Alkenyl group containing aromatic carboxamide compounds and their use thereof

Abstract

The present invention discloses an alkenyl group containing aromatic carboxamide compounds of formula (I), wherein, ring-A, Q, R1a, R1b, R2, R3a and R3b are as defined in the detailed description. The present invention further discloses methods for their preparation and the use of the compounds of formula (I) as pest control agents.

Description

[0001] Title: ALKENYL GROUP CONTAINING AROMATIC CARBOXAMIDE COMPOUNDS AND THEIR USE THEREOF

[0002] FIELD OF THE INVENTION:

[0003] The present invention relates to compounds of formula (I). More particularly, the present invention relates to aromatic carboxamide compounds of formula (I) containing an alkenyl group and a process for the preparation thereof. The present invention further relates to compositions comprising these compounds, and to their use as pest control agents.

[0004] BACKGROUND OF THE INVENTION:

[0005] Invertebrate pests, in particular arthropods and nematodes, destroy growing and harvested crops causing severe economic loss to the food supply. Further, insects attack on wooden dwellings and commercial structures, thereby causing large economic losses to property. Therefore, there is an ongoing need for new agents for combating invertebrate pests such as insects, arachnids and nematodes. The currently available modem insecticides and acaricides must satisfy many requirements, for example regarding the level of activity, long lasting efficacy, broadness of insecticidal spectrum and other beneficial effects, and the possible use thereof. Efforts have been made during the past decades to develop selective insecticides that are acting specifically on biochemical modes of action being present only in insects or mites, but additionally showing properties that differ from known insecticides in an advantageous way.

[0006] Certain heteroaryl-azole compounds for the use in controlling ectoparasites on animals and for the control of animal pests including arthropods and insects in the field of plant protection are disclosed in the prior art for example: W02021099303, WO 2020002563, WO 2020053364, WO 2020053365, WO 2020079198, WO 2020094363, WO 2019197468, WO 2019201835, WO 2019202077 and WO 2019206799.

[0007] However, there is still a continuous need for new compounds which are more effective in combating invertebrate pests, but are less toxic and environmentally safer and / or have different modes of action. Surprisingly, it has now been found that the certain novel pesticidally active aromatic carboxamide compounds containing an alkenyl group, being the subject of this invention, have favorable properties as pesticides and are environmentally safer, as desired.

[0008] SUMMARY OF THE INVENTION:

[0009] Accordingly, the present invention provides an alkenyl group containing aromatic carboxamide compounds of formula (I) or salts, stereoisomers, metal complexes, polymorphs, or N-oxides thereof,OR3® R3b

[0010] R1b-r k-xxJ IJT R %2V j Q

[0011] R1a

[0012]

[0013] (I)

[0014] wherein, ring-A, Q, Rla, Rlb, R2, R3aand R3bare as defined in the detailed description.

[0015] In one embodiment, the present invention provides a process for preparing compounds of formula (I) or salts thereof.

[0016] In another embodiment, the present invention provides a composition for controlling or preventing invertebrate pests comprising a biologically effective amount of the compound of formula (I), salts, stereoisomers, metal complexes, polymorphs, or N-oxides thereof and at least one additional component selected from the group consisting of surfactants and auxiliaries.

[0017] 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, biostimulants or nutrients.

[0018] In yet another embodiment, the present invention provides a combination comprising the compound of formula (I) or salts, stereoisomers, polymorphs, metal complexes or N-oxides thereof and at least one additional biologically active and compatible compound selected from fiingicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, or nutrients.

[0019] In still another embodiment, the present invention provides the use of the compounds of formula (I), salts, stereoisomers, metal complexes, polymorphs, or N-oxides, compositions or combinations thereof, for combating invertebrate pests in agricultural crops and / or horticultural crops, in wooden dwellings and commercial structures or parasites on animals.

[0020] In yet still another embodiment, the present invention provides a method of combating invertebrate pests comprising contacting the invertebrate pests, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the invertebrate pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from pest attack or infestation with a biologically effective amount of the compound of formula (I) or salts, stereoisomers, metal complexes, polymorphs, or N-oxides thereof as well as compositions or combinations thereof.

[0021] DETAILED DESCRIPTION OF THE INVENTION:

[0022] DEFINITIONS:The definitions provided herein for the terminologies used in the present disclosure are for illustrative purpose only and in no manner limit the scope of the present invention disclosed in the present disclosure. As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", "contains", "containing", "characterized by" or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.

[0023] The transitional phrase "consisting of' excludes any element, step or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consisting of' appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0024] The transitional phrase "consisting essentially of' is used to define a composition or method that includes materials, steps, features, components or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term "consisting essentially of' occupies a middle ground between "comprising" and "consisting of'.

[0025] Further, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not to an exclusive "or". For example, a condition A "or" B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0026] Also, the indefinite articles "a" and "an" preceding an element or component of the present invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore "a" or "an" should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular. As referred to in this disclosure, the term "invertebrate pest" includes arthropods, gastropods and nematodes of economic importance as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans. The term "gastropod" includes snails, slugs and other Stylommatophora. The term "nematode" refers to a living organism of the Phylum Nematoda. The term "helminths" includes roundworms, heartworms, phytophagous nematodes (Nematoda), flukes (Trematoda), acanthocephala and tapeworms (Cestoda).The term "agronomic" refers to the production of field crops such as for food, feed and fiber and includes the growth of com, soybeans and other legumes, rice, cereals (e.g., wheat, oats, barley, rye, rice, maize), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweetpotatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruits (berries, cherries) and other specialty crops (e.g., canola, sunflower, olives).

[0027] The term "nonagronomic" refers to other than field crops, such as horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored products, agro-forestry and vegetation management, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.

[0028] Nonagronomic applications include protecting an animal from an invertebrate parasitic pest by administering a parasiticidally effective (i.e. biologically effective) amount of a compound of the present invention, typically in the form of a composition formulated for veterinary use, to the animal to be protected. As referred to in the present disclosure and claims, the terms "parasiticidal" and "parasiticidally" refers to observable effects on an invertebrate parasite pest to provide protection of an animal from the pest. Parasiticidal effects typically relate to diminishing the occurrence or activity of the target invertebrate parasitic pest. Such effects on the pest include death, retarded growth, diminished mobility or lessened ability to remain on or in the host animal, reduced feeding and inhibition of reproduction. These effects on invertebrate parasite pests provide control (including prevention, reduction or elimination) of parasitic infestation or infection of the animal.

[0029] The compounds of the present disclosure may be present either in pure form or as mixtures of different possible isomeric forms such as stereoisomers or constitutional isomers. The various stereoisomers include enantiomers, diastereomers, chiral isomers, atropisomers, conformers, rotamers, tautomers, optical isomers, polymorphs, and geometric isomers. Any desired mixtures of these isomers fall within the scope of the claims of the present disclosure. One skilled in the art will appreciate that one stereoisomer may be more active and / or may exhibit beneficial effects when enriched relative to the other isomer(s) or when separated from the other isomer(s). Additionally, the person skilled in the art knows processes or methods or technology to separate, enrich, and / or to selectively prepare said isomers.

[0030] The meaning of various terms used in the description shall now be illustrated.

[0031] The term "enantiomerically enriched" refers to a chiral substance whose enantiomeric ratio is greater than 50:50 but less than 100:0.The term "aliphatic compound / s" or "aliphatic group / s" used herein is an organic compound / s whose carbon atoms are linked in straight chains, branched chains, or non-aromatic rings.

[0032] The term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" or -N(alkyl) or alkylcarbonylalkyl or alkylsuphonylamino includes straight-chain or branched Ci to C12 alkyl, preferably Ci to C8alkyl, more preferably Ci to Ce 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 l-ethyl-2-methylpropyl or the different isomers. If the alkyl is at the end of a composite substituent, as, for example, in alkylcycloalkyl, the part of the composite substituent at the start, for example the cycloalkyl, may be mono- or polysubstituted identically or differently and independently by alkyl. The same also applies to composite substituents in which other radicals, for example alkenyl, alkynyl, hydroxyl, halogen, carbonyl, carbonyloxy and the like, are at the end.

[0033] The term "cyanoalkyl" as used herein refers to straight-chain or branched alkyl groups having 1 to 6 (" Ci-Ce -cyanoalkyl") or 1 to 4 (" Ci-C4-cyanoalkyl") carbon atoms (as mentioned above), where 1 or 2, preferably 1, of the hydrogen atoms in these groups are replaced by a cyano (CN) group. Non limiting examples are cyanomethyl, 1 -cyanoethyl, 2-cyanoethyl, 1 -cyanopropyl, 2- cyanopropyl, 3 -cyanopropyl, 1 -cyanobutyl, 2-cyanobutyl, 3-cyanobutyl, 4-cyanobutyl and the like.

[0034] The term "alkenyl", used either alone or in compound words includes straight-chain or branched CT to C12 alkenes, preferably CT to CT alkenes, more preferably CT to Ce 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-l-propenyl, l-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, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl -2 -propenyl, 1,2-dimethyl-l -propenyl, l,2-dimethyl-2 -propenyl, 1 -ethyl- 1 -propenyl, l-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 -methyl- 1 -pentenyl, 2-methyl-l-pentenyl, 3-methyl- 1 -pentenyl, 4-methyl-l -pentenyl, l-methyl-2-pentenyl, 2-methyl-2 -pentenyl, 3-methyl-2-pentenyl, 4-methyl-2 -pentenyl, l-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, l,l-dimethyl-2-butenyl, l,l-dimethyl-3-butenyl, 1,2-dimethyl-l-butenyl, l,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-l-butenyl, 1,3 -dimethyl -2-butenyl, l,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-l-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-l-butenyl, 3,3-dimethyl-2-butenyl, 1 -ethyl- 1-butenyl, l-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl- 1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl -2 -propenyl, l-ethyl-l-methyl-2-propenyl, 1-ethyl-2-methyl-l-propenyl and l-ethyl-2-methyl-2 -propenyl and the different isomers. " Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. This definition also applies to alkenyl as a part of a composite substituent, for example haloalkenyl and the like, unless defined specifically elsewhere. The term "alkynyl", used either alone or in compound words includes straight-chain or branched CT to C12 alkynes, preferably CT to Cs alkynes, more preferably CT to Ce alkynes. Non-limiting examples of alkynes include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-l-butynyl, l,l-dimethyl-2-propynyl, 1-ethyl -2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, l-methyl-3 -pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3 -methyl-1 -pentynyl, 3-methyl-4-pentynyl, 4-methyl-l -pentynyl, 4-methyl-2-pentynyl, l,l-dimethyl-2-butynyl, l,l-dimethyl-3-butynyl, l,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-l-butynyl, l-ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-l-methyl-2-propynyl and the different isomers. This definition also applies to alkynyl as a part of a composite substituent, for example haloalkynyl etc., unless specifically defined elsewhere. The term "alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.

[0035] The term "cycloalkyl" means alkyl closed to form a ring. Non-limiting examples include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. This definition also applies to cycloalkyl as a part of a composite substituent, for example cycloalkylalkyl etc., unless specifically defined elsewhere.

[0036] The term "cycloalkenyl" means alkenyl closed to form a ring including monocyclic, partially unsaturated hydrocarbyl groups. Non-limiting examples include but are not limited to cyclopropenyl, cyclopentenyl and cyclohexenyl. This definition also applies to cycloalkenyl as a part of a composite substituent, for example cycloalkenylalkyl etc., unless specifically defined elsewhere.

[0037] The term "cyanocycloalkyl" as used herein refers to alkyl closed to form a ring, groups having 3 to 8 (" C3-Cs-cyanoalkyl") carbon atoms (as mentioned above), where 1 or 2, preferably 1, of the hydrogen atoms in these groups are replaced by a cyano (CN) group. Non limiting examples are 1 -cyanocyclopropyl, 2-cyanocyclopropyl, 1 -cyanocyclobutyl, 2-cyanocyclobutyl, 3 -cyanocyclobutyl, 1 -cyanocyclopentyl, 2-cyanocyclopentyl, 3-cyclopentyl, 4-cyclopentyl, 1-cyanohexyl, 2-cyanohexyl, 3 -cyanocyclohexyl, 4-cyanocyclohexyl and the like.

[0038] The term "alkoxy" used either alone or in compound words includes Ci to C12 alkoxy, preferably Ci to Cs alkoxy, more preferably Ci to Ce 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 l-ethyl-2-methylpropoxy and the different isomers. This definition also applies to alkoxy as a part of a composite substituent, for example haloalkoxy, alkynylalkoxy, etc., unless specifically defined elsewhere.

[0039] The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said 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, l,l-dichloro-2,2,2-trifluoroethyl, and l,l,l-trifluoroprop-2-yl. This definition also applies to haloalkyl as a part of a composite substituent, for example haloalkylaminoalkyl etc., unless specifically defined elsewhere.

[0040] The terms "haloalkenyl", "haloalkynyl" are defined analogously except that, instead of alkyl groups, alkenyl and alkynyl groups are present as a part of the substituent.

[0041] Halocycloalkyl, halocycloalkenyl, alkylcycloalkyl, halocycloalkylalkyl, cycloalkylalkyl, cycloalkoxyalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, haloalkylcarbonyl, cycloalkylcarbonyl, haloalkoxylalkyl, and the like, are defined analogously to the above examples.

[0042] The term "hydroxy" means -OH, amino means -NRR, wherein R can be H or any possible substituent such as alkyl. Carbonyl means -C(O)-, carbonyloxy means -OC(O)-, sulfinyl means SO, sulfonyl means SiOfi. The term "amide" means A-R'C=ONR"-B, wherein R' and R" indicates substituents and A and B indicate any group.

[0043] The term "thioamide" means A-R'C=SNR"-B, wherein R' and R" indicates substituents and A and B indicate any group.

[0044] " Alkylamino", "dialkylamino", and the like, are defined analogously to the above examples.As used herein, the term " Ci-Ce-alkcnyloxy" refers to -OR, wherein R is the Ci-Ce-alkcnyl group as defined above.

[0045] As used herein, the term " Ci-Ce-haloalkcnyloxy" refers to -OR, wherein R is the Ci-Ce-alkcnyl group as defined above, substituted by one or more of the same or different halogen atoms.

[0046] As used herein, the term " Ci-Ce-alkynyloxy " refers to -OR, wherein R is the Ci-Ce-alkynyl group as defined above.

[0047] As used herein, the term " Ci-Ce-haloalkynyloxy" refers to -OR, wherein R is the Ci-Ce-alkynyl group as defined above, substituted by one or more of the same or different halogen atoms.

[0048] As used herein, the term “Ci-Ce-alkylsulfanyl” or Ci-Ce-alkylthio refers to a radical of the formula -SR wherein R is a Ci-Ce-alkyl radical as generally defined above.

[0049] As used herein, the term “Ci-Ce-alkylsulfinyl” refers to a radical of the formula -S(O)R wherein R is a Ci-Ce-alkyl radical as generally defined above.

[0050] As used herein, the term “Ci-Ce-alkylsulfonyl” refers to a radical of the formula -S(O)? R wherein R is a Ci-Ce-alkyl radical as generally defined above.

[0051] As used herein, the term Ci-Ce-haloalkylsulfanyl" refers to a Ci-Ce-alkylsulfanyl group, as defined above, substituted by one or more of the same or different halogen atoms.

[0052] As used herein, the term Ci-Ce-haloalkylsulfinyl" refers to a Ci-Ce-alkylsulfinyl group, as defined above, substituted by one or more of the same or different halogen atoms.

[0053] As used herein, the term Ci-Ce-haloalkylsulfonyl" refers to a Ci-Ce-alkylsulfonyl group, as defined above, substituted by one or more of the same or different halogen atoms.

[0054] As used herein, the term " C3-Cn-cycloalkyl" refers to three (3) to n membered cycloalkyl radicals. Examples include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0055] As used herein, the term “C3-C6 -cycloalkyloxy” refers to three (3) to six (6) membered cycloalkoxy radicals. Examples include but are not limited to cyclopropyloxy, cyclobutyloxy and cyclopentyloxy.

[0056] As used herein, the term " C3-Cn-cycloalkenyl" refers to a stable, monocyclic ring radical that is partially unsaturated and contains 3 to n carbon atoms. C3-C4-cycloalkenyl is to be construed accordingly. Examples of C3-Ce-cycloalkenyl include but are not limited to, 1 -cyclopropenyl, 2-cyclopropenyl, 1-cyclobutenyl, 2-cyclobutenyl, 1 -cyclopentenyl, 2-cyclopentenyl, 1,3 -cyclopentadienyl, 1, 4-cyclopentadienyl, 2, 4-cyclopentadienyl, 1 -cyclohexenyl, 2-cyclohexenyl, 3 -cyclohexenyl, 1, 3 -cyclohexadienyl, 1, 4-cyclohexadienyl and 2,5-cyclohexadienyl.As used herein, the term “C3-C6-cycloalkyl-Ci-Cn-alkyl-” refers to a Ci-Cn-alkyl radical as generally defined above substituted by one or more C3-C6-cycloalkyl groups as generally defined above. C3-C6-cycloalkyl-Ci-C3-alkyl is to be construed accordingly. Examples include but are not limited to, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopentylethyl and cyclohexylmethyl.

[0057] As used herein, the term " C3-C6-halocycloalkyl" refers to a C3-Ce-cycloalkyl radical, as generally defined above, substituted by one or more of the same or different halogen atoms.

[0058] As used herein, the term " C3-C6-halocycloalkyloxy" refers to a C3-C6-cycloalkyloxy radical, as generally defined above, substituted by one or more of the same or different halogen atoms.

[0059] As used herein, “C3-C6-cycloalkylamino” refers to a substituent of the formula -NH-C3-C6-cycloalkyl, wherein the cycloalkyl group is unsubstituted or substituted as defined for cycloalkyl.

[0060] As used herein, the term “phenyl-Ci-Ce-alkyl-” refers to a phenyl ring attached to a Ci-Ce-alkyl radical as generally defined above, substituted by one phenyl group. Examples include but are not limited to, phenylmethyl (benzyl) and phenylethyl.

[0061] As used herein, the term “C3-C6-cycloalkyloxy-Ci-C6-alkyl-” refers to a Ci-Ce-alkyl radical, as generally defined above, substituted by one C3-C6-cycloalkyloxy group. Examples include but are not limited to, cyclopropyloxymethyl, cyclobutyloxymethyl, cyclopropyloxyethyl and cyclopentyloxymethyl.

[0062] As used herein, the term “-C(O)NH-Ci-C6-alkyl-C3-C6-cycloalkyl” refers to a carbamoyl group (C(O)NH-) attached through a straight or branched alkyl chain of 1 to 6 carbon atoms to a cycloalkyl group containing 3 to 6 carbon atoms. Examples include but are not limited to -C(O)NH-methyl-cyclopropyl, -C(O)NH-ethyl-cyclobutyl and -C(O)NH-propyl-cyclopentyl.

[0063] As used herein, the term “-C(O)N(Ci-C6-alkyl)(Ci-C6-alkoxy)” refers to an amide group in which the nitrogen atom is substituted with one Ci-Ce-alkyl and one Ci-Ce-alkoxy group.

[0064] As used herein, the term “-C3-C6-cycloalkyl nitrile” refers to a C3-C6-cycloalkyl ring substituted with a nitrile (-CN) group. Examples include but are not limited to cyclopropyl-CN, cyclobutyl-CN and cyclopentyl-CN.

[0065] As used herein, the term “Ci-Ce-alkoxy-Ci-Ce-alkyl” refers to a a straight or branched alkyl chain containing from 1 to 6 carbon atoms, substituted with a Ci-Ce-alkoxy group. Examples include but are not limited to methoxy-methyl, methoxy-ethyl, ethoxy -methyl, ethoxy -ethyl, propoxy-methyl, propoxy -ethyl, butoxy -butyl.As used herein, the term “-C(0)NH-Ci-C6-alkyl” refers to an amide moiety in which a carbonyl group is bound to a nitrogen atom bearing one hydrogen atom and one alkyl substituent, wherein the alkyl substituent is a straight-chain or branched alkyl group having from one to six carbon atoms.

[0066] As used herein the term “-C(O)-N(Ci-C6-alkyl)2” refers to a carbonyl group bound to a nitrogen atom bearing two alkyl substituents, wherein each alkyl substituent is independently a straight-chain or branched alkyl group having from one to six carbon atoms.

[0067] As used herein the term “-C(O)-NH-Ci-C6-alkoxy” refers to a carbonyl group bound to a nitrogen atom bearing one hydrogen atom and one alkoxy substituent, wherein the alkoxy substituent is a straight-chain or branched alkoxy group having from one to six carbon atoms. As used herein, “SF5” refers to a pentafluorosulfanyl substituent (-SF5).

[0068] As used herein, “CN” refers to a cyano substituent (-CN).

[0069] As used herein, “SCN” refers to a thiocyanato substituent (-S-ON or -SCN).

[0070] As used herein, “nitro” refers to -NO2 group.

[0071] As used herein, “3- to 4-membered carbocyclic ring” refers to cyclopropyl or cyclobutyl rings, which may be unsubstituted or substituted.

[0072] As used herein, the term wherein heteroatom(s) or substituent(s) are “independently” selected from means that substituent(s) or heteroatom(s) can be identical or different.

[0073] The terms “carbocycle” or “carbocyclic” or “carbocyclyl” include “aromatic carbocyclic ring systems” and “nonaromatic carbocylic ring systems” or polycyclic or bicyclic (spiro, fused, bridged, nonfused) ring compounds in which the ring may be aromatic or non-aromatic (where aromatic indicates that the Huckel rule is satisfied, and non-aromatic indicates that the Huckel rule is not satisfied).

[0074] Non limiting examples of non-aromatic carbocyclic ring systems are cyclopropyl, cyclobutyl, cyclopentyl, norbomyl and the like. Non limiting examples of aromatic carbocyclic ring systems are phenyl, naphthyl and the like.

[0075] The term “aryl” as used herein, is a group that contains any carbon-based aromatic group including, but not limited to, phenyl, naphthalene, biphenyl, anthracene, and the like. The aryl group can be substituted or unsubstituted. In addition, the aryl group can be a single ring structure or comprise multiple ring structures that are either fused ring structures or attached via one or more bridging groups such as a carbon-carbon bond.

[0076] The term “aryl” also comprising “aralkyl” refers to aryl hydrocarbon radicals including an alkyl portion as defined above. Examples include benzyl, phenylethyl, and 6-napthylhexyl. As used herein, the term“aralkenyl” refers to aryl hydrocarbon radicals including an alkenyl portion, as defined above, and an aryl portion, as defined above. Examples include styryl, 3-(benzyl) prop-2-enyl, and 6-napthylhex-2-enyl. The term "hetero" in connection with rings refers to a ring in which at least one ring atom is not carbon and which can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs.

[0077] The term "aromatic" indicates that the Huckel rule is satisfied, and the term "non-aromatic" indicates that the Huckel rule is not satisfied.

[0078] The term "heterocycle" or "heterocyclic" or "heterocyclic ring system " includes an "aromatic heterocycle" or a "heteroaryl bicyclic ring system" and a "nonaromatic heterocycle ring system" or polycyclic or bicyclic (spiro, fused, bridged, non-fused) ring compounds in which the ring may be aromatic or non-aromatic, wherein the heterocycle ring contains at least one heteroatom selected from N, O, S(0)o-2, and or a C ring member of the heterocycle may be replaced by C(=O), C(=S), C(=CR*R*) and C=NR*, * indicates integers.

[0079] The term "non-aromatic heterocycle" or "non-aromatic heterocyclic" means three- to fifteen-membered, preferably three- to twelve-membered, saturated or partially unsaturated heterocycles containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur: mono, bi- or tricyclic heterocycles which contain, in addition to the carbon ring members, one to three nitrogen atoms and / or one oxygen or sulphur atom or one or two oxygen and / or sulphur atoms; if the ring contains more than one oxygen atom, they are not directly adjacent; for example (but not limited to) oxiranyl, oxetanyl, aziridinyl, azetidinyl, thietanyl, thietanyl 1 -oxide, thietanyl 1,1 -dioxide, 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, l,2,4-oxadiazolidin-3-yl, l,2,4-oxadiazolidin-5-yl, l,2,4-thiadiazolidin-3-yl, l,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-l-yl, 1,2,4-triazolidin-3-yl, l,3,4-oxadiazolidin-2-yl, l,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-l-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-l-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-l-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-l-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, l,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, l,2,4-hexahydrotriazin-3-yl, cycloserines,. This definition also applies to heterocyclyl as a part of a composite substituent, for example heterocyclylalkyl etc., unless specifically defined elsewhere.

[0080] The term "heteroaryl" or "aromatic heterocyclic" means a 5 or 6-membered, fully unsaturated monocyclic ring system containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur; if the ring contains more than one oxygen atom, they are not directly adjacent; 5 -membered heteroaryl ring systems containing one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom: 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom as ring members, for example (but not limited thereto) 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 groups containing one to four nitrogen atoms, or benzofused nitrogen-bonded 5-membered heteroaryl systems containing one to three nitrogen atoms: 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms as ring members and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member may be bridged by a buta-l,3-diene-l,4-diyl group in which one or two carbon atoms may be replaced by nitrogen atoms, where these rings are attached to the skeleton via one of the nitrogen ring members, for example (but not limited to) 1 -pyrrolyl, 1 -pyrazolyl, 1,2,4-triazol-1- yl, 1-imidazolyl, 1,2,3 -triazol -1-yl and 1,3,4-triazol-l-yl.

[0081] 6-membered heteroaryl which contains one to four nitrogen atoms: 6-membered heteroaryl groups which, in addition to carbon atoms, may contain, respectively, one to three and one to four nitrogen atoms as ring members, for example (but not limited thereto) 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, l,3,5-triazin-2-yl, l,2,4-triazin-3-yl and 1, 2, 4, 5 -tetrazin-3 -yl; benzofused 5-membered heteroaryl containing one to three nitrogen atoms or onenitrogen atom and one oxygen or sulphur atom: for example (but not limited to) indol-l-yl, indol-2-yl, indol- 3-yl, indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl, benzimidazol-l-yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, indazol-l-yl, indazol-3-yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl, l-benzofuran-2-yl, l-benzofuran-3-yl, l-benzofuran-4-yl, l-benzofuran-5-yl, 1 -benzofuran- 6-yl, l-benzofuran-7-yl, l-benzothiophen-2-yl, l-benzothiophen-3-yl, l-benzothiophen-4-yl, 1-benzothiophen-5-yl, l-benzothiophen-6-yl, l-benzothiophen-7-yl, l,3-benzothiazol-2-yl, 1,3- benzothiazol- 4-yl, l,3-benzothiazol-5-yl, l,3-benzothiazol-6-yl, l,3-benzothiazol-7-yl, l,3-benzoxazol-2-yl, 1,3-benzoxazol-4-yl, l,3-benzoxazol-5-yl, l,3-benzoxazol-6-yl and l,3-benzoxazol-7-yl; benzofused 6-membered heteroaryl which contains one to three 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. This definition also applies to heteroaryl as a part of a composite substituent, for example heteroarylalkyl etc., unless specifically defined elsewhere.

[0082] As used herein, “N(CH3)” in a heterocycle refers to a ring nitrogen bearing a methyl substituent.

[0083] As used herein, the term “5- or 6-membered heteroaryl ring” refers to an aromatic ring containing 1, 2 or 3 heteroatoms independently selected from nitrogen (N), oxygen (O) or sulfur (S).

[0084] The term " Trialkylsilyl" includes three branched and / or straight-chain alkyl radicals attached to and linked through a silicon atom such as trimethylsilyl, triethylsilyl and t-butyl-dimethylsilyl. "Halotrialkylsilyl" denotes at least one of the three alkyl radicals is partially or fully substituted with halogen atoms which may be the same or different. The term "alkoxytrialkylsilyl" denotes at least one of the three alkyl radicals is substituted with one or more alkoxy radicals which may be the same or different. The term "trialkylsilyloxy" denotes a trialkylsilyl moiety attached through oxygen.

[0085] The total number of carbon atoms in a substituent group is indicated by the " Ci-Cj" prefix where i and j are numbers from 1 to 21. For example, C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxyalkyl designates CH3OCH2; C3 alkoxyalkyl designates, for example, CH3CH(OCH3). CH3OCH2CH2 or CH3CH2OCH2; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2. In the above recitations, when a compound of formula (I) is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by a replacement of a hydrogen on said carbon or nitrogen.

[0086] When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the groupof defined substituents. Further, when the subscript m in (R)mindicates an integer ranging from for example 0 to 4, then the number of substituents may be selected from the integers between 0 and 4 inclusive. When a group contains a substituent which can be hydrogen, then, when this substituent is taken as hydrogen, it is recognized that said group is being unsubstituted.

[0087] When a substituent is independently selected from a list, it is recognized that said substituent can be identical or different.

[0088] The embodiments herein and the various features and advantageous details thereof are explained with reference to the non-limiting embodiments in the description. Descriptions of well-known components and processing techniques are omitted to not unnecessarily obscure the embodiments herein. The examples used herein are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those, skilled in the art, to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein.

[0089] The description of the specific embodiments will so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and / or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.

[0090] Any discussion of documents, acts, materials, devices, articles and the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application.

[0091] The numerical values mentioned in the description and the description / claims though might form a critical part of the present invention, any deviation from such numerical values shall still fall within the scope of the present invention if that deviation follows the same scientific principle as that of the present invention disclosed in the present invention. The inventive compounds of the present invention may, if appropriate, be present as mixtures of different possible isomeric forms, especially of stereoisomers, for example E and Z, threo and erythro, and also optical isomers, but if appropriate also of tautomers. Both the E and the Zisomers, and also the threo and erythro isomers, and the optical isomers, any desired mixtures of these isomers and the possible tautomeric forms are disclosed and claimed.

[0092] The term "pest" for the purpose of the present disclosure includes but is not limited to fungi, stramenopiles (oomycetes), bacteria, nematodes, mites, ticks, insects and rodents. Also, pest is an animal or plant detrimental to humans or human concerns including crops, livestock and forestry.

[0093] The term "plant" is understood here 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 which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which are protectable and non-protectable by plant breeders' rights.

[0094] For the purpose of the present disclosure the term "plant" includes a living organism of the kind exemplified by trees, shrubs, herbs, grasses, fems, and mosses, typically growing in a site, absorbing water and required substances through its roots, and synthesizing nutrients in its leaves by photosynthesis.

[0095] Examples of "plant" for the purpose of the present invention include but are not limited to agricultural crops such as wheat, rye, barley, triticale, oats or rice; beet, e.g. sugar beet or fodder beet; fruits and fruit trees, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit and citrus trees, such as oranges, lemons, grapefruits or mandarins; any horticultural plants, vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; cucurbitaceae; oleaginous plants; energy and raw material plants, such as cereals, com, soybean, other leguminous plants, rape, sugar cane or oil palm; tobacco; nuts; coffee; tea; cacao; bananas; peppers; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e.g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.

[0096] Preferably, the plant for the purpose of the present invention include but is not limited to cereals, com, rice, soybean and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceae, oleaginous plants, tobacco, coffee, tea, cacao, sugar beet, sugar cane, cotton, potato, tomato, onions, peppers and vegetables, ornamentals, any floricultural plants and other plants of use for humans and animals.The term "plant parts" is understood to mean all parts and organs of plants above and below the ground. For the purpose of the present disclosure the term plant parts include but is not limited to cuttings, leaves, twigs, tubers, flowers, seeds, branches, roots including taproots, lateral roots, root hairs, root apex, root cap, rhizomes, slips, shoots, fruits, fruit bodies, bark, stem, buds, auxiliary buds, meristems, nodes and internodes.

[0097] The term "locus thereof' includes soil, surroundings of plant or plant parts and equipment or tools used before, during or after sowing / planting a plant or a plant part.

[0098] The application of the compounds of the present disclosure or the compound of the present disclosure in a composition, optionally comprising other compatible compounds, to a plant or a plant material or locus thereof include applications by a technique known to a person skilled in the art which includes but is not limited to spraying, coating, dipping, fumigating, impregnating, injecting and dusting.

[0099] The term "applied" means adhered to a plant or plant part either physically or chemically including impregnation.

