl, and C ３ to C ６ -heterocyclyl, and each aliphatic group may optionally be substituted with one or more R ２ａ groups, and the cyclic group of R ２ may optionally be substituted with one or more R ２ｂ groups. m is an integer in the range of 0 to 2, n is an integer in the range of 0 to 4, R １１ is selected from the group consisting of halogen, cyano, C １ to C ６ -alkyl, C １ to C ６ -haloalkyl, C ３ to C ８ -cycloalkyl, OR ４ , NR ５ R ６ , C ６ to C １０ -aryl, C ７ to C １４ -aralkyl, and C ３ to C １０ -heterocyclyl, and each aliphatic group may be optionally substituted with one or more R １１ａ groups, and the cyclic group of R １１ may be optionally substituted with one or more R １１ｂ groups. the compound according to claim 1.

3. The compound is 2-(1-(3,5-dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(ethylsulfonyl)imidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 6-(1-bromo-2-(ethylsulfonyl)indolizin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine; 2-(2-(ethylsulfonyl)imidazo[1,2-a]pyridin-3-yl)-5-(trifluoromethyl)benzo[d]oxazole; 2-(2-(ethylsulfonyl)-7-(trifluoromethyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(8-(3,5-dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(1-(3,5-dichlorophenyl)-2-(ethylsulfonyl)-7-(trifluoromethyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-(3,5-dichlorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole; 2-(2-(Ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5,7-dimethylpyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole; 2-(2-(Ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole; 2-(2-(Ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole; 2-(2-(Ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-7-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-7-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole; 2-(2-(Ethylsulfonyl)-7-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole; 2-(2-(Ethylthio)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole; 2-(2-(Ethylsulfonyl)-7-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole; 2-(7-(4-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(4-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(4-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(4-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole; 2-(7-(4-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(4-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole; 2-(7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole; 2-(7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole; 2-(2-(Ethylthio)-5-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-5-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-5-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-Chloro-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-6-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-Chloro-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-Chloro-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-Chloro-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-6-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-5-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-(4-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-5-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-5-(4-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-(4-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-6-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(5-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-6-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(5-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(5-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(5-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-Bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-Bromo-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-(4-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-(4-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-5-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-5-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-5-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-5-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(6-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(6-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-6-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-6-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(5-(4-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(5-(4-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-6-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylthio)-7-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(5-(4-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(5-(4-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-7-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 3-(7-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine; 2-(2-(Ethylthio)-7-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 3-(7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine; 2-(2-(Ethylthio)-6-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-6-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3-Chlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3,5-Difluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3-Chlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-6-(4-(trifluoromethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3,5-Difluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3-Chloro-5-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3-Chloro-5-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3,4-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 7-(3,5-Dichlorophenyl)-2-(ethylthio)-3-(1-methyl-5-(trifluoromethyl)-1H-benzo[d]imidazol-2-yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylthio)-3-(1-methyl-5-(trifluoromethyl)-1H-benzo[d]imidazol-2-yl)pyrazolo[1,5-a]pyrimidine; 7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)-3-(1-methyl-5-(trifluoromethyl)-1H-benzo[d]imidazol-2-yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylsulfonyl)-3-(1-methyl-5-(trifluoromethyl)-1H-benzo[d]imidazol-2-yl)pyrazolo[1,5-a]pyrimidine; 2-(2-(ethylsulfonyl)-6-(4-(1,1,2,2-tetrafluoroethoxy)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 3-(7-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine; 3-(7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine; 2-(7-(2,3-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(ethylthio)-7-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(2,3-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-phenylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(4-Chloro-3-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3,5-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(4-Chloro-3-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(4-Chloro-3-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(2,4-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(2,4-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(2,4-Dichlorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3-Chloro-5-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3-Chloro-5-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3,5-Bis(trifluoromethyl)phenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(3-(trifluoromethyl)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(3-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(3,5-Bis(trifluoromethyl)phenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(3-(trifluoromethyl)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(3-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-methylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(3-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(Ethylsulfonyl)-7-methylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylthio)-7-(3-(trifluoromethyl)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; (7-(3,5-dichlorophenyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-6-sulfanone; 2-(2-(ethylsulfonyl)-7-(3-(trifluoromethyl)phenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(ethylsulfonyl)-7-(3-fluorophenyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(2-(ethylthio)-7-methylpyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine; 2-(7-(3-chloro-4-fluorophenyl)-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(ethylthio)-5,7-bis(trifluoromethyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(ethylsulfonyl)-5,7-bis(trifluoromethyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one; 2-(7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(ethylsulfonyl)-N-methyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 6-(8-(4-Chloro-3-fluorophenyl)-2-(ethylsulfonyl)indolizin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine; 2-(2-(Ethylsulfonyl)-7-(5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(Ethylthio)-N-methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2-(2-(Ethylsulfonyl)-7-(3-fluorophenoxy)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 6-(8-(4-Chloro-3-fluorophenyl)-2-(ethylsulfonyl)imidazo[1,2-a]pyridin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine; 2-(6-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)imidazo[1,2-a]pyrazine; 4-(2-(Ethylsulfonyl)-3-(7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazin-6-yl)indolizin-8-yl)-2-fluorobenzonitrile; 2-(8-(Cyclopropylmethyl)-2-(ethylsulfonyl)imidazo[1,2-a]pyridin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-(4-Chloro-1H-pyrazol-1-yl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(5-methyl-1H-1,2,4-triazol-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(1-methyl-1H-pyrazol-5-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-Cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyrazine; 2-(2-(Ethylsulfonyl)-7-(1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine; 4-(2-(Ethylsulfonyl)-3-(7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)morpholine; 2-(7-(4-Chloro-3-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidine; 2-(2-(Ethylsulfonyl)-7-(1H-1,2,4-triazol-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidine; 2-(2-(Ethylsulfonyl)-5,7-bis(trifluoromethyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 6-(1-Bromo-2-(ethylsulfonyl)-8-methylindolizin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine; 6-(8-Bromo-2-(ethylsulfonyl)indolizin-3-yl)-3-(difluoromethyl)-7-methyl-7H-imidazo[4,5-c]pyridazine; 2-(2-(Ethylsulfonyl)-7-methoxypyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(2-(Ethylsulfonyl)-7-(methylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(Ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-thione; 2-(2-(Ethylsulfonyl)-7-(1,1,2,2-tetrafluoroethoxy)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine; 2-(7-Ethoxy-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)imidazo[1,2-a]pyrazine; Diethyl ((2-(ethylsulfonyl)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)-16-sulfanon; 2-(Ethylsulfonyl)-N,N-dimethyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)imidazo[1,2-a]pyridin-8-amine; 6-(2-(Ethylsulfonyl)-7-(5-(trifluoromethyl)pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine; 2-(7-(4-Chloro-3-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3,5-dimethyl-6-(trifluoromethyl)-3,5-dihydro-4H-imidazo[4,5-c]pyridin-4-one; 2-(2-(Ethylsulfonyl)-7-(3-(trifluoromethyl)-1H-1,2,4-triazol-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3,5-dimethyl-6-(trifluoromethyl)-3,5-dihydro-4H-imidazo[4,5-c]pyridin-4-one; 2-(7-(3-Chloro-5-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyrazine; 2-(7-(3,5-Dichlorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidine; 2-(7-(4-Chloro-3-fluorophenyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-methyl-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidin-5(6H)-one; 2-(7-(5-Chloropyridin-2-yl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine; 2-(2-(Ethylsulfonyl)-7-(5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-methyl-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidin-5(6H)-one; 2-(2-(Ethylsulfonyl)-7-(3-(trifluoromethyl)-1H-1,2,4-triazol-1-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-c]pyrimidine; Ethyl (3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(methylimino)-16-sulfanon, selected from The compound according to claim 1.