[0100] Accordingly, the present invention provides an alkenyl group containing aromatic carboxamide compounds of formula (I),

[0101]

[0102] wherein,

[0103] Rlais C2-C3-alkenyl; wherein said Rlais unsubstituted or substituted with one to three groups independently selected from hydrogen, halogen, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-haloalkyl, C3-C5-cycloalkyl, C3-C5-halocycloalkyl, -S(0)o-2-Ci-C4-alkyl, S(0)o-2-Ci-C4-haloalkyl or -NR'R";

[0104] Rlbis selected from the group consisting of hydrogen, halogen, cyano, nitro, SF5, Ci-Ce-alkyl, C2-C6-alkenyl, C2-Ce-alkynyl, Ci-Ce-haloalkyl, C2-Ce-haloalkenyl, C2-Ce-haloalkynyl, Ci-Ce-alkoxy, C2-C6-alkenyloxy, C2-Ce-alkynyloxy, Ci-Ce-haloalkoxy, C2-Ce-haloalkenyloxy, C2-Ce-haloalkynyloxy, Ci-Ce-alkylsulfanyl, Ci-Ce-alkylsulfinyl, Ci-Ce-alkylsulfonyl, Ci-Ce-haloalkylsulfanyl, Ci-Ce-haloalkylsulfinyl, Ci-Ce-haloalkylsulfonyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkyl-Ci-C6-alkyl and C3-Ce -cycloalkyl nitrile;R2is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C1-C6-alkoxy, Ci-Ce-alkoxy-Ci-Ce-alkyl-, Ci-Ce-alkylcarbonyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkyl-Ci-C6-alkyl and C3-C6-halocycloalkyl-Ci-C6-alkyl; R3aand R3bare independently selected from the group consisting of hydrogen, halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl and C1-C6-alkylnitrile;

[0105] or

[0106] R3aand R3bas substituents, together with the carbon atom to which they are attached, form a 3- to 4-membered carbocyclic or heterocyclic ring; wherein said 3- to 4- membered heterocyclic ring contains 1 or 2 heteroatoms independently selected from N, O or S; wherein said carbocyclic or heterocyclic ring is unsubstituted or substituted with one to three substituents independently selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or Ci-Ce-alkoxy;

[0107] ring-A is selected from triazolyl or pyrazinyl, wherein said ring-A is unsubstituted or substituted with one or two substituents independently selected from R4;

[0108] R4is selected from the group consisting of hydrogen, halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C1-C6-alkoxy and C3-C6-cycloalkyl; Q is selected from the group consisting of phenyl and a 5- or 6- membered heteroaryl ring; wherein said phenyl and heteroaryl ring are unsubstituted or substituted with one to three substituents independently selected from R5;

[0109] or

[0110] Q is selected from the group consisting of -C(R6)=NOR7, -C(O)NR6R7and -C(O)N=S(O)R6R7;

[0111] R5is selected from the group consisting of hydrogen, halogen, hydroxy, cyano, nitro, SCN, SF5, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkylsulfanyl, Ci-Ce-alkylsulfinyl, Ci-Ce-alkylsulfonyl, C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-Ci-C6-alkyl, C3-Ce-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkyloxy-Ci-Cs-alkyl, -C(O)NH-Ci-C3-alkyl, -C(O)-N(Ci-C6-alkyl)2, -C(O)-NH-Ci-C6-alkoxy, -C(O)-N-(Ci-C6-alkyl)(Ci-Ce-alkoxy), -C(O)-NH-C3-Ce -cycloalkyl wherein C3-C6-cycloalkyl is substituted with Ci-C3-haloalkyl, -C(O)-NH-C3-Ce-cycloalkyl, -C(O)-NH-Ci-C6-alkyl-C3-C6-cycloalkyl, -C(0)-NH-3-to 4- membered non-aromatic heterocyclic ring wherein said ring is substituted with Ci-C3-alkyl, -C(O)-NH-3- to 4- membered non-aromatic heterocyclic ring, -NH-C(O)Ci-Ce-alkyl, -NR6C(O)NR6R7, -OC(O)NR6R7, -NR6C(O)OR7, -NR'R", -C(=O)-OH, -C(=O)-R", CR'=NR", Si(R8)3, -C(O)-N=S(O)0-iR6aR6b, -N=S(0)o-iR6aR6band a 3- to 4- membered non-aromatic heterocyclic ring; wherein each nonaromatic heterocyclic ring in R5contains 1 or 2 heteroatoms independently selected from N, N(CH3), O or S;

[0112] wherein each of the C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C2-C6-alkenyloxy, Ci-Ce-alkynyloxy, Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylsulfanyl, Ci-Ce-alkylsulfinyl, Ci-Ce-alkylsulfonyl, C3-Ce-cycloalkyl, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-Ci-Ce-alkyl, C3-Ce-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkyloxy-Ci-C6-alkyl, -C(O)NHCi-Ce-alkyl, -C(O)NH-C3-C6-cycloalkyl and -NH-C(O)Ci-Ce-alkyl groups of R5are unsubstituted or substituted with one to three substituents independently selected from halogen, hydroxy or cyano;

[0113] R6and R7are independently selected from the group consisting of hydrogen, Ci-Ce-alkyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkyl, Ci-Ce-haloalkoxy, C3-Ce-cycloalkyl, C3-C6-halocycloalkyl, Ci-Ce-alkoxy-Ci-Ce-alkyl and a 3- to 4-membered non-aromatic heterocyclic ring; wherein said 3- to 4-membered non-aromatic heterocyclic ring contains 1 or 2 heteroatoms independently selected from N, O or S;

[0114] R' and R" are independently selected from the group consisting of hydrogen, Ci-Ce-alkyl, Ci-Ce-alkoxy and C3-Ce-cycloalkyl; wherein said alkyl and cycloalkyl groups are unsubstituted or substituted with one to three substituents independently selected from halogen, hydroxy or cyano;

[0115] R6ais selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl and NRaRb;

[0116] R6bis selected from Ci-Ce-alkyl or C3-C6-cycloalkyl;

[0117] or

[0118] R6aand R6btogether with the sulfur atom to which they are attached may form a 3 - to 6-membered non- aromatic heterocyclic ring; wherein said heterocyclic ring contains an additional 1 or 2 heteroatoms independently selected from N, O or S;

[0119] Raand Rbare independently selected from hydrogen or Ci-Ce-alkyl;

[0120] R8is independently selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, and C3-C6-cycloalkyl;

[0121] or salts, stereoisomers, metal complexes, polymorphs, or N-oxides thereof.In one embodiment of the present invention, the compounds of formula (I) containing a stereogenic center are represented by the compounds of formula (I*) which is indicated with an asterisk in the structure below;

[0122]

[0123] (l‘)

[0124] wherein, R3bis hydrogen; ring-A, Q, Rla, Rlb, R2and R3aare as defined in the detailed description provided that R3ais other than hydrogen.

[0125] In another embodiment of the present invention, the compounds of formula (I) are represented by the compounds of formula (IA);

[0126]

[0127] wherein, Q, Rla, Rlb, R2, R3a, R3band R4are as defined in the detailed description.

[0128] In yet another embodiment of the present invention, the compounds of formula (IA) are represented by the compounds of formula (IA-1) wherein, R4is selected from hydrogen or Ci-Ce-alkyl; and Q is selected from a 5- or 6- membered heteroaryl ring; said heteroaryl ring is unsubstituted or substituted with one to three substituents independently selected from R5; wherein R5is as defined in the detailed description.

[0129] In a preferred embodiment of the present invention, the compounds of formula (I) or (IA) or (IA-1) are represented by the compounds of formula (IA-2);

[0130] O R3aQ

[0131]

[0132] wherein, Rlbis selected from hydrogen, halogen or C1-C3 -haloalky 1 preferably trifluoromethyl, R2is selected from hydrogen or Ci-Ce-alkyl preferably hydrogen, R3ais Ci-Ce-alkyl preferably methyl, R4is selected from hydrogen or Ci-Ce-alkyl preferably hydrogen or methyl, Q is a 5- or 6- membered heteroaryl ring preferably selected from thiazolyl, pyridinyl, pyrimidinyl or pyrazinyl, wherein said Q is unsubstitutedor substituted with one to three substituents independently selected from R5; Rlaand R5are as defined in the detailed description.

[0133] In another preferred embodiment of the present invention, the compounds of formula (I) or (IA) or (IA-1) or (IA-2) are represented by the compounds of formula (IA-3);

[0134]

[0135] R1ac

[0136] (IA-3)

[0137] wherein, R1aa, R1ab, R1acare independently selected from hydrogen, halogen, CN, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C3-haloalkyl, C3-C5-cycloalkyl, C3-C5-halocycloalkyl, -S(O)0-2-C1-C3-alkyl, S(O)0-2-C1-C3-haloalkyl or -NR′R″; Rlbis Ci-Ce-haloalkyl preferably trifluoromethyl, R2is selected from hydrogen or Ci-Ce-alkyl preferably hydrogen, R3ais Ci-Ce-alkyl preferably methyl, R4is selected from hydrogen or Ci-Ce-alkyl preferably hydrogen or methyl, Q is a 5 - or 6- membered heteroaryl ring preferably selected from thiazolyl, pyridinyl, pyrimidinyl or pyrazinyl wherein said Q is unsubstituted or substituted with one to three substituents independently selected from R5; R', R", and R5are as defined in the detailed description.

[0138] In yet another embodiment of the present invention, the compounds of formula (I) are represented by the compounds of formula (IB);

[0139] OR3a

[0140]

[0141] N R4

[0142] R1a

[0143] (IB)

[0144] wherein, Q, Rla, Rlb, R2, R3a, R3band R4are as defined in the detailed description.

[0145] In yet another embodiment of the present invention, the compounds of formula (IB) are represented by the compounds of formula (IB-1) wherein, R4is selected from hydrogen or Ci-Ce-alkyl; and Q is selected from -C(R6)=NOR7, -CONR6R7, -CON=S(O)R6R7or a 5- or 6- membered heteroaryl ring; said heteroaryl ring is unsubstituted or substituted with one to three substituents independently selected from R5; wherein R5is as defined in the detailed description.In a preferred embodiment of the present invention, the compounds of formula (I) or (IB) or (IB-1) are represented by the compounds of formula (IB-2);

[0146] O R3aQ

[0147]

[0148] wherein, R1bis selected from hydrogen, halogen or C1-C3-haloalkyl preferably trifluoromethyl, R2is selected from hydrogen or C1-C6-alkyl preferably hydrogen, R3ais C1-C6-alkyl preferably methyl, Q is selected from -C(R6)=NOR7, -CONR6R7, -CON=S(O)R6R7or a 5- or 6- membered heteroaryl ring preferably selected from thiazolyl, pyridinyl, pyrimidinyl or pyrazinyl, wherein said Q is unsubstituted or substituted with one to three substituents independently selected from R5; Rla, R5, R6and R7are as defined in the detailed description.

[0149] In another preferred embodiment of the present invention, the compounds of formula (I) or (IB) or (IB-1) or (IB-2) are represented by the compounds of formula (IB-3);

[0150] O R3aQ

[0151]

[0152] R1ac(IB-3)

[0153] wherein, R1aa, R1ab, R1acare independently selected from hydrogen, halogen, CN, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C3-haloalkyl, C3-C5-cycloalkyl, C3-C5-halocycloalkyl, -S(O)0-2-C1-C3-alkyl, S(O)0-2-C1-C3-haloalkyl or -NR′R″; R1bis selected from hydrogen, halogen or C1-C3-haloalkyl preferably trifluoromethyl, R2is selected from hydrogen or C1-C6-alkyl preferably hydrogen, R3ais C1-C6-alkyl preferably methyl, Q is selected from -C(R6)=NOR7, -CONR6R7, -CON=S(O)R6R7or a 6- membered heteroaryl ring preferably selected from pyridinyl, pyrimidinyl or pyrazinyl, wherein said Q is unsubstituted or substituted with one to three substituents independently selected from R5; wherein R', R", R5, R6and R7are as defined in the detailed description.

[0154] The following list provides definitions, including preferred definitions, for the substituents Rla, Rlb, R2, R3a, R3b, ring-A, R4, Q, R5, R6, R7, R8, R', R", Ra, Rb, R6aand R6bwith reference to the compounds of formula (I) or (I*) or (IA) or (IA-1) or (IA-2) or (IA-3) or (IB) or (IB-1) or (IB-2) or (IB-3) of the present invention. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this patent document.In one embodiment of the present invention, R1ais C2-C3-alkenyl; wherein said R1ais unsubstituted or substituted with one to three groups independently selected from hydrogen, halogen, CN, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C3-haloalkyl, C3-C5-cycloalkyl, C3-C5-halocycloalkyl, -S(O)0-2-C1-C3-alkyl, S(O)0-2-C1-C3-haloalkyl or -NR′R″.

[0155] In another embodiment of the present invention, Rlais C2-C3-alkenyl; wherein substituents on Rlais referred as Rlaa, Rlabor Rlacwhich are independently selected from hydrogen, halogen, CN, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy, Ci-C3-haloalkyl, C3-C5-cycloalkyl, C3-C5-halocycloalkyl, -S(0)o-2-Ci-C3-alkyl, S(O)0-2-Ci-C3-haloalkyl or -NR'R"

[0156] In yet another embodiment of the present invention, Rlais C2-C3-alkenyl; wherein said Rlais unsubstituted or substituted with one to three groups independently selected from hydrogen, halogen, CN, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy, Ci-C3-haloalkyl or C3-C5-cycloalkyl.

[0157] In yet another embodiment of the present invention, Rlais C2-C3-alkenyl; wherein substituents on Rlais referred as Rlaa, Rlabor Rlacwhich are independently selected from hydrogen, halogen, CN, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy, Ci-C3-haloalkyl, C3-C5-cycloalkyl or C3-C5-halocycloalkyl.

[0158] In a preferred embodiment of the present invention, Rlais C2-alkenyl; wherein said Rlais unsubstituted or substituted with one to three groups independently selected from hydrogen, halogen, CN, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy, Ci-C3-haloalkyl, C3-C5-cycloalkyl, C3-C5-halocycloalkyl, -S(0)o-2-Ci-C3-alkyl, S(O)0-2-Ci-C3-haloalkyl or -NR'R".

[0159] In a more preferred embodiment of the present invention, R1ais C2-alkenyl; wherein said R1ais unsubstituted or substituted with one to three groups independently selected from hydrogen, halogen, CN, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C3-haloalkyl, C3-C5-cycloalkyl or C3-C5-halocycloalkyl In one embodiment of the present invention, Rlbis selected from the group consisting of hydrogen, halogen, cyano, nitro, SF5, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-haloalkenyl, C2-C6-haloalkynyl, Ci-Ce-alkoxy, Ci-Ce-haloalkoxy, C2-Ce-haloalkenyloxy, C2-C6-haloalkynyloxy, Ci-Ce-alkylsulfanyl, Ci-Ce-alkylsulfmyl and Ci-Ce-alkylsulfonyl.

[0160] In another embodiment of the present invention, Rlbis selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy and Ci-Ce-haloalkoxy.

[0161] In a preferred embodiment of the present invention, Rlbis selected from hydrogen, halogen or C1-C3-haloalkyl.

[0162] In a more preferred embodiment of the present invention, R1bis trifluoromethyl.In one embodiment of the present invention, R2is selected from the group consisting of hydrogen, C1-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and C3-C5-cycloalkyl.

[0163] In another embodiment of the present invention, R2is selected from the group consisting of hydrogen, Ci-C3-alkyl, Ci-C3-haloalkyl, Ci-C3-alkoxy and C3-C5-cycloalkyl.

[0164] In a preferred embodiment of the present invention, R2is selected from hydrogen or Ci-C3-alkyl;

[0165] In a more preferred embodiment of the present invention, R2is hydrogen.

[0166] In one embodiment of the present invention, R3aand R3bare independently selected from the group consisting of hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-Ce-cycloalkyl and C3-C6-halocycloalkyl.

[0167] In another embodiment of the present invention, R3aand R3bare independently selected from the group consisting of hydrogen, Ci-C3-alkyl, C1-C3 -haloalky 1, C3-C5-cycloalkyl and C3-C5-halocycloalkyl.

[0168] In a preferred embodiment of the present invention, R3aand R3bare independently selected from hydrogen or Ci-C3-alkyl.

[0169] In a more preferred embodiment of the present invention, R3ais Ci-C3-alkyl preferably methyl; R3bis hydrogen.

[0170] In one embodiment of the present invention, R3aand R3bas substituents, together with the carbon atom to which they are attached, form a 3- to 4-membered carbocyclic or heterocyclic ring; wherein said 3-to 4- membered heterocyclic ring contains 1 or 2 heteroatoms independently selected from N, O or S; wherein said carbocyclic or heterocyclic ring is unsubstituted or substituted with one to three substituents independently selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or Ci-Ce-alkoxy. In another embodiment of the present invention, R3aand R3bas substituents, together with the carbon atom to which they are attached, form a 3- to 4-membered carbocyclic or heterocyclic ring; wherein said 3- to 4- membered heterocyclic ring contains 1 or 2 heteroatoms independently selected from N, O or S; wherein said carbocyclic or heterocyclic ring is unsubstituted or substituted with one or two substituents independently selected from halogen, CN, Ci-C3-alkyl, Ci-C3-haloalkyl or Ci-C3-alkoxy. In one embodiment of the present invention, ring-A is selected from triazolyl or pyrazinyl; wherein said ring-A is unsubstituted or substituted with one or two substituents independently selected from R4. In another embodiment of the present invention, ring-A is selected from triazolyl or pyrazinyl; wherein said triazolyl ring is unsubstituted or substituted with one R4and said pyrazinyl ring is unsubstituted or substituted with one or two substituents independently selected from R4.In a preferred embodiment of the present invention, ring-A is triazolyl; wherein the triazolyl ring is unsubstituted or substituted with one R4.

[0171] In another preferred embodiment of the present invention, ring-A is pyrazinyl; wherein the pyrazinyl ring is unsubstituted or substituted with one or two substituents independently selected from R4.

[0172] In yet another preferred embodiment of the present invention, ring-A is selected from triazolyl or pyrazinyl, wherein the triazolyl is selected from lH-l,2,4-triazol-l-yl, lH-l,2,4-triazol-3-yl, lH-l,2,4-triazol-4-yl, or lH-l,2,4-triazol-5-yl, and wherein the pyrazinyl is selected from pyrazin-2-yl, pyrazin-3-yl, pyrazin-5-yl, or pyrazin-6-yl; wherein the said ring-A is unsubstituted or substituted with one substituent independently selected from R4.

[0173] In yet another preferred embodiment of the present invention, ring-A is selected from ring-A 1 or ring-A2

[0174]

[0175] ring-A1 ring-A2

[0176] wherein, JJJJindicates the point of attachment to the carbon atom that is bonded to the amide nitrogen and # indicates the point of attachment to the Q substituent and R4is as defined in the detailed description of the invention.

[0177] In one embodiment of the present invention, R4is selected from the group consisting of hydrogen, halogen, cyano, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, C2-C4-haloalkenyl, C2-C4-haloalkynyl, Ci-C4-alkoxy and C3-C6-cycloalkyl.

[0178] In another embodiment of the present invention, R4is selected from hydrogen, halogen, cyano, Ci-C3-alkyl, Ci-C3-alkoxy or C3-C6-cycloalkyl.

[0179] In a preferred embodiment of the present invention, R4is selected from hydrogen or Ci-C3-alkyl.

[0180] In a more preferred embodiment of the present invention, R4is selected from hydrogen or methyl.

[0181] In one embodiment of the present invention, Q is selected from the group consisting of phenyl and a 5- or 6- membered heteroaryl ring; wherein said phenyl and heteroaryl ring are unsubstituted or substituted with one or two substituents independently selected from R5.

[0182] In another embodiment of the present invention, Q is selected from a 5- or 6- membered heteroaryl ring; wherein said heteroaryl ring is unsubstituted or substituted with one or two substituents independently selected from R5.In yet another embodiment of the present invention, Q is selected from a 5- or 6- membered heteroaryl ring; wherein said heteroaryl ring is unsubstituted or substituted with one R5substituent.

[0183] In a preferred embodiment of the present invention, Q is a 5- or 6- membered heteroaryl ring selected from thiazolyl, pyridinyl, pyridazinyl pyrimidinyl or pyrazinyl; wherein said heteroaryl ring is unsubstituted or substituted with one or two substituents independently selected from R5.

[0184] In a more preferred embodiment of the present invention, Q is a 6- membered heteroaryl ring selected from pyridinyl, pyrimidinyl or pyrazinyl; wherein said heteroaryl rings are unsubstituted or substituted with one or two substituents independently selected from R5.

[0185] In one embodiment of the present invention, when ring-A is pyrazinyl; Q is selected from the group consisting of -C(R6)=NOR7, -C(O)NR6R7and -C(O)N=S(O)R6R7.

[0186] In one embodiment of the present invention, R5is selected from the group consisting of hydrogen, halogen, hydroxy, cyano, nitro, SCN, SF5, Ci-Ce-alkyl, G-G-alkenyl, G-G-alkynyl, Ci-Ce-alkoxy, G-G-alkenyloxy, G-G,-alkynyloxy. Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkylsulfanyl, G-G-alkylsulfmyl, Ci-Ce-alkylsulfonyl, Cz-Ce-cycloalkyl, G-G-cycloalkylamino, Cz-Ce-cycloalkyl-Ci-Ce-alkyl, Cz-Ce-cycloalkenyl, G-G, -cycloalkyloxy, G-G-cycloalkyloxy-G-G-alkyl, -C(O)NHG-C6-alkyl, -C(O)N(Ci-C6-alkyl)2, -C(O)NHG-G-alkoxy, -C(O)N(Ci-C6-alkyl)(Ci-C6-alkoxy), -C(O)NH-G-CS-cycloalkyl wherein G-G, -cycloalkyl is substituted with G-G-haloalkyl. -C(O)NH-G-C6-cycloalkyl, -C(O)NH-G-C6-alkyl-G-C6-cycloalkyl, -C(O)NH-3- to 4- membered non-aromatic heterocyclic ring wherein said ring is substituted with G-G-alkyl, -C(O)NH-3- to 4- membered non-aromatic heterocyclic ring, -NHC(O)G-G-alkyl, -NR6C(O)NR6R7, -OC(O)NR6R7, -NR6C(O)OR7, -NR'R", -C(=O)-OH, -C(=O)-R", CR-NR", Si(R8)3, -C(0)-N=S(0)o-iR6aR6b, -N=S(0)o-iR6aR6band a 3- to 4-membered non-aromatic heterocyclic ring; wherein each non-aromatic heterocyclic ring in R5contains 1 or 2 heteroatoms independently selected from N, N(CH3), O or S;

[0187] wherein each of the G-G-alkyl, G-G, -alkenyl. G-G,-alkynyl. G-G-alkoxy, G-Ce-alkenyloxy, G-Ce-alkynyloxy, G-G-alkoxy-G-G-alkyl, G-G-alkylsulfanyl, G-G-alkylsulfmyl, G-G-alkylsulfonyl, G-Ce-cycloalkyl, G-G-cycloalkylamino, G-G-cycloalkyl-G-G-alkyl, G-G-cycloalkenyl, G-G-cycloalkyloxy, G-G-cycloalkyloxy-G-G-alkyl, -C(O)NHG-G-alkyl, -C(O)NH-G-G-cycloalkyl and -NHC(O)G-G-alkyl groups of R5are unsubstituted or substituted with one to three substituents independently selected from halogen, hydroxy or cyano.

[0188] In another embodiment of the present invention, R5is selected from the group consisting of hydrogen, halogen, hydroxy, cyano, nitro, SCN, SF5, G-G-alkyl, G-G-alkenyl, G-G-alkynyl, G-G-alkoxy, G-G-alkenyloxy, C2-C4-alkynyloxy, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylsulfanyl, C1-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-Ci-C6-alkyl, C3-Ce-cycloalkenyl, C3-C6 -cycloalkyloxy, C3-C6-cycloalkyloxy-Ci-C4-alkyl, -C(O)NHCi-C5-alkyl, -C(O)N(Ci-C4-alkyl)2, -C(O)NHCi-C4-alkoxy, -C(O)N(Ci-C4-alkyl)(Ci-C4-alkoxy), -C(O)NHC3-C5-cycloalkyl wherein C3-Ce-cycloalkyl is substituted with C1-C3 -haloalky 1, -C(O)NHC3-C5-cycloalkyl, -C(O)NH-Ci-C4-alkyl-C3-C6-cycloalkyl, -C(0)NH-3- to 4- membered non-aromatic heterocyclic ring wherein said ring is substituted with Ci-C3-alkyl, -C(0)NH-3- to 4- membered non-aromatic heterocyclic ring, -NHC(O)Ci-C4-alkyl, -NR6C(O)NR6R7, -OC(O)NR6R7, -NR6C(O)OR7, -NR'R",-C(=O)-OH, -C(=O)-R", CR-NR", Si(R8)3, -C(0)-N=S(0)o-iR6aR6b, -N=S(0)o-iR6aR6band a 3- to 4-membered non-aromatic heterocyclic ring; wherein each non-aromatic heterocyclic ring in R5contains 1 or 2 heteroatoms independently selected from N, N(CH3), O or S;

[0189] wherein each of the Ci-C4-alkyl, Ci-Ch-alkcnyl. Ci-Oalkynyl. Ci-C4-alkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-Ci-C6-alkyl, C3-Ce-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkyloxy-Ci-C4-alkyl, -C(O)NHCi-C5-alkyl, -C(O)NHC3-C5-cycloalkyl and -NHC(O)Ci-C4-alkyl groups of R5are unsubstituted or substituted with one or two substituents independently selected from halogen, hydroxy or cyano.

[0190] In yet another embodiment of the present invention, R5is selected from the group consisting of hydrogen, halogen, hydroxy, cyano, nitro, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-alkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C3-haloalkyl, Ci-C4-alkylsulfanyl, C1-C4-alkylsulfmyl, Ci-C4-alkylsulfonyl, C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-Ci-C6-alkyl, C3-Ce-cycloalkenyl, C3-C6 -cycloalkyloxy, C3-C6-cycloalkyloxy-Ci-C4-alkyl, -C(O)NHCi-C5-alkyl, -C(O)N(Ci-C3-alkyl)2, -C(O)NHCi-C4-alkoxy, -C(O)N(Ci-C3-alkyl)(Ci-C3-alkoxy), -C(O)NHC3-C5-cycloalkyl wherein C3-C6-cycloalkyl is substituted with Ci-C2-haloalkyl, -C(O)NHC3-C5-cycloalkyl, -C(O)NH-Ci-C3-alkyl-C3-C6-cycloalkyl, -C(0)NH-4-membered non-aromatic heterocyclic ring wherein said ring is substituted with Ci-C3-alkyl, -C(0)NH-4-membered non-aromatic heterocyclic ring, -NHC(O)Ci-C4-alkyl, -NR6C(O)NR6R7, -OC(O)NR6R7, -NR6C(O)OR7, -NR'R",-C(=O)-OH, -C(=O)-R", CR-NR", Si(R8)3, -C(O)-N=S(O)R6aR6b, -N=S(0)o-iR6aR6band a 3- to 4-membered non-aromatic heterocyclic ring; wherein each non-aromatic heterocyclic ring in R5contains 1 or 2 heteroatoms independently selected from N, N(CH3), O or S;

[0191] wherein each of the Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-alkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfmyl, Ci-C4-alkylsulfonyl,C3-Ce-cycloalkyl, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-Ci-Ce-alkyl, C3-Ce-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkyloxy-Ci-C4-alkyl, -C(O)NHCi-C5-alkyl, -C(O)NHC3-C5-cycloalkyl and -NHC(O)Ci-C4-alkyl groups of R5are unsubstituted or substituted with one or two substituents independently selected from halogen, hydroxy or cyano. For example, when Ci-Ce-alkyl substituted with halogen, it refers to Ci-Ce-haloalkyl; when Ci-Ce-alkyl substituted with hydroxy, it refers to Ci-Ce-hydroxyalkyl; when Ci-Ce-alkyl substituted with cyano, it refers to Ci-Ce-cyanoyalkyl. The other terms mentioned above shall be construed in a similar manner.

[0192] In yet another embodiment of the present invention, R5is selected from the group consisiting of hydrogen, halogen, hydroxy, cyano, nitro, Ci-C4-alkyl, Ci-C4-alkoxy, C1-C4- haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C3-alkyl, -C(O)NHCi-C5-alkyl, -C(O)N(Ci-C3-alkyl)2, -C(O)NHCi-C4-alkoxy, -C(O)N(Ci-C3-alkyl)(Ci-C3-alkoxy), -C(O)NHC3-C5-cycloalkyl wherein C3-C5-cycloalkyl is substituted with C1-C2-haloalkyl, C(O)NHC3-C5-cycloalkyl, -C(O)NH-Ci-C3-alkyl-C3-C6-cycloalkyl, -C(0)NH-4-membered nonaromatic heterocyclic ring wherein said ring is substituted with Ci-C3-alkyl, -C(0)NH-4-membered nonaromatic heterocyclic ring, -NHC(O)Ci-C4-alkyl, -C(=O)-OH, -C(=O)-R", -C(O)-N=S(O)R6aR6b, -N=S(0)o-iR6aR6band a 3- to 4-membered non-aromatic heterocyclic ring; wherein each non-aromatic heterocyclic ring in R5contains 1 or 2 heteroatoms independently selected from N, N(CH3), O or S; wherein each of the Ci-Cr-alkyl, Ci-Cr-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C6- alkyl, -C(0)NHCI-C5-alkyl, -C(O)NHC3-C5-cycloalkyl and -NHC(O)Ci-C4-alkyl groups of R5are unsubstituted or substituted with one or two substituents independently selected from halogen, hydroxy or cyano.

[0193] In one embodiment of the present invention, R' and R" are independently selected from the group consisting of hydrogen, Ci-C4-alkyl, Ci-C4-alkoxy and C3-Ce-cycloalkyl; wherein alkyl and cycloalkyl groups are unsubstituted or substituted with one to three substituents independently selected from halogen, hydroxy or cyano.

[0194] In another embodiment of the present invention, R' and R" are independently selected from the group consisting of hydrogen, Ci-C3-alkyl, Ci-C3-alkoxy and C3-C5-cycloalkyl; wherein alkyl and cycloalkyl groups are unsubstituted or substituted with one or two substituents independently selected from halogen, hydroxy or cyano.

[0195] In yet another embodiment of the present R" is selected from the group consisting of hydrogen, Ci-C3-alkyl and Ci-Ce-alkoxy.

[0196] In one embodiment of the present invention, R6and R7are independently selected from the group consisting of hydrogen, Ci-Ce-alkyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkyl, Ci-Ce-haloalkoxy, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-Ce-alkoxy-Ci-Ce-alkyl and a 3- to 4-membered non-aromaticheterocyclic ring; wherein said 3- to 4- membered heterocyclic ring contains 1 or 2 heteroatoms independently selected from N, O or S.

[0197] In another embodiment of the present invention, R6and R7are independently selected from the group consisting of hydrogen, Ci-C4-alkyl, Ci-C4-cyanoalkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl and a 3- to 4-membered non-aromatic heterocyclic ring; wherein said 3- to 4- membered non-aromatic heterocyclic ring contains 1 or 2 heteroatoms independently selected from N, O or S.

[0198] In one embodiment of the present invention, R6ais selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl and NRaRb. In another embodiment of the present invention, R6ais selected from the group consisting of Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, C2-C4-haloalkenyl, C3-C6-cycloalkyl andNRaRb.

[0199] In a preferred embodiment of the present invention, R6ais selected from the group consisting of hydrogen, Ci-C4-alkyl, and Ci-C4-haloalkyl.

[0200] In a more preferred embodiment of the present invention, R6ais Ci-C3-alkyl.

[0201] In one embodiment of the present invention, R6bis selected from Ci-Ce-alkyl or C3-C6-cycloalkyl.

[0202] In another embodiment of the present invention, R6bis selected from Ci-C4-alkyl or C3-Ce-cycloalkyl. In a preferred embodiment of the present invention, R6bis Ci-C3-alkyl.

[0203] In one embodiment of the present invention, R6aand R6btogether with the sulfur atom to which they are attached may form a 4- to 6-membered non-aromatic heterocyclic ring; wherein said heterocyclic ring contains an additional 1 or 2 heteroatoms independently selected from N, O or S.

[0204] In another embodiment of the present invention, R6aand R6btogether with the sulfur atom to which they are attached may form a 5- to 6-membered non-aromatic heterocyclic ring; wherein said heterocyclic ring contains an additional 1 or 2 heteroatoms independently selected from N or O or S.

[0205] In yet another embodiment of the present invention, R6aand R6btogether with the sulfur atom to which they are attached may form a 5- to 6-membered non-aromatic heterocyclic ring; wherein said heterocyclic ring contains an additional one heteroatom selected from N or O.

[0206] In yet another embodiment of the present invention, R6aand R6btogether with the sulfur atom to which they are attached may form a 5-membered non-aromatic heterocyclic ring; wherein said heterocyclic ring contains an additional one heteroatom selected from N or O.In another embodiment of the present invention, R6aand R6btogether with the sulfur atom to which they are attached may form a 6-membered non-aromatic heterocyclic ring; wherein said heterocyclic ring contains an additional one heteroatom selected from N or O.

[0207] In one embodiment of the present invention, Raand Rbare independently selected from hydrogen or Ci-Cs-alkyl.

[0208] In another embodiment of the present invention, Raand Rbare independently selected from hydrogen or Ci-C4-alkyl.

[0209] In one embodiment of the present invention, R8is independently selected from the group consisting of Ci-Ce-alkyl, Cz-Ce-alkenyl, Cz-Ce-alkynyl, and C3-C6-cycloalkyl.

[0210] In another embodiment of the present invention, R8is independently selected from the group consisting of Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, and C3-Ce-cycloalkyl.

[0211] For the substituents defined herein above, any or more of the definitions provided above may be combined with any definition of any other substituent defined herein above. Such combinations include all variations within the scope of the definitions provided. For example, but not limited to, the present invention provides compounds of formula (I) or salts, stereoisomers, metal complexes, polymorphs or N-oxides thereof,

[0212]

[0213] wherein,

[0214] Rlais Ci-G-alkcnyl: wherein said Rlais unsubstituted or substituted with one to three groups independently selected from hydrogen, halogen, CN, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy, Ci-C3-haloalkyl or C3-Cs-cycloalkyl;

[0215] Rlbis selected from the group consisiting of hydrogen, halogen and Ci-C3-haloalkyl;

[0216] R2is selected from the group consisting of hydrogen and Ci-C3-alkyl;

[0217] R3ais Ci-C3-alkyl;

[0218] R3bis hydrogen;

[0219] ring-A is selected from ring-Al or ring-A2,

[0220]

[0221] ring-A1 ring-A2

[0222] wherein, JJJJindicates the point of attachment to the carbon atom that is bonded to the amide nitrogen and # indicates the point of attachment to the Q substituent;

[0223] R4is selected from the group consisiting of hydrogen and Ci-C3-alkyl;

[0224] Q is selected from 5- or 6- membered heteroaryl ring; wherein said heteroaryl ring is unsubstituted or substituted with one or two substituents independently selected from R5;

[0225] R5is selected from the group consisiting of hydrogen, halogen, hydroxy, cyano, nitro, Ci-C4-alkyl, C1-C4-alkoxy, C1-C4- haloalkyl, C3-Ce-cycloalkyl, C3-C6-cycloalkyl-Ci-C3-alkyl, -C(O)NHCi-C5-alkyl, -C(O)N(Ci-C3-alkyl)2, -C(O)NHCi-C4-alkoxy, -C(O)N(Ci-C3-alkyl)(Ci-C3-alkoxy), -C(O)NHC3-C5-cycloalkyl wherein C3-C5-cycloalkyl is substituted with Ci-C’i-haloalkyl. C(O)NHC3-C5-cycloalkyl, -C(O)NH-Ci-C3-alkyl-C3-C6-cycloalkyl, -C(0)NH-4-membered non-aromatic heterocyclic ring wherein said ring is substituted with Ci-C3-alkyl, -C(0)NH-4-membered non-aromatic heterocyclic ring, -NHC(O)Ci-C4-alkyl, -C(=O)-OH, -C(=O)-R", -C(O)-N=S(O)R6aR6b, -N=S(0)o-iR6aR6band a 3- to 4-membered non-aromatic heterocyclic ring; wherein each non-aromatic heterocyclic ring in R5contains 1 or 2 heteroatoms independently selected from N, N(CH3), O or S; wherein each of the Ci-C4-alkyl, C1-C4-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C3-alkyl, -C(O)NHCi-C5-alkyl, -C(O)NHC3-C5-cycloalkyl and -NHC(O)Ci-C4-alkyl groups of R5are unsubstituted or substituted with one or two substituents independently selected from halogen, hydroxy or cyano;

[0226] R" is selected from the group consisting of hydrogen, Ci-C3-alkyl and Ci-Ce-alkoxy;

[0227] R6ais selected from the group consisting of hydrogen, Ci-C4-alkyl, and C1-C4 -haloalkyl;

[0228] R6bis Ci-C3-alkyl;

[0229] or

[0230] R6aand R6btogether with the sulfur atom to which they are attached may form a 5- to 6-membered non-aromatic heterocyclic ring; wherein said heterocyclic ring contains an additional 1 or 2 heteroatoms independently selected from N or O or S.

[0231] In one embodiment, the present invention provides an intermediate compound of formula (IC),o

[0232]

[0233] (IC)

[0234] wheren,

[0235] R1ais C2-alkenyl; wherein said R1ais unsubstituted or substituted with one to three groups independently selected from hydrogen, halogen, CN, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-haloalkyl, C3-C5-cycloalkyl or C3-C5-halocycloalkyl; with the provisio that the compound of formula (IC) excludes 3- (l-Cyclopropyl-2,2-difluoroethenyl)-5-(trifluoromethyl)benzoic acid and 3-(l-Cyclopropyktbenyl)-5- (triiluoroniethyl)benzoic acid.

[0236] The compounds of the present invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and / or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and / or selectively prepare said stereoisomers. The compounds of the present invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form.

[0237] An anion part of the salt, in case the compound of formula (I) is a cationic or capable of forming a cation, can be inorganic or organic. Alternatively, a cation part of the salt, in case the compound of formula (I) is an anionic or capable of forming anion, can be inorganic or organic. Examples of inorganic anion parts of the salt include but are not limited to chloride, bromide, iodide, fluoride, sulfate, phosphate, nitrate, nitrite, hydrogen carbonates and hydrogen sulfate. Examples of organic anion part of the salt include but are not limited to formate, alkanoates, carbonates, acetates, trifluoroacetate, trichloroacetate, propionate, glycolate, thiocyanate, lactate, succinate, malate, citrates, benzoates, cinnamates, oxalates, alkylsulphates, alkylsulphonates, arylsulphonates aryldisulphonates, alkylphosphonates, arylphosphonates, aryldiphosphonates, p-toluenesulphonate, and salicylate. Examples of inorganic cation parts of the salt include but are not limited to alkali and alkaline earth metals. Examples of organic cation parts of the salt include but are not limited to pyridine, methyl amine, imidazole, benzimidazole, hitidine, phosphazene, tetramethyl ammonium, tetrabutylammonium, choline and trimethylamine.

[0238] Metal ions in metal complexes of the compound of formula (I) are especially ions of the elements of the second main group, especially calcium and magnesium, of the third and fourth main group, especiallyaluminium, tin and lead, and of the first to eighth transition groups, especially chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Particular preference is given to the metal ions of the elements of the fourth period and the first to eighth transition groups. Here, the metals can be present in the various valencies that they can assume.

[0239] In one embodiment, the present invention provides a compound of formula (I) or salts, metal complexes, stereo-isomers, polymorphs or N-oxides thereof and its composition with the excipient, inert carrier or any other essential ingredient such as surfactants, additives, solid diluents and liquid diluents.

[0240] Salts of the compounds of the formula (I) are veterinary and / or agriculturally acceptable salts, preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (I) has a basic functionality.

[0241] The term " N-oxide" includes any compound of formula (I) which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.

[0242] The compounds of formula (I), (including all stereoisomers, N-oxides, and salts thereof), typically exist in more than one form, and formula (I) thus includes all crystalline and non-crystalline forms of the compounds that formula (I) represents. Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The term "polymorph" refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and / or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound represented by formula (I) can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by formula (I). Preparation and isolation of a particular polymorph of a compound represented by formula (I) can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures.In one embodiment, the present invention provides a process for preparing the compounds of formula (I) or salts thereof,

[0243]

[0244] (I)

[0245] The compounds of the present invention as defined by formula (I) and / or in table (1) may be prepared, basically in a known manner, in a variety of ways as described in the schemes. Compounds of the present invention can be made as shown in the following general synthetic schemes, in which, unless otherwise stated, the definition of each variable is as defined above for the compounds of formula (I).

[0246] General Synthetic Schemes

[0247] Compounds of formula (I) can be prepared as shown in scheme 1, wherein Yxstands for OH or Cl or Ci-Ce-alkoxy.

[0248] Scheme 1:

[0249]

[0250] The compounds of formula (a) can be reacted with carboxylic acids of formula (b) (wherein Yxis OH) in the presence of suitable amide coupling reagents such as propylphosphonic anhydride (T3P®), 1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU), N,N'-Dicyclohexylcarbodiimide (DCC), hydroxybenzotriazole (HOBt) and the like, a suitable base such as triethyl amine, N,N-diisopropylethylamine (DIPEA) and the like, in a suitable solvent such as N,N-dimethylformamide (DMF), dichloromethane (CH2Cl2), acetonitrile and the like, at a temperature ranging from 0 to 100 °C to provide compounds of formula (I) which may then be isolated and purified if necessary by using chromatographic purification techniques or by crystallization techniques using suitable solvents.

[0251] Carboxylic acids of formula (b) and the compounds of formula (a) are commercially available or may be synthesized by methods known in the literature, for example in WO2017192385 and WO2021177160.The compounds of formula (a) wherein ring-A is triazolyl substituted with R4can be prepared as shown in scheme 2.

[0252] Scheme 2:

[0253] Q

[0254] R3" R3bR3’ R3bI Boc.„^C _NH N2R”R3b Boc-deprotection Boc R2O R4= H, Alkyl or 'N-Y cycloalkyl etc R2O

[0255] (fl)

[0256]

[0257] (c)R4

[0258] Amide compounds of formula (c) can be reacted with an N,N-dimethylamide dimethyl acetal of formula (d) in a suitable solvent such as dichloromethane and the like, at reflux to form compounds of formula (e). After removal of the solvent, the compounds of formula (e) can subsequently be reacted with substituted hydrazine of formula (f) under acidic conditions in a suitable solvent such as 1,4-dioxane, acetic acid or a mixture of solvents and the like, at a temperature ranging from 20-100 °C to form compounds of formula (g). Further compounds of formula (g) can then be subjected to Boc-deprotection with an acid such as trifluoroacetic acid, hydrogen chloride and the like, in a suitable solvent such as dichloromethane, 1,4-dioxane and the like, at a temperature ranging from 0-40 °C to form amines of formula (a). The compounds of formula (a) may be isolated as their salts or, after base treatment, as a free amine and purified through chromatographic technique if necessary.

[0259] Compounds of formula (a) wherein ring-A is pyrazinyl substituted or unsubstituted with one to two R4can be prepared as shown in scheme 3.

[0260] Scheme 3:

[0261] . Q

[0262] (n-Bu)3-Sn

[0263] 0-1)

[0264] Rd catalysed R2-NH2R3’R3b®

[0265] Stille reaction (k)

[0266] HN >f

[0267] or

[0268] R

[0269] . Q reductive amination2

[0270] AB

[0271] (i-2)

[0272] Suzuki coupling Step-2

[0273]

[0274] Step-1

[0275] Compounds of formula (h) wherein LG is selected from halogen or sulfonate groups (such as frifhrromethanesulfonate) are commercially available (CAS NO 121246-90-0 & 2645412-51-0) or can be synthesized by methods known in the literature, for example in WO2021068179 and WO2021069575.

[0276] Compounds of formula (h) can undergo a Stille coupling with compounds of formula (i-1) in the presence of a palladium catalyst, for example tetrakis(triphenylphosphine)palladium(0), palladium chloride (PdCl2),palladium acetate (Pd(OAc)2), 1,1' bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane complex and the like, in an inert solvent such as N,N-dimethylformamide (DMF), acetonitrile, 1,4-dioxane and the like, optionally in the presence of an additive, such as potassium or cesium fluoride, lithium chloride, tetrabutyl ammonium fluoride and the like, and optionally in the presence of a further catalyst, for example, copper(I)iodide to give compounds of formula (j). Such Stille couplings are also well described in the literature, for example in W02020201398.

[0277] Alternatively, compounds of formula (j) can also be synthesized through a Suzuki coupling by reacting compounds of formula (h) with compounds of formula (i-2) (wherein group BA is selected from boronic acids or pinacol boronate ester or tritiates) in the presence of a palladium catalyst for example tetrakis(triphenylphosphine)palladium(0), palladium chloride (PdCh), palladium acetate (Pd(OAc)2), 1,1 'bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane complex and the like, in the presence of a base, such as sodium carbonate, potassium phosphate, cesium fluoride and the like, in a solvent or a solvent mixture, for example, a mixture of 1,2-dimethoxy ethane and water, 1,4-dioxane and water, ethanol and water or N, A -dimcth I formamide and water, preferably under an inert atmosphere. The reaction temperature can preferentially range from 25 °C to the reflux of the reaction mixture. Such Suzuki reactions are well known in the literature, for example in WO2023072849.

[0278] Reductive amination of compounds of formula (j) can be performed with amines of formula (k) in the presence of suitable reducing agents such as sodium triacetoxyborohydrides (NaBH(OAc)3), (J. Org. Chem., 1996, 61, 3849-3862), or sodium cyanoborohydride (NaCNBH3) as reductive reagent, in a suitable solvent, such as methanol, dichloroethane, dichloromethane or tetrahydrofuran and the like, in the presence of acetic acid at a temperature ranging from 25 °C to 75 °C to form compounds of formula (a).

[0279] Compounds of formula (I) can also be prepared as shown in scheme 4.

[0280] Scheme 4:

[0281]

[0282] Reductive amination of compounds of formula (h) can be performed with amines of formula (k) in the presence of reducing agents such as sodium triacetoxyborohydrides (NaBH(OAc)3), (J. Org. Chem., 1996, 61, 3849-3862), or sodium cyanoborohydride (NaCNBH3), in a suitable solvent, such asmethanol, dichloroethane, dichloromethane or tetrahydrofuran and the like, in the presence of acetic acid at a temperature ranging from 25 °C to 75 °C to form compounds of formula (L). The compounds of formula (L) can be coupled with carboxylic acids of formula (b) (wherein Yxis OH), in the presence of suitable amide coupling reagents such as propylphosphonic anhydride (T3P®), 1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxid hexafluorophosphate (HATU), N,N'-Dicyclohexylcarbodiimide (DCC), Hydroxybenzotriazole (HOBt) and the like, a suitable base such as triethyl amine, N, N-diisopropylethylamine (DIPEA) and the like, in a suitable solvent such as N,N-dimethylformamide, dichloromethane, acetonitrile and the like, at a temperature ranging from 0 to 100 °C to provide compounds of formula (m) which may then be isolated and purified if necessary by using chromatographic purification techniques or by crystallization techniques using suitable solvents.

[0283] Compounds of formula (m) may undergo a Stille coupling with compounds of formula (i-3) in the presence of a palladium catalyst, for example, tetrakis(triphenylphosphine)palladium(0), palladium chloride (PdCl2), palladium acetate (Pd(OAc)2), 1,1' bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane complex and the like, in an inert solvent such as N,N-dimethylformamide, acetonitrile, 1,4-dioxane and the like, optionally in the presence of an additive, such as potassium or cesium fluoride, lithium chloride, tetrabutyl ammonium fluoride and the like, and optionally in the presence of a further catalyst, for example copper(I)iodide to give compounds of formula (I). Such Stille couplings are also well described in the literature, for example in W02020201398.

[0284] Alternatively, compounds of formula (I) can also be synthesized through a Suzuki coupling by reacting compounds of formula (m) with compounds of formula (i-4) (wherein group BA is selected from boronic acids or pinacol boronate ester or tritiates) in the presence of a palladium catalyst for example tetrakis(triphenylphosphine)palladium(0), palladium chloride (PdCl2), palladium acetate (Pd(OAc)2), 1,1'bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane complex and the like, in the presence of a base, such as sodium carbonate, potassium phosphate, cesium fluoride and the like, in a solvent or a solvent mixture, for example a mixture of 1,2-dimethoxyethane and water, 1,4-dioxane and water, ethanol and water or N,N-dimethylformamide and water preferably under an inert atmosphere. The reaction temperature can preferentially range from 25 °C to the boiling point of the reaction mixture. Such Suzuki reactions are well known in the literature, for example in J. Org. Chem., 2007, 72, 4067-4072. Compounds of formula (p & q) can be prepared as shown in scheme 5. Such chemical synthesis is also described in the literature, for example in WO2021170881.

[0285] Scheme 5:

[0286]

[0287] Compounds of formula (m) can react with stannane reagents of formula (i-5) wherein Rx, Ryand Rzare selected from hydrogen, Ci-Ce-alkyl or Ci-Ce-alkoxy, to provide compounds of formula (n) following a Stille coupling protocol as described in scheme-4. Compounds of formula (o) can be synthesized from compounds of formula (n) by treating the compounds of formula (n) with oxidizing reagents for example, potassium permanganate, sodium chromate and the like, in a suitable solvent such as acetone and water, 1,4-dioxane and water, acetonitrile and water and the like, at a temperature ranging from 0 to 100 °C to provide compounds of formula (o) which may then be isolated and purified if necessary by using chromatographic purification techniques or by crystallization techniques using suitable solvents.

[0288] The compounds of formulas (p & q) can be obtained by reacting a carboxylic acid of formula (o) with amine analogues (r-1 and r-2) respectively, in the presence of suitable amide coupling reagents such as propylphosphonic anhydride (T3P®), 1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxid hexafluorophosphate (HATU), N,N'-Dicyclohexylcarbodiimide (DCC), Hydroxybenzotriazole (HOBt) and the like, a suitable base such as triethyl amine, N,N-diisopropylethylamine and the like, in a suitable solvent such as N,N-dimethylformamide, dichloromethane, acetonitrile and the like, at a temperature ranging from 0 to 100 °C to provide compounds of formulas (p and q) which may then be isolated and purified if necessary by using chromatographic purification techniques or by a crystallization technique using suitable solvents.

[0289] Compounds of formula (u) can be prepared as shown in scheme 6.

[0290] Scheme 6:

[0291]

[0292] The compounds of formula (n) wherein Rx=OEt, OMe, Ry=Rz=H, can be reacted with an acid for example, hydrochloric acid, sulfuric acid, acetic acid and the like, in a suitable solvent such as acetone, acetonitrile, 1,4-dioxane and the like, at a temperature ranging from 0 to 100 °C to provide compounds of formula (s) which may then be isolated and purified if necessary by using chromatographic purification techniques or by crystallization techniques using suitable solvents. Such chemical synthesis is known in the literature, for example in Bioorganic & Medicinal Chemistry Letters (2010), 20(2), 679-683).

[0293] The ketone analogues of formula (s) can be treated with amines of formula (t) (wherein Y= O, NR’ wherein R’ is Ci-C4-alkyl or hydrogen, in the presence of acids for example, hydrochloric acid, sulfuric acid, acetic acid and the like, in a suitable solvent such as tetrahydrofuran, ethanol, methanol, 1,4-dioxane and the like, at a temperature ranging from 0 to 100 °C to provide compounds of formula (u) which may then be isolated and purified if necessary by using chromatographic purification techniques or by a crystallization technique using suitable solvents. Such chemical synthesis is known in the literature, for example in W02023025602. Carboxylic ester analogues of formula (x) can be prepared as shown in scheme 7. Such chemical synthesis is described in the literature, for example in W02023090337.

[0294] Scheme 7:

[0295] R1ac Cl / Br

[0296] i^CI / Br

[0297] R(w)

[0298] Zn, Acid,

[0299]

[0300] (X) Step-2 (b)

[0301] The ketone and aldehyde compounds of formula (v) can be reacted with the compounds of formula (w) in the presence of a metal such as Zn, Cu and the like, with a metal catalyst for example, copper (I) chloride, copper (II) chloride and the like, in appropriate solvents such as tefrahydrofuran, N,N-dimethylformamide, chloroform, acetonitrile and the like, at a temperature ranging from 0 to 100 °C to provide compounds of formula (x) which may then be isolated and purified if necessary by using chromatographic purification techniques or by a crystallization technique using suitable solvents. The compounds of formula (b) wherein YX=OH, can be prepared from compounds of formula (x) by reacting with a base for example, lithium hydroxide, sodium hydroxide, potassium hydroxide and the like, in the presence of suitable solvents such as tetrahydrofuran, methanol, ethanol or water and their mixtures, at a temperature ranging from 0 to 100 °C to provide compounds of formula (b) which may then be isolated and purified if necessary by using chromatographic purification techniques or by a crystallization technique using suitable solvents.Alternatively, carboxylic ester analogues of formula (x) can also be prepared as shown in scheme 8. Such synthetic protocol is described in the literature, for example in W02008042639 and W02020002563.

[0302] Scheme 8:

[0303] Step-2

[0304]

[0305] Step-1 Compounds of formula (y) wherein W is selected from halogen (Cl, Br and I) and OTf, may undergo a coupling reaction for example, a Stille coupling with stannanes (z-i) (wherein ML represents=SnBu3) or a Suzuki coupling with boronic acid / ester analogues (z-i) (wherein ML= boronic acid or boronate ester), and the like, in the presence of a palladium catalyst, for example tetrakis(triphenylphosphine)palladium(0), palladium chloride (PdCL). palladium acetate (Pd(OAc)2), 1,1' bis(diphenylphosphino)-ferrocene)dichloropalladium -dichloromethane complex and the like, optionally in the presence of a suitable base such as potassium carbonate, potassium phosphate and the like, in a suitable solvent such as toluene, acetonitrile, A'. A'-dimcthylformamidc and the like or a solvent mixture thereof, for example, a mixture of 1,2-dimethoxyethane and water, 1,4-dioxane and water, ethanol and water or N, A'-dimcth l formamide and water; preferably under an inert atmosphere, at a temperature ranging from 60-120 °C in an inert solvent, optionally in the presence of an additive, such as potassium or cesium fluoride, lithium chloride, tetrabutyl ammonium fluoride and the like, and optionally in the presence of a further catalyst, for example copper(I)iodide to give compounds of formula (x). Such couplings are also well described in the literature, for example in WO2015058129 (Suzuki coupling) and W02020201079 (Stille coupling). Compounds of formula (x) can also be synthesized through a Heck coupling by reacting compounds of formula (z-ii) in the presence of a palladium catalyst, for example, tetrakis(triphenylphosphine)palladium(0), palladium chloride (PdCl2), palladium acetate (Pd(OAc)2), 1,1 'bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane complex and the like, in the presence of a base, such as sodium carbonate, potassium phosphate, cesium fluoride and the like, in a solvent for example, toluene, acetonitrile, N, N-dimethylformamide and the like or a solvent mixture thereof, for example, a mixture of 1,2-dimethoxyethane and water, 1,4-dioxane and water, ethanol and water or AfA'-dimcthylfonnamidc and water preferably under an inert atmosphere, optionally in the presence of a ligand, such as X-Phos, Xantphos and the like, at a temperature in the range of 25 °C to the boiling point of the reaction mixture.Alternatively, compounds of formula (x) can be synthesized from compounds of formula (aa), wherein ML is SnBu3 for a Stille coupling, ML is a boronic acid or boronate ester for a Suzuki coupling and ML is a magnesium bromide or chloride for a Kumada coupling, reacting with compounds of formula (ab) wherein W is selected from halogen (Cl, Br and I) and OTf following a Stille coupling, Suzuki coupling and Kumada coupling. The compounds of formula (x) may then be isolated and purified if necessary, by using chromatographic purification techniques or by crystallization techniques using suitable solvents.

[0306] Carboxylic ester analogues of formula (x) can also be prepared as shown in scheme 9, wherein Rlb, Rlaa, Rlaband Rlacare as described above. Such synthetic protocol is described in the literature, for example in Synthesis (2009), (13), 2249-2259.

[0307] Scheme 9:

[0308] o

[0309] R1ac

[0310] (ad)

[0311]

[0312] Compounds of formula (ac) and (ad) can be reacted with nucleophiles of formula (ae-i) and (ae-ii) respectively wherein M is selected from sodium metal (Na) or potassium metal (K) and Rlaaand Rlabare selected from Cl, Br, F, CN, methoxy, ethoxy or thio methyl (SMe), in a suitable solvent such as acetonitrile, N,N-dimethylformamide, dichloromethane and the like, at a temperature in the range of 25 °C to the boiling point of the reaction mixture to provide compounds of formula (x). The compounds of formula (x) may then be isolated and purified if necessary, by using chromatographic purification techniques or by crystallization techniques using suitable solvents.

[0313] Starting material(s) of the above schemes are either commercially available or prepared according to the methods known in the literature(s).

[0314] Depending on the nature of the substituents, the compounds of formula (I), and the intermediates thereof may be present either in pure form or as mixtures of different possible isomeric forms such as stereoisomers or constitutional isomers. The various stereoisomers include enantiomers, diastereomers, chiral isomers, atropisomers, conformers, rotamers, tautomers, optical isomers, polymorphs, and geometric isomers. Depending on the nature of the substituents, the compounds of formula (I) and intermediates thereof, as mentioned in the general schemes, can also exist in one or more geometric isomer forms depending on the relative position (syn / anti or cis / frans) of the substituents. The invention thus relates equally to all syn / anti (or cis / frans) isomers and to all possible syn / anti (or cis / frans) mixtures, in all proportions. The syn / anti (orcis / trans) isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art.

[0315] In another embodiment, the present invention provides a process for the preparation of the compound of formula (I) or the salts thereof.

[0316] The compounds of formula (I), including their stereoisomers, salts, and N-oxides, and their precursors in the synthesis process, can be prepared by the methods described above. If individual compounds can not be prepared via the above-described routes, they can be prepared by derivatization of other compounds (I) or the respective precursor or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds of formula (I) can advantageously be prepared from other compounds of formula (I) by derivatization, e.g. by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like, or by customary modifications of the synthesis routes described.

[0317] The reaction mixtures are worked up in a customary manner, e.g. by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colourless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.

[0318] If individual compounds (I) cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds of formula (I). However, if the synthesis yields mixtures of isomers, separation is generally not necessarily required since in some cases the individual isomers can be interconverted during a work-up for use or during application (e.g. under the action of light, acids or bases). Such conversions may also take place after use, e.g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.

[0319] In one embodiment, the present invention provides a composition for controlling or preventing invertebrate pests. The composition comprises a biologically effective amount of the compound of formula (I) or salts, stereo-isomers, metal complexes, polymorphs, or N-oxides thereof and at least one additional component selected from the group consisting of surfactants and auxiliaries.

[0320] In yet another embodiment, the composition additionally comprises at least one additional biologically active and compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, biostimulants, antibiotics, fertilizers or nutrients.In yet another embodiment, the present invention provides compounds of formula (I) or its N-oxides and salts in customary types of agrochemical compositions / formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition / formulations types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further composition / formulation types are defined in the " Catalogue of pesticide formulation types and international coding system", in the Technical Monograph No. 2, 6thEd. May 2008, CropLife International.

[0321] The compositions / formulations are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation or in Agrow Reports DS243, T and in F Informa, London, 2005. In one another embodiment, the present invention provides agrochemical compositions with the compound of formula (I), which comprise an active substance content between 0.01 and 95% by weight, preferably between 0.1 and 90%, and more preferably between 1 and 70 %, by weight of active substance. The active substances are employed in a purity from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).

[0322] 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 employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready -to-use preparations. Applications can be carried out before or during sowing. Methods for applying or treating compounds of formula (I) and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and infurrow application methods of the propagation material. Preferably, the compound of formula (I) or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that the germination is not induced, e.g. by seed dressing, pelleting, coating and dusting.

[0323] When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.02 to 0.9 kg per ha, in particular from 0.05 to 0.75 kg per ha.In the treatment of plant propagation materials such as seeds, e.g. by dusting, coating or drenching seed, amounts of active substance from 0.1 to 1000 g, preferably from 1 to 500 g, more preferably from 5 to 200 g and most preferably from 10 to 100 g per 100 kilogram of plant propagation material (preferably seed) are generally required.

[0324] When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active substance per cubic meter of treated material.

[0325] Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners, antibiotics, fertilizers, nutrients and biostimulants) may be added to the active substances or the compositions comprising them as premix or, if appropriate, not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the present invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0326] The user can apply the composition according to the present invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and / or further auxiliaries to the desired application concentration and the ready -to-use spray liquor or the agrochemical composition according to the present invention is thus obtained. Usually, 20 to 6000 liters, preferably 35 to 1000 litres, more preferably 50 to 500 liters, of the ready -to-use spray liquor are applied per hectare of the agricultural useful area.

[0327] According to one embodiment, individual components of the composition according to the present invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.

[0328] The compounds and compositions of the present invention are thus useful agronomically for protecting field crops from phytophagous invertebrate pests, as well as nonagronomically for protecting other horticultural crops and plants from phytophagous invertebrate pests. This utility includes protecting crops and other plants (i.e. both agronomic and nonagronomic) that contain genetic material introduced by genetic engineering (i.e. transgenic) or modified by mutagenesis to provide advantageous traits.

[0329] The compounds of the present invention are characterized by favorable metabolic and / or soil residual patterns and exhibit activity controlling a wide spectrum of agronomic and non-agronomic invertebrate pests. The compounds of the present invention are preventively and / or curatively valuable active ingredients in the field of pest control, even at low rates of application, which can be used against insecticide resistant pests such as insects and mites, and are well tolerated by warm-blooded species, fish and plants.In the context of the present invention "invertebrate pest control" means inhibition of invertebrate pest development (including mortality) that causes a significant reduction in feeding or other injury or damage caused by the pest; related expressions are defined analogously. As referred to in the present invention, the term "invertebrate pest" includes arthropods, gastropods and nematodes of economic importance as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.

[0330] The term "gastropod" includes snails, slugs and other stylommatophora. The term "nematode" includes all helminths, such as: roundworms, heartworms, and phytophagous nematodes (Nematoda), flukes (Trematoda), acanthocephala, and tapeworms (Cestoda). Those skilled in the art will recognize that not all compounds are equally effective against all pests.

[0331] The compounds of the present invention display activity against economically important agronomic, forest, greenhouse, nursery, ornamentals, turfgrass, food and fiber, public and animal health, domestic and commercial structure, household, and stored product pests. These include larvae of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (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); borers, casebearers, webworms, coneworms, cabbageworms and skeletonizers from the family Pyralidae (e.g., European com borer (Ostrinia nubilalis Hubner), navel orangeworm (Amyelois transitella Walker), com root webworm (Crambus caliginosellus Clemens), sod webworm (Herpelogramma licarsisalis Walker)); leafrollers, budworms, seed worms, and fruit worms in the family Tortricidae (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruit moth (Grapholita molesta Busck)); and many other economically important lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymanlria dispar Linnaeus)); nymphs and adults of the order Blattodea including cockroaches from the families Blattellidae and Blattidae (e.g., oriental cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella gemnanica Linnaeus), brownbanded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius)); foliar feeding larvae and adults of the order Coleoptera including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus)); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafminers in the family Chrysomelidae (e.g., Colorado potato beetle (Leptinotarsa decemlineata Say),western com rootworm {Diabrotica virgifera virgifera LeConte)); chafers and other beetles from the family Scaribaeidae (e.g., Japanese beetle {Popillia japonica Newman) and European chafer {Rhizotrogus majalis Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae. In addition it includes: adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig {Forficula auricularia Linnaeus), black earwig (Chelisoches mono Fabricius)); adults and nymphs of the orders Hemiptera and Homoptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g. Empoasca spp.) from the family Cicadellidae, planthoppers from the families Fulgoroidae and Delphacidae, treehoppers from the family Membracidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink bugs from the family Pentatomidae, cinch bugs (e.g., Blissus spp.) and other seed bugs from the family Lygaeidae, spittlebugs from the family Cercopidae squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae. Also included are adults and larvae of the order Acari (mites) such as spider mites and red mites in the family Tetranychidae (e.g., European red mite I’anonychus ulmi Koch), two spotted spider mite Tetranychus urticae Koch), McDaniel mite (Tetranychus mcdanieli McGregor)), flat mites in the family Tenuipalpidae (e.g., citrus flat mite {Brevipalpus lewisi McGregor)), rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e. dust mites in the family Epidermoptidae, follicle mites in the family Demodicidae, grain mites in the family Glycyphagidae, ticks in the order 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 and itch mites in the families Psoroptidae, Pyemotidae, and Sarcoptidae; adults and immatures of the order Orthoptera including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locust {Schistocerca gregaria Forskal), migratory locust (Locusta migratoria Linnaeus), house cricket {Acheta domesticus Linnaeus), mole crickets (Gryllotalpa spp.));, adults and immatures of the order Diptera including 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., Chrysomya spp., Phormia 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; adults and immatures of the order Thysanoptera including onion thrips (Thrips tabaci Lindeman) and other foliar feeding thrips; insect pests of the order Hymenoptera including 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 Forster), odorous house ant (Tapinoma sessile Say)), bees (including carpenter bees), hornets, yellow jackets and wasps; insect pests of the order Isoptera including the 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 termites of economic importance; insect pests of the order Thysanura such as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard); insect pests of the order Mallophaga and including the head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitszch), dog biting louse (Trichodectes canis De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haemalopinus eurystemus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera including the oriental rat flea (Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felis Bouche), dog flea (Clenocephalides canis Curtis), hen flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea (Pulex irritans Linnaeus) and other fleas afflicting mammals and birds. Additional arthropod pests covered include: spiders in the order Araneae such as the brown recluse spider (Loxosceles reclusa Gertsch and Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and centipedes in the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus). Activity also includes members of the Classes Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e. all economically important flukes, tapeworms, and roundworms, such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.).The compounds of the present invention show particularly high activity against pests in the order Lepidoptera (e.g., Alabama argillacea Hubner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice leaf roller), Crambus caliginosellus Clemens (com root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Hübner (Cotton bollworm), Helicoverpa zea Boddie (com earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod webworm), Lobesia botrana Denis and grape berry moth, Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Hubner (beet army worm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm), Trichoplusia ni Hübner (cabbage looper) and Tula absoluta Meyrick (tomato leafminer)).

[0332] Compounds of the present invention also have commercially significant activity on members from the order Homoptera including: Acyrthosiphon 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 Passerini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffrey (mealy plum aphid), Lipaphis erysimi Kaltenbach (turnip aphid), Metopolophium dirrhodum Walker (cereal aphid), Macrosiphum euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (com leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry -oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii, Boyer de Fonscolombe (black citrus aphid), and Toxoptera citricida Kirkaldy (brown citrus aphid); Adelges spp. (adelgids); 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 striatellus Fallen (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 (com planthopper), Sogatella furcifera Horvath (white-backed planthopper),Sogatodes orizicola Muir (rice delphacid), Typhlocyba pomaria McAfee white apple leafhopper, Erythroneoura spp. (grape leafhoppers); Magicidada septendecim Linnaeus (periodical cicada); Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotus perniciosus Comstock (San Jose scale); Pianococcus citri Risso (citrus mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmon psylla).

[0333] These compounds also have activity on members from the order 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-S chaffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolrius Palisot deBeauvois (one-spotted stink bug), Graptosthetus spp. (complex of seed bugs), 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 Dallas (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper). Other insects which are controlled by compounds of formula (I) of the present invention include: Thysanoptera (e.g., Frankliniella occidentalis Pergande (western flower thrip), Scirtothrips citri Moulton (citrus thrip), Sericothrips variabilis Beach (soybean thrip), and Thrips tabaci Lindeman (onion thrip); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes, Athous or Limonius).

[0334] Particularly, the compounds of formula (I), their N-oxides, their stereoisomers, their polymorphs and their salts are especially suitable for efficiently combating the following pests: Insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ipsilon, 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, Ostrinia 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

[0335] 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 ruflmanus, Bruchus pisorum, Bruchus lends, 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 hordeola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria; 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; termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes,Reticulitermes virginicus, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus; cockroaches (Blattaria Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis; ants, bees, wasps, sawflies (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; crickets, grasshoppers, locusts (Orthoptera), e.g. 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; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa; fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, silverfish, firebrat (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 gallinae, Menacanthus stramineus and Solenopotes capillatus. Collembola (springtails), e.g. Onychiurus ssp. The compounds of formula (I) of the present invention are also suitable for controlling Nematodes: plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, 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 nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species;Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.

[0336] The compounds of formula (I) and their salts are also useful for controlling arachnids (Arachnoidea), such as acarians (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius 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.

[0337] In one embodiment of the present invention, the present invention provides the compounds of formula (I) which are useful for controlling insects selected from sucking or piercing insects such as insects from the genera Thysanoptera, Diptera and Hemiptera, in particular the following species:

[0338] Thysanoptera: Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,

[0339] 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, GeomyzaTripunctata, 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;

[0340] 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, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii.

[0341] In one embodiment, the present invention of the compound of formula (I) is useful for controlling diamondback moth (Plutella xylostella), american bollworm Húbner (Helicoverpa armigera), fall army worm (Spodoptera frugiperda), tobacco cutworm, cluster caterpillar Fabricius (Spodoptera litura), western flower thrips (Frankliniella occidentalis), potato leafhopper (Empoasca fabae), cotton melon aphid (Aphis gossypii), green peach aphid (Myzus persicae), brown planthopper Stal (Nilaparvata lugens), and sweetpotato whitefly (Bemisia tabaci).

[0342] In a preferred embodiment, the present invention provides compounds of formula (I) or compositions or combinations comprising compounds of formula (I), which are effective against pest including: Lepidopteran pests, including but not limited to: Spodoptera spp. (e.g., S. litura, S. frugiperda), Plutella xylostella (diamondback moth), Helicoverpa armigera, Stem borers (e.g., Scirpophaga incertulas), leaf folders, leaf rollers, leaf miners, and loopers. Hemipteran pests, including but not limitedto: Myzus persicae (Aphids), Amrasca bigutula bigutula (jassids), Bemisia tabaci (whiteflies), Nilaparvata lugens (brown plant hoppers), Nezara viridula (stink bugs), Miridae (mirid bugs), plant bugs, scales and mealybugs. Thysanopteran pests, such as Thrips spp., Acarine pests, including mites, Coleopteran pests, including weevils and beetles, and soil insects

[0343] In one embodiment, the present invention provides a composition comprising a biologically effective amount of the compound of formula (I) and at least one additional biological active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, nutrients and biostimulants. The compounds used in the composition and in combination with the compound of formula (I) are also termed as active compatible compounds.

[0344] The known and reported fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics and nutrients can be combined with at least one compound of the formula (I) of the present disclosure. For example, fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, and nutrients disclosed and reported in WO2016156129 and / or W02017153200 can be combined with at least one compound of formula (I) of the present disclosure.

[0345] The fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers and nutrients reported in WO2016156129 and or W02017153200 are incorporated herein by way of reference as non-limiting examples to be combined with at least one compound of the formula (I) of the present disclosure.

[0346] Particularly, the compounds of the present invention can be mixed with at least one additional biologically active compatible compound (mixing partner) which includes but is not limited to insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators such as rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural utility.

[0347] Examples of such biologically active compounds or agents / mixing partners with which the compound of formula (I) of the present invention can be combined / formulated are disclosed in W02019072906A1 (page 27 to 37).

[0348] In one embodiment, the biological agents for mixing with compounds of the present invention include Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin as well as naturally occurring and genetically modified viral insecticides including members of the family Baculoviridae as well as entomophagous fungi.In certain instances, combinations with other invertebrate pest control compounds or agents, having a similar spectrum of control but a different mode of action, will be particularly advantageous for resistance management. Thus, compositions of the present invention can further comprise a biologically effective amount of at least one additional invertebrate pest control compound or agent having a similar spectrum of control but a different mode of action. Contacting a plant genetically modified to express a plant protection compound (e.g., protein) or the locus of the plant with a biologically effective amount of a compound of the invention can also provide a broader spectrum of plant protection and be advantageous for resistance management.

[0349] In one embodiment of the present invention, the biologically effective amount of the compound of formula (I) in the composition ranges from 0.1 % to 99 % by weight with respect to the total weight of the composition, preferably from 5 % to 50 % by weight with respect to the total weight of the composition. The present invention furthermore provides a method of combating invertebrate pests, said method comprising contacting the invertebrate pests, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the invertebrate pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from pest attack or infestation with a biologically effective amount of the compound of formula (I) or agriculturally acceptable salts, stereoisomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides thereof, composition or combination thereof.