4. A composition for controlling or preventing insect and / or mite pests, A biologically effective amount of the compound according to claim 1, or an agriculturally acceptable salt, stereoisomer, diastereoisomer, enantiomer, tautomer, polymorph, metal complex, or N-oxide thereof, and At least one additional component selected from the group consisting of surfactants and adjuvants, Composition.

5. Further comprising at least one additional biologically active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, or nutrients The composition according to claim 4.

6. The biologically effective amount of the compound is in the range of 0.1 to 99% by weight based on the total weight of the composition. The composition according to claim 4.

7. The biologically effective amount of the compound is in the range of 5 to 50% by weight based on the total weight of the composition. The composition according to claim 4.

8. A biologically effective amount of the compound according to claim 1 and At least one additional biologically active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, and nutrients, comprising Mixture.

9. A method for controlling insect and mite pests, comprising Contacting the insect and mite pests, their habitats, breeding grounds, food supplies, plants, seeds, soil, areas, materials, or environments where the insect and mite pests grow or can grow, or materials, plants, seeds, soil, surfaces, or spaces protected from pest attacks or invasions, with a biologically effective amount of the compound, or a salt, metal complex, N-oxide, stereoisomer, diastereoisomer, enantiomer, tautomer, or polymorph thereof, contained in the composition according to claim 1, or the composition according to claim 4, or the mixture according to claim 8. Method.

10. A method for protecting crops from attack or invasion by insects and mite pests, comprising Contacting the crop with a biologically effective amount of the compound, or a salt, metal complex, N-oxide, stereoisomer, diastereoisomer, enantiomer, tautomer, or polymorph thereof, contained in the composition according to claim 1, or the composition according to claim 4, or the mixture according to claim 8. Method.

11. Applying an effective dosage amount of the compound in the range of 1 gai to 5000 gai per hectare to agricultural or horticultural crops, comprising The method according to claim 9 or 10.

12. A method for protecting seeds, plants, and plant parts from soil insects and protecting the roots and shoots of seedlings from soil and foliar insects, comprising contacting the seeds with a biologically effective amount of a compound, or a salt, metal complex, N-oxide, stereoisomer, diastereoisomer, enantiomer, tautomer or polymorph thereof, contained in the composition according to claim 1 or claim 4 or the mixture according to claim 8, before and / or after green cutting and / or after germination Method

13. Use of a compound, or a salt, metal complex, N-oxide, stereoisomer, diastereoisomer, enantiomer, tautomer or polymorph thereof, contained in the composition according to claim 1 or claim 4 or the mixture according to claim 8, for controlling insect and mite pests in agricultural and horticultural crops Use

14. The use according to claim 13, wherein the agricultural crops are cereals, maize, sorghum, bajra, rice, soybeans, oilseed and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus fruits and citrus trees, any horticultural plants, cucurbitaceous plants, oil-producing plants, tobacco, coffee, tea, cocoa, sugar beet, sugar cane, cotton, potatoes, tomatoes, onions, peppers, other vegetables, and ornamental plants The use according to claim 13

15. A seed comprising a compound, or a salt, metal complex, N-oxide, stereoisomer, diastereoisomer, enantiomer, tautomer or polymorph thereof, contained in the composition according to claim 1 or claim 4 or the mixture according to claim 8 wherein the amount of the compound in the seed ranges from 0.0001% to 1% by weight Seed

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