[0350] Invertebrate pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of the present invention, in an effective amount, to the environment of the pests including the agronomic and / or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Thus, the present invention further comprises a method for the control of foliar- and soil-inhabiting invertebrates and protection of agronomic and / or nonagronomic crops, comprising contacting the invertebrates or their environment with a biologically effective amount of one or more of the compounds of the present invention, or with a composition comprising at least one such compound or a composition comprising at least one such compound and an effective amount of at least one additional biologically active compound or agent. A preferred method of contact is by spraying. Alternatively, a granular composition comprising a compound of the present invention can be applied to the plant foliage or the soil. Compounds of the present invention are effective in delivery through plant uptake by contacting the plant with a composition comprising a compound of the present invention applied as a soil drench of a liquid formulation, a granular formulation to the soil, a nursery box treatment or a dip of transplants. Other methods of contact include application of a compound or a composition of the present invention by direct and residual sprays, aerial sprays, seedcoats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others.

[0351] The compounds of the present invention can be incorporated into baits that are consumed by the invertebrates or within devices such as traps and the like. Granules or baits comprising between 0.01-5 % active ingredient, 0.05-10 % moisture retaining agent(s) and 40-99 % vegetable flour are effective in controlling soil insects at very low application rates, particularly at doses of active ingredient that are lethal by ingestion rather than by direct contact. The compounds of the present invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader, stickers, adjuvants, other solvents, and synergists such as piperonyl butpxide often enhance compound efficacy. The rate of application required for effective control (i.e. "biologically effective amount") will depend on such factors as the species of invertebrate to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.0001 kg / hectare may be sufficient or as much as 8 kg / hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg / square meter but as little as 0.1 mg / square meter may be sufficient or as much as 150 mg / square meter may be required. One skilled in the art can easily determine the biologically effective amount necessary for the desired level of invertebrate pest control.

[0352] The term "animal pest" includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects. Insects, which are of particular relevance for crops, are typically referred to as crop insect pests.

[0353] The animal pest, i.e. the arthropods, gastropods, and nematodes, the plant, soil or water in which the plant is growing can be contacted with compounds of formula (I), their N-oxides and salts or composition(s) containing them by any application method known in the art. As used herein, "contacting" includes both direct contact (applying the compounds / compositions directly on the animal pest or plant typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds / compositions to the locus of the animal pest or plant).

[0354] The compounds of the present invention or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae orarachnids by contacting the plant / crop with a pesticidally effective amount of at least one compound of the present invention. The term "crop" refers both to growing and harvested crops.

[0355] The compounds of the invention are also suitable for use in combating or controlling animal pests. Therefore, the invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, such as seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a compound of the invention.

[0356] In one embodiment, the present invention provides a method for protecting crops from an attack or infestation by insect and mite pests, which comprises contacting the crop with a biologically effective amount of the compound or the composition of the present invention, stereoisomer, polymorph, N-oxide or salt thereof.

[0357] In another embodiment, said method of above embodiment comprises applying effective dosages of compound of formula (I) in amounts ranging from 1 gai to 5000 gai per hectare in agricultural or horticultural crops.

[0358] The compounds of the present invention are employed as such or in form of compositions by treating the insects or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with an insecticidally effective amount of the active compounds. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.

[0359] In one embodiment, the present invention provides a method for the protection of seeds, plants and plants parts from soil insects and of the seedlings roots and shoots from soil and foliar insects comprising contacting the seeds before sowing and / or after pre -germination with the compound or the composition of the present invention, N-oxide or salt thereof.

[0360] Furthermore, the present invention provides a method for treating or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a biologically effective amount of compound or composition of the present invention, stereoisomer, polymorph, N-oxide or veterinary acceptable salt thereof.

[0361] For use in treating crop plants, the rate of application (applying effective dosages) of the compound of the present invention may be in the range of 1g a.i.to 2000g a.i. per hectare in agricultural or horticultural crops, preferably from 10 g to 600 g per hectare, more preferably from 50 g to 500 g per hectare.The compounds and the compositions of the present invention are particularly useful in the control of a multitude of insects on various cultivated plants, such as cereal, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field com), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin / squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium / pelargoniums, pansies and impatiens.

[0362] Particularly, the compound or the composition of the present invention are useful in protecting agricultural crops such as cereals, com, sorghum, bajra, rice, soybean, oil seeds and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus and citms trees, any horticultural plants, cucurbitaceae, oleaginous plants, tobacco, coffee, tea, cacao, sugar beet, sugar cane, cotton, potato, tomato, onions, peppers, other vegetables and ornamentals.

[0363] The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development.

[0364] The compounds and compositions of the present invention are thus useful agronomically for protecting field crops from phytophagous invertebrate pests, and also nonagronomically for protecting other horticultural crops and plants from phytophagous invertebrate pests. This utility includes protecting crops and other plants (i.e. both agronomic and nonagronomic) that contain genetic material introduced by genetic engineering (i.e. transgenic) or modified by mutagenesis to provide advantageous traits.

[0365] Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo or polypeptides for example, by glycosylation or polymer additions such as prenylated, acetylated or famesylated moieties or PEG moieties.

[0366] Plants that have been modified by breeding, mutagenesis or genetic engineering, for example, have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4-D; bleacher herbicides such as hydroxylphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas orimidazolinones; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005, 269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1185; and references quoted therein. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), for example Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, for example imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, for example fribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, com, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U. S. A.), Cultivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate -tolerant, Bayer CropScience, Germany).

[0367] Furthermore, plants capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus (Bacillus), by the use of recombinant DNA techniques are within the scope of the present invention. The Bacillus are particularly from Bacillus thuringiensis, such as δ-endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome -inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO02 / 015701).Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, for example, in EP374753, WO93 / 007278, WO95 / 34656, EP427529, EP451878, W003 / 18810 and W003 / 52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants, producing these proteins, tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coeloptera), twowinged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (com cultivars producing the CrylAb toxin), YieldGard® Plus (com cultivars producing CrylAb and Cry3Bbl toxins), Starlink® (com cultivars producing the Cry9c toxin), Herculex® RW (com cultivars producing Cry34Abl, Cry35Abl and the enzyme phosphinothricin-A'-acctyltransfcrasc [PAT]); NuCOTN® 33B (cotton cultivars producing the CrylAc toxin), Bollgard® I (cotton cultivars producing the Cryl Ac toxin), Bollgard® II (cotton cultivars producing CrylAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf®(potato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb toxin and PAT enzyme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03 / 018810), MON 863 from Monsanto Europe S. A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S. A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cryl F toxin and PAT enzyme); Btl 1 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified Zea mays which has been rendered resistant to attack by the European com borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Btll maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium; Btl76 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified Zea mays which has been rendered resistant to attack by the European com borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Btl 76 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium; MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 1, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810; MON 863 Maize from Monsanto Europe S. A. 270-272 Avenuede Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses a Cry3Bbl toxin and has resistance to certain Coleoptera insects; IPC 531 Cotton from Monsanto Europe S. A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02; 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize for the expression of the protein Cryl F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium; and NK603 x MON 810 Maize from Monsanto Europe S. A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cryl Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European com borer.

[0368] Furthermore, plants capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens by the use of recombinant DNA techniques are also within the scope of the present invention. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, for example EP392225), plant disease resistance genes (e.g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.

[0369] Furthermore, plants capable to synthesize one or more proteins, by the use of recombinant DNA techniques, to increase the productivity (e. g. biomass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants are within the scope of the present invention. Furthermore, plants that contain a modified amount of substances of content or new substances of content, by the use of recombinant DNA techniques, to improve human or animal nutrition, e.g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada) are also within the scope of the present invention.

[0370] Furthermore, plants that contain a modified amount of substances of content or new substances of content, by the use of recombinant DNA techniques, to improve raw material production, e.g. potatoes that produceincreased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany) are also within the scope of the present invention.

[0371] The compounds of the present invention are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait or plant part).

[0372] The compounds of the present invention may also be applied against non-crop invertebrate pests, such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches. For use against said non-crop pests, compounds of the present invention are preferably used in a bait composition.

[0373] As used herein, the term "non-crop insect pest" refers to pests, which are particularly relevant for non-crop targets, such as ants, termites, wasps, flies, ticks, mosquitos, crickets, or cockroaches.

[0374] The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics.

[0375] The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and / or plant proteins (meat-, fish or blood meal, insect parts, egg yolk), from fats and oils of animal and / or plant origin, or mono-, oligo or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. 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.

[0376] For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5 weight % of active compound.

[0377] Formulations of compounds of the present invention as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges of approximately 50 to 250 °C, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylatehaving 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.

[0378] The oil spray formulations differ from the aerosol recipes in that no propellants are used. For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.

[0379] In case of an application against ants doing harm to crops, wooden dwellings or human beings, a compound of the present invention is applied to the crops or the surrounding soil or is directly applied to the nest of ants or the like.

[0380] A preferred method of application in the field of crop protection is the application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.

[0381] Digital Technologies

[0382] The compounds of the invention can be used in combination with models e.g. embedded in computer programs for site specific crop management, satellite farming, precision farming or precision agriculture. Such models support the site specific management of agricultural sites with data from various sources such as soils, weather, crops (e.g. type, growth stage, plant health), weeds (e.g. type, growth stage), diseases, pests, nutrients, water, moisture, biomass, satellite data, yield etc. with the purpose to optimize profitability, sustainability and protection of the environment. In particular, such models can help to optimize agronomical decisions, control the precision of pesticide applications and record the work performed.

[0383] As an example, the compounds of the invention can be applied to a crop plant according to an appropriate dose regime if a model models the development of a pest and calculates that a threshold has been reached for which it is recommendable to apply the compound of the invention to the crop plant.

[0384] Commercially available systems which include agronomic models are e.g. FieldScriptsTM from The Climate Corporation, XarvioTM from BASF, AGLogicTM from John Deere, etc.The compounds of the invention can also be used in combination with smart spraying equipment such as e.g. spot spraying or precision spraying equipment attached to or housed within a farm vehicle such as a tractor, robot, helicopter, airplane, unmanned aerial vehicle (UAV) such as a drone, etc. Such an equipment usually includes input sensors (such as e.g. a camera) and a processing unit configured to analyze the input data and configured to provide a decision based on the analysis of the input data to apply the compound of the invention to the crop plants (respectively the weeds) in a specific and precise manner. The use of such smart spraying equipment usually also requires positions systems (e.g. GPS receivers) to localize recorded data and to guide or to control farm vehicles; geographic information systems (GIS) to represent the information on intelligible maps, and appropriate farm vehicles to perform the required farm action such as the spraying.

[0385] For example, pests can be detected from imagery acquired by a camera. In an example the pests can be identified and / or classified based on that imagery. Such identification and / classification can make use of image processing algorithms. Such image processing algorithms can utilize machine learning algorithms, such as trained neutral networks, decision trees and utilize artificial intelligence algorithms. In this manner, the compounds described herein can be applied only where needed.

[0386] Seed treatment

[0387] The present invention further provides a seed comprising the compounds of the present invention, particularly in an amount ranging from about 0.0001% to about 1% by weight of the seed before treatment. The compounds of the present invention are also suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect and mite pests and the resulting plant's roots and shoots against soil pests and foliar insects.

[0388] The compounds of the present invention are particularly useful for the protection of the seed from soil pests and the resulting plant's roots (white grub, termites, wireworms) and shoots against soil pests and foliar insects. The protection of the resulting plant's roots and shoots is preferred. More preferred is the protection of resulting plant's shoots from piercing and sucking insects, wherein the protection from aphids, jassids, thrips and white flies is most preferred.

[0389] The present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedling roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and / or after pregermination with a compound of the present invention thereof. Particularly preferred is a method, wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected form piercing and sucking insects, most preferably a method, wherein the plants shoots are protected from aphids.The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.

[0390] The term seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.

[0391] The present invention also comprises seeds coated with or containing the active compound. The seeds can be coated with seed coating compositions containing the compounds of the present invention. For example, seed coating compositions reported in EP3165092, EP3158864, WO2016198644, WO2016039623, WO2015192923, CA2940002, US2006150489, US2004237395, WO2011028115, EP2229808, W02007067042, EP1795071, EP1273219, W0200178507, EP1247436, NL1012918 and CA2083415. The term "coated with and / or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the propagation product is (re)planted, it may absorb the active ingredient along with moisture.

[0392] Suitable seed is seeds of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field com), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin / squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium / pelargoniums, pansies and impatiens.

[0393] In addition, the compounds of the present invention may be used for treating seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.

[0394] For example, the compounds of the present invention can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP242236, EP242246) (W092 / 00377) (EP257993, US5013659) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP 142924, EP 193259).

[0395] Furthermore, the compound of the present invention can be used for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants, which can be generated for exampleby traditional breeding methods and / or the generation of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO92 / 11376, WO92 / 14827, WO91 / 19806) or of transgenic crop plants having a modified fatty acid composition (WO91 / 13972).

[0396] The seed treatment application of the compound of the present invention is carried out by spraying or by dusting the seeds before sowing of the plants and before the emergence of the plants.

[0397] Compositions which are especially useful for seed treatment are e.g.:

[0398] A. Soluble concentrates (SL, LS)

[0399] B. Emulsions (EW, EO, ES)

[0400] C. Suspensions (SC, OD, FS)

[0401] D. Water-dispersible granules and water-soluble granules (WG, SG)

[0402] E. Water-dispersible powders and water-soluble powders (WP, SP, WS)

[0403] F. Gel-Formulations (GF)

[0404] G. Dustable powders (DP, DS)

[0405] Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter.

[0406] In one embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1-800 g / 1 of active ingredient, 1-200 g / 1 surfactant, 0 to 200 g / 1 antifreezing agent, 0 to 400 g / 1 of binder, 0 to 200 g / 1 of a pigment and up to 1 liter of a solvent, preferably water.

[0407] Especially FS formulations of compounds of the present invention for seed treatment usually comprise from 0.1 to 80% by weight ( 1 to 800 g / 1) of the active ingredient, from 0.1 to 20 % by weight ( 1 to 200 g / 1) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and / or a dye, from 0 to 40 % by weight, e.g. 1 to 40 % by weight of a binder (sticker / adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler / vehicle up to 100 % by weight. Seed treatment formulations may additionally comprise binders and optionally colorants.Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are homo and copolymers from alkylene oxides like ethylene oxide or propylene oxide, polyvinylacetate, polyvinylalcohols, polyvinylpyrrolidones, and copolymers thereof, ethylene -vinyl acetate copolymers, acrylic homo and copolymers, polyethyleneamines, polyethyleneamides and polyethylenepyrimidines, polysaccharides like celluloses, tylose and starch, polyolefin homo and copolymers like olefin / maleic anhydride copolymers, polyurethanes, polyesters, polystyrene homo and copolymers.

[0408] Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C. I. Pigment Red 1 12, 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 1 12, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

[0409] An example of a gelling agent is carrageen (Satiagel®).

[0410] In the treatment of seed, the application rates of the compounds of the present invention are generally from 0.1 g to 5 kg per 100 kg of seed, preferably from 1 g to 1 kg per 100 kg of seed, more preferably from 1 g to 200 g per 100 kg of seed and in particular from 5 g to 150 g per 100 kg of seeds and 10 g to 100g per 100 kg of seed. The present invention therefore also provides to seeds comprising a compound of formula (I), or an agriculturally useful salt of the compound of formula (I), as defined herein. The amount of the compound of formula (I) or the agriculturally useful salt thereof will in general vary from 0.1 g to 5 kg per 100 kg of seed, preferably from 1 g to 1 kg per 100 kg of seed, more preferably from 1 g to 200 g per 100 kg of seed and in particular from 5 g to 150 g per 100 kg of seeds and 10 g to 100 g per 100 kg of seeds.

[0411] Animal health

[0412] The present invention also provides an agricultural and / or veterinary composition comprising at least one compound of formula (I).

[0413] In one embodiment, the present invention provides the use of the compound of formula (I), salts, stereoisomers, metal complexes, polymorphs, or N-oxides, composition or combination thereof, for combating insects and mite pests in agricultural crops and / or horticultural crops, household and vector control or parasites on animals.

[0414] The compounds of formula (I), their N-oxides and / or veterinarily acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals.The present invention also provides compositions containing a parasiticidally effective amount of at least one compound of formula (I), N-oxide or veterinarily acceptable salt thereof and an acceptable carrier, for combating parasites in and on animals.

[0415] The present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically, or parenteral administering or applying to the animals a parasiticidally effective amount of a compound of the present invention or a composition comprising it.

[0416] The present invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a compound of the present invention or a composition comprising it. Activity of compounds against agricultural pests does not suggest their suitability for control of endo and ectoparasites in and on animals which require, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling. Surprisingly it has now been found that compounds of the present invention are suitable for combating endo and ectoparasites in and on animals.

[0417] Compounds of the present invention and compositions comprising them are preferably used for controlling and preventing infestations and infections in animals including warm-blooded animals and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as freshand salt-water fish as trout, carp and eels.

[0418] Compounds of the present invention and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.

[0419] Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes and fleas. The compounds of the present invention and compositions comprising them are suitable for systemic and / or non-systemic control of ecto and / or endoparasites. They can be active against all or some stages of development.

[0420] The compounds of the present invention are especially useful for combating ectoparasites.

[0421] The compounds of the present invention are especially useful for combating parasites of the following orders and species, respectively: fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides cams,Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, cockroaches (Blattaria Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis, 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, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoidesfurens, Culex pi pi ens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus argentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus. ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus gallinae, Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis 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., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp, Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus, Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp, Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp.

[0422] Roundworms Nematoda:

[0423] Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Trichuridae,) Trichuris spp., Capillaria spp, Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,Strongylida, e.g. Strongylus spp., 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), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi, Camallanida, e.g. Dracunculus medinensis (guinea worm) Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofllari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habronema spp, Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracanthorhynchus hirudinaceus and Oncicola spp, Planarians (Plathelminthes): Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria a lata, Paragonimus spp., and Nanocyetes spp, Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. 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.

[0424] The compounds of formula (I) and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.

[0425] In one embodiment, the present invention provides use of the compounds of formula (I) and compositions containing them for combating mosquitoes.

[0426] In one embodiment, the present invention provides use of the compounds of formula (I) and compositions containing them for combating flies.

[0427] In one embodiment, the present invention provides use of the compounds of formula (I) and compositions containing them for combating fleas.

[0428] The use of the compounds of the present invention and compositions containing them for combating ticks is still another embodiment of the present invention.

[0429] The compounds of the present invention are also especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).

[0430] In one embodiment, the administration of the compounds of the present invention can be carried out both prophylactically and therapeutically.In another embodiment, administration of the compounds of the present invention is carried out directly or in the form of suitable preparations, orally, topically / dermally or parenterally.

[0431] For oral administration to warm-blooded animals, compounds of the present invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the compounds of the present invention may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg / kg to 100 mg / kg of animal body weight per day of the compound of the present invention, preferably with 0.5 mg / kg to 100 mg / kg of animal body weight per day.

[0432] Alternatively, the compounds of the present invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds of the present invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of the present invention may be formulated into an implant for subcutaneous administration. In addition, the compound of the present invention may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg / kg to 100 mg / kg of animal body weight per day of the compound of the present invention. The compounds of the present invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compound of the present invention. In addition, the compounds of the present invention may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.

[0433] Suitable preparations are: Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels; Emulsions and suspensions for oral or dermal administration; semi-solid preparations; Formulations in which the active compound is processed in an ointment base or in an oil-in-water or water-in-oil emulsion base; Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.

[0434] The 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 solubilizers. Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N-methylpyrrolidone, 2-pyrrolidone, and mixtures thereof.The active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.

[0435] Suitable solubilizers are solvents which 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 ester.

[0436] Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol. Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the used concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.

[0437] Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.

[0438] Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.

[0439] Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.

[0440] Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency results. The thickeners employed are the thickeners given above.

[0441] Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically. Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers and adhesives are added.

[0442] Suitable solvents are 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 such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and / or aliphatic hydrocarbons,vegetable or synthetic oils, dimethylformamide, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or noctylpyrrolidone, N-methylpyrrolidone, 2-pyrrolidone, 2,2-dimethyl -4-oxy -methylene- 1,3-dioxolane or glycerol formal.

[0443] Suitable colorants are for example, all colorants permitted for the use on animals and which can be dissolved or suspended.

[0444] Suitable absorption-promoting substances are for example, dimethyl sulfoxide, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides or fatty alcohols.

[0445] Suitable antioxidants are for example, sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole or tocopherol.

[0446] 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. Emulsions can be administered orally, dermally or as injections. Emulsions are either of the water-in-oil type or of the oil-in-water type.

[0447] They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity -enhancing substances.

[0448] Suitable hydrophobic phases (oils) are:

[0449] Liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic / capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length C1-C12 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, monoand diglycerides of the Cs-do fatty acids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C16-C18, isopropyl myristate, isopropyl palmitate, caprylic / capric acid esters of saturated fatty alcohols of chain length C12-C18, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and mixtures thereof. Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.Suitable emulsifiers are for example, non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol poly glycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin. Suitable anionic surfactants are for example, sodium lauryl sulfate, fatty alcohol ether sulfates, mono / dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; suitable cation-active surfactants are cetyltrimethylammonium chloride.

[0450] Suitable further auxiliaries are for example, substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.

[0451] Suspensions can be administered orally or topically / dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.

[0452] Liquid suspending agents are all homogeneous solvents and solvent mixtures.

[0453] Suitable wetting agents (dispersants) are the emulsifiers given above.

[0454] Other auxiliaries which may be mentioned are those given above.

[0455] Semi-solid preparations can be administered orally or topically / dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.

[0456] For the production of solid preparations, the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.

[0457] Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.

[0458] Suitable auxiliaries are preservatives, antioxidants, and / or colorants which have been mentioned above. Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of death, retardation of development, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds / compositions used in the present invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like. The compositions which can be used in the present invention generally comprise about 0.001 to 95% of the compound of the present invention.

[0459] Generally, it is favorable to apply the compounds of the present invention in total amounts of 0.5 mg / kg to 100 mg / kg per day, preferably 1 mg / kg to 50 mg / kg per day. Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 percent by weight, preferably from 0.1 to 65 percent by weight, more preferably from 1 to 50 percent by weight, most preferably from 5 to 40 percent by weight. Preparations diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 percent by weight, preferably of 1 to 50 percent by weight. Furthermore, the preparations comprise the compounds of the present invention against endoparasites in concentrations of 10 ppm to 2 percent by weight, preferably of 0.05 to 0.9 percent by weight, very particularly preferably of 0.005 to 0.25 percent by weight.

[0460] In one embodiment, the compositions comprising the compounds of the present invention are applied dermally / topically.

[0461] In another embodiment, the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils. Generally, it is favorable to apply solid formulations which release compounds of the present invention in total amounts 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 body weight of the treated animal in the course of three weeks.

[0462] For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the compounds of the present invention. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 2003086075.

[0463] Positive crop response:

[0464] The compounds of the present invention not only control insect and mite pests effectively but also induce a positive crop response such as plant growth enhancement effects like enhanced root growth, enhancedtolerance to drought, high salt content, high temperature, chill, frost or light radiation, improved flowering, enhanced nutrient utilization (such as improved nitrogen assimilation), enhanced quality of plant products, higher number of productive tillers, enhanced resistance to fungi, insects, pests and the like, which results in higher yields.

[0465] Without further elaboration, it is believed that any person skilled in the art who is using the preceding description can utilize the present invention to its fullest extent. The following examples are therefore to be interpreted as merely illustrative and not limiting of the disclosure in any way whatsoever.

[0466] CHEMISTRY EXAMPLES:

[0467] The following examples set forth the manner and process of making compounds of the present invention without representing any limitations thereof.

[0468] Synthetic Scheme 1:

[0469]

[0470] TFA Example-1: Synthesis of (S)-6-(5-(l-aminoethyl)-lH-l,2,4-triazol-l-yl)nicotinonitrile 2,2,2-trifluoroacetate

[0471] Step-1: Synthesis of tert-butyl (S)-(l-(l-(5-cyanopyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)carbamate To a stirred suspension of tert-butyl (7?)-(l -amino- l-oxopropan-2-yl)carbamate (25 g, 133 mmol) in dichloromethane (250 mL), 1,1-dimethoxy-N,N-dimethylmethanamine (26.5 mL, 199 mmol) was added and the reaction mixture was stirred at 50 °C for 1 h. The solvent was removed under reduced pressure. The resulting reaction mixture was dissolved in 1,4-dioxane (125 mL) and acetic acid (125 mL), treated with 6-hydrazineylnicotinonitrile (21.38 g, 159 mmol), and stirred at 80 °C for 4 h. After completion of reaction, the reaction mixture was concentrated under reduced pressure to get a crude product, which was dissolved in ethyl acetate (100 mL), and washed with water (50 mL), saturated aqueous NaHCO₃ solution (50 mL) followed by brine solution (30 mL). The organic layer was dried over anhydrous sodium sulphate and concentrated under reduced pressure to get a crude product which was purified by flash chromatography to obtain tert-butyl (S)-(l-(l-(5-cyanopyridin-2-yl)-l / / -l,2,4-triazol-5-yl)ethyl)carbamate (18 g, 57.3 mmol, 43 % yield). LCMS (m / z) 315.00 [M+H]+.

[0472] Step-2: Synthesis of (S)-6-(5-(l-aminoethyl)-lH-l,2,4-triazol-l-yl)nicotinonitrile 2,2,2-trifluoroacetateTo a stirred solution of tert-butyl (S)-(l-(l-(5-cyanopyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)carbamate (10 g, 31.8 mmol) in dichloromethane (50 mL), trifluoroacetic acid (25.01 mL, 318 mmol) was added dropwise, and the resulting mixture was stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. The residue was basified by using 1 N NaOH solution, extracted with ethyl acetate (2 x 250 mL), dried over anhydrous sodium sulphate, and concentrated to get a crude product, which was purified by flash chromatography to obtain (S)-6-(5-(l-aminoethyl)-l / T-l,2,4-triazol-l-yl)nicotinonitrile 2,2,2-trifluoroacetate (5g, 23.34 mmol, 73 % yield).1H-NMR (400 MHz, CDCl₃) δ 8.80-8.78 (m, 1H), 8.16-8.10 (m, 2H), 7.96 (s, 1H), 4.94 (q, J= 6.8 Hz, 1H), 1.59 (d, J= 7.0 Hz, 3H); LCMS (m / z) 215.00 [M+H]+.

[0473] Synthetic Scheme 2:

[0474]

[0475] Example-2: Synthesis of (S)-l-(l-(pyrimidin-2-yl)-l / 7-l,2,4-triazol-5-yl)ethan-l-amine 2,2,2-trifluoroacetate

[0476] Step-1: Synthesis of tert-butyl (S)-(l-(l-(pyrimidin-2-yl)-l / 7-l,2,4-triazol-5-yl)ethyl)carbamate To a stirred suspension of tert-butyl (R)-(1-amino-1-oxopropan-2-yl)carbamate (23 g, 122 mmol) in dichloromethane (230 mL), 1,1-dimethoxy-N,N-dimethylmethanamine (24.35 mL, 183 mmol) was added and the reaction mixture was stirred at 50 °C for 1 h. The solvent was removed under reduced pressure. The resulting reaction mixture was dissolved in 1,4-dioxane (120 mL) and acetic acid (80 mL), treated with 2-hydrazineylpyrimidine (16.15 g, 147 mmol), and was stirred at 80 °C for 2 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to get a crude product, which was dissolved in ethyl acetate (75 mL), and washed with water (50 mL), saturated aqueous NaHCO₃ solution (25 mL) followed by brine solution (25 mL). The organic layer was dried over anhydrous sodium sulphate and concentrated under reduced pressure to get a crude product, which was purified by flash chromatography to obtain tert-butyl (S)-(l-(l-(pyrimidin-2-yl)-l / / -l,2,4-triazol-5-yl)ethyl)carbamate (12 g, 41.3 mmol, 34 % yield). LCMS (m / z) 291.1 [M+H]+.

[0477] Step-2: Synthesis of (S)-l-(l-(pyrimidin-2-yl)-l / 7-l, 2, 4-triazol-5-yl)ethan-l-amine 2,2,2-trifluoroacetate

[0478] To a stirred solution of methyl tert-butyl (S)-( l-( l-(pyrimidin-2-yl)- 1H- l,2,4-triazol-5-yl)ethyl)carbamate (20.0 g, 68.9 mmol) in dichloromethane (100 mL), trifluoroacetic acid (54.2 mL, 689 mmol) was addeddropwise at 0 °C, and the resulting reaction mixture was stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude product as a TFA salt, which was purified by trituration with hexane and mixture of pentane and diethyl ether to obtain (S)-1-(1-(pyrimidin-2-yl)-1H-1,2,4-triazol-5-yl)ethan-1-amine 2,2,2-trifluoroacetate (36.0 g, 67.6 mmol, 98 % yield) as off white solid. LCMS (m / z) 190.80 [M+H]+.

[0479] Synthetic Scheme 3:

[0480]

[0481] Example-3: Synthesis of (5)-l-(3-methyl-l-(pyrimidin-2-yl)-l / 7-l,2,4-triazol-5-yl)ethan-l-amine 2,2,2-trifluoroacetate

[0482] Step-1: Synthesis of tert-butyl (5)-(l-(3-methyl-l-(pyrimidin-2-yl)-l / 7-l,2,4-triazol-5-yl)ethyl)carbamate

[0483] To a stirred suspension of tert-butyl (S)-(l -amino- l-oxopropan-2-yl)carbamate (8 g, 42.5 mmol) in dichloromethane (50 mL), 1,1-dimethoxy-N,N-dimethylethan-1-amine (9.94 mL, 68.0 mmol) was added and the reaction mixture was stirred at 50 °C for 1 h. The solvent was removed under reduced pressure. The residue was then dissolved in 1,4-dioxane (25 mL) and acetic acid (15 mL), and treated with 2-hydrazineylpyrimidine (5.15 g, 46.8 mmol). The resulting reaction mixture was stirred at 80 °C for 5 h. After completion of the reaction, the reaction mixture was concentrated to get a crude product, which was purified by flash chromatography to obtain tert-butyl (S)-( 1 -(3-methyl- 1 -(pyrimidin-2-yl)- 1H- 1,2,4-triazol-5-yl)ethyl)carbamate (10.8 g, 35.5 mmol, 83 % yield) as white solid. LCMS (m / z) 305.20 [M+H]+.

[0484] Step-2: Synthesis of (5)-l-(3-methyl-l-(pyrimidin-2-yl)-l / 7-l,2,4-triazol-5-yl)ethan-l-amine 2,2,2-trifluoroacetate

[0485] To a stirred solution of tert-butyl (S)-(l-(3-methyl-l-(pyrimidin-2-yl)-l / / -l,2,4-triazol-5-yl)ethyl)carbamate (10.8 g, 35.5 mmol) in dichloromethane (100 mL), TFA (19.14 mL, 248 mmol) was added slowly, and the resulting mixture was stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain crude (S)-l-(3-methyl-l-(pyrimidin-2-yl)-lH-l,2,4-triazol-5-yl)ethan-l-amine 2,2,2-trifluoroacetate (13 g, 40.8 mmol). LCMS (m / z) 204.85 [M+H]+.

[0486] Synthetic Scheme 4:

[0487]

[0488] Example-4: Synthesis of l-(3-(pyridin-2-yl)pyrazin-2-yl)ethan-l-amine

[0489] Step-1: Synthesis of l-(3-(pyridin-2-yl)pyrazin-2-yl)ethan-l-one

[0490] A solution of l-(3-chloropyrazin-2-yl)ethan- 1-one (5 g, 31.9 mmol) and l-(3-chloropyrazin-2-yl)ethan-l- one (5 g, 31.9 mmol) in toluene (50 mL) was degassed with nitrogen for 5 min. To this reaction mixture, tetrakis(triphenylphosphine)palladium(0) (3.69 g, 3.19 mmol) was added, and stirred at 100 °C for 12 h under nitrogen. After completion of the reaction, the reaction mixture was diluted with ethyl acetate (250 mL) and washed with water (150 mL). The organic layer was dried over anhydrous sodium sulphate and concentrated under reduced pressure to get a crude product, which was purified by flash chromatography to obtain l-(3-(pyridin-2-yl)pyrazin-2-yl)ethan-l-one (4.4 g, 22.09 mmol, 86 % yield).1H-NMR (400 MHz, CDCl3) 58.66 (q, J= 2.4 Hz, 1H), 8.58 (dq, J= 4.8, 0.9 Hz, 1H), 8.54 (d, J= 2.4 Hz, 1H), 8.19 (dt, J= 7.9, 1.0 Hz, 1H), 7.86-7.80 (m, 1H), 7.34-7.29 (m, 1H), 2.75-2.68 (m, 3H); LCMS (m / z) 200.1 [M+H]+.

[0491] Step-2: Synthesis of l-(3-(pyridin-2-yl)pyrazin-2-yl)ethan-l-amine

[0492] To a stirred solution of l-(3-(pyridin-2-yl)pyrazin-2-yl)ethan-l-one (10 g, 50.2 mmol) in methanol (120 mL), NH+OAc (77 g, 1004 mmol) was added, and the resulting reaction mixture was stirred at 25 °C for 2 h, followed by treatment with NaCNBfL (7.89 g, 125 mmol), and stirred for 12 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude product, which was diluted with a IN NaOH solution. The aqueous layer was extracted with ethyl acetate (3 xlOO mL), the combined organic layers were separated, washed with brine solution (50 mL), dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure to obtain a crude product which was purified by flash chromatography to obtain l-(3-(pyridin-2-yl)pyrazin-2-yl)ethan-l-amine (5.0 g, 24.97 mmol, 50 % yield) as pale brown solid.1H-NMR (400 MHz, DMSO-< A) 5 8.72-8.70 (m, 2H), 8.67 (d, J= 2.4 Hz, 1H), 8.05-7.99 (m, 2H), 7.55-7.52 (m, 1H), 5.53 (d, J= 6.1 Hz, 1H), 5.24-5.18 (m, 1H), 1.44 (d, J= 6.4 Hz, 3H); LCMS (m / z) 201.90 [M+H]+.

[0493] Synthetic Scheme 5:

[0494]

[0495] Example-5: Synthesis of (S)-((6-(5-(l-aminoethyl)-lH-l,2,4-triazol-l-yl)pyridin-3-yl)imino)dimethyl-k6-sulfanone 2,2,2-trifluoroacetate

[0496] Step-1: Synthesis of (S)-(l-(l-(5-bromopyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)carbamate

[0497] To a stirred solution of tert-butyl (S)-(l -amino- l-oxopropan-2-yl)carbamate (21.69 g, 115 mmol) in dichloromethane (220 mL), 1,1 -dimethoxy -N,N-dimethylmethanamine (22.96 mL, 173 mmol) was added dropwise at 25 °C. The resulting reaction mixture was stirred at 50 °C for 1 h and cooled to 25 °C and concentrated under reduced pressure. The residue was dissolved in 1,4-dioxane / acetic acid (110 mL / 110 mL) to which 5-bromo-2-hydrazineylpyridine (26 g, 138 mmol) was added and stirred at 90 °C for 4 h. After completion of the reaction, the reaction mixture was diluted with ethyl acetate and quenched with saturated NaHCO₃ solution and washed with brine solution. The organic layer was dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude product which was purified by flash chromatography to obtain the desired tert-butyl (S)-(l-(l-(5-bromopyridin-2-yl)- 1H- 1,2,4-triazol-5-yl)ethyl)carbamate (17 g, 46.2 mmol, 40.1 % yield) as a brownish solid.1H-NMR (400 MHz, CHLOROFORM-D) 5 8.55 (d, J = 2.1 Hz, 1H), 7.98 (dd, J = 8.7, 2.3 Hz, 1H), 7.94 (s, 1H), 7.83-7.81 (m, 1H), 5.96-5.87 (m, 2H), 1.56-1.50 (m, 3H), 1.47-1.19 (m, 9H) LCMS (m / z) 367.9 [M]+.

[0498] Step-2: Synthesis of tert-butyl (S)-(l-(l-(5-((dimethyl(oxo)-k6-sulfaneylidene)amino)pyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)carbamate

[0499] A 10 mL thermal vial was charged with tert-butyl (S)-(l-(l-(5-bromopyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)carbamate (510 mg, 1.385 mmol) and iminodimethyl-X6-sulfanone (155 mg, 1.662 mmol) in toluene (5 mL). The reaction mixture was degassed with nitrogen for 10 minutes followed by the addition of Pd2dba3(1268 mg, 1.385 mmol), xantphos (80 mg, 0.138 mmol) and potassium phosphate tribasic (294 mg, 1.385 mmol). The resulting reaction mixture was stirred at 110 °C for 12 h. After completion of the reaction, the reaction mixture was filtered and the aqueous layer was extracted with ethyl acetate (3 x 100 mL). The organic layer was washed with brine solution (50 mL) and dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude product which was purified by flash chromatography to obtain the desired tert-butyl (S)-(l-(l-(5-((dimethyl(oxo)-X6-sulfaneylidene)amino)pyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)carbamate (420 mg, 1.104 mmol, 80 % yield) as a dark brownish gel.

[0500] 1H-NMR (400 MHz, CHLOROFORM-D) 58.22 (d, J = 2.1 Hz, 1H), 7.89 (s, 1H), 7.70 (d, J = 8.6 Hz, 1H), 7.56 (dd, J = 8.7, 2.6 Hz, 1H), 5.78-5.72 (m, 2H), 3.21 (dd, J = 14.8, 12.7 Hz, 6H), 1.54 (d, J = 6.7 Hz, 3H), 1.40 (s, 9H) LCMS (m / z) 380.55 [M]+.Step-3: Synthesis of (S)-((6-(5-(1-aminoethyl)-1H-1,2,4-triazol-1-yl)pyridin-3-yl)imino)dimethyl-λ6-sulfanone 2,2,2-trifluoroacetate

[0501] To a stirred solution of tert-butyl (S)-(l-(l-(5-((dimethyl(oxo)-X6-sulfaneylidene)amino)pyridin-2-yl)-lH- l,2,4-triazol-5-yl)ethyl)carbamate (2.27 g, 5.97 mmol) in dichloromethane (100 mL), trifluoroacetic acid, (4.60 mL, 59.7 mmol) was slowly added, and the resulting reaction mixture was stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure followed by triturating with dried toluene and concentrated under reduced pressure to obtain the crude 2,2,2- (S)-((6-(5-( 1 -aminoethyl)- 1 H- 1,2,4-triazol- 1 -yl)pyridin-3 -y 1 )imino)dimethy 1 -λ6-sulfanone 2,2,2-trifluoroacetate (3.43 g, 5.97 mmol) as a brownish gel.’H-NMR (400 MHz, CHLOROFORM-D) 58.20 (d, J = 2.1 Hz, 1H), 8.10 (d, J = 10.2 Hz, 1H), 7.82 (d, J = 9.2 Hz, 1H), 7.68 (dd, J = 8.7, 2.6 Hz, 1H), 5.23 (q, J = 6.9 Hz, 1H), 3.31-3.17 (m, 6H), 1.85 (d, J = 7.0 Hz, 3H) LCMS (m / z) 280.60 [M]+.

[0502] Synthetic Scheme 6:

[0503]

[0504] Example-6: Synthesis of ethyl (S)-2-(5-(l-aminoethyl)-lH-l,2,4-triazol-l-yl)thiazole-5-carboxylate 2,2,2-trifluoroacetate

[0505] Step-1: Synthesis of ethyl (S)-2-(5-(l-((tert-butoxycarbonyl)amino)ethyl)-lH-l,2,4-triazol-l-yl)thiazole-5-carboxylate

[0506] To a stirred suspension of tert-butyl (S)-(l -amino- l-oxopropan-2-yl)carbamate (13.41 g, 71.2 mmol) in dichloromethane (150 mL), DMF-DMA (14.30 mL, 107 mmol) was added dropwise, and the resulting reaction mixture was stirred at 50 °C for 1 h. The reaction mixture was concentrated to obtain an intermediate, which was dissolved in 1,4-dioxane (150 mL) and ethyl 2-hydrazineylthiazole-5-carboxylate (20.0 g, 107 mmol) followed by acetic acid (150 mL), and the resulting mixture was stirrred at 50 °C for 16 h. After completion of the reaction, the reaction mixture was evaporated under reduced pressure to obtain a crude compound, which was purified by flash chromatography to obtain the desired ethyl (S)-2-(5-( 1-((tert-butoxycarbonyl)amino)ethyl)-lH-l,2,4-triazol-l-yl)thiazole-5-carboxylate (4.5 g, 12.25 mmol, 17.20 % yield).1H-NMR (400 MHz, CHLOROFORM-D) 5 8.20 (s, 1H), 7.92 (s, 1H), 5.88 (d, J = 6.8 Hz, 1H), 5.60 (s, 1H), 4.39 (q, J = 7.1 Hz, 2H), 1.56 (d, J = 6.8 Hz, 3H), 1.46-1.38 (m, 12H) LCMS (m / z) 367.9 [M]+.

[0507] Step-2: Synthesis of ethyl (S)-2-(5-(l-aminoethyl)-lH-l,2,4-triazol-l-yl)thiazole-5-carboxylate 2,2,2-trifluoroacetateTo a stirred solution of ethyl (S)-2-(5-(l-((tert-butoxycarbonyl)amino)ethyl)-lH-l,2,4-triazol-l-yl)thiazole-5 -carboxylate (2 g, 5.44 mmol) in dichloromethane (20 mL), trifluoroacetic acid, (4.19 mL, 54.4 mmol) was added slowly, and the resulting mixture was stirred at 25 °C for 16 h. After completion of the reaction, reaction mixture was evaporated under reduced pressure to obtain a crude gum, which was used as such without any purification.

[0508] LCMS (m / z) 268.3 [M+H]+.

[0509] Synthetic Scheme 7:

[0510] Step-1

[0511]

[0512] mixture of compounds mixture of compounds Example-7: Synthesis of 3-(2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-5-(trifluoromethyl)benzoic acid and 3-(trifhioromethyl)-5-(3,3,3-trifluoroprop-l-en-l-yl)benzoic acid

[0513] Step-1: Synthesis of methyl 3-(2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-5-(trifluoromethyl)benzoate and methyl 3-(trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-l-yl)benzoate

[0514] To a stirred solution of methyl 3-formyl-5-(trifluoromethyl)benzoate (960 mg, 4.14 mmol) in N, N-dimethylformamide (15 mL), 1,1,1-trichlorotrifluoroethane (0.981 mL, 8.27 mmol), Zn (1.35 g, 20.68 mmol), acetic anhydride (0.585 mL, 6.20 mmol), and copper (I) chloride (40.9 mg, 0.414 mmol) were added at 25 °C. The resulting reaction mixture was stirred at 60 °C for 16 h in a sealed tube. After completion of the reaction, the reaction mixture was quenched cautiously with aqueous sodium potassium tartrate solution, and the aqueous layer was extracted with ethyl acetate (2x50 mL). The combined organic layers were washed with water (2 x 25 mL) and brine solution (25 mL), dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure to obtain a crude liquid which was purified by flash chromatography to obtain methyl 3-(2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-5-(trifluoromethyl)benzoate and methyl 3-(trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-l-yl)benzoate as a colourless oil mixture. ¹H-NMR (400 MHz, CDCl₃) δ 8.53 (s, 1H), 8.34-8.31 (m, 3H), 8.15 (s, 1H), 7.87 (s, 1H), 7.39 (s, 1H), 7.25-7.21 (m, 1H), 6.43-6.34 (m, 1H), 3.99 (d, J= 1.2 Hz, 6H); GCMS (m / z) 332.0 [M]+, 298.1 [M]+.

[0515] Step-2: Synthesis of 3-(2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-5-(trifluoromethyl)benzoic acid and 3-(trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-l-yl)benzoic acidTo a stirred solution of a mixture of methyl 3-(2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-5-(trifluoromethyl)benzoate and methyl 3-(trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-l-yl)benzoate (0.35 g, 1.052 mmol) in tetrahydrofuran (3 mL) and ethanol (1 mL), LiOH (0.076 g, 3.16 mmol) in water (3 mL) was added and the resulting mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude product, which was diluted with ice water, and acidified by using a 10 % HC1 solution. The resulting solid was filtered and dried to obtain 0.17 g of 3-(2-chloro-3,3,3-trifhioroprop-l-en-l-yl)-5-(trifluoromethyl)benzoic acid and 3-(trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-l-yl)benzoic acid as a white solid mixture. LCMS (m / z) 317.00 [M-H]’ and 283.00 [M-H]’.

[0516]

[0517] Example-8: Synthesis of (E)-3-(2-cyclopropylvinyl)-5-(trifluoromethyl)benzoic acid

[0518] Step-1: Synthesis of methyl (E)-3-(2-cyclopropylvinyl)-5-(trifluoromethyl)benzoate

[0519] To a stirred solution of methyl 3-bromo-5-(trifluoromethyl)benzoate (0.5 g, 1.767 mmol) in toluene (2 mL) and water (0.200 mL), (£)-2-(2-cyclopropylvinyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (0.686 g, 3.53 mmol) and K2CO3 (0.732 g, 5.30 mmol) were added. The resulting reaction mixture was stirred at 25 °C and degassed with nitrogen for 10 min., followed by the addition of (1,1 -Bis(diphenylphosphino)ferrocene)-dichloropalladium(II) (0.129 g, 0.177 mmol), and stirred at 100 °C for 5 h. After completion of the reaction, the reaction mixture was diluted with water (10 mL) and extracted with ethyl acetate (50 mL). The organic layer was washed with brine solution (15 mL), dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure to obtain a crude product which was purified by flash chromatography to obtain methyl (E)-3-(2-cyclopropylvinyl)-5-(trifluoromethyl)benzoate (0.4 g, 1.480 mmol, 84 % yield). ¹H-NMR (400 MHz, CDCl₃) δ 8.12 (s, 1H), 8.07 (s, 1H), 7.68 (s, 1H), 6.51 (d, J= 15.9 Hz, 1H), 5.88 (dd, J= 15.9, 9.0 Hz, 1H), 3.95 (s, 3H), 1.65-1.58 (m, 1H), 0.92-0.86 (m, 2H), 0.63-0.55 (m, 2H).

[0520] Step-2: Synthesis of (E)-3-(2-cyclopropylvinyl)-5-(trifluoromethyl)benzoic acidTo a stirred solution of methyl (E)-3-(2-cyclopropylvinyl)-5-(trifluoromethyl)benzoate (0.4 g, 1.480 mmol) in tetrahydrofuran (2 mL) and ethanol (0.2 mL), LiOH (0.106 g, 4.44 mmol) in water (2 mL) was added and the resulting reaction mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude product which was diluted with ice water and acidified using 10 % HC1 solution. The resulting solid was filtered and dried to obtain (E)-3-(2-cyclopropylvinyl)-5-(trifluoromethyl)benzoic acid (0.3 g, 1.171 mmol, 79 % yield). ¹H-NMR (400 MHz, DMSO-d₆) δ 13.49 (s, 1H), 8.13 (s, 1H), 7.93 (s, 2H), 6.64 (d, J= 15.9 Hz, 1H), 6.12 (dd, J= 15.9, 9.3 Hz, 1H), 1.60 (tt, J= 12.7, 4.3 Hz, 1H), 0.85-0.79 (m, 2H), 0.63-0.58 (m, 2H); LCMS (m / z) 255 [M-H]’.

[0521]

[0522] Example-9: Synthesis of 3-(trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-2-yl)benzoic acid

[0523] Step-1: Synthesis of methyl 3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)benzoate

[0524] To a stirred solution of methyl 3-bromo-5-(trifluoromethyl)benzoate (5 g, 17.67 mmol) and bis(pinacolato)diboron (5.83 g, 22.96 mmol) in 1,4-dioxane (50 mL), potassium acetate (3.47 g, 35.3 mmol) was added at 25 °C under nitrogen purging for 10 minutes. The resulting reaction mixture was treated with dichloro[l, T-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (0.721 g, 0.883 mmol) and stirred at 100 °C for 6 h. After completion of the reaction, the reaction mixture was filtered through a Celite® bed. The filtrate was concentrated under reduced pressure to obtain a crude product which was purified by flash chromatography to obtain methyl 3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)benzoate (5 g, 15.15 mmol, 86 % yield) as a white solid. ¹H-NMR (400 MHz, CDCl₃) δ 8.62 (s, 1H), 8.37 (d, J= 0.5 Hz, 1H), 8.23 (s, 1H), 3.95 (s, 3H), 1.36 (s, 12H).

[0525] Step-2: Synthesis of methyl 3-(trifluoromethyl)-5-(3,3,3-trifhioroprop-l-en-2-yl)benzoate

[0526] To a stirred solution of methyl 3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)benzoate (2.5 g, 7.57 mmol) in toluene (25 mL) and water (6.25 mL), 2-bromo-3,3,3-trifluoroprop-l-ene (0.883 mL, 8.33 mmol) and NaiCCf (3.21 g, 30.3 mmol) were added. The reaction mixture was degassed with nitrogen for 15 min., followed by the addition oftetrakis(triphenylphosphine)palladium(0) (0.438 g, 0.379 mmol). The resulting reaction mixture was stirred at 85 °C for 6 h. After completion of the reaction, the reaction mixture was filtered through Celite® and the cake was washed with ethyl acetate. The filtrate was concentrated under reduced pressure to obtain a crude product which was purified by flash chromatography to obtain methyl 3-(trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-2-yl)benzoate (1.4 g, 4.70 mmol, 62 % yield). ¹H-NMR (500 MHz, CDCl₃) δ 8.33 (d, J = 0.6 Hz, 1H), 8.30 (s, 1H), 7.87 (s, 1H), 6.14 (d, J= 1.0 Hz, 1H), 5.92-5.91 (m, 1H), 3.98 (s, 3H).

[0527] Step-3: Synthesis of 3-(trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-2-yl)benzoic acid

[0528] To a stirred solution of methyl 3-(trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-2-yl)benzoate (0.2 g, 0.671 mmol) in tetrahydrofuran (0.6 mL) and ethanol (0.2 mL), LiOH (0.048 g, 2.012 mmol) in water (0.6 mL) was added. The resulting mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude product, which was diluted with ice water and acidified using a 10% HC1 solution. The resulting solid was filtered and dried to obtain 3-(trifhroromethyl)-5-(3,3,3-trifluoroprop-l-en-2-yl)benzoic acid (0.190 g, 0.669 mmol, 99 % yield). ’H-NMR (500 MHz, DMSO-rZs) 5 8.25 (s, 1H), 8.22 (s, 1H), 7.89 (s, 1H), 6.32 (s, 1H), 6.24 (s, 1H) GCMS (m / z) 284.1 [M]+.

[0529] Synthetic Scheme 10:

[0530]

[0531] Example-10: Synthesis of (E)-3-(2-ethoxyvinyl)-5-(trifluoromethyl)benzoic acid

[0532] Step-1: Synthesis of methyl (E)-3-(2-ethoxyvinyl)-5-(trifluoromethyl)benzoate

[0533] To a stirred solution of methyl 3-bromo-5-(trifluoromethyl)benzoate (2.0 g, 7.07 mmol) in toluene (20 mL) and water (2 mL), (E)-2-ethoxyvinylboronic acid pinacol ester (1.400 g, 7.07 mmol) and potassium carbonate (2.93 g, 21.20 mmol) were added. The resulting mixture was degassed with nitrogen for 10 min. followed by the addition of (l, T-Bis(diphenylphosphino)ferrocene)-dichloropalladium(II) (0.517 g, 0.707 mmol). The resulting reaction mixture was stirred at 100 °C for 5 h. After completion of the reaction, the reaction mixture was diluted with water and extracted with ethyl acetate (2 x 50 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure to obtain a crude product, which was purified by flash chromatography to obtain methyl (E)-3-(2-ethoxyvinyl)-5-(trifluoromethyl)benzoate (1.6 g, 5.83 mmol, 83 % yield).1H-NMR (400 MHz, CDCl3) 58.03 (d, J= 14.4 Hz, 2H), 7.59 (s, 1H), 7.12 (d, J= 13.0 Hz, 1H), 5.87 (d, J= 13.0 Hz, 1H), 3.97 (t, J= 2.1 Hz, 1H), 3.95 (t, J = 3.5 Hz, 4H), 1.36 (t, J = 7.0 Hz, 3H).

[0534] Step-2: Synthesis of (E)-3-(2-ethoxyvinyl)-5-(trifluoromethyl)benzoic acid

[0535] To a stirred solution of methyl (£)-3-(2-ethoxyvinyl)-5-(trifluoromethyl)benzoate (1.57 g, 5.72 mmol) in tetrahydrofuran (10 mL) and ethanol (3.33 mL), LiOH (0.411 g, 17.17 mmol) in water (10 mL) was added and the resulting reaction mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude product, which was diluted with ice water and then acidified by using a 10% HC1 solution. The resulting solid was filtered and dried under vacuum to obtain (E)-3-(2-ethoxyvinyl)-5-(trifluoromethyl)benzoic acid (1.49 g, 5.73 mmol, 99 % yield) as a white solid.1¹H-NMR (400 MHz, DMSO-d₆) δ 8.07 (s, 1H), 7.87 (d, J= 23.0 Hz, 2H), 7.51 (d, J= 13.0 Hz, 1H), 6.01 (d, J= 13.0 Hz, 1H), 3.93 (q, J= 7.0 Hz, 2H), 1.25 (t, J= 7.0 Hz, 3H); LCMS (m / z) 258.90 [M-H]-.

[0536] Synthetic Scheme 11:

[0537] SnBu3F3C

[0538]

[0539] Br %

[0540] Example-11: Synthesis of 3-(trifluoromethyl)-5-vinylbenzoic acid

[0541] Step-1: Synthesis of methyl 3-(trifluoromethyl)-5-vinylbenzoate

[0542] To a stirred solution of methyl 3-bromo-5-(trifluoromethyl)benzoate (2 g, 7.07 mmol) in toluene (20 mL), tributyl(vinyl)stannane (2.168 mL, 7.42 mmol) was added. The reaction mixture was purged with nitrogen for 5 min. followed by the addition of bis(triphenylphosphine)palladium(II) chloride (0.248 g, 0.353 mmol). The resulting reaction mixture was stirred at 100 °C for 3 h. After completion of the reaction, the reaction mixture was diluted with water, and the aqueous layer was extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with brine solution (50 mL), dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure to obtain a crude product which was purified by flash chromatography to obtain methyl 3-(trifluoromethyl)-5-vinylbenzoate (1.5 g, 6.52 mmol, 92 % yield). ’H-NMR (400 MHz, CDCh) 5 8.24 (s, 1H), 8.17 (s, 1H), 7.81 (s, 1H), 6.78 (dd, J= 17.6, 11.0 Hz, 1H), 5.91 (d, J= 17.6 Hz, 1H), 5.45 (d, J= 10.8 Hz, 1H), 3.96 (s, 3H); GCMS (m / z) 230.2 [M+],

[0543] Step-2: Synthesis of 3-(trifluoromethyl)-5-vinylbenzoic acid

[0544] To a stirred solution of methyl 3-(trifluoromethyl)-5-vinylbenzoate (1 g, 4.34 mmol) in tetrahydrofuran (0.6 mL) and ethanol (0.200 mL), LiOH (0.312 g, 13.03 mmol) in water (0.600 mL) was added and the resultingreaction mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude product, which was diluted with ice water and then acidified by using 10% HC1 solution. The resulting solid was filtered and dried to obtain 3-(trifluoromethyl)-5-vinylbenzoic acid (0.9 g, 4.16 mmol, 96 % yield). ¹H-NMR (400 MHz, DMSO-d₆) δ 13.54 (s, 1H), 8.27 (s, 1H), 8.10 (s, 1H), 8.04 (s, 1H), 6.92 (dd, J= 17.7, 11.0 Hz, 1H), 6.10 (d, J= 17.7 Hz, 1H), 5.47 (d, J= 11.1 Hz, 1H); GCMS (m / z) 216.1 [M]+.

[0545]

[0546] Example-12: Synthesis of 3-(3-methylbut-2-en-2-yl)-5-(trifhioromethyl)benzoic acid

[0547] Step-1: Synthesis of methyl 3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-5- (trifluoromethyl)benzoate

[0548] To a stirred solution of methyl 3-bromo-5-(trifluoromethyl)benzoate (10 g, 35.3 mmol) and bis(pmacolato)di boron (11.66 g, 45.9 mmol) in 1,4-dioxane (100 mL), potassium acetate (6.93 g, 70.7 mmol) was added at 25 °C under nitrogen purging for 10 min. followed by the addition of dichloro[l,l'-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (1.443 g, 1.767 mmol). The resulting reaction mixture was stirred at 95 °C for 12 h. After completion of the reaction, the reaction mixture was filtered through a Celite® bed, and the filtrate was concentrated under reduced pressure to obtain a crude product, which was purified by flash chromatography to obtain methyl 3-(4, 4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)benzoate (10 g, 30.3 mmol, 86 % yield) as an off white solid.

[0549] ¹H-NMR (400 MHz, CDCl₃) δ 8.62 (s, 1H), 8.37 (d, J= 0.5 Hz, 1H), 8.22 (s, 1H), 3.95 (s, 3H), 1.36 (s, 12H).

[0550] Step-2: Synthesis of methyl 3-(3-methylbut-2-en-2-yl)-5-(trifluoromethyl)benzoate

[0551] To a stirred solution of methyl 3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)benzoate (3 g, 9.09 mmol) in toluene (30 mL) and water (3 mL), 2-bromo-3-methyl-2-butene (2.032 g, 13.63 mmol) and NaiCCf (1.926 g, 18.18 mmol) were added. The reaction mixture was degassed with nitrogen for 15 min., followed by the addition of tetrakis(triphenylphosphine)palladium(0) (0.525 g, 0.454 mmol). The resulting reaction mixture was stirred at 85 °C for 6 h. After completion of the reaction, the reaction mixture was filtered through a Celite® bed, washed with ethyl acetate. The filtrate was concentrated under reduced pressure to obtain a crude product, which was purified by flash chromatographyto obtain methyl 3-(3-methylbut-2-en-2-yl)-5-(trifluoromethyl)benzoate (2 g, 7.35 mmol, 81 % yield) as an oil. ¹H-NMR (400 MHz, CDCl₃) δ 8.13 (d, J= 0.7 Hz, 1H), 7.99 (s, 1H), 7.57 (s, 1H), 3.95 (s, 3H), 1.83 (s, 3H), 1.57 (d, J= 1.2 Hz, 6H).

[0552] Step-3: Synthesis of 3-(3-methylbut-2-en-2-yl)-5-(trifluoromethyl)benzoic acid

[0553] To a stirred solution of methyl 3-(3-methylbut-2-en-2-yl)-5-(trifluoromethyl)benzoate (1.8 g, 6.61 mmol) in tetrahydrofuran (6 mL) and ethanol (2 mL), LiOH (0.475 g, 19.83 mmol) in water (6.00 mL) was added, and the resulting reaction mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a crude product, which was diluted with ice water and acidified by using a 10% HC1 solution. The resulting solid was filtered and dried to obtain 3-(3-methylbut-2-en-2-yl)-5-(trifluoromethyl)benzoic acid (1.5 g, 5.81 mmol, 88 % yield). ¹H-NMR (400 MHz, CDCl₃) δ 8.21 (d, J= 0.7 Hz, 1H), 8.06 (s, 1H), 7.63 (s, 1H), 2.00 (t, J= 1.2 Hz, 3H), 1.85 (s, 3H), 1.59 (d, J= 1.5 Hz, 3H); LCMS (m / z) 257.20 [M-H]’.

[0554] Synthetic Scheme 13:

[0555] Step-1 Step-2

[0556] .ci •Cl

[0557]

[0558] Example-13: Synthesis of 3-(2,2-dichlorovinyl)benzoic acid

[0559] Step-1: Synthesis of ethyl 3-(2,2-dichlorovinyl)benzoate

[0560] To a stirred solution of ethyl 3-formylbenzoate (3 g, 16.84 mmol) in tetrahydrofuran (30 mL), triphenylphosphine (9.72 g, 37.0 mmol) and carbon tetrachloride (16.25 mL, 168 mmol) were added at 25 °C. The resulting reaction mixture was stirred at 60 °C for 6 h. After completion of the reaction, the reaction mixture was quenched with ammonium chloride solution (20 mL), and extracted with ethyl acetate (3 x 50 mL). The combined organic layers were washed with water (25 mL) and brine solution (25 mL), dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure to obtain a crude product, which was purified by flash chromatography to obtain ethyl 3-(2,2-dichlorovinyl)benzoate (3.5 g, 14.28 mmol, 85 % yield) as a colourless solid product.1H-NMR (400 MHz, CHLOROFORM-D) 5 8.18 (t, J = 1.7 Hz, 1H), 7.99 (dt, J = 7.8, 1.5 Hz, 1H), 7.74 (d, J = 7.8 Hz, 1H), 7.47-7.42 (m, 1H), 6.90 (d, J = 5.6 Hz, 1H), 4.43-4.36 (m, 3H), 1.43-1.38 (m, 4H).

[0561] Step-2: Synthesis of 3-(2,2-dichlorovinyl)benzoic acid

[0562] To a stirred solution of methyl ethyl 3-(2,2-dichlorovinyl)benzoate (3.5 g, 14.28 mmol) in tetrahydrofuran (12 mL) and water (12 mL), lithium hydroxide (1.026 g, 42.8 mmol) in water (12 mL) was added at 0 °Cand the resulting mixture was stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was evaporated under reduced pressure to obtain a crude product, which was diluted with ice water and then acidified by using 10% HC1 (pH~3). The resulting solid was filtered and dried to obtain 3-(2,2-dichlorovinyl)benzoic acid (2.5 g, 11.52 mmol, 81 % yield).1H-NMR (500 MHz, CHLOROFORM-D) 5 8.27 (s, 1H), 8.06 (dd, J = 6.6, 1.3 Hz, 1H), 7.79 (dd, J = 7.8, 0.7 Hz, 1H), 7.51-7.48 (m, 1H), 6.92 (s, 1H).

[0563] Synthetic Scheme 14:

[0564]

[0565] Example-14: Synthesis of 3-(2,2-difluorovinyl)benzoic acid

[0566] Step-1: Synthesis of ethyl 3-(2,2-difluorovinyl)benzoate

[0567] To a stirred solution of ethyl 3 -formylbenzoate (7.0 g, 39.3 mmol) in N,N-dimethylformamide (60 mL), triphenylphosphine (13.40 g, 51.1 mmol) was added at 25 °C. The resulting reaction mixture was stirred at 100 °C for 30 min. and then sodium chlorodifluoroacetate (8.98 g, 58.9 mmol) in N,N-dimethylformamide was added slowely to reaction mixture. Then reaction mixture was continued stirring at 100 °C for 30 min. After completion of the reaction, the reaction mixture was quenched with water (100 mL) and the aqueous layer was extracted with ethyl acetate (2 x 70 mL), combined organic layers were washed with water (75 mL), brine solution (75 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude liquid, which was purified by flash chromatography to obtain ethyl 3-(2,2-difluorovinyl)benzoate (5 g, 23.56 mmol, 60 % yield) as a white solid product. ¹H-NMR (400 MHz, CDCl₃) δ 7.98 (t, J = 1.6 Hz, 1H), 7.91 (dt, J = 7.7, 1.3 Hz, 1H), 7.53 (d, J = 8.1 Hz, 1H), 7.43-7.39 (m, 1H), 5.33 (dd, J = 25.9, 3.7 Hz, 1H), 4.38 (q, J = 7.1 Hz, 2H), 1.40 (t, J = 7.2 Hz, 3H).

[0568] Step-2: Synthesis of 3-(2,2-difhiorovinyl)benzoic acid

[0569] To a stirred solution of methyl ethyl 3-(2,2-difluorovinyl)benzoate (4.5 g, 21.21 mmol) in tetrahydrofuran (40 mL), lithium hydroxide (1.524 g, 63.6 mmol) in water (40 mL) was added and the resulting reaction mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was evaporated under reduced pressure to obtain a crude product, which was diluted with ice water and then acidified by using 10% HC1 (pH~3). The resulting solid was filtered and dried to obtain 3-(2,2-difluorovinyl)benzoic acid (3.5 g, 19.01 mmol, 90 % yield) as an off-white solid. ¹H-NMR (500 MHz, CDCl₃) δ 8.06 (t, J = 1.6 Hz, 1H), 7.98 (dt, J = 7.8, 1.2 Hz, 1H), 7.59 (d, J = 7.8 Hz, 1H), 7.48-7.44 (m, 1H), 5.35 (dd, J = 25.8, 3.5 Hz, 1H); LCMS (m / z) 182.95 [M-H]+.Synthetic Scheme 15:

[0570]

[0571] Example-15: Synthesis of mixture of 3-(2,2-difluorovinyl)-5-(trifluoromethyl)benzoic acid and 3-(2-fluoro-2-methoxyvinyl)-5-(trifluoromethyl)benzoic acid

[0572] Step-1: Synthesis of methyl 3-(2,2-difluorovinyl)-5-(trifluoromethyl)benzoate

[0573] To a stirred solution of methyl 3-formyl-5-(trifluoromethyl)benzoate (2 g, 8.61 mmol) in N. N-dimethylformamide (20 mL), triphenylphosphine (2.94 g, 11.20 mmol) was added to it at 25 °C and the resulting reaction mixture was stirred at 100 °C for 30 min. A solution of sodium chlorodifluoroacetate (1.970 g, 12.92 mmol) in N,N-dimethylformamide (10 mL) was added dropwise to reaction mixture and continued stirring at 100 °C for 30 min. After completion of the reaction, the reaction mixture was quenched with water (50 mL) and the aqueous layer was extracted with ethyl acetate (2 x 50 mL), the combined organic layers were washed with water (2 x 25 mL), brine solution (25 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude liquid, which was purified by flash chromatography to obtain methyl 3-(2,2-difluorovinyl)-5-(trifluoromethyl)benzoate (2 g, 7.51 mmol, 87 % yield) as a white solid product. ¹H-NMR (400 MHz, CDCl₃) δ 8.16 (d, J = 1.0 Hz, 2H), 7.76 (s, 1H), 5.39 (dd, J = 25.4, 3.2 Hz, 1H), 3.96 (s, 3H).

[0574] Step-2: Synthesis of 3-(2-fluoro-2-methoxyvinyl)-5-(trifluoromethyl)benzoic acid

[0575] To a stirred solution of methyl methyl 3-(2,2-difluorovinyl)-5-(trifluoromethyl)benzoate (0.2 g, 0.751 mmol) in tetrahydrofuran (0.6 mL) and water (0.6 mL), lithium hydroxide (0.027 g, 1.127 mmol) was added at 0 °C and the resulting mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was evaporated under reduced pressure to obtain a crude product, which was diluted with ice water, acidified by using 10% HC1 ( pH~3). The resulting solid was filtered and dried to obtain the mixture of products 3-(2,2-difluorovinyl)-5-(trifluoromethyl)benzoic acid and 3-(2-fluoro-2-methoxyvinyl)-5-(trifluoromethyl)benzoic acid as off white solid. LCMS (m / z) 262.90 [M-H]+, LCMS (m / z) 250.90 [M-H]+.

[0576] Synthetic Scheme 16:Step-1

[0577]

[0578] Example-16: Synthesis of 3-(3,3,3-trifhioro-2-methoxyprop-l-en-l-yl)-5-(trifluoromethyl)benzoic acid

[0579] Step-1: Synthesis of methyl 3-(2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-5-(trifluoromethyl)benzoate To a stirred solution of methyl 3-formyl-5-(trifluoromethyl)benzoate (3 g, 12.92 mmol) in N. N-dimethylformamide (30 mL), zinc (4.22 g, 64.6 mmol), acetic anhydride (3.66 mL, 38.8 mmol) and 1,1,1-trichlorotrifluoroethane (2.452 mL, 20.68 mmol) were added to the reaction mass at 25 °C and the resulting reaction mixture was stirred at 25 °C for 3 h. After completion of the reaction, the reaction mixture was quenched with NH4CI solution (50 mL) and the aqueous layer was extracted with ethyl acetate (2 x 50 mL), the combined organic layers were washed with water (2 x 25 mL), brine solution (25 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude liquid, which was purified by flash chromatography to obtain the desired methyl 3-(2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-5-(trifluoromethyl)benzoate (2 g, 6.01 mmol, 46 % yield) as a colourless oil. GCMS (m / z) 332.0 [M]+.

[0580] Step-2: Synthesis of 3-(3,3,3-trifluoro-2-methoxyprop-l-en-l-yl)-5-(trifluoromethyl)benzoic acid To a stirred solution of methyl 3-(2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-5-(trifluoromethyl)benzoate (3.5 g, 10.52 mmol) in methanol (40 mL), sodium methoxide (2.274 g, 42.1 mmol) was added to it, and the resulting mixture was stirred at 60 °C for 6 h. After completion of the reaction, the reaction mixture was evaporated, diluted with water (25 mL) and acidified with IN HC1 solution (pH~3) and the aqueous layer was extracted with ethyl acetate (2 x 40 mL). The combined organic layers were washed with brine solution (25 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude solid, which was washed with n-pentane to obtain the pure compound 3-(3,3,3-trifluoro-2-methoxyprop-l-en-l-yl)-5-(trifluoromethyl)benzoic acid as an off white solid (2.5 g, 7.96 mmol, 76 % yield). LCMS (m / z) 312.90 [M-H]+.

[0581] Synthetic Scheme 17:o o

[0582]

[0583] Scheme-17: Synthesis of (E)-3-bromo-5-(2-cyanovinyl)benzoic acid

[0584] Step-1: Synthesis of methyl 3-bromo-5-(2-chloro-2-cyanovinyl)benzoate

[0585] To a stirred solution of methyl 3-bromo-5-formylbenzoate (6 g, 24.69 mmol) in N,N-dimethylformamide (50 mL), zinc (8.07 g, 123 mmol), acetic anhydride (6.99 ml, 74.1 mmol) and 2,2,2-trichloroacetonitrile (3.96 mL, 39.5 mmol) were added to it at 0 °C and the resulting reaction mixture was stirred at 25 °C for 14 h. After completion of the reaction, the reaction mixture was quenched with NH4CI solution (50 mL) and the aqueous layer was extracted with ethyl acetate (2 x 100 mL), the combined organic layers were washed with water (50 mL) and brine solution (50 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude liquid, which was purified by flash chromatography to obtain methyl 3-bromo-5-(2-chloro-2-cyanovinyl)benzoate (6 g, 19.96 mmol, 81 % yield) as a pale yellow solid. LCMS (m / z) 300.9 [M+H]+.

[0586] Step-2: Synthesis of (E)-3-bromo-5-(2-cyanovinyl)benzoate & methyl (Z)-3-bromo-5-(2-cyanovinyl)benzoate

[0587] To a stirred solution of methyl 3-bromo-5-formylbenzoate (15 g, 61.7 mmol) in N,N-dimethylformamide (100 mL), zinc (40.3 g, 617 mmol), acetic anhydride (34.9 ml, 370 mmol) and 2,2,2-trichloroacetonitrile (9.90 ml, 99 mmol) were added at 0 °C and the resulting reaction mixture was warmed to 25 °C and continued stirring for 14 h. After completion of the reaction, the reaction mixture was quenched with ammonium chloride solution (50 mL) and the aqueous layer was extracted with ethyl acetate (2 x 200 mL), the combined organic layers were washed with water (2 x 50 mL), brine solution (50 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude liquid, which was purified by flash chromatography to obtain methyl (E)-3-bromo-5-(2-cyanovinyl)benzoate (6.89 g, 42 % yield),1H-NMR (400 MHz, CHLOROFORM-D) 58.22 (t, J = 1.6 Hz, 1H), 8.05 (t, J = 1.2 Hz, 1H), 7.76(t, J = 1.6 Hz, 1H), 7.36 (d, J = 16.6 Hz, 1H), 5.99 (d, J = 16.9 Hz, 1H), 3.95 (d, J = 5.9 Hz, 3H); GC-MS (m / z) 264.8 and methyl (Z)-3-bromo-5-(2-cyanovinyl)benzoate (4.02g, 24 % yield).1H-NMR (400 MHz, CHLOROFORM-D) 5 8.30 (t, J = 1.3 Hz, 1H), 8.24 (t, J = 1.6 Hz, 1H), 8.17 (t, J = 1.6 Hz, 1H), 7.12 (d, J = 12.2 Hz, 1H), 5.60 (d, J = 12.0 Hz, 1H), 3.95 (d, J = 2.0 Hz, 3H), GC-MS (m / z) 264.8.

[0588] Step-3: Synthesis of (E)-3-bromo-5-(2-cyanovinyl)benzoic acid

[0589] To a stirred solution of methyl (E)-3-bromo-5-(2-cyanovinyl)benzoate (3.5 g, 13.15 mmol) in tetrahydrofuran (30 mL) and water (30 mL), lithium hydroxide (0.472 g, 19.73 mmol) in water (30 mL) was added at 0 °C and the resulting mixture was stirred at 25 °C for 24 h. After completion of the reaction, the reaction mixture was evaporated under reduced pressure to obtain a crude product, which was diluted with ice water, acidified by using 10% HC1 ( pH~3). The resulting solid was filtered and dried to obtain pure (E)-3-bromo-5-(2-cyanovinyl)benzoic acid (3.2 g, 12.70 mmol, 97 % yield).1H-NMR (400 MHz, DMSO-d6) 5 12.80-14.22 (1H), 8.17 (d, J = 10.5 Hz, 2H), 8.07 (d, J = 12.5 Hz, 1H), 7.72 (d, J = 16.9 Hz, 1H), 6.70 (d, J = 16.6 Hz, 1H). LCMS (m / z) 249.90 [M-H]’.

[0590] Synthetic Scheme 18:

[0591] CN

[0592]

[0593] Example-18: Synthesis of (N)- / V-(l-(l-(5-cyanopyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- (trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-2-yl)benzamide (Compound No.21)

[0594] To a stirred solution of 3-(trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-2-yl)benzoic acid (0.15 g, 0.528 mmol) in N,N-dimethylformamide (2 mL), HATU (0.261 g, 0.686 mmol) was added. The reaction mixture was stirred at 25 °C for 10 min. followed by the addition of / V, / V-diisopropylethylamine (0.230 mL, 1.320 mmol) and (S)-6-(5-(l-aminoethyl)-l / / -l,2,4-triazol-l-yl)nicotinonitrile (0.124 g, 0.581 mmol). The resulting reaction mixture was stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was diluted with water (15 mL), and extracted with ethyl acetate (3 x 25 mL). The combined organic layers were washed with a saturated NaHCO3solution (25 mL) and brine solution (25 mL), dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure to obtain a crude product which was purified by flash chromatography to obtain (S)-N- 1 -( 1 -(5-cyanopyridin-2-yl)- 1H- 1,2,4-triazol-5-yl)ethyl)-3-(trifhioromethyl)-5-(3,3,3-trifluoroprop-l-en-2-yl)benzamide (0.055g, 0.114 mmol,22 % yield) as an off white solid.1H-NMR (500 MHz, DMSO-d6) 59.46 (d, J= 6.9 Hz, 1H), 9.05 (dd, J= 2.2, 0.7 Hz, 1H), 8.58-8.55 (m, 1H), 8.24 (d, J= 3.5 Hz, 2H), 8.13 (s, 1H), 8.06 (dd, J= 8.6, 0.6 Hz, 1H), 7.92 (s, 1H), 6.35-6.28 (m, 2H), 6.12-6.07 (m, 1H), 1.64 (d, J= 7.0 Hz, 3H); LCMS (m / z) 481.1 [M+H]+.

[0595] Scheme 19:

[0596]

[0597] Example-19: Synthesis of / V-(l-(3-(pyridin-2-yl)pyrazin-2-yl (ethyl )-3-(trifluoromethyl)-5-(3, 3,3-trifluoroprop-1-en-2-yl)benzamide (Compound No. 22)

[0598] To a stirred solution of 3-(trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-2-yl)benzoic acid (0.15 g, 0.528 mmol) in N,N-dimethylformamide (2 mL), HATU (0.261 g, 0.686 mmol) was added. The resulting mixture was stirred at 25 °C for 10 min. followed by the addition of N,N-diisopropylethylamine (0.230 ml, 1.320 mmol) and l-(3-(pyridin-2-yl)pyrazin-2-yl)ethan-l-amine (0.116 g, 0.581 mmol). The resulting reaction mixture was stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was diluted with water, and extracted with ethyl acetate (3 x 25 mL). The combined organic layers were washed with a saturated NaHCO3solution (25 mL) and brine solution (25 mL), dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure to obtain a crude product which was purified by flash chromatography to obtain A-(l-(3-(pyridin-2-yl)pyrazin-2-yl)ethyl)-3-(trifluoromethyl)-5-(3,3,3-trifluoroprop-l-en-2-yl)benzamide (0.074g, 0.159 mmol, 30 % yield) as an off white solid.1H-NMR (500 MHz, DMSO-d6) 5 9.27 (d, J= 6.9 Hz, 1H), 8.72-8.70 (m, 1H), 8.68 (d, J= 2.4 Hz, 1H), 8.64 (d, J= 2.4 Hz, 1H), 8.23 (s, 1H), 8.10 (s, 1H), 8.00-7.97 (m, 2H), 7.88 (s, 1H), 7.51-7.48 (m, 1H), 6.33-6.26 (m, 2H), 5.87-5.81 (m, 1H), 1.65 (d, J= 6.9 Hz, 3H); LCMS (m / z) 467.3 [M+H]+.

[0599] Synthetic Scheme 20:o

[0600]

[0601] Example-20: Synthesis of (S)-2-(5-(l-(3-(2,2-dichlorovinyl)benzamido)ethyl)-lH-l,2,4-triazol-l-yl)-N-isopropylthiazole-5-carboxamide (Compound No.135 ) & (S)-2-(5-(l-(3-(2,2-dichlorovinyl)benzamido)ethyl)-l H-l,2,4-triazol-l-yl)-N-(diethyl(oxo)-X6-sulfaneylidene)thiazole-5-carboxamide (Compound No.146 )

[0602] Step-1: Synthesis of ethyl (S)-2-(5-(l-(3-(2,2-dichlorovinyl)benzamido)ethyl)-lH-l,2,4-triazol-l-yl)thiazole-5-carboxylate (Compound No. 134 )

[0603] A solution of 3-(2,2-dichlorovinyl)benzoic acid (2.5 g, 11.52 mmol) and HATU (5.69 g, 14.97 mmol) in N,N-dimethylformamide (30 mL) was stirred at 25 °C for 10 min., treated with DIPEA (5.03 mL, 28.8 mmol) and ethyl (S)-2-(5-(l-aminoethyl)-lH-l,2,4-triazol-l-yl)thiazole-5-carboxylate--2,2,2-trifluoroacetate (7.76 g, 13.82 mmol), and the resulting reaction mixture was stirred for 16 h. After completion of the reaction, the reaction mixture was diluted with water (25 mL), extracted with ethyl acetate (3 x 25 mL). The combined organic layers were washed with NaHCO3solution (25 mL), brine solution (25 mL). dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure to obtain a crude product which was purified by flash chromatography to obtain ethyl (S)-2-(5-(l-(3-(2,2-dichlorovinyl)benzamido)ethyl)-lH-l,2,4-triazol-l-yl)thiazole-5-carboxylate (5 g, 10.72 mmol, 93 % yield) as off white solid.1H-NMR (400 MHz, CHLOROFORM-D) 58.25 (s, 1H), 7.96 (t, J = 2.6 Hz, 2H), 7.74 (d, J = 7.8 Hz, 1H), 7.70 (d, J = 7.8 Hz, 1H), 7.50 (d, J = 8.3 Hz, 1H), 7.46 (t, J = 7.8 Hz, 1H), 6.90 (s, 1H), 6.35 (dt, J = 14.9, 6.8 Hz, 1H), 4.41 (q, J = 7.1 Hz, 2H), 1.72-1.69 (m, 3H), 1.41 (t, J = 7.1 Hz, 3H) LCMS (m / z) 465.9 [M+H]+.

[0604] Step-2: Synthesis of (S)-2-(5-(l-(3-(2,2-dichlorovinyl)benzamido)ethyl)-lH-l,2,4-triazol-l-yl)thiazole-5-carboxylic acid (Compound No. 136)

[0605] To a stirred solution of methyl ethyl (S)-2-(5-(l-(3-(2,2-dichlorovinyl)benzamido)ethyl)-lH-l,2,4-triazol-l-yl)thiazole-5 -carboxylate (5 g, 10.72 mmol) in tetrahydrofuran (15 mL) and water (15 mL), lithiumhydroxide (0.770 g, 32.2 mmol) in water (15 mL) was added at 0 °C and the resulting mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was evaporated under reduced pressure to obtain a crude product, which was diluted with ice water and then acidified by using 10% HC1 (pH~3). The resulting solid was filtered and dried to obtain (S)-2-(5-(l-(3-(2,2-dichlorovinyl)benzamido)ethyl)-lH-l,2,4-triazol-l-yl)thiazole-5-carboxylic acid (4.6 g, 10.50 mmol, 98 % yield).1H-NMR (400 MHz, DMSO-d6) 5 13.87 (s, OH), 9.17 (d, J = 6.6 Hz, 1H), 8.31 (s, 1H), 8.24 (s, 1H), 8.01 (s, 1H), 7.85 (d, J= 8.1 Hz, 1H), 7.74 (d, J = 7.8 Hz, 1H), 7.51 (t, J = 7.8 Hz, 1H), 7.30 (s, 1H), 6.07-6.00 (m, 1H), 1.60 (d, J = 7.1 Hz, 3H) LCMS (m / z) 437.7 [M-H]+.

[0606] Step-3a: Synthesis of (S)-2-(5-(l-(3-(2,2-dichlorovinyl)benzamido)ethyl)-lH-l,2,4-triazol-l-yl)-N-isopropylthiazole-5-carboxamide (Compound No. 135)

[0607] A solution of (S)-2-(5-(l-(3-(2,2-dichlorovinyl)benzamido)ethyl)- 1H- 1,2,4-triazol- l-yl)thiazole-5-carboxylic acid (0.2 g, 0.456 mmol) and HATU (0.226 g, 0.593 mmol) in N,N-dimethylformamide (2 mL) was stirred at 25 °C for 10 min., treated with DIPEA (0.199 mL, 1.141 mmol) and propan-2-amine (0.040 g, 0.684 mmol) and stirred for 16 h. After completion of the reaction, the reaction mixture was diluted with water (25 mL), extracted with ethyl acetate (3 x 25 mL). The combined organic layers were washed with NaHCO3solution (25 mL), brine solution (25 mL), dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure to obtain a crude product which was purified by flash chromatography to obtain (S)-2-(5-( l-(3-(2,2-dichlorovinyl)benzamido)ethyl)- 1H- 1,2,4-triazol-1-yl)-N-isopropylthiazole-5-carboxamide (50 mg, 0.104 mmol, 23 % yield) as off white solid.1H-NMR (400 MHz, CHLOROFORM-D) 57.96-7.94 (m, 3H), 7.72 (dd, J = 17.5, 7.9 Hz, 2H), 7.51-7.44 (m, 2H), 6.90 (s, 1H), 6.37-6.30 (m, 1H), 5.84 (d, J = 7.3 Hz, 1H), 4.32-4.23 (m, 1H), 1.69 (d, J = 6.8 Hz, 3H), 1.29 (d, J = 6.6 Hz, 6H) 480.3 [M+H]+.

[0608] Step-3b: (S)-2-(5-(l-(3-(2,2-dichlorovinyl)benzamido)ethyl)-lH-l,2,4-triazol-l-yl)-N-(diethyl(oxo)-%6-sulfaneylidene)thiazole-5-carboxamide (Compound No. 146)

[0609] A solution of (S)-2-(5-(l-(3-(2,2-dichlorovinyl)benzamido)ethyl)- 1H- 1,2,4-triazol- l-yl)thiazole-5-carboxylic acid (0.2 g, 0.456 mmol) and HATU (0.226 g, 0.593 mmol) in N,N-dimethylformamide (2 mL), was stirred at 25 °C for 10 min., treated with DIPEA (0.199 mL, 1.141 mmol), and S, S-diethyl-sulfoximine (0.083 g, 0.684 mmol), and the resulting reaction mixture was stirred for 16 h. After completion of the reaction, the reaction mixture was diluted with water (15 mL), the solid obtained was filtered, washed with water and dried to obtain a crude product, which was purified by preperative HPLC to obtain (S)-2-(5-( 1-(3-(2,2-dichlorovinyl)benzamido)ethyl)- 1H- 1,2,4-triazol- l-yl)-N-(diethyl(oxo)-X6-sulfaneylidene)thiazole-5-carboxamide (69mg, 0.127 mmol, 28 % yield) as an off white solid.1H-NMR(400 MHz, CHLOROFORM-D) 5 8.20 (s, 1H), 7.97 (s, 1H), 7.94 (s, 1H), 7.74 (d, J = 7.8 Hz, 1H), 7.70-7.68 (m, 2H), 7.45 (t, J = 7.8 Hz, 1H), 6.89 (s, 1H), 6.33 (dt, J = 15.2, 7.0 Hz, 1H), 3.63-3.54 (m, 2H), 3.46 (ddd, J = 21.4, 7.5, 6.5 Hz, 2H), 1.69 (d, J = 7.1 Hz, 3H), 1.49 (t, J = 7.3 Hz, 6H) 542.3 [M+H]+.

[0610] Synthetic Scheme 21

[0611] CN

[0612] Step-1

[0613]

[0614] Example-21: Synthesis of (S)-N-(l-(l-(5-cyanopyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)-3-(2,2-difluorovinyl)benzamide (Compound No. 127)

[0615] Step-1: Synthesis of (S)-N-(l-(l-(5-cyanopyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)-3-(2,2-difluorovinyl)benzamide (Compound No. 127)

[0616] A solution of 3-(2,2-difluorovinyl)benzoic acid (200 mg, 1.086 mmol) and HATU (537 mg, 1.412 mmol) in N,N-dimethylformamide (3 mL), was stirred at 25 °C for 10 min., treated with DIPEA (0.569 mL, 3.26 mmol) and (S)-6-(5-(l-aminoethyl)-lH-l,2,4-triazol-l-yl)nicotinonitrile 2,2,2-trifluoroacetate (604 mg, 1.086 mmol), and the resulting reaction mixture was stirred for 16 h. After completion of the reaction, the reaction mixture was diluted with water (25 mL), the solid obtained was filtered, washed with water and n-pentane, dried to obtain solid crude product, which was further purified by flash chromatography to obtain (S)-N-(l-(l-(5-cyanopyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)-3-(2,2-difluorovinyl)benzamide (74 mg, 0.195 mmol, 18 % yield) as an off-white solid. ‘H-NMR (400 MHz, CDCl3) 5 8.86 (q, J = 1.0 Hz, 1H), 8.18-8.13 (m, 2H), 8.01-7.99 (m, 1H), 7.75 (d, J = 8.1 Hz, 1H), 7.66 (d, J = 7.6 Hz, 1H), 7.52-7.49 (m, 1H), 7.42 (t, J = 7.7 Hz, 1H), 7.31 (d, J = 7.8 Hz, 1H), 6.42 (dt, J = 14.7, 6.8 Hz, 1H), 5.33 (dd, J = 25.9, 3.7 Hz, 1H), 1.70 (d, J = 6.8 Hz, 3H); LCMS (m / z) 380.85 [M+H]+.

[0617] Synthetic Scheme 22

[0618]

[0619] Example-22: Synthesis of (S)-N-(l-(l-(5-cyanopyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)-3-(2-fluoro-2-methoxyvinyl)-5-(trifluoromethyl)benzamide (Compound No. 101)

[0620] Step-1: Synthesis of (S)-N-(l-(l-(5-cyanopyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)-3-(2-fluoro-2-methoxyvinyl)-5-(trifluoromethyl)benzamide (Compound No. 101)

[0621] A solution of 3-(2,2-difluorovinyl)-5-(trifluoromethyl)benzoic acid (0.4 g, 1.586 mmol) and HATU (0.784 g, 2.062 mmol) in N,N-dimethylformamide (5 mL), was stirred at 25 °C for 10 min., treated with DIPEA (0.831 mL, 4.76 mmol) and (S)-6-(5-(l -aminoethyl)- 177-1, 2, 4-triazol-l-yl)nicotinonitrile 2,2,2-trifluoroacetate (1.059 g, 1.904 mmol), and the resulting reaction mixture was stirred for 16 h. After completion of the reaction, the reaction mixture was diluted with water (25 mL). The resulting solid was filtered, washed with water and w-pentane, dried under reduced pressure to obtain a crude product, which was further purified by flash chromatography to obtain (S)-N-(l-(l-(5-cyanopyridin-2-yl)- 1H- 1,2,4-triazol-5-yl)ethyl)-3-(2-fluoro-2-methoxyvinyl)-5-(trifluoromethyl)benzamide (35 mg, 0.076 mmol, 5 % yield) as an off white solid.1H-NMR (500 MHz, CDCl3) 5 8.86 (q, J = 1.0 Hz, 1H), 8.19-8.14 (m, 2H), 8.01-8.00 (m, 1H), 7.95 (s, 1H), 7.78 (d, J = 9.7 Hz, 2H), 7.38-7.34 (m, 1H), 6.42 (dt, J = 14.7, 6.8 Hz, 1H), 5.21 (d, J = 7.1 Hz, 1H), 3.97-3.91 (m, 3H), 1.74-1.71 (m, 3H); LCMS (m / z) 461.30 [M+H]+.

[0622]

[0623] Example-23: Synthesis of (S)-N-(l-(3-methyl-l-(pyrimidin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)-3-(3,3,3-trifluoro-2-methoxyprop-1-en-1-yl)-5-(trifluoromethyl)benzamide (Compound No.68)

[0624] Step-1: Synthesis of (S)-N-(l-(3-methyl-l-(pyrimidin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)-3-(3,3,3-trifluoro-2-methoxyprop-1-en-1-yl)-5-(trifluoromethyl)benzamide (Compound No.68)

[0625] A solution of 3-(3,3,3-trifluoro-2-methoxyprop-l-en-l-yl)-5-(trifluoromethyl)benzoic acid (0.3 g, 0.955 mmol) and HATU (0.472 g, 1.241 mmol) in N,N-dimethylformamide (5 mL), was stirred at 25 °C for 10 min., treated with DIPEA (0.417 mL, 2.387 mmol) and (S)-l-(3-methyl-l-(pyrimidin-2-yl)-lH-l,2,4-triazol-5-yl)ethan-l -amine 2,2,2-trifluoroacetate (0.571 g, 1.146 mmol), and stirred for 16 h. After completion of the reaction, the reaction mixture was diluted with water (25 mL) and extracted with ethyl acetate (3 x 25 mL). The combined organic layers were washed with NaHCO3solution (25 mL), brine solution (25 mL), dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressureto obtain a crude product which was purified by flash chromatography and further purified by prep HPLC to obtain (S)-N-(l-(3-methyl-l-(pyrimidin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)-3-(3,3,3-trifluoro-2-methoxyprop-l-en-l-yl)-5-(trifluoromethyl)benzamide (64 mg, 0.128 mmol, 14 % yield) as an off white solid.1H-NMR (400 MHz, CDCl3) δ 8.89 (dd, J = 4.9, 1.7 Hz, 2H), 8.24 (s, 1H), 8.06 (d, J = 5.9 Hz, 1H), 8.03 (s, 1H), 7.55-7.52 (m, 1H), 7.36 (t, J = 4.8 Hz, 1H), 6.46 (s, 1H), 6.44-6.40 (m, 1H), 3.85 (d, J = 1.0 Hz, 3H), 2.50 (s, 3H), 1.69 (d, J = 6.6 Hz, 3H); LCMS (m / z) 501.4 [M+H]+.

[0626] Step-1 Step-2

[0627]

[0628] Examples-24: Synthesis of (S, E)-3-bromo-5-(2-cyanovinyl)-N-methyl-N-(l -(3-methyl- 1-(5- (trifluoromethyl)pyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)benzamide (Compound No.243) Step-1: Synthesis of (S, E)-3-bromo-5-(2-cyanovinyl)-N-(l-(3-methyl-l-(5-(trifluoromethyl)pyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)benzamide (Compound No.218 )

[0629] A solution of (S)- 1 -(3 -methyl- 1 -(5 -(trifluoromethyl)pyridin-2-yl)- 1 H- 1,2,4-triazol-5 -yl)ethan- 1 -amine 2,2,2-trifluoroacetate (487 mg, 0.793 mmol), (E)-3-bromo-5-(2-cyanovinyl)benzoic acid (200 mg, 0.793 mmol) and N,N-Diisopropylethylamine (DIPEA) (0.554 mL, 3.17 mmol) in N,N-dimethylformamide (2 mL), was stirred at 25 °C for 20 min, treated with HATU (453 mg, 1.190 mmol) and stirred for 16 h. After completion of the reaction, the reaction mixture was diluted with water (25 mL), extracted with ethyl acetate (3 x 25 mL). The combined organic layers were washed with NaHCO3solution (25 mL), brine solution (25 mL), dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure to obtain a crude product which was purified by preparative HPLC to obtain (S, E)-3-bromo-5-(2-cyanovinyl)-N-(l-(3-methyl- l-(5-(trifluoromethyl)pyridin-2-yl)- 1H- l,2,4-triazol-5-yl)ethyl)benzamide (262 mg, 0.519 mmol, 65 % yield).1H-NMR (400 MHz, DMSO-d6) 5 9.18 (d, J = 7.1 Hz, 1H), 8.94 (t, J = 1.2 Hz, 1H), 8.43 (dd, J = 8.7, 2.1 Hz, 1H), 8.05-8.01 (m, 4H), 7.65 (d, J = 16.6 Hz, 1H), 6.60 (d, J = 16.6 Hz, 1H), 6.10-6.03 (m, 1H), 2.34 (s, 3H), 1.61 (d, J = 6.8 Hz, 3H); LCMS (m / z) 506.70 [M+H]+.

[0630] Step-2: (S, E)-3-bromo-5-(2-cyanovinyl)-N-methyl-N-(l-(3-methyl-l-(5-(trifluoromethyl)pyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)benzamide (Compound No.243)

[0631] A suspension of (S, E)-3-bromo-5-(2-cyanovinyl)-N-(l-(3-methyl-l-(5-(trifluoromethyl)pyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)benzamide (158 mg, 0.313 mmol) and NaH (18.76 mg, 0.469 mmol) in N. N-dimethylformamide (1 mL) was cooled to 0 °C for 30 min., treated with a solution of iodomethane (0.039 mL, 0.625 mmol) in N,N-dimethylformamide (1 mL), and the resulting reaction mixture was stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was diluted with water (25 mL), extracted with ethyl acetate (3 x 25 mL). The combined organic layers were washed with NaHCO3solution (25 mL), brine solution (25 mL), dried over anhydrous sodium sulphate, filtered, and concentrated under reduced pressure to obtain a crude product which was purified by preparative HPLC to obtain (S, E)-3-bromo-5-(2-cyanovinyl)-N-methyl-N-(l-(3-methyl-l-(5-(trifluoromethyl)pyridin-2-yl)-lH-l,2,4-triazol-5-yl)ethyl)benzamide (85 mg, 0.164 mmol, 52 % yield).1H-NMR (400 MHz, DMSO-d6) 5 8.83-7.27 (m, 7H), 6.61-6.09 (m, 2H), 3.20-2.72 (m, 3H), 2.38 (s, 3H), 1.67-1.62 (m, 3H); LCMS (m / z) 520.70 [M+H]+. The following compounds (Table- 1) of the present invention were obtained using analogous procedures as described in the schemes or in the examples.Comp. No. refer to Compound Number T able- 1

[0632] Comp.

[0633] Compound IUPAC Name Analytical Data

[0634] No.

[0635] (S)-3-(2-chloro-3,3,3-1H-NMR (400 MHz, DMSO-d6) 59.44 (dd, J= 10.4, 7.0 trifluoroprop- 1 -en- 1 -yl)- / V-( 1 -( 1 - Hz, 1H), 9.06-9.05 (m, 1H), 8.56 (dd, J= 8.6, 2.2 Hz, 1H), (5-cyanopyridin-2-yl)- 1H- 1,2,4- 8.47 (d, J= 20.1 Hz, 1H), 8.38-8.26 (m, 2H), 8.24 (s, 1H), 1

[0636] triazol-5 -y l)ethyl) -5 - 8.07-8.05 (m, 1H), 7.96 (s, 1H), 6.10 (t, J= 6.8 Hz, 1H), (trifluoromethyl)benzamide 1.64 (dd, J= 7.0, 2.1 Hz, 3H); LCMS (m / z) 514.95

[0637] [M+H]+.

[0638] (SJL)-N -( 1 -( 1 -(5-cy anopyridin-2-1H-NMR (400 MHz, DMSO-d6) 59.35 (d, J= 7.1 Hz, 1H), yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- 9.06 (q, J= 1.0 Hz, 1H), 8.56 (dd, J= 8.7, 2.3 Hz, 1H), 8.38 (trifluoromethyl)-5-(3,3,3- (s, 1H), 8.25 (d, J= 6.4 Hz, 2H), 8.12 (s, 1H), 8.06 (dd, J= 2 trifluoroprop- 1 -en- 1 - 8.6, 0.7 Hz, 1H), 7.49 (dd, J= 16.4, 2.2 Hz, 1H), 7.07-6.98 yl)benzamide (m, 1H), 6.14-6.07 (m, 1H), 1.65 (d, J= 7.1 Hz, 3H);

[0639] LCMS (m / z) 481 [M+H]+.

[0640] (S, Z)-N-( 1 -( 1 -(5-cyanopyridin-2-1H-NMR (400 MHz, DMSO-d6) 59.40 (d, J= 7.1 Hz, 1H), yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- 9.04 (q, J= 1.1 Hz, 1H), 8.56 (dd, J= 8.6, 2.2 Hz, 1H), 8.24 (trifluoromethyl)-5-(3,3,3- (s, 1H), 8.19 (s, 1H), 8.06 (dd, J= 8.7, 0.9 Hz, 2H), 7.85 (s, 3

[0641] trifluoroprop- 1 -en- 1 - 1H), 7.33 (d, J= 12.5 Hz, 1H), 6.35-6.25 (m, 1H), 6.09 (t, J yl)benzamide = 7.0 Hz, 1H), 1.63 (d, J = 6.8 Hz, 3H); LCMS (m / z)

[0642] 480.95 [M+H]+.

[0643] (S) -N-( 1 -( 1 -(pyrimidin-2-yl)- 1H-1H-NMR (400 MHz, DMSO-d6) 59.30 (d, J= 7.1 Hz, 1H), l,2,4-triazol-5-yl)ethyl)-3- 8.98 (d, J = 4.9 Hz, 2H), 8.34 (s, 1H), 8.24 (s, 1H), 8.16 (s, (trifluoromethyl)-5-(3,3,3- 1H), 8.07 (s, 1H), 7.62 (t, J= 4.9 Hz, 1H), 7.49 (dd, J = 4

[0644] trifluoroprop- 1 -en- 1 - 16.4, 2.2 Hz, 1H), 7.01 (dd, J= 16.1, 6.8 Hz, 1H), 6.01 (t, J yl)benzamide = 7.0 Hz, 1H), 1.65 (d, J= 6.8 Hz, 3H); LCMS (m / z)456.85 [M+H]+.

[0645] (S)-3-(2-chloro-3,3,3-1H-NMR (400 MHz, DMSO-d6) 59.39 (d, J= 7.1 Hz, 1H), trifluoroprop- 1 -en- 1 -yl)- / V-( 1 -( 1 - 8.97 (d, J= 4.9 Hz, 2H), 8.46 (s, 1H), 8.25 (s, 1H), 8.20 (s, 5 (pyrimidin-2-yl)- 1 / 7- 1,2,4-triazol- 1H), 8.16 (s, 1H), 7.96 (s, 1H), 7.61 (t, J = 4.9 Hz, 1H),

[0646] 5-yl)ethyl)-5- 6.01 (t, J= 7.1 Hz, 1H), 1.64 (d, J= 7.1 Hz, 3H); LCMS (trifluoromethyl)benzamide (m / z 490.80 [M+H]+.

[0647] 3-(2-chloro-3,3,3-trifluoroprop-l-1H-NMR (400 MHz, DMSO-d6) 59.22 (d, J= 7.1 Hz, 1H), en-l-yl)- / V-(l-(3-(pyridin-2- 8.72-8.71 (m, 1H), 8.68 (d, J= 2.4 Hz, 1H), 8.64 (d, J = 2.4 yl)pyrazin-2-yl)ethyl)-5- Hz, 1H), 8.45 (s, 1H), 8.23 (d, J= 9.3 Hz, 2H), 8.00-7.99 6

[0648] (trifluoromethyl)benzamide (m, 2H), 7.93 (s, 1H), 7.51-7.48 (m, 1H), 5.85 (t, J= 6.8 Hz, 1H), 1.65 (d, J= 7.1 Hz, 3H); LCMS (m / z) 501.4 [M+H]+.

[0649] / V-(l-(3-(pyridin-2-yl)pyrazin-2-1H-NMR (400 MHz, DMSO-d6) 59.13 (d, J = 6.8 Hz, 1H), yl)ethyl)-3-(trifluoromethyl)-5- 8.72 (d, J= 4.6 Hz, 1H), 8.68 (d, J= 2.4 Hz, 1H), 8.64 (d, J (3,3,3-trifluoroprop- 1-en- 1- = 2.4 Hz, 1H), 8.36 (s, 1H), 8.21 (s, 1H), 8.11 (s, 1H), 7.99 7

[0650] yl)benzamide (d, J= 3.4 Hz, 2H), 7.51-7.45 (m, 2H), 7.01 (dd, J= 16.3,

[0651] 7.0 Hz, 1H), 5.84 (t, J= 7.0 Hz, 1H), 1.66 (d, J= 6.8 Hz, 3H); LCMS (m / z) 467.25 [M+H]+.

[0652] (S)-3-chloro-5-(2-chloro-3,3,3-1H-NMR (400 MHz, DMSO-d6) 59.24 (d, J= 7.3 Hz, 1H), 8 trifluoroprop- 1 -en- 1 -yl)- / V-( 1 -( 1 - 9.03 (d, J= 1.7 Hz, 1H), 8.56 (dd, J= 8.8, 2.2 Hz, 1H), 8.23

[0653]

[0654] (s, 1H), 8.06 (d, J= 8.6 Hz, 1H), 7.91 (s, 1H), 7.79 (s, 1H),(5-cyanopyridin-2-yl)- 177- 1,2,4- 7.68 (s, 1H), 7.57 (s, 1H), 6.05 (t, J= 7.0 Hz, 1H), 1.61 (d, triazol-5-yl)ethyl)benzamide J= 6.8 Hz, 3H); LCMS (m / z) 481.2 [M+H]+.

[0655] (S,£)-3-chloro- / V-(l-(l-(5-1H-NMR (400 MHz, DMSO-<7.) 59.19 (d, J = 6.6 Hz, 1H), cyanopyridin-2-yl)- 1H- 1,2,4- 9.06 (d, J = 1.7 Hz, 1H), 8.56 (dd, J= 8.6, 2.2 Hz, 1H), 8.23 triazol-5-yl)ethyl)-5-(3,3,3- (s, 1H), 8.06 (d, J= 8.8 Hz, 2H), 7.98 (s, 1H), 7.85 (s, 1H), trifluoroprop- 1 -en- 1 - 7.37 (dd, J= 16.3, 2.1 Hz, 1H), 6.92 (dd, J= 16.4, 6.8 Hz, yl)benzamide 1H), 6.07 (t, J= 7.0 Hz, 1H), 1.63 (d, J= 7.1 Hz, 3H);

[0656] LCMS (m / z) 446.9 [M+H]+.

[0657] (S, E)-3 -(2-cy clopropyl vinyl )-A' - ‘H-NMR (400 MHz, DMSO-<7.) 59.24 (d, J= 7.3 Hz, 1H), ( 1 -( 1 -(pyrimidin-2-yl)- 1H- 1,2,4- 8.97 (d, J= 4.9 Hz, 2H), 8.15 (s, 1H), 7.97 (s, 1H), 7.81 (d, triazol-5 -y l)ethyl) -5 -.7= 8.8 Hz, 2H), 7.61 (t,.7= 4.9 Hz, 1H), 6.57 (d, J= 15.9 (trifluoromethyl)benzamide Hz, 1H), 6.07 (dd, J= 15.9, 9.3 Hz, 1H), 6.01-5.94 (m, 1H),

[0658] 1.64-1.56 (m, 4H), 1.10.85-0.81 (m, 2H), 0.59-0.55 (m, 2H); LCMS (m / z) 429.05 [M+H]+.

[0659] (SJL)-N -( 1 -( 1 -(5-cy anopyridin-2-1H-NMR (400 MHz, DMSO-<7.) 59.28 (d, J= 7.1 Hz, 1H), yl)-177-l,2,4-triazol-5-yl)ethyl)-3- 9.05 (d, J= 1.7 Hz, 1H), 8.55 (dd, J= 8.6, 2.2 Hz, 1H), 8.23 (2-cyclopropylvinyl)-5- (s, 1H), 8.06 (d, J= 8.6 Hz, 1H), 8.02 (s, 1H), 7.87 (s, 1H), (trifluoromethyl)benzamide 7.81 (s, 1H), 6.58 (d, J= 15.9 Hz, 1H), 6.11-6.05 (m, 2H),

[0660] 1.64-1.57 (m, 4H), 0.85-0.81 (m, 2H), 0.59-0.55 (m, 2H); LCMS (m / z) 452.95 [M+H]+.

[0661] (SJL)-N -( 1 -( 1 -(5-cy anopyridin-2-1H-NMR (400 MHz, DMSO-<7.) 59.26 (d, J= 7.1 Hz, 1H), yl)-3-methyl- 1H- l,2,4-triazol-5- 9.01 (d, J= 1.7 Hz, 1H), 8.51 (dd, J = 8.8, 2.2 Hz, 1H), 8.04 yl)ethyl)-3-(2-cyclopropylvinyl)- (s, 1H), 7.99 (d, J = 8.6 Hz, 1H), 7.90 (s, 1H), 7.81 (s, 1H), 5-(trifluoromethyl)benzamide 6.58 (d, J= 15.9 Hz, 1H), 6.11-6.04 (m, 2H), 2.32 (s, 3H),

[0662] 1.62-1.55 (m, 4H), 0.85-0.81 (m, 2H), 0.59-0.55 (m, 2H); LCMS (m / z) 467.35 [M+H]+.

[0663] (S, E)-3 -(2-cy clopropyl vinyl )-A' -1H-NMR (400 MHz, DMSO-<7.) 59.23 (d, J= 7.1 Hz, 1H), (l-(3-methyl-l-(5- 8.92 (s, 1H), 8.42 (dd, J= 8.7, 2.3 Hz, 1H), 8.02-8.00 (m, (trifluoromethyl)pyridin-2-yl)- 1H- 2H), 7.85 (s, 1H), 7.80 (s, 1H), 6.57 (d, J= 15.6 Hz, 1H), l,2,4-triazol-5-yl)ethyl)-5- 6.11-6.04 (m, 2H), 2.33 (s, 3H), 1.63-1.58 (m, 4H), 0.85- (trifluoromethyl)benzamide 0.81 (m, 2H), 0.58-0.55 (m, 2H); LCMS (m / z) 510.2

[0664] [M+H]+.

[0665] 1 -( 1 -(5-bromopyridin-2-1H-NMR (400 MHz, DMSO-<7.) 59.22 (d, J= 7.1 Hz, 1H), yl)-177-l,2,4-triazol-5-yl)ethyl)-3- 8.68 (d, J= 2.4 Hz, 1H), 8.29 (dd, J= 8.6, 2.4 Hz, 1H), 8.16 (2-cyclopropylvinyl)-5- (s, 1H), 7.98 (s, 1H), 7.83 (s, 1H), 7.80 (d, J= 8.6 Hz, 2H), (trifluoromethyl)benzamide 6.57 (d, J= 15.9 Hz, 1H), 6.08 (dd, J= 15.8, 9.4 Hz, 1H),

[0666] 5.96 (t, J= 7.1 Hz, 1H), 1.63-1.57 (m, 4H), 0.85-0.81 (m, 2H), 0.59-0.55 (m, 2H); LCMS (m / z) 507.5 [M+H]+. (S, E)-3-(2-cyclopropylvinyl)-5-1H-NMR (400 MHz, DMSO-<7.) 59.24 (d, J= 7.1 Hz, 1H), (tri fl uoromethy 1 )- / V-( 1 -( 1 -(5- 8.96 (s, 1H), 8.46 (dd, J= 8.8, 2.2 Hz, 1H), 8.22 (s, 1H), (trifluoromethyl)pyridin-2-yl)- 1H- 8.06 (d, J= 8.6 Hz, 1H), 7.98 (s, 1H), 7.81 (d, J= 7.3 Hz, l,2,4-triazol-5-yl)ethyl)benzamide 2H), 6.57 (d, J= 15.9 Hz, 1H), 6.10-6.04 (m, 2H), 1.64 (d, J = 7.1 Hz, 3H), 1.59 (td, J= 168.4, 4.2 Hz, 1H), 0.85-0.81 (m, 4H), 0.58-0.55 (m, 2H); LCMS (m / z) 496.05 [M+H]+. (S, E)-3 -(2-cy clopropyl vinyl )-A'' -1H-NMR (400 MHz, DMSO-<7.) 59.22 (d, J= 7.1 Hz, 1H), ( 1 -(3-methyl- 1 -(pyrimidin-2-yl)- 8.93 (d, J= 4.9 Hz, 2H), 7.99 (s, 1H), 7.85 (s, 1H), 7.80 (s, 1H- l,2,4-triazol-5-yl)ethyl)-5- 1H), 7.56 (t, J = 4.9 Hz, 1H), 6.57 (d, J= 15.9 Hz, 1H), (trifluoromethyl)benzamide 6.07 (dd, J= 15.9, 9.3 Hz, 1H), 5.98 (t, J= 7.0 Hz, 1H),

[0667] 2.32 (s, 3H), 1.62-1.57 (m, 4H), 0.85-0.81 (m, 2H), 0.59-

[0668]

[0669] 0.55 (m, 2H); LCMS (m / z) 443.2 [M+H]+.(S, E)-N-( 1 -( 1 -(5-bromopyrimidin-1H-NMR (400 MHz, DMSO-d6) 59.24 (d, J= 7.1 Hz, 1H), 2-yl)- 1 / 7- l,2,4-triazol-5-yl)ethyl)- 9.16 (s, 2H), 8.17 (s, 1H), 7.98 (s, 1H), 7.82 (d, J= 10.8 Hz, 3 -(2-cyclopropyl vinyl) -5 - 2H), 6.57 (d, J= 15.9 Hz, 1H), 6.08 (dd, J= 15.9, 9.3 Hz, (trifluoromethyl)benzamide 1H), 5.98-5.91 (m, 1H), 1.63-1.56 (m, 4H), 0.85-0.79 (m,

[0670] 2H), 0.59-0.55 (m, 2H); LCMS (m / z) 506.8 [M+H]+. (S, E)-3-(2-cyclopropylvinyl)-N-1H-NMR (400 MHz, DMSO-d6) 59.18 (d, J = 7.3 Hz, 1H), (l-(l-(5-((dimethyl(oxo)-L6- 8.06 (d, J= 3.4 Hz, 2H), 7.98 (s, 1H), 7.86 (s, 1H), 7.79 (s, sulfaneylidene)amino)pyridin-2- 1H), 7.61 (d, J= 8.3 Hz, 1H), 7.53 (dd, J= 8.6, 2.7 Hz, yl)-l / Z-l,2,4-triazol-5-yl)ethyl)-5- 1H), 6.57 (d, J= 15.9 Hz, 1H), 6.07 (dd, J= 15.9, 9.3 Hz, (trifluoromethyl)benzamide 1H), 5.86 (q, J= 7.0 Hz, 1H), 3.27 (d, J= 1.7 Hz, 6H),

[0671] 1.64-1.56 (m, 4H), 0.86-0.81 (m, 2H), 0.59-0.55 (m, 2H); LCMS (m / z) 519 [M+H]+.

[0672] (S, E)-3 -(2-cy clopropyl vinyl )-A' -1H-NMR (400 MHz, DMSO-d6) δ 9.18 (d, J = 7.3 Hz, 1H), (1-(1-(5-((dimethyl(oxo)-λ6- 8.44 (s, 2H), 8.08 (s, 1H), 7.95 (s, 1H), 7.81 (d, J= 12.0 Hz, sulfaneylidene)amino)pyrimidin- 2H), 6.57 (d, J= 15.9 Hz, 1H), 6.07 (dd, J= 15.9, 9.3 Hz, 2-yl)- 1H- l,2,4-triazol-5-yl)ethyl)- 1H), 5.87-5.80 (m, 1H), 3.34 (d, J= 5.9 Hz, 6H), 1.63-1.54 5-(trifluoromethyl)benzamide (m, 4H), 0.85-0.81 (m, 2H), 0.59-0.55 (m, 2H); LCMS (m / z) 520.35 [M+H]+.

[0673] (S) -N-( 1 -( 1 -(pyrimidin-2-yl)- 177-1H-NMR (500 MHz, DMSO-d6) 59.42 (d, J= 7.2 Hz, 1H), l,2,4-triazol-5-yl)ethyl)-3- 8.97 (d, J= 4.9 Hz, 2H), 8.17 (d, J= 7.9 Hz, 2H), 8.09 (s, (trifluoromethyl)-5-(3,3,3- 1H), 7.91 (s, 1H), 7.61 (t, J= 4.8 Hz, 1H), 6.33-6.28 (m, trifluoroprop- 1 -en-2- 2H), 6.00 (t, J = 7.1 Hz, 1H), 1.65 (d, J= 7.0 Hz, 3H); yl)benzamide LCMS (m / z) 457.05 [M+H]+.

[0674] (S)-N-( 1 -( 1 -(5 -cyanopyridin-2-1H-NMR (500 MHz, DMSO-d6) 59.46 (d, J= 6.9 Hz, 1H), yl)-l / Z-l,2,4-triazol-5-yl)ethyl)-3- 9.05 (dd, J= 2.2, 0.7 Hz, 1H), 8.58-8.55 (m, 1H), 8.24 (d, J (trifluoromethyl)-5-(3,3,3- = 3.5 Hz, 2H), 8.13 (s, 1H), 8.06 (dd, J= 8.6, 0.6 Hz, 1H), trifluoroprop- 1 -en-2- 7.92 (s, 1H), 6.35-6.28 (m, 2H), 6.12-6.07 (m, 1H), 1.64 (d, yl)benzamide J= 7.0 Hz, 3H); LCMS (m / z) 481.1 [M+H]+.

[0675] JV-( 1 -(3-(pyridin-2-yl)pyrazin-2-1H-NMR (500 MHz, DMSO-d6) δ 9.27 (d, J= 6.9 Hz, 1H), yl)ethyl)-3-(trifluoromethyl)-5- 8.72-8.70 (m, 1H), 8.68 (d, J= 2.4 Hz, 1H), 8.64 (d, J= 2.4 (3,3,3-trifluoroprop- l-en-2- Hz, 1H), 8.23 (s, 1H), 8.10 (s, 1H), 8.00-7.97 (m, 2H), 7.88 yl)benzamide (s, 1H), 7.51-7.48 (m, 1H), 6.33-6.26 (m, 2H), 5.87-5.81 (m, 1H), 1.65 (d, J = 6.9 Hz, 3H); LCMS (m / z) 467.3 [M+H]+.

[0676] (S)- / V-(l-(3-methyl-l-(5-1H-NMR (500 MHz, DMSO-d6) 59.40 (d, J= 7.2 Hz, 1H), (trifluoromethyl)pyridin-2-yl)- 1 / 7- 8.91-8.91 (m, 1H), 8.42 (dd, J= 8.7, 2.3 Hz, 1H), 8.21 (s, l,2,4-triazol-5-yl)ethyl)-3- 1H), 8.12 (s, 1H), 8.02 (d, J= 8.6 Hz, 1H), 7.91 (s, 1H), (trifluoromethyl)-5-(3,3,3- 6.33-6.27 (m, 2H), 6.09 (t, J= 7.1 Hz, 1H), 2.34 (s, 3H), trifluoroprop- 1 -en-2- 1.64 (d, J= 7.0 Hz, 3H); LCMS (m / z) 538.35 [M+H]+. yl)benzamide

[0677] (S)- / V-( 1 -( 1 -(5 -bromopyridin-2-1H-NMR (400 MHz, DMSO-d6) δ 9.41 (d, J= 7.1 Hz, 1H), yl)-l / / -l,2,4-triazol-5-yl)ethyl)-3- 8.68 (d, J= 2.0 Hz, 1H), 8.29 (dd, J= 8.6, 2.4 Hz, 1H), 8.20 (trifluoromethyl)-5-(3,3,3- (s, 1H), 8.17 (s, 1H), 8.11 (s, 1H), 7.91 (s, 1H), 7.81-7.79 trifluoroprop- 1 -en-2- (m, 1H), 6.31 (dt, J= 21.7, 1.3 Hz, 2H), 6.02-5.95 (m, 1H), yl)benzamide 1.63 (d, J= 6.8 Hz, 3H); LCMS (m / z) 534.2 [M+H]+. (S)-3 -(tri fluoromethy 1 )-7V-( 1 -( 1 -1H-NMR (400 MHz, DMSO-d6) 59.42 (d, J= 7.1 Hz, 1H), (5-(trifluoromethyl)pyridin-2-yl)- 8.94 (d, J= 0.7 Hz, 1H), 8.49-8.44 (m, 1H), 8.23 (s, 1H), 1H- 1,2,4-triazol-5 -yl)ethyl)-5- 8.18 (s, 1H), 8.10 (s, 1H), 8.07 (d, J= 8.6 Hz, 1H), 7.91 (s, (3,3,3-trifluoroprop- l-en-2- 1H), 6.33-6.27 (m, 2H), 6.12-6.05 (m, 1H), 1.66 (d, J= 6.8

[0678]

[0679] yl)benzamide Hz, 3H); LCMS (m / z) 524.3 [M+H]+.(S)-N-( 1 -(3 -methyl- 1 -(pyrimidin-1H-NMR (400 MHz, DMSO-d6) 59.41 (d, J= 7.3 Hz, 1H), 2-yl)- 1H- l,2,4-triazol-5-yl)ethyl)- 8.94 (d, J= 4.9 Hz, 2H), 8.21 (s, 1H), 8.12 (s, 1H), 7.91 (s, 3-(trifluoromethyl)-5-(3,3,3- 1H), 7.56 (t, J= 4.9 Hz, 1H), 6.33-6.28 (m, 2H), 6.04-5.97 trifluoroprop- 1 -en-2- (m, 1H), 2.32 (s, 3H), 1.62 (d, J= 7.1 Hz, 3H); LCMS yl)benzamide (m / z) 471.2 [M+H]+.

[0680] (S) -#-( 1 -( 1 -(pyrimidin-2-yl)- 1H-1H-NMR (400 MHz, DMSO-d6) 59.31 (d, J= 1.3 Hz, 1H), l,2,4-triazol-5-yl)ethyl)-3- 8.98 (d, J= 4.6 Hz, 2H), 8.16 (s, 1H), 8.13 (s, 1H), 7.95 (d, (trifluoromethyl) -5 - J= 7.1 Hz, 2H), 7.61 (t, J= 4.9 Hz, 1H), 6.85 (dd, J= 17.6, vinylbenzamide 11.0 Hz, 1H), 6.06 (d, J= 17.9 Hz, 1H), 5.99 (t, J= 7.0 Hz,

[0681] 1H), 5.45 (d, J= 11.2 Hz, 1H), 1.64 (d, J= 6.8 Hz, 3H); LCMS (m / z) 389 [M+H]+.

[0682] (S)-N-( 1 -( 1 -(5 -cyanopyridin-2-1H-NMR (400 MHz, DMSO-d6) 5 9.36 (d, J= 7.1 Hz, 1H), yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- 9.06 (d, J= 1.5 Hz, 1H), 8.56 (dd, J= 8.7, 2.3 Hz, 1H), 8.24 (trifluoromethyl) -5 - (s, 1H), 8.18 (s, 1H), 8.07-8.05 (m, 1H), 7.98 (d, J= 6.4 Hz, vinylbenzamide 2H), 6.86 (dd, J= 17.6, 11.0 Hz, 1H), 6.07 (dd, J= 12.2, 5.4

[0683] Hz, 2H), 5.46 (d, J= 11.2 Hz, 1H), 1.64 (d, J= 7.1 Hz, 3H); LCMS (m / z) 413 [M+H]+.

[0684] (S)- / V-( 1 -(3 -methyl- 1 -(pyrimidin-1H-NMR (400 MHz, DMSO-d6) 59.29 (d, J= 7.3 Hz, 1H), 2-yl)- 1H- l,2,4-triazol-5-yl)ethyl)- 8.94 (d, J= 4.9 Hz, 2H), 8.16 (s, 1H), 7.97 (d, J= 3.4 Hz, 3 -(trifluoromethyl) -5 - 2H), 7.56 (t, J = 4.9 Hz, 1H), 6.85 (dd, J= 17.6, 11.0 Hz, vinylbenzamide 1H), 6.07 (d, J= 17.6 Hz, 1H), 6.00 (t, J= 7.2 Hz, 1H),

[0685] 5.45 (d, J= 11.0 Hz, 1H), 2.32 (s, 3H), 1.62 (d, J= 6.8 Hz, 3H); LCMS (m / z) 403.5 [M+H]+.

[0686] (S)-N-( 1 -( 1 -(5 -cyanopyridin-2-1H-NMR (400 MHz, DMSO-d6) δ 9.34 (d, J= 7.1 Hz, 1H), yl)-3-methyl- 1H- l,2,4-triazol-5- 9.02 (dd, J= 2.2, 0.5 Hz, 1H), 8.52 (dd, J= 8.7, 2.3 Hz, yl)ethyl)-3-(trifluoromethyl)-5- 1H), 8.20 (s, 1H), 8.02-7.98 (m, 3H), 6.87 (dd, J= 17.6, vinylbenzamide 11.0 Hz, 1H), 6.08 (dd, J= 12.5, 5.4 Hz, 2H), 5.46 (d, J=

[0687] 11.0 Hz, 1H), 2.34 (d, J= 7.6 Hz, 3H), 1.62 (d, J = 6.8 Hz, 3H); LCMS (m / z) 427.25 [M+H]+.

[0688] (S)- / V-( 1 -( 1 -(5 -((dimethyl(oxo)-1H-NMR (400 MHz, DMSO-d6) 59.25 (d, J= 6.8 Hz, 1H), X6-sulfaneylidene)amino)pyridin- 8.15 (s, 1H), 8.06 (s, 2H), 7.97 (d, J= 11.5 Hz, 2H), 7.57 2-yl)- 1H- l,2,4-triazol-5-yl)ethyl)- (dd, J= 30.1, 8.8 Hz, 2H), 6.86 (dd, J= 17.9, 11.2 Hz, 1H), 3 -(trifluoromethyl) -5 - 6.07 (d, J= 17.6 Hz, 1H), 5.89 (q, J= 6.6 Hz, 1H), 5.46 (d, vinylbenzamide J= 11.0 Hz, 1H), 3.27 (s, 6H), 1.61 (d, J= 6.6 Hz, 3H);

[0689] LCMS (m / z) 479.25 [M+H]+.

[0690] (S)-3-(3-methylbut-2-en-2-yl)- / V-1H-NMR (400 MHz, CDCl3) 58.99-8.96 (m, 2H), 8.22-8.19 ( 1 -( 1 -(pyrimidin-2-yl)- 1H- 1,2,4- (m, 1H), 8.09 (t, J = 7.9 Hz, 1H), 7.97 (s, 1H), 7.83 (s, 1H), triazol-5 -y l)ethyl) -5 - 7.52-7.48 (m, 2H), 6.55-6.48 (m, 1H), 1.99 (d, J = 7.1 Hz, (trifluoromethyl)benzamide 3H), 1.86-1.78 (m, 6H), 1.57 (d, J = 1.5 Hz, 3H); LCMS (m / z) 431.25 [M+H]+.

[0691] (S)-N-( 1 -( 1 -(5 -cyanopyridin-2-1H-NMR (400 MHz, CDCl3) 58.87 (d, J = 1.2 Hz, 1H), yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- 8.20-8.14 (m, 2H), 8.03 (s, 1H), 7.90 (s, 1H), 7.76 (s, 1H), (3-methylbut-2-en-2-yl)-5- 7.52 (s, 1H), 7.43 (d, J = 6.8 Hz, 1H), 6.48-6.41 (m, 1H), (trifluoromethyl)benzamide 1.99 (d, J = 9.0 Hz, 3H), 1.83 (s, 3H), 1.78-1.73 (m, 3H),

[0692] 1.57 (d, J = 1.2 Hz, 3H); LCMS (m / z) 455.15 [M+H]+. (S)-N-( 1 -( 1 -(5 -cyanopyridin-2-1H-NMR (400 MHz, CDCl3) 58.84 (q, J= 1.0 Hz, 1H), yl)-3-methyl- 1H- l,2,4-triazol-5- 8.16 (dd, J = 8.6, 2.2 Hz, 1H), 8.10 (dd, J= 8.7, 0.9 Hz, yl)ethyl)-3-(3-methylbut-2-en-2- 1H), 7.91 (s, 1H), 7.78 (s, 1H), 7.52 (s, 2H), 6.46-6.38 (m,

[0693]

[0694] yl)-5 -(trifluoromethyl)benzamide 1H), 2.48 (s, 3H), 1.98 (d, J= 1.2 Hz, 3H), 1.83 (s, 3H),1.74 (d, J= 6.8 Hz, 3H), 1.57 (d, J= 1.5 Hz, 3H); LCMS (m / z) 469.45 [M+H]+.

[0695] (S)-7V-(l-(3-methyl-l-(5-1H-NMR (400 MHz, CDCl3) 58.84 (t, J= 1.2 Hz, 1H), 8.13 (trifluoromethyl)pyridin-2-yl)- 1H- (dd, J= 8.6, 2.0 Hz, 1H), 8.08 (d, J= 8.8 Hz, 1H), 7.92 (s, l,2,4-triazol-5-yl)ethyl)-3-(3- 1H), 7.78 (s, 1H), 7.61 (d, J= 13 Hz, 1H), 7.52 (s, 1H), methylbut-2-en-2-yl)-5 - 6.42 (dt, J= 14.8, 6.8 Hz, 1H), 2.47 (s, 3H), 1.98 (t, J= 1.1 (trifluoromethyl)benzamide Hz, 3H), 1.83 (s, 3H), 1.74 (d, J= 6.6 Hz, 3H), 1.57 (d, J=

[0696] 1.5 Hz, 3H); LCMS (m / z) 512.55 [M+H]+.

[0697] (S)-7V-( 1 -( 1 -(5 -bromopyridin-2-1H-NMR (400 MHz, CDCl3) δ 8.64-8.63 (m, 1H), 8.04 (dd, yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- J= 8.7, 2.3 Hz, 1H), 8.00 (s, 1H), 7.91 (s, 1H), 7.88 (dd, J= (3-methylbut-2-en-2-yl)-5- 8.7, 0.6 Hz, 1H), 7.76 (s, 1H), 7.60 (d, J= 8.1 Hz, 1H), 7.51 (trifluoromethyl)benzamide (s, 1H), 6.40-6.33 (m, 1H), 1.98 (t, J= 1.2 Hz, 3H), 1.83 (s,

[0698] 3H), 1.72 (d, J= 6.6 Hz, 3H), 1.57 (d, J= 1.5 Hz, 3H); LCMS (m / z) 508.3 [M+H]+.

[0699] (S)-3-(3-methylbut-2-en-2-yl)-5-1H-NMR (400 MHz, CDCl3) 58.87 (t, J= 1.1 Hz, 1H), (tri fl uoromethy 1 )- / V-( 1 -( 1 -(5- 8.18-8.13 (m, 2H), 8.03 (s, 1H), 7.91 (s, 1H), 7.76 (s, 1H), (trifluoromethyl)pyridin-2-yl)- 1 / 7- 7.55 (d, J = 8.1 Hz, 1H), 7.52 (s, 1H), 6.46 (dt, J= 14.8, 6.9 l,2,4-triazol-5-yl)ethyl)benzamide Hz, 1H), 1.98 (t, J= 1.1 Hz, 3H), 1.83 (d, J= 0.5 Hz, 3H),

[0700] 1.75 (d, J= 6.8 Hz, 3H), 1.57 (d, J= 1.2 Hz, 3H); LCMS (m / z) 498.45 [M+H]+.

[0701] (S)-7V-( 1 -(3 -methyl- 1 -(pyrimidin-1H-NMR (400 MHz, CDCl3) 58.91 (d, J= 4.9 Hz, 2H), 2-yl)- 1H- l,2,4-triazol-5-yl)ethyl)- 7.94 (s, 1H), 7.78 (s, 1H), 7.61-7.75 (1H), 7.52 (s, 1H), 7.41 3-(3-methylbut-2-en-2-yl)-5- (t, J= 4.9 Hz, 1H), 6.48-6.45 (m, 1H), 2.54 (s, 3H), 1.98 (d, (trifluoromethyl)benzamide J= 1.2 Hz, 3H), 1.83 (s, 3H), 1.75 (d, J = 6.8 Hz, 3H), 1.57

[0702] (d, J= 1.5 Hz, 3H); LCMS (m / z) 445.35 [M+H]+.

[0703] (S)-N-( 1 -( 1 -(5-bromopyrimidin-2-1H-NMR (400 MHz, CDCl3) 58.96 (s, 2H), 8.09 (s, 1H), yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- 7.91 (s, 1H), 7.75 (s, 1H), 7.52 (d, J= 1.5 Hz, 1H), 7.45 (d, (3-methylbut-2-en-2-yl)-5- J= 8.1 Hz, 1H), 6.41 (t, J= 7.5 Hz, 1H), 1.98 (t, J= 1.2 Hz, (trifluoromethyl)benzamide 3H), 1.83 (s, 3H), 1.73 (d, J= 6.6 Hz, 3H), 1.57 (d, J= 1.5

[0704] Hz, 3H); LCMS (m / z) 509.1 [M+H]+.

[0705] (S)-JV-( 1 -( 1 -(5 -((dimethyl(oxo)-1H-NMR (400 MHz, CDCl3) 58.27 (d, J= 2.2 Hz, 1H), X6-sulfaneylidene)amino)pyridin- 8.06 (d, J= 7.8 Hz, 1H), 7.98 (s, 1H), 7.94 (d, J= 1.7 Hz, 2-yl)- 1H- l,2,4-triazol-5-yl)ethyl)- 1H), 7.81 (s, 1H), 7.76 (ddd, J= 8.7, 3.5, 0.6 Hz, 1H), 7.61 3-(3-methylbut-2-en-2-yl)-5- (dd, J= 8.6, 2.7 Hz, 1H), 7.50 (s, 1H), 6.29 (dd, J= 8.2, 7.0 (trifluoromethyl)benzamide Hz, 1H), 3.23 (d, J= 1.2 Hz, 6H), 1.98 (t, J= 1.2 Hz, 3H),

[0706] 1.83 (s, 3H), 1.70 (d,.7= 6.8 Hz. 3H), 1.57 (d, J= 1.5 Hz, 3H); LCMS (m / z) 521.25 [M+H]+.

[0707] (S,£)-3-(2-ethoxyvinyl)-7V-( 1 -( 1 -1H-NMR (400 MHz, DMSO-d6) δ 9.19 (d, J = 7.1 Hz, 1H), (pyrimidin-2-yl)- 1H- 1,2,4-triazol- 8.97 (d, J= 4.9 Hz, 2H), 8.15 (s, 1H), 7.90 (s, 1H), 7.74 (d,

[0708] 5-yl)ethyl)-5- J= 13.7 Hz, 2H), 7.61 (t, J = 4.9 Hz, 1H), 7.45 (d, J= 13.0 (trifluoromethyl)benzamide Hz, 1H), 5.99-5.92 (m, 2H), 3.92 (q, J= 7.0 Hz, 2H), 1.63

[0709] (d, J = 7.1 Hz, 3H), 1.25 (t, J= 7.0 Hz, 3H); LCMS (m / z) 433.10 [M+H]+.

[0710] (SJL)-N -( 1 -( 1 -(5-cy anopyridin-2-1H-NMR (400 MHz, DMSO-d6) δ 9.24 (d, J= 7.1 Hz, 1H), yl)-1H-1,2,4-triazol-5-yl)ethyl)-3- 9.05 (d, J= 1.5 Hz, 1H), 8.56 (dd, J= 8.6, 2.2 Hz, 1H), 8.23 (2-ethoxy vinyl) -5 - (s, 1H), 8.06 (d, J= 8.6 Hz, 1H), 7.94 (s, 1H), 7.78 (s, 2H), (trifluoromethyl)benzamide 7.46 (d, J= 13.0 Hz, 1H), 6.06 (t, J = 7.0 Hz, 1H), 5.95 (d,

[0711] J= 13.0 Hz, 1H), 3.93 (q, J= 7.0 Hz, 2H), 1.63 (d, J= 7.1 Hz, 3H), 1.26 (t, J= 7.1 Hz, 3H); LCMS (m / z) 457.25

[0712]

[0713] [M+H]+.1 -( 1 -(5-bromopyridin-2-1H-NMR (400 MHz, DMSO-d6) 59.18 (d, J = 7.1 Hz, 1H), yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- 8.69 (d, J= 2.2 Hz, 1H), 8.29 (dd, J= 8.8, 2.4 Hz, 1H), 8.16 (2-ethoxy vinyl) -5 - (s, 1H), 7.91 (s, 1H), 7.80 (d, J= 8.6 Hz, 1H), 7.75 (d, J= (trifluoromethyl)benzamide 9.3 Hz, 2H), 7.46 (d, J= 13.0 Hz, 1H), 5.97-5.93 (m, 2H),

[0714] 3.93 (q, J= 7.0 Hz, 2H), 1.62 (d, J= 6.8 Hz, 3H), 1.26 (t, J = 7.0 Hz, 3H); LCMS (m / z) 510.10 [M+H]+.

[0715] (S,£)-3-(2-ethoxyvinyl)- / V-(l-(3-1H-NMR (400 MHz, DMSO-d6) 59.18 (d, J = 7.1 Hz, 1H), methyl-l-(5- 8.93 (s, 1H), 8.43 (dd, J= 8.8, 2.2 Hz, 1H), 8.01 (d, J= 8.8 (trifluoromethyl)pyridin-2-yl)- 1 / 7- Hz, 1H), 7.94 (s, 1H), 7.76 (s, 2H), 7.45 (d, J= 13.0 Hz, l,2,4-triazol-5-yl)ethyl)-5- 1H), 6.07 (t, J = 7.1 Hz, 1H), 5.94 (d, J= 13.0 Hz, 1H), (trifluoromethyl)benzamide 3.92 (q, J = 7.0 Hz, 2H), 2.34 (s, 3H), 1.62 (d, J = 7.1 Hz,

[0716] 3H), 1.24 (q, J= 7.2 Hz, 3H); LCMS (m / z) 514.45 [M+H]+. (SJL)-N-( 1 -( 1 -(5-((dimethyl(oxo)-1H-NMR (400 MHz, DMSO-d6) 59.13 (d, J = 7.1 Hz, 1H), L6-sulfaneylidene)amino)pyridin- 8.06-8.05 (m, 2H), 7.91 (s, 1H), 7.77 (d, J= 6.6 Hz, 2H), 2-yl)- 1H- l,2,4-triazol-5-yl)ethyl)- 7.61 (d, J= 8.6 Hz, 1H), 7.53 (dd, J= 8.6, 2.7 Hz, 1H), 7.45 3-(2-ethoxyvinyl)-5- (d, J= 13.0 Hz, 1H), 5.94 (d, J= 13.0 Hz, 1H), 5.90-5.83 (trifluoromethyl)benzamide (m, 1H), 3.93 (q, J= 7.0 Hz, 2H), 3.27 (d, J= 1.7 Hz, 6H),

[0717] 1.59 (d, J = 7.1 Hz, 3H), 1.26 (t, J= 7.0 Hz, 3H); LCMS (m / z) 523.40 [M+H]+.

[0718] (S,£)-3-(2-ethoxyvinyl)- / V-(l-(3-1H-NMR (500 MHz, DMSO-d6) 59.17 (d, J= 7.4 Hz, 1H), methyl- 1 -(pyrimidin-2-yl)- 1H- 8.94 (d, J= 4.9 Hz, 2H), 7.92 (s, 1H), 7.76 (s, 2H), 7.57 (t, l,2,4-triazol-5-yl)ethyl)-5- J= 4.9 Hz, 1H), 7.45 (d, J= 13.0 Hz, 1H), 5.98 (t, J= 7.1 (trifluoromethyl)benzamide Hz, 1H), 5.94 (d, J= 12.8 Hz, 1H), 3.95-3.90 (m, 2H), 2.32

[0719] (s, 3H), 1.61 (d, J= 7.0 Hz, 3H), 1.25 (t, J= 7.0 Hz, 3H); LCMS (m / z) 447.20 [M+H]+.

[0720] (SJL)-N -( 1 -( 1 -(5-cyanopyridin-2-1H-NMR (500 MHz, DMSO-d6) 59.21 (d, J= 7.1 Hz, 1H), yl)-3-methyl-lH-l,2,4-triazol-5- 9.02 (d, J= 1.6 Hz, 1H), 8.51 (dd, J= 8.6, 2.2 Hz, 1H), yl)ethyl)-3 -(2 -ethoxy vinyl)-5 - 8.00-7.99 (m, 1H), 7.97 (s, 1H), 7.79 (d, J= 14.0 Hz, 2H), (trifluoromethyl)benzamide 7.47 (d, J= 12.9 Hz, 1H), 6.07 (t, J= 7.0 Hz, 1H), 5.95 (d,

[0721] J= 13.0 Hz, 1H), 3.93 (q, J= 7.0 Hz, 2H), 2.33 (s, 3H), 1.61 (d, J= 7.0 Hz, 3H), 1.27-1.24 (m, 3H); LCMS (m / z) 471.35 [M+H]+.

[0722] (S,£)-3-(2-ethoxyvinyl)-5-1H-NMR (500 MHz, DMSO-d6) 59.20 (d, J= 7.1 Hz, 1H), (tri fl uoromethy 1 )- / V-( 1 -( 1 -(5- 8.96 (s, 1H), 8.47-8.45 (m, 1H), 8.22 (s, 1H), 8.09-8.06 (m, (trifluoromethyl)pyridin-2-yl)- 1H- 1H), 7.91 (s, 1H), 7.74 (d, J= 18.8 Hz, 2H), 7.45 (d, J= l,2,4-triazol-5-yl)ethyl)benzamide 12.9 Hz, 1H), 6.09-6.03 (m, 1H), 5.94 (d, J= 13.0 Hz, 1H),

[0723] 3.92 (q, J= 7.0 Hz, 2H), 1.64 (d, J= 7.0 Hz, 3H), 1.25 (t, J = 7.0 Hz, 3H); LCMS (m / z) 500.15 [M+H]+.

[0724] (S)-3-(2-chloro-3,3,3-1H-NMR (400 MHz, DMSO-d6) 59.38 (d, J= 7.1 Hz, 1H), trifluoroprop- 1 -en- 1 -yl)- / V-( 1 -( 1 - 9.00 (d, J= 1.5 Hz, 1H), 8.51 (dd, J= 8.6, 2.2 Hz, 1H), 8.22 (5-cyanopyridin-2-yl)-3-methyl- (s, 1H), 8.04 (s, 1H), 8.00 (d, J= 8.6 Hz, 1H), 7.87 (d, J = 1H- 1,2,4-triazol-5 -yl)ethyl)-5- 4.9 Hz, 2H), 6.08 (s, 1H), 2.33 (d, J= 2.7 Hz, 3H), 1.61 (d, (trifluoromethyl)benzamide J= 6.8 Hz, 3H); LCMS (m / z) 529.15 [M+H]+.

[0725] (S)-N-( 1 -( 1 -(5 -cyanopyridin-2-1H-NMR (400 MHz, DMSO-d6) 59.32 (d, J= 7.1 Hz, 1H), yl)-3-methyl-l / / -l,2,4-triazol-5- 9.02 (q, J= 1.0 Hz, 1H), 8.51 (dd, J= 8.6, 2.2 Hz, 1H), 8.40 yl)ethyl)-3-(trifluoromethyl)-5- (s, 1H), 8.26 (s, 1H), 8.15 (s, 1H), 8.00 (dd, J = 8.7, 0.6 Hz, (3,3,3-trifluoroprop- 1-en- 1- 1H), 7.50 (dd, J= 16.1, 2.2 Hz, 1H), 7.07-6.98 (m, 1H), yl)benzamide 6.14-6.07 (m, 1H), 2.33 (s, 3H), 1.63 (d, J= 6.8 Hz, 3H);

[0726]

[0727] LCMS (m / z) 495.15 [M+H]+.(S)-3-(2-chloro-3,3,3-1H-NMR (400 MHz, DMSO-d6) δ 9.34 (d, J= 7.1 Hz, 1H), trifluoroprop- 1 -en- 1 -yl)- / V-( 1 -(3- 8.93 (d, J= 4.9 Hz, 2H), 8.17 (s, 1H), 8.00 (s, 1H), 7.87 (s, methyl- 1 -(pyrimidin-2-yl)- 1H- 1H), 7.85 (s, 1H), 7.56 (t, J= 4.9 Hz, 1H), 6.03-5.96 (m, l,2,4-triazol-5-yl)ethyl)-5- 1H), 2.32 (s, 3H), 1.61 (d, J= 6.8 Hz, 3H); LCMS (m / z) (trifluoromethyl)benzamide 505.10 [M+H]+.

[0728] (S, E)-N-(l-(3-methyl-l-1H-NMR (400 MHz, DMSO-d6) δ 9.28 (d, J= 7.1 Hz, 1H), (pyrimidin-2-yl)- 1 H- 1,2,4-triazol- 8.94 (d, J = 4.9 Hz, 2H), 8.36 (s, 1H), 8.24 (s, 1H), 8.10 (s, 5 -yl)ethyl)-3 -(trifluoromethyl) -5 - 1H), 7.57 (t, J= 4.8 Hz, 1H), 7.49 (dd, J= 16.3, 1.8 Hz, (3,3,3-trifluoroprop- 1-en- 1- 1H), 7.01 (dd, J= 16.1, 6.8 Hz, 1H), 6.02 (t, J = 7.1 Hz, yl)benzamide 1H), 2.32 (s, 3H), 1.63 (d, J= 6.8 Hz, 3H); LCMS (m / z)

[0729] 471.10 [M+H]+.

[0730] (S, E)-N-( 1 -( 1 -(5-bromopyrimidin-1H-NMR (400 MHz, DMSO-d6) δ 9.20 (d, J= 7.1 Hz, 1H), 2-yl)- 1H- l,2,4-triazol-5-yl)ethyl)- 9.16 (s, 2H), 8.18 (s, 1H), 7.91 (s, 1H), 7.77 (s, 1H), 7.73 (s, 3-(2-ethoxyvinyl)-5- 1H), 7.46 (d, J= 13.0 Hz, 1H), 5.96-5.92 (m, 2H), 3.93 (q, J (trifluoromethyl)benzamide = 6.9 Hz, 2H), 1.62 (d, J= 6.8 Hz, 3H), 1.25 (t, J= 7.0 Hz,

[0731] 3H); LCMS (m / z) 511.05 [M+H]+.

[0732] (S)-N-(l-(l-(pyrimidin-2-yl)-lH-1H-NMR (400 MHz, CDCl3) 58.93 (d, J = 4.9 Hz, 2H), l,2,4-triazol-5-yl)ethyl)-3- 8.18 (s, 1H), 8.07-8.03 (m, 2H), 7.71 (d, J = 8.3 Hz, 1H), (trifluoromethyl)-4-(3,3,3- 7.67 (d, J = 7.8 Hz, 1H), 7.57-7.52 (m, 1H), 7.42 (t, J = 4.9 trifluoroprop- 1 -en- 1 - Hz, 1H), 6.52-6.45 (m, 1H), 6.30-6.21 (m, 1H), 1.72 (d, J = yl)benzamide 6.6 Hz, 3H); LCMS (m / z) 457.05 [M+H]+.

[0733] (S)-N-( 1 -( 1 -(5-cy anopyridin-2-1H-NMR (400 MHz, CDCl3) 58.87 (q, J = 1.1 Hz, 1H), yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- 8.20-8.15 (m, 3H), 8.04-8.00 (m, 2H), 7.71 (d, J = 8.1 Hz, (trifluoromethyl)-4-(3,3,3- 1H), 7.55 (d, J = 15.9 Hz, 1H), 7.49 (d, J = 8.1 Hz, 1H), trifluoroprop- 1 -en- 1 - 6.44 (dt, J= 14.6, 6.8 Hz, 1H), 6.30-6.21 (m, 1H), 1.73-1.70 yl)benzamide (m, 3H); LCMS (m / z) 481.10 [M+H]+.

[0734] (S, E)-N-(l-(l-(5-((dimethyl(oxo)- ’H-NMR (400 MHz, CHLOROFORM-D) 58.29 (dd, J = X6-sulfaneylidene)amino)pyridin- 2.7, 0.7 Hz, 1H), 8.14 (s, 1H), 8.10 (s, 1H), 7.98 (s, 1H), 2-yl)- 1H- l,2,4-triazol-5-yl)ethyl)- 7.84 (s, 1H), 7.80 (dd, J = 8.7, 0.6 Hz, 1H), 7.65 (dd, J = 3-(trifluoromethyl)-5-(3,3,3- 8.8, 2.7 Hz, 1H), 7.27-7.23 (m, 1H), 6.44-6.35 (m, 1H), trifluoroprop- 1 -en- 1 - 6.28 (dd, J = 8.2, 7.0 Hz, 1H), 3.26 (s, 6H), 1.68 (d, J = 6.8 yl)benzamide Hz, 3H); LCMS (m / z) 547.40 [M+H]+.

[0735] (S)-3-(2-chloro-3,3,3-1H-NMR (400 MHz, CHLOROFORM-D) 58.31 (s, 1H), trifluoroprop- 1 -en- 1 -yl)-N-( 1 -( 1 - 8.26 (d, J = 2.4 Hz, 1H), 8.11 (s, 2H), 7.95 (s, 1H), 7.77 (d, (5 -((dimethyl(oxo) -X6- J = 8.8 Hz, 1H), 7.62 (dt, J = 8.6, 2.5 Hz, 1H), 7.38 (s, 1H), sulfaneylidene)amino)pyridin-2- 6.28-6.24 (m, 1H), 3.23 (s, 6H), 1.65 (q, J = 3.4 Hz, 3H); yl)-lH-l,2,4-triazol-5-yl)ethyl)-5- LCMS (m / z) 581.9 [M+H]+.

[0736] (trifluoromethyl)benzamide

[0737] (S)-N-( 1 -( 1 -(5-cyanopyridin-2-1H-NMR (400 MHz, CHLOROFORM-D) 58.87-8.86 (m, yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- 1H), 8.21-8.19 (m, 1H), 8.18-8.17 (m, 2H), 8.06 (d, J = 8.6 (3, 3, 3-trifluoro-2 -methoxyprop- 1- Hz, 1H), 8.01 (s, 1H), 8.00 (s, 1H), 7.47-7.42 (m, 1H), 6.43 en-l-yl)-5- (dt, J = 14.7, 6.8 Hz, 2H), 3.84 (t, J = 1.1 Hz, 3H), 1.72 (d, J (trifluoromethyl)benzamide = 6.6 Hz, 3H); LCMS (m / z) 511.40 [M+H]+.

[0738] (S)-N-(l-(l-(pyrimidin-2-yl)-lH-1H-NMR (400 MHz, CHLOROFORM-D) 58.92 (dd, J = l,2,4-triazol-5-yl)ethyl)-3-(3,3,3- 4.9, 1.5 Hz, 2H), 8.23 (s, 1H), 8.06 (s, 2H), 8.02 (s, 1H), trifluoro-2-methoxyprop- 1 -en- 1 - 7.53 (d, J = 8.1 Hz, 1H), 7.41 (t, J = 4.9 Hz, 1H), 6.49-6.43 yl)-5 -(trifluoromethyl)benzamide (m, 2H), 3.85 (d, J = 1.0 Hz, 3H), 1.71 (d, J = 6.6 Hz, 3H);

[0739] LCMS (m / z) 487.40 [M+H]+.

[0740] (S, Z)-3-chloro-N-(l-(l-(5-1H-NMR (400 MHz, CHLOROFORM-D) 58.86 (q, J = 1.0

[0741]

[0742] cyanopyridin-2-yl)- 1 H- 1,2,4- Hz, 1H), 8.19-8.14 (m, 2H), 8.01 (s, 1H), 7.77 (t, J= 1.7triazol-5-yl)ethyl)-5-(3,3,3- Hz, 1H), 7.67 (s, 1H), 7.51 (d, J = 4.2 Hz, 1H), 7.36 (d, J = trifluoroprop- 1 -en- 1 - 7.8 Hz, 1H), 6.92 (d, J = 12.5 Hz, 1H), 6.40 (dd, J = 7.8, 6.8 yl)benzamide Hz, 1H), 5.96-5.86 (m, 1H), 1.71 (d, J = 6.6 Hz, 3H);

[0743] LCMS (m / z) 446.95 [M+H]+.

[0744] (S, E)-3-(2-chloro-3,3,3-1H-NMR (400 MHz, CHLOROFORM-D) 58.87 (d, J = 1.0 trifluoroprop- 1 -en- 1 -y 1) - 5 - Hz, 1H), 8.30 (s, 1H), 8.18-8.09 (m, 4H), 8.01 (d, J = 1.5 (trifluoromethyl)-N-(l-(l-(5- Hz, 1H), 7.56 (d, J = 8.1 Hz, 1H), 7.38 (s, 1H), 6.45 (dd, J = (trifluoromethyl)pyridin-2-yl)- 1H- 7.8, 6.8 Hz, 1H), 1.73 (dd, J = 6.8, 2.4 Hz, 3H)

[0745] l,2,4-triazol-5-yl)ethyl)benzamide

[0746] (S, Z)-3-(2-chloro-3,3,3-1H-NMR (400 MHz, CHLOROFORM-D) 58.86 (s, 1H), trifluoroprop- 1 -en- 1 -y 1) - 5 - 8.18-8.13 (m, 2H), 8.03 (d, J= 17.4 Hz, 2H), 7.90 (s, 1H), (trifluoromethyl)-N-(l-(l-(5- 7.66 (s, 1H), 7.54 (d, J = 8.1 Hz, 1H), 7.30 (s, 1H), 6.43 (t, J (trifluoromethyl)pyridin-2-yl)- 1H- = 7.3 Hz, 1H), 1.73 (d, J = 6.8 Hz, 3H); LCMS (m / z) l,2,4-triazol-5-yl)ethyl)benzamide 558.13 [M+H]+.

[0747] (S, E)-3-(trifluoromethyl)-N-(l-(l-1H-NMR (400 MHz, CHLOROFORM-D) 58.87 (s, 1H), (5-(trifluoromethyl)pyridin-2-yl)- 8.16 (dd, J = 11.0, 8.8 Hz, 2H), 8.09 (s, 1H), 8.05 (s, 1H), 1H- l,2,4-triazol-5-yl)ethyl)-5- 8.01 (s, 1H), 7.83 (s, 1H), 7.56 (d, J = 7.6 Hz, 1H), 7.22 (dd, (3,3,3-trifluoroprop- 1-en- 1- J = 16.3, 2.1 Hz, 1H), 6.47-6.33 (m, 2H), 1.74 (d, J = 6.6 yl)benzamide Hz, 3H); LCMS (m / z) 524.12 [M+H]+.

[0748] (S, E)-N-( 1 -( 1 -(5 -bromopyridin-2-1H-NMR (400 MHz, CHLOROFORM-D) 58.63 (dd, J = yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- 2.4, 0.7 Hz, 1H), 8.09 (s, 1H), 8.06-8.03 (m, 2H), 7.98 (s, (trifluoromethyl)-5-(3,3,3- 1H), 7.89 (dd, J = 8.7, 0.6 Hz, 1H), 7.82 (s, 1H), 7.57 (d, J = trifluoroprop- 1 -en- 1 - 8.1 Hz, 1H), 7.24-7.20 (m, 1H), 6.40-6.34 (m, 2H), 1.70 (d, yl)benzamide J = 6.8 Hz, 3H); LCMS (m / z) 535.55 [M+H]+.

[0749] (S)-N-(l-(l-(5-bromopyridin-2-1H-NMR (500 MHz, CHLOROFORM-D) 58.63 (dd, J = yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- 2.4, 0.7 Hz, 1H), 8.29 (s, 1H), 8.09 (d, J = 6.3 Hz, 2H), 8.04 (2-chloro-3,3,3-trifluoroprop- 1 - (dq, J = 8.7, 1.2 Hz, 1H), 7.98 (d, J = 1.9 Hz, 1H), 7.89 (dd, en-l-yl)-5- J = 8.7, 0.6 Hz, 1H), 7.63 (d, J = 7.9 Hz, 1H), 7.37 (s, 1H), (trifluoromethyl)benzamide 6.36 (dd, J = 7.8, 6.8 Hz, 1H), 1.70 (dd, J = 6.8, 3.1 Hz,

[0750] 3H); LCMS (m / z) 569.70 [M+H]+.

[0751] (S)-N-( 1 -(3-methyl- 1 -(5 -1H-NMR (400 MHz, CHLOROFORM-D) 58.84 (t, J = 1.1 (trifluoromethyl)pyridin-2-yl)- 1H- Hz, 1H), 8.23 (s, 1H), 8.12 (dd, J = 8.7, 2.3 Hz, 1H), 8.08 l,2,4-triazol-5-yl)ethyl)-3-(3,3,3- (d, J = 8.6 Hz, 1H), 8.03 (d, J = 15.4 Hz, 2H), 7.56 (d, J = trifluoro-2-methoxyprop- 1 -en- 1 - 8.1 Hz, 1H), 6.45 (s, 1H), 6.39 (dd, J = 8.1, 6.8 Hz, 1H), yl)-5 -(trifluoromethyl)benzamide 3.84 (t, J= 1.1 Hz, 3H), 2.46 (s, 3H), 1.71 (d, J = 6.6 Hz,

[0752] 3H); LCMS (m / z) 568.40 [M+H]+.

[0753] (S)-3-(3,3,3-trifluoro-2-1H-NMR (400 MHz, CHLOROFORM-D) 58.87 (t, J = 1.0 methoxyprop- 1 -en- 1 -y l)-5 - Hz, 1H), 8.22 (s, 1H), 8.18-8.13 (m, 2H), 8.06 (s, 1H), 8.01 (trifluoromethyl)-N-(l-(l-(5- (s, 2H), 7.56-7.52 (m, 1H), 6.47-6.40 (m, 2H), 3.84 (t, J = (trifluoromethyl)pyridin-2-yl)- 1H- 1.1 Hz, 3H), 1.73 (d, J = 6.6 Hz, 3H); LCMS (m / z) 554.30 l,2,4-triazol-5-yl)ethyl)benzamide [M+H]+.

[0754] (S)-N-( l-(3-methyl- l-(pyrimidin-1H-NMR (400 MHz, CHLOROFORM-D) 58.89 (dd, J = 2-yl)- lH-l,2,4-triazol-5-yl)ethyl)- 4.9, 1.7 Hz, 2H), 8.24 (s, 1H), 8.06 (d, J = 5.9 Hz, 1H), 8.03 3-(3,3,3-trifluoro-2-methoxyprop- (s, 1H), 7.55-7.52 (m, 1H), 7.36 (t, J = 4.8 Hz, 1H), 6.46 (s, l-en-l-yl)-5- 1H), 6.44-6.40 (m, 1H), 3.85 (d, J = 1.0 Hz, 3H), 2.50 (s, (trifluoromethyl)benzamide 3H), 1.69 (d, J = 6.6 Hz, 3H); LCMS (m / z) 501.40 [M+H]+. (S)-N-(l-(l-(5-((dimethyl(oxo)-1H-NMR (400 MHz, CHLOROFORM-D) 58.27 (dd, J = X6-sulfaneylidene)amino)pyridin- 2.7, 0.5 Hz, 1H), 8.24 (s, 1H), 8.05 (s, 2H), 8.03 (s, 1H), 2-yl)- 1H- l,2,4-triazol-5-yl)ethyl)- 7.94 (s, 1H), 7.78-7.75 (m, 1H), 7.62 (dd, J = 8.7, 2.6 Hz,

[0755]

[0756] 3-(3, 3, 3-trifluoro-2 -methoxyprop- 1H), 6.45 (s, 1H), 6.26 (dd, J = 8.1, 6.8 Hz, 1H), 3.83 (d, J =l-en-l-yl)-5- 1.0 Hz, 3H), 3.23 (s, 6H), 1.65 (d, J = 6.8 Hz, 3H); LCMS (trifluoromethyl)benzamide (m / z) 577.50 [M+H]+.

[0757] (S)-3-chloro-5-(2-chloro-3,3,3-1H-NMR (400 MHz, CHLOROFORM-D) 58.92 (d, J = 4.9 trifluoroprop- 1 -en- 1 -yl)-N-( 1 -( 1 - Hz, 2H), 8.07 (d, J = 1.2 Hz, 1H), 7.97-7.92 (m, 1H), 7.92 (pyrimidin-2-yl)- 1 H- 1,2,4-triazol- (t, J = 1.7 Hz, 1H), 7.88 (d, J = 1.7 Hz, 1H), 7.68 (t, J = 1.6 5 -y l)ethyl)benzamide Hz, 1H), 7.45-7.40 (m, 2H), 6.43 (q, J = 6.6 Hz, 1H), 1.70

[0758] (dd, J = 6.7, 2.1 Hz, 3H); LCMS (m / z) 456.90 [M+H]+. (S, E)-3-chloro-N-(l-(l-1H-NMR (400 MHz, CHLOROFORM-D) 58.92 (d, J = 4.6 (pyrimidin-2-yl)- 1 H- 1,2,4-triazol- Hz, 2H), 8.06 (s, 1H), 7.79 (t, J = 1.8 Hz, 2H), 7.58 (t, J = 5-yl)ethyl)-5-(3,3,3-trifluoroprop- 1.6 Hz, 1H), 7.44 (d, J = 8.1 Hz, 1H), 7.41 (t, J = 4.8 Hz, 1 -en- 1 -yl)benzamide 1H), 7.14 (dd, J = 16.1, 2.2 Hz, 1H), 6.44 (dd, J = 7.9, 6.7

[0759] Hz, 1H), 6.35-6.26 (m, 1H), 1.70 (d, J = 6.8 Hz, 3H);

[0760] LCMS (m / z) 422.90 [M+H]+.

[0761] (S)-N-( 1 -( 1 -(5 -bromopyrimidin-2-1H-NMR (400 MHz, CHLOROFORM-D) 58.96 (s, 2H), yl)-lH-l,2,4-triazol-5-yl)ethyl)-3- 8...

Claims

CLAIMS:

1. A compound of formula (I),OR3aR3bR,b-Q / (I)wherein,Rlais C2-C3-alkenyl; wherein said Rlais unsubstituted or substituted with one to three groups independently selected from hydrogen, halogen, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-haloalkyl, C3-C5-cycloalkyl, C3-C5-halocycloalkyl, -S(0)o-2-Ci-C4-alkyl, S(0)o-2-Ci-C4-haloalkyl or - NR'R";Rlbis selected from the group consisting of hydrogen, halogen, cyano, nitro, SF5, Ci-Ce-alkyl, C2-C6- alkenyl, C2-Ce-alkynyl, Ci-Ce-haloalkyl, C2-Ce-haloalkenyl, C2-Ce-haloalkynyl, Ci-Ce-alkoxy, C2-C6- alkenyloxy, C2-Ce-alkynyloxy, Ci-Ce-haloalkoxy, C2-Ce-haloalkenyloxy, C2-Ce-haloalkynyloxy, Ci-Ce- alkylsulfanyl, Ci-Ce-alkylsulfinyl, Ci-Ce-alkylsulfonyl, Ci-Ce-haloalkylsulfanyl, Ci-Ce-haloalkylsulfinyl, Ci-Ce-haloalkylsulfonyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkyl-Ci-C6-alkyl and C3- Ce -cycloalkyl nitrile;R2is selected from the group consisting of hydrogen, Ci-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce- haloalkyl, C2-Ce-haloalkenyl, Ci-Ce-alkoxy, Ci-Ce-alkoxy-Ci-Ce-alkyl-, Ci-Ce-alkylcarbonyl, C3-C6- cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkyl-Ci-C6-alkyl and C3-C6-halocycloalkyl-Ci-C6-alkyl; R3aand R3bare independently selected from the group consisting of hydrogen, halogen, cyano, Ci-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-haloalkyl, C3-Cs-cycloalkyl, C3-Cs-halocycloalkyl and Ci-Ce- alkylnitrile;orR3aand R3bas substituents, together with the carbon atom to which they are attached, form a 3- to 4- membered carbocyclic or heterocyclic ring; wherein said 3- to 4- membered heterocyclic ring contains 1 or 2 heteroatoms independently selected from N, O or S; wherein said carbocyclic or heterocyclic ring is unsubstituted or substituted with one to three substituents independently selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or Ci-Ce-alkoxy;ring-A is selected from triazolyl or pyrazinyl, wherein said ring-A is unsubstituted or substituted with one or two substituents independently selected from R4;R4is selected from the group consisting of hydrogen, halogen, cyano, Ci-Ce-alkyl, Ci-Ce-alkcnyl. C -Ce-alkynyl, Ci-Ce-haloalkyl, Ci-Ce-haloalkcnyl. Ci-Ce-haloalkynyl. Ci-Ce-alkoxy and C3-Ce-cycloalkyl; Q is selected from the group consisting of phenyl and a 5- or 6- membered heteroaryl ring; wherein said phenyl and heteroaryl ring are unsubstituted or substituted with one to three substituents independently selected from R5;orQ is selected from the group consisting of -C(R6)=NOR7, -C(O)NR6R7and -C(O)N=S(O)R6R7;R5is selected from the group consisting of hydrogen, halogen, hydroxy, cyano, nitro, SCN, SF5, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkylsulfanyl, Ci-Ce-alkylsulfinyl, Ci-Ce-alkylsulfonyl, C3-C6-cycloalkyl, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-Ci-C6-alkyl, C3-Ce-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkyloxy-Ci-Cs-alkyl, -C(O)NH-Ci-C3-alkyl, -C(O)-N(Ci-C6-alkyl)2, -C(O)-NH-Ci-C6-alkoxy, -C(O)-N-(Ci-C6-alkyl)(Ci-Ce-alkoxy), -C(O)-NH-C3-Ce -cycloalkyl wherein C3-C6-cycloalkyl is substituted with Ci-C3-haloalkyl, -C(O)-NH-C3-Ce-cycloalkyl, -C(O)-NH-Ci-C6-alkyl-C3-C6-cycloalkyl, -C(O)-NH-3-to 4- membered non-aromatic heterocyclic ring wherein said ring is substituted with Ci-C3-alkyl, -C(O)-NH-3- to 4- membered non-aromatic heterocyclic ring, -NH-C(O)Ci-Ce-alkyl, -NR6C(O)NR6R7, -OC(O)NR6R7, -NR6C(O)OR7, -NR'R", -C(=O)-OH, -C(=O)-R", CR'=NR", Si(R8)3, -C(O)-N=S(O)0- iR6aR6b, -N=S(0)o-iR6aR6band a 3- to 4- membered non-aromatic heterocyclic ring; wherein each non-aromatic heterocyclic ring in R5contains 1 or 2 heteroatoms independently selected from N, N(CH3), O or S;wherein each of the Ci-Ce-alkyl, Ci-Ce-alkcnyl. Ci-Ce-alkynyl. Ci-Ce-alkoxy, Ci-Ce-alkcnyloxy. C2-C6-alkynyloxy, Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-alkylsulfanyl, Ci-Ce-alkylsulfinyl, Ci-Ce-alkylsulfonyl, C3-Ce-cycloalkyl, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-Ci-Ce-alkyl, C3-Ce-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkyloxy-Ci-C6-alkyl, -C(O)NH-Ci-C6-alkyl, -C(O)NH-C3-Ce-cycloalkyl and -NH-C(O)Ci-Ce-alkyl groups of R5are unsubstituted or substituted with one to three substituents independently selected from halogen, hydroxy or cyano;R6and R7are independently selected from the group consisting of hydrogen, Ci-Ce-alkyl, Ci-Ce-cyanoalkyl, Ci-Ce-alkoxy, Ci-Ce-haloalkyl, Ci-Ce-haloalkoxy, C3-Ce-cycloalkyl, C3-C6-halocycloalkyl, Ci-Ce-alkoxy-Ci-Ce-alkyl and a 3- to 4-membered non-aromatic heterocyclic ring; wherein said 3- to 4-membered non-aromatic heterocyclic ring contains 1 or 2 heteroatoms independently selected from N, O or S;R' and R" are independently selected from the group consisting of hydrogen, Ci-Ce-alkyl, Ci-Ce-alkoxy and C3-Ce-cycloalkyl; wherein said alkyl and cycloalkyl groups are unsubstituted or substituted with one to three substituents independently selected from halogen, hydroxy or cyano;R6ais selected from the group consisting of hydrogen, Ci-Ce-alkyl, CT-G, -alkenyl. G-G,-alkynyl. Ci- Ce-haloalkyl, G-G,-haloalkcnyl. C3-Cs-cycloalkyl and NRaRb;R6bis selected from Ci-Ce-alkyl or C3-C6-cycloalkyl;orR6aand R6btogether with the sulfur atom to which they are attached may form a 3 - to 6-membered non- aromatic heterocyclic ring; wherein said heterocyclic ring contains an additional 1 or 2 heteroatoms independently selected from N, O or S;Raand Rbare independently selected from hydrogen or Ci-Ce-alkyl;R8is independently selected from the group consisting of Ci-Ce-alkyl, CT-G, -alkenyl. Ci-G.-alkynyl. and C3-C6-cycloalkyl;or salts, stereoisomers, metal complexes, polymorphs, or N-oxides thereof.

2. The compound of formula (I) according to claim 1, wherein Rlais G-G-alkcn l: wherein said Rlais unsubstituted or substituted with one to three groups independently selected from hydrogen, halogen, CN, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy, Ci-C3-haloalkyl, C3-C5-cycloalkyl, C3-C5- halocycloalkyl, -S(0)o-2-Ci-C3-alkyl, S(0)o-2-Ci-C3-haloalkyl or -NR'R".

3. The compound of formula (I) according to claim 1 or 2, wherein Rlbis selected from the group consisting of hydrogen, halogen and Ci-C3-haloalkyl.

4. The compound of formula (I) according to any one of claims 1 to 3, wherein R2is selected from the group consisting of hydrogen and Ci-C3-alkyl.

5. The compound of formula (I) according to any one of claims 1 to 4, wherein R3ais Ci-C3-alkyl.

6. The compound of formula (I) according to any one of claims 1 to 5, wherein R3bis hydrogen.

7. The compound of formula (I) according to any one of claims 1 to 6, wherein ring-A is selected from ring-Al orring-A2,ring-A1 ring-A2wherein, indicates the point of attachment to the carbon atom that is bonded to the amide nitrogen and # indicates the point of attachment to the Q substituent, and R4is as defined in claim 1.

8. The compound of formula (I) according to any one of claims 1 to 7, wherein R4is selected from the group consisiting of hydrogen and Ci-C3-alkyl.

9. The compound of formula (I) according to any one of claims 1 to 8, wherein R5is selected from the group consisiting of hydrogen, halogen, hydroxy, cyano, nitro, Ci-C4-alkyl, Ci-C4-alkoxy, C1-C4- haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C3-alkyl, -C(O)NHCi-C5-alkyl, -C(O)N(CI-C3- alkyl)2, -C(O)NHCi-C4-alkoxy, -C(O)N(Ci-C3-alkyl)(Ci-C3-alkoxy), -C(O)NHC3-C5-cycloalkyl wherein C3-C5-cycloalkyl is substituted with Ci-CT-haloalkyl. -C(O)NHC3-C5-cycloalkyl, -C(O)NH-Ci- C3-alkyl-C3-C6-cycloalkyl, -C(0)NH-4-membered non-aromatic heterocyclic ring wherein said ring is substituted with Ci-C3-alkyl, -C(0)NH-4-membered non-aromatic heterocyclic ring, -NHC(0)CI-C4- alkyl, -C(=O)-OH, -C(=O)-R", -C(O)-N=S(O)R6aR6b, -N=S(0)o-iR6aR6band a 3- to 4-membered non- aromatic heterocyclic ring; wherein each non-aromatic heterocyclic ring in R5contains 1 or 2 heteroatoms independently selected from N, N(CH3), O or S; wherein each of the Ci-C4-alkyl, C1-C4- alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C6-alkyl, -C(O)NHCi-C5-alkyl, -C(O)NHC3-C5- cycloalkyl and -NHC(O)Ci-C4-alkyl groups of R5are unsubstituted or substituted with one or two substituents independently selected from halogen, hydroxy or cyano.

10. The compound of formula (I) according to any one of claims 1 to 9, wherein Q is a 5- or 6- membered heteroaryl ring; wherein said heteroaryl ring is unsubstituted or substituted with one or two substituents independently selected from R5; and wherein R5is as defined in claim 1 or 9.

11. The compound of formula (I) according to any one of claims 1 to 10, wherein Rlais C2-C3-alkenyl;wherein said Rlais unsubstituted or substituted with one to three groups independently selected from hydrogen, halogen, CN, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy, Ci-C3-haloalkyl or C3-C5- cycloalkyl;Rlbis selected from the group consisiting of hydrogen, halogen and Ci-C3-haloalkyl;R2is selected from the group consisting of hydrogen and Ci-C3-alkyl;R3ais Ci-C3-alkyl;R3bis hydrogen;ring-A is selected from ring-Al or ring-A2,ring-A1 ring-A2wherein, indicates the point of attachment to the carbon atom that is bonded to the amide nitrogen and # indicates the point of attachment to the Q substituent;R4is selected from the group consisiting of hydrogen and Ci-C3-alkyl;Q is selected from 5- or 6- membered heteroaryl ring; wherein said heteroaryl ring is unsubstituted or substituted with one or two substituents independently selected from R5;R5is selected from the group consisiting of hydrogen, halogen, hydroxy, cyano, nitro, Ci-C4-alkyl, Ci- C4-alkoxy, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C3-alkyl, -C(O)NHCi-C5-alkyl, - C(O)N(Ci-C3-alkyl)2, -C(O)NHCi-C4-alkoxy, -C(O)N(Ci-C3-alkyl)(Ci-C3-alkoxy), -C(O)NHC3-C5- cycloalkyl wherein C3-C5-cycloalkyl is substituted with Ci-C’i-haloalkyl. -C(O)NHC3-C5-cycloalkyl, - C(O)NH-Ci-C3-alkyl-C3-C6-cycloalkyl, -C(0)NH-4-membered non-aromatic heterocyclic ring wherein said ring is substituted with Ci-C3-alkyl, -C(0)NH-4-membered non-aromatic heterocyclic ring, - NHC(O)Ci-C4-alkyl, -C(=O)-OH, -C(=O)-R", -C(O)-N=S(O)R6aR6b, -N=S(0)o-iR6aR6band a 3- to 4- membered non-aromatic heterocyclic ring; wherein each non-aromatic heterocyclic ring in R5contains 1 or 2 heteroatoms independently selected from N, N(CH3), O or S; wherein each of the Ci-C4-alkyl, Ci-C4-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C3-alkyl, -C(O)NHCi-C5-alkyl, -C(O)NHC3-C5- cycloalkyl and -NHC(O)Ci-C4-alkyl groups of R5are unsubstituted or substituted with one or two substituents independently selected from halogen, hydroxy or cyano;R" is selected from the group consisting of hydrogen, Ci-C3-alkyl and Ci-Ce-alkoxy;R6ais selected from the group consisting of hydrogen, Ci-C4-alkyl, and Ci-C4-haloalkyl;R6bis Ci-C3-alkyl;orR6aand R6btogether with the sulfur atom to which they are attached may form a 5- to 6-membered non- aromatic heterocyclic ring; wherein said heterocyclic ring contains an additional 1 or 2 heteroatoms independently selected from N or O or S.

12. A composition comprising the compound of formula (I) or salts, stereoisomers, metal complexes, polymorphs or N-oxides thereof according to claim I and at least one additional component selected from the group consisting of surfactants and auxiliaries.

13. The composition according to claim 12, wherein said composition additionally comprises at least one biological active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, or nutrients.

14. The composition according to claim 12, wherein said compound of formula (I) or salts, stereoisomers, polymorphs, metal complexes or N-oxides thereof ranges from 0.1 % to 99 % by weight with respect to the total weight of the composition.

15. A combination comprising the compound of formula (I) or salts, stereoisomers, polymorphs, metal complexes or N-oxides thereof according to claim 1 and at least one additional biological active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers or nutrients.

16. A method for protecting crops from atack or infestation by insects and mite pests comprises contacting the crop with the compound of formula (1) or salts, stereoisomers, polymorphs, metal complexes or N- oxides thereof according to claim 1, composition thereof according to claim 12, or combination thereof according to claim 15.

17. The method according to claim 16, wherein said method comprises applying effective dosages of compound of formula (I) in amounts ranging from 1 gai to 5000 gai per hectare in agricultural or horticultural crops.

18. A method for the protection of seeds, plants and plant parts from soil insects and of the seedlings roots and shoots from soil and foliar insects comprising contacting the seeds before sowing and / or after pre- germination with the compound of formula (I) or salts, stereoisomers, polymorphs, metal complexes or N-oxides thereof according to claim 1, composition thereof according to claim 12, or combination thereof according to claim 15.

19. Use of the compound of formula (I) or salts, stereoisomers, polymorphs, metal complexes, or N-oxides thereof according to claim 1, the composition thereof according to claim 12, or the combination thereof according to claim 15, for combating insects and mite pests in agricultural crops, horticultural crops, household and vector control and parasites on animals.

20. A seed comprising the compound of formula (I) or salts, stereoisomers, polymorphs, metal complexes, or N-oxides thereof according to claim 1, the composition thereof according to claim 12 or the combination thereof according to claim 1, wherein the amount of compound of formula (I) in said seed ranges from about 0.0001 % to about 1 % by weight,21. An intermediate compound of formula (IC),(IC)wheren,Rlais Ci-alkcnyl: wherein said Rlais unsubstituted or substituted with one to three groups independently selected from hydrogen, halogen, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-haloalkyl, C3-C5-cycloalkyl or C3-C5-halocycloalkyl; with the provisio that the compound of formula (IC) excludes 3-(l-Cyclopropyl-2,2-difluoroethenyl)-5-(trifluoromethyl)benzoic acid and 3-(l-Cyclopropyletiienyl)-5-(trifluoromethyl)benzoic acid.

